热力学Eh-pH相图在大姚铜矿分带模式研究中的应用

滇中地区的中生代砂岩型铜矿具有辉铜矿-斑铜矿-黄铜矿-黄铁矿的分带顺序,经典理论认为这种分带顺序主要是由Eh值控制的。对大姚铜矿床的矿物分带的研究证实此分带是成立的,然该矿S同位素推演成矿温度(323.8 K),计算发现在还原条件下(Eh0.314),这个分带主要受pH值控制,以辉铜矿作为主要矿石矿物的富集带是在碱性(pH6.23)环境中形成的。此理论分析与实际矿物分带中的胶结物组分分析相吻合,即碱性胶结物(碳酸盐胶结)处可出现富矿,此规律对大姚铜矿的找矿有指导意义。     

滇中地区砂岩铜矿矿物分带特征及其成因意义

滇中地区砂岩铜矿形成于紫色层向浅色层过渡的氧化还原界面附近，矿体具明显的矿物分带，从紫色层向浅色层，金属矿物依次按赤铁矿→辉铜矿→斑铜矿→黄铜矿→黄铁矿变化，这种分带有两种表现形式：一种为顺层分带，另一种为垂直分带，引起矿物分带的原因是由于具氧化性的含铜卤水和具还原性的含硫溶液相互反应，造成了不同矿物的先后沉淀。     

云南六苴砂岩型铜矿床地球化学异常模式

云南六苴铜矿床是楚雄陆相红层盆地砂(页)岩型铜矿的典型代表.矿体(平均品位1.34%)赋存于K2ml1中紫色砂岩与浅色砂岩交互带,从紫色砂岩到浅色砂岩,依次呈现赤铁矿、辉铜矿、斑铜矿、黄铜矿、黄铁矿水平分带.采集9个钻孔岩芯样品,分析其主元素与微量元素地球化学异常特征,指示成矿元素组合为Cu-Ag-As-Sb-Hg.K2ml1中铜矿体,从上至下具有v-Ni-Cu-Ag-Hg-(As-Sb)-Pb-(Zn)-V-(Ni)垂向分带;由西(全紫带)至东(全浅带)具有Sb-Hg-v-Cu-As-Sb-Ag-Co-Ni-Pb-Zn横向分带.通过不同剖面地球化学异常特征对比,建立矿床的地球化学异常模式:Co-Ni-V组合异常位于矿体上方,Pb-Zn组合异常位于矿体下方,矿体处元素组合异常为Cu-Ag-As-Sb-Hg.出现Cu-Ag-As-Sb-Hg组合异常,Cu/Ag>315、Cu/(Pb Zn)>320、Cu/(As sb Hg)为1000-5800时,矿体较富,品位稳定;出现Pb-Zn-Co-(Ni)组合异常,Cu/Ag<105、Cu/(Pb Zn)<7、Cu/(As Sb Hg)<36时无矿;出现Sb-Hg-V组合异常,Cu/(As Sb Hg)>5800时则无矿.Cu、Ag、As、Sb、Hg含量及元素对比值沿矿床走向从北向南降低,预示"矿化能力"减弱或矿体中心位置偏移.该地球化学异常模式为深部成矿预测提供了重要依据.     

云南楚雄盆地砂(页)岩型铜矿床成矿规律及成矿模式

云南楚雄盆地是我国砂(页)岩型铜矿重要矿集区。本文在前人研究基础上,根据近年来危机矿山勘查成果,从铜矿的空间分布、地层层位与成矿、构造与成矿、岩性与成矿、浅紫色砂岩交互带控矿、金属矿物组合等方面,总结了云南楚雄盆地砂(页)岩矿床的成矿规律,认为区内铜矿床为典型的沉积-改造型层控矿床,并建立了成矿模式。     

大姚六苴砂岩型铜矿床构造演化时间序列及构造-流体耦合成矿模式

楚雄盆地砂岩型铜矿床分布于扬子地块西南缘,集铜、油气与煤、盐为一体的中新生代陆相红色盆地中,分布煤(T_3-J)、铜(K_2)及膏盐(K_2-E)矿床组合,是我国著名的砂岩型铜矿集区.其中,大姚六苴铜矿床是其典型代表.     

