深穿透地球化学样品中铜活动态提取条件研究与初步应用

深穿透地球化学是通过提取地表土壤中深部隐伏矿发出的元素直接信息的找矿方法,元素活动态提取是应用最广的方法之一。但地表土壤中元素活动态含量信息微弱,活动态提取、元素分析的过程复杂,分析误差容易掩盖有效信息。目前的研究对提取过程条件缺乏有效的控制,方法标准化程度不高。本文研究了深穿透地球化学样品中活动态铜的提取条件,包括提取固液比、提取时间、提取液pH、固液分离方法、提取温度等,对提取过程进行优化,采用电感耦合等离子体质谱法测定铜的含量,方法检出限为0.03μg/g,精密度(RSD)为4.95%～7.39%。方法操作简单,精密度较好,应用于河南某隐伏铜多金属矿的探测,通过分析矿床的铜总量和活动态铜的含量,发现在矿床土壤中探测到了较为明显的与深部矿体成矿元素的活动态异常,探测结果所圈定的异常与实际矿(化)体相符。     

土壤样品中贵金属活动态提取技术

介绍了土壤样品中贵金属铂、钯、金的水提取态、黏土吸附态与可交换态、有机质结合态以及铁锰氧化物结合态等不同相态的提取方法与测定方法。方法检出限为铂0.03 ng/g,钯和金0.01 ng/g。实验了铂、钯、金活动态金属各种提取液介质中痕量贵金属的稳定性、固-液分离方法、提取温度的影响及提取液的处理方法。通过在南非隐伏铂钯矿或矿化区的试验,结果表明所圈定的异常与实际矿(化)体相符,为识别隐伏贵金属铂钯矿床提供了有效信息,对寻找隐伏矿床具有一定的指导意义。     

金活动态提取ICP-MS法测定王家坪金矿床深穿透地球化学样品中的金

金属活动态测量方法是寻找隐伏矿的有效手段之一，但在方法应用过程中发现不同地球化学景观条件下金元素的有效活动态类型不尽相同，并且提取过程中固液比、温度、时间等条件会对活动态提取数据产生较大影响。为了探讨金元素活动态选择性提取及方法在秦岭地区的指示效果等问题，本文利用电感耦合等离子体质谱（ICP-MS）分析技术对秦岭地区王家坪金矿床金元素活动态提取的不同实验条件及不同粒级样品进行对比研究，确定了针对金元素水提取态、黏土吸附态、有机结合态和铁锰氧化物结合态的最佳提取条件为：固液比1：5，提取时间24h，提取温度35℃，采样粒级为-80目。金元素四个相态的方法检出限分别为：水提取态0.03ng/g，黏土吸附态0.03ng/g，有机结合态0.04ng/g，铁锰氧化物结合态0.05ng/g，精密度（RSD）为7.25%～9.02%。该方法应用于王家坪金矿床23线，经分析金元素各形态平均含量为：水提取态0.19×10^-9，黏土吸附态0.30×10^-9，有机结合态11.16×10^-9，铁锰氧化物结合态0.20×10^-9，其中有机结合态为矿区土壤中金元素赋存的主要活动相态，金的有机结合态异常与隐伏金矿体位置一致。     

金活动态提取剂提取-电感耦合等离子体质谱法测定深穿透地球化学样品中的金

金的地球化学勘查基于金的准确测定,地球化学样品中金含量通常处于ng/g水平,需先进行分离富集,再采用电感耦合等离子体质谱法(ICP-MS)或石墨炉原子吸收光谱法(GFAAS)进行测定。当前,隐伏矿床勘查是地球化学探测技术的发展前沿,金活动态提取技术是寻找隐伏金矿的有效手段之一。相比于全量分析,金的活动态含量更低,需要解决选择性提取、高效预富集与准确测定等一系列难题。本文采用柠檬酸铵与土壤中黏土矿物及次生矿物作用促使吸附和可交换组分的金进入提取液,以硫脲和硫代硫酸钠络合金使活动态金向提取液中扩散,达到选择性提取的目的,建立了提取液中金的预富集及ICP-MS测定方法。实验确定的分析条件为:采用5g/L柠檬酸铵-2g/L硫脲-5g/L硫代硫酸钠为提取剂,提取时间24h,在酸性硫脲介质下用活性炭富集金,金吸附率可达89.6%～109.2%,灰化解吸温度为650～700℃。本方法检出限为0.05ng/g,相对标准偏差(RSD)为9.4%～10.2%,加标回收率为91.2%～93.4%。与已报道的硫酸铁-硫脲-硫代硫酸钠溶液提取再GFAAS测定的方法相比,本方法具有检出限低、测试线性范围宽、测试速度快的优势;应用于森林覆盖区黑龙江东安金矿区地球化学探测试验,金活动态异常与隐伏金矿位置一致。     

河南省罗山县山店地区地球化学方法找铜钼矿实践

大别山北麓山店地区发现的斑岩型铜钼矿床均为隐伏矿床,在地质勘探过程中采用土壤地球化学测量方法,查明地球化学晕指示元素为金、银、铜、铜、锌、钨、锡、钼、砷、锑、铋,结合地球化学异常选定勘查靶区;综合研究元素组合的前缘晕、近矿晕和尾晕及各元素的叠合情况,判断是否为矿致异常及矿体赋存部位。实践证明,运用地球化学方法预测隐伏铜钼矿床是一种经济有效的找