滇东北茂租热液型铅锌矿床矿物组合共生分异的热力学Eh—pH相图

滇东北地区广泛分布的热液型铅锌矿床具有普遍的矿物组合分带特征,研究矿床矿物组合的共生分异特征,是了解该类型矿床的成矿流体在演化过程中,成矿元素迁移和沉淀的核心问题之一,通过共生矿物的热力学Eh—pH相图可以有效的诠释成矿流体中成矿元素在迁移、沉淀过程中的物理化学条件。本文以滇东北茂租铅锌矿床为例,对滇东北热液型铅锌矿床的金属矿物共生组合在时间、空间分带特征进行热力学相图分析,选取373K、423K、473K、523K四个温度截面对金属矿物共生组合稳定存在的Eh—pH范围进行计算,相图显示成矿流体中矿物迁移、沉淀机制主要是由于成矿流体的Eh、p H值双重制约:Eh值的变化控制着硫化物沉淀的时间分带,成矿流体从深部向浅部运移,Eh值将会逐渐增大,主要矿物从黄铁矿→方铅矿→闪锌矿依次开始析出;p H值控制硫化物的空间分带,随着p H值的增大,成矿元素从离子的形式转变为硫酸盐矿物进行迁移。研究表明,控制成矿流体中硫化物迁移、沉淀的物理化学条件除了温度、压力、金属离子浓度及流体的氧硫逸度之外,流体的酸碱度及氧化还原电位同样是控制矿物组合共生分异的重要影响因素,此研究对该类型矿床的成矿流体的演化和成矿机制提供了一定的理论依据。     

楚雄盆地六苴铜矿床两期成矿流体来源的C-O同位素示踪

<正>楚雄中新生代红层盆地是扬子地台西南缘受印度板块与欧亚板块碰撞及后期构造活动改造所形成的汇聚型后陆盆地(张志斌和曹德斌,2002)。盆地东侧牟定斜坡带上发育一系列陆相砂岩型铜矿床,大姚六苴矿床为其中规模最大、最典型的砂岩铜矿床。     

楚雄盆地砂岩铜矿床同位素特征及矿床成因

楚雄盆地砂岩铜矿形成于白垩系高峰寺组凹地苴段、马头山组六苴段和大村段,以六苴、郝家河及大村铜矿床为代表。不论是硫同位素,还是氢氧同位素、铅同位素,六苴铜矿床和郝家河铜矿床均不相同。六苴铜矿硫化物中的硫以来自围岩为主,成矿溶液来自上部天水和建造水,成矿金属物质来自围岩,推测成岩成矿作用是主要矿化机制。而郝家河铜矿,成矿物质更多的是来自地下深处,与深部地下水循环作用有关,表明郝家河铜矿床以改造成矿为主。     

地洼盆地砂岩铜矿床成矿作用的化学动力学和热力学研究

对我国南方中新生代地洼盆地中的砂岩铜矿床进行了化学动力学与热力学的理论与实验研究。矿源岩中以辉铜矿和黄铜矿最有利于溶解和迁移，ＮａＣｌ对Ｃｕ的溶解和含矿流体的形成起了催化作用。溶液中Ｃｕ以络合物的形式迁移，其中以一价铜氯络合物为主；温度的降低和溶液中性化导致了络合物的失稳、分解和铜矿物的沉淀。铜矿物的化学动力学和热力学制约了砂岩铜矿中以辉铜矿为主及矿床分带的形成。     

云南大姚地区上白垩统马头山组六苴段中亚段

上白垩统马头山组六苴段中亚段(K2ml2)是云南六苴砂岩型铜矿区内含铜层位之一。六苴段中亚段含铜砂岩Mo、Cd、As、Cu等亲硫元素富集。微量元素多富集于浅色砂岩中,向紫色砂岩一侧逐渐亏损,呈现分带特征。铜矿石V/(V+Ni)值大于0.7,反映缺氧环境的特点。稀土元素总量(∑REE)101.71×10-6～157.55×10-6,稀土元素分配模式为Eu、Ce亏损-轻稀土元素富集型。从铜矿石→浅色矿化砂岩→浅色无矿砂岩,随着铜含量的降低,Mo、Cd、As、Hg平均含量逐渐降低,∑REE与高场强元素Nb、 Zr、 Hf、Th平均含量逐渐升高。六苴段中亚段砂岩具“矿源层”的特征,铜矿石与围岩具物源一致性,铜矿石在弱碱性、还原条件下由砂岩经水-岩作用形成,与六苴铜矿床(K2ml1)成矿机理相似。小河地段纵向上从北向南,六苴段中亚段中铜矿化的能力逐渐减弱,推测矿化带在走向上向西(紫色砂岩一侧)发生了偏移。     

Isotopic systematics of He,Ar, S,Cu, Ni,Re, Os,Pb, U,Sm, Nd,Rb, Sr,Lu, and Hf in the rocks and ores of the Norilsk deposits

This paper reports the first results of a study of 11 isotope systems (³He/⁴He, ⁴⁰Ar/³⁶Ar, ³⁴S/³²S, ⁶⁵Cu/⁶³Cu, ⁶²Ni/⁶⁰Ni, ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ^206–208Pb/²⁰⁴Pb, Hf–Nd, U–Pb, and Re–Os) in the rocks and ores of the Cu–Ni–PGE deposits of the Norilsk ore district. Almost all the results were obtained at the Center of Isotopic Research of the Karpinskii All-Russia Research Institute of Geology. The use of a number of independent genetic isotopic signatures and comprehensive isotopic knowledge provided a methodic basis for the interpretation of approximately 5000 isotopic analyses of various elements. The presence of materials from two sources, crust and mantle, was detected in the composition of the rocks and ores. The contribution of the crustal source is especially significant in the paleofluids (gas–liquid microinclusions) of the ore-forming medium. Crustal solutions were probably a transport medium during ore formation. Air argon is dominant in the ores, which indicates a connection between the paleofluids and the atmosphere. This suggests intense groundwater circulation during the crystallization of ore minerals. The age of the rocks and ores of the Norilsk deposits was determined. The stage of orebody formation is restricted to a narrow age interval of 250 ± 10 Ma. An isotopic criterion was proposed for the ore-bearing potential of mafic intrusions in the Norilsk–Taimyr region. It includes several interrelated isotopic ratios of various elements: He, Ar, S, and others.     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案(1999/30/EC),对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提     

Wavelength-dispersive X-ray fluorescence spectrometric determination of Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites

Komatiites are mantle-derived ultramafic volcanic rocks. Komatiites have been discovered in several States of India, notably in Karnataka. Studies on the distribution of trace-elements in the komatiites of India are very few. This paper proposes a simple, accurate, precise, rapid, and non-destructive wavelength-dispersive x-ray fluorescence (WDXRF) spectrometric technique for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites, and discusses the accuracy, precision, limits of detection, x-ray spectral-line interferences, inter-element effects, speed, advantages, and limitations of the technique. The accuracy of the technique is excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Zr, Nb, Ba, Pb, and Th and very good (within 4%) for Y. The precision is also excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th. The limits of detection are: 1 ppm for Sc and V; 2 ppm for Cr, Co, and Ni; 3 ppm for Cu, Zn, Rb, and Sr; 4 ppm for Y and Zr; 6 ppm for Nb; 10 ppm for Ba; 13 ppm for Pb; and 14 ppm for Th. The time taken for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in a batch of 24 samples of komatiites, for a replication of four analyses per sample, by one operator, using a manual WDXRF spectrometer, is only 60 hours.     

Regional distribution of Al,B, Ba,Ca, K,La, Mg,Mn, Na,P, Rb,Si, Sr,Th, U and Y in terrestrial moss within a 188,000 km2 area of the central Barents region: influence of geology,seaspray and human activity

Five hundred and ninety-eight samples of terrestrial moss (Hylocomium splendens and Pleurozium schreberi) collected from a 188,000 km² area of the central Barents region (NE Norway, N Finland, NW Russia) were analysed by ICP-AES and ICP-MS. Analytical results for Al, B, Ba, Ca, K, La, Mg, Mn, Na, P, Rb, Si, Sr, Th, U and Y concentrations are reported here. Graphical methods of data analysis, such as geochemical maps, cumulative frequency diagrams, boxplots and scatterplots, are used to interpret the origin of the patterns for these elements. None of the elements reported here are emitted in significant amounts from the smelting industry on the Kola Peninsula. Despite the conventional view that moss chemistry reflects atmospheric element input, the nature of the underlying mineral substrate (regolith or bedrock) is found to have a considerable influence on moss composition for several elements. This influence of the chemistry of the mineral substrate can take place in a variety of ways. (1) It can be completely natural, reflecting the ability of higher plants to take up elements from deep soil horizons and shed them with litterfall onto the surface. (2) It can result from naturally increased soil dust input where vegetation is scarce due to harsh climatic conditions for instance. Alternatively, substrate influence can be enhanced by human activity, such as open-cast mining, creation of ‘technogenic deserts’, or handling, transport and storage of ore and ore products, all of which magnify the natural elemental flux from bedrock to ground vegetation. Seaspray is another natural process affecting moss composition in the area (Mg, Na), and this is most visible in the Norwegian part of the study area. Presence or absence of some plant species, e.g., lichens, seems to influence moss chemistry. This is shown by the low concentrations of B or K in moss on the Finnish and Norwegian side of the (fenced) border with Russia, contrasting with high concentrations on the other side (intensive reindeer husbandry west of the border has selectively depleted the lichen population).     

Petrographic, mineralogy, and geochemistry of coals of Pabedana, Kerman Province, Central Iran

This paper discusses the result of the detailed investigations carried out on the coal characteristics, including coal petrography and its geochemistry of the Pabedana region. A total of 16 samples were collected from four coal seams d2, d4, d5, and d6 of the Pabedana underground mine which is located in the central part of the Central-East Iranian Microcontinent. These samples were reduced to four samples through composite sampling of each seam and were analyzed for their petrographic, mineralogical, and geochemical compositions. Proximate analysis data of the Pabedana coals indicate no major variations in the moisture, ash, volatile matter, and fixed carbon contents in the coals of different seams. Based on sulfur content, the Pabedana coals may be classified as low-sulfur coals. The low-sulfur contents in the Pabedana coal and relatively low proportion of pyritic sulfur suggest a possible fresh water environment during the deposition of the peat of the Pabedana coal. X-ray diffraction and petrographic analyses indicate the presence of pyrite in coal samples. The Pabedana coals have been classified as a high volatile, bituminous coal in accordance with the vitrinite reflectance values (58.75–74.32 %) and other rank parameters (carbon, calorific value, and volatile matter content). The maceral analysis and reflectance study suggest that the coals in all the four seams are of good quality with low maceral matter association. Mineralogical investigations indicate that the inorganic fraction in the Pabedana coal samples is dominated by carbonates; thus, constituting the major inorganic fraction of the coal samples. Illite, kaolinite, muscovite, quartz, feldspar, apatite, and hematite occur as minor or trace phases. The variation in major elements content is relatively narrow between different coal seams. Elements Sc,, Zr, Ga, Ge, La, As, W, Ce, Sb, Nb, Th, Pb, Se, Tl, Bi, Hg, Re, Li, Zn, Mo, and Ba show varying negative correlation with ash yield. These elements possibly have an organic affinity and may be present as primary biological concentrations either with tissues in living condition and/or through sorption and formation of organometallic compounds.     

Mercury,arsenic, antimony,and selenium contents of sediment from the Kuskokwim River,Bethel, Alaska,USA

The Kuskokwim River at Bethel, Alaska, drains a major mercury-antimony metallogenic province in its upper reaches and tributaries. Bethel (population 4000) is situated on the Kuskokwim floodplain and also draws its water supply from wells located in river-deposited sediment. A boring through overbank and floodplain sediment has provided material to establish a baseline datum for sediment-hosted heavy metals. Mercury (total), arsenic, antimony, and selenium contents were determined; aluminum was also determined and used as normalizing factor. The contents of the heavy metals were relatively constant with depth and do not reflect any potential enrichment from upstream contaminant sources.     

Coprecipitation of Ti,Mo, Sn and Sb with fluorides and application to determination of B,Ti, Zr,Nb, Mo,Sn, Sb,Hf and Ta by ICP-MS

We examined the coprecipitation behavior of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides under two different fluoride forming conditions: at < 70 °C in an ultrasonic bath (denoted as the ultrasonic method) and at 245 °C using a Teflon bomb (denoted as the bomb method). In the ultrasonic method, small amounts of Ti, Mo and Sn coprecipitation were observed with 100% Ca and 100% Mg fluorides. No coprecipitation of Ti, Mo, Sn and Sb in Ca–Al–Mg fluorides occurred when the sample was decomposed by the bomb method except for 100% Ca fluoride. Based on our coprecipitation observations, we have developed a simultaneous determination method for B, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by Q-pole type ICP-MS (ICP-QMS) and sector field type ICP-MS (ICP-SFMS). 9–50 mg of samples with Zr–Mo–Sn–Sb–Hf spikes were decomposed by HF using the bomb method and the ultrasonic method with B spike. The sample was then evaporated and re-dissolved into 0.5 mol l^− 1 HF, followed by the removal of fluorides by centrifuging. B, Zr, Mo, Sn, Sb and Hf were measured by ID method. Nb and Ta were measured by the ID-internal standardization method, based on Nb/Mo and Ta/Mo ratios using ICP-QMS, for which pseudo-FI was developed and applied. When 100% recovery yields of Zr and Hf are expected, Nb/Zr and Ta/Hf ratios may also be used. Ti was determined by the ID-internal standardization method, based on the Ti/Nb ratio from ICP-SFMS. Only 0.053 ml sample solution was required for measurement of all 9 elements. Dilution factors of ≤ 340 were aspirated without matrix effects. To demonstrate the applicability of our method, 4 carbonaceous chondrites (Ivuna, Orgueil, Cold Bokkeveld and Allende) as well as GSJ and USGS silicate reference materials of basalts, andesites and peridotites were analyzed. Our analytical results are consistent with previous studies, and the mean reproducibility of each element is 1.0–4.6% for basalts and andesites, and 6.7–11% for peridotites except for TiO₂.     

Roles of xenomelts,xenoliths, xenocrysts,xenovolatiles, residues,and skarns in the genesis,transport, and localization of magmatic Fe-Ni-Cu-PGE sulfides and chromite

Most sulfide-rich magmatic Ni-Cu-(PGE) deposits form in dynamic magmatic systems by partial melting S-bearing wall rocks with variable degrees of assimilation of miscible silicate and volatile components, and generation of barren to weakly-mineralized immiscible Fe sulfide xenomelts into which Ni-Cu-Co-PGE partition from the magma. Some exceptionally-thick magmatic Cr deposits may form by partial melting oxide-bearing wall rocks with variable degrees of assimilation of the miscible silicate and volatile components, and generation of barren Fe ± Ti oxide xenocrysts into which Cr-Mg-V ± Ti partition from the magma. The products of these processes are variably preserved as skarns, residues, xenoliths, xenocrysts, xenomelts, and xenovolatiles, which play important to critical roles in ore genesis, transport, localization, and/or modification. Incorporation of barren xenoliths/autoliths may induce small amounts of sulfide/chromite to segregate, but incorporation of sulfide xenomelts or oxide xenocrysts with dynamic upgrading of metal tenors (PGE > Cu > Ni > Co and Cr > V > Ti, respectively) is required to make significant ore deposits. Silicate xenomelts are only rarely preserved, but will be variably depleted in chalcophile and ferrous metals. Less dense felsic xenoliths may aid upward sulfide transport by increasing the effective viscosity and decreasing the bulk density of the magma. Denser mafic or metamorphosed xenoliths may also increase the effective viscosity of the magma, but may aid downward sulfide transport by increasing the bulk density of the magma. Sulfide wets olivine, so olivine xenocrysts may act as filter beds to collect advected finely dispersed sulfide droplets, but other silicates and xenoliths may not be wetted by sulfides. Xenovolatiles may retard settling of – or in some cases float – dense sulfide droplets. Reactions of sulfide melts with felsic country rocks may generate Fe-rich skarns that may allow sulfide melts to fractionate to more extreme Cu-Ni-rich compositions. Xenoliths, xenocrysts, xenomelts, and xenovolatiles are more likely to be preserved in cooler basaltic magmas than in hotter komatiitic magmas, and are more likely to be preserved in less dynamic (less turbulent) systems/domain/phases than in more dynamic (more turbulent) systems/domains/phases. Massive to semi-massive Ni-Cu-PGE and Cr mineralization and xenoliths are often localized within footwall embayments, dilations/jogs in dikes, throats of magma conduits, and the horizontal segments of dike-chonolith and dike-sill complexes, which represent fluid dynamic traps for both ascending and descending sulfides/oxides. If skarns, residues, xenoliths, xenocrysts, xenomelts, and/or xenovolatiles are present, they provide important constraints on ore genesis and they are valuable exploration indicators, but they must be included in elemental and isotopic mass balance calculations.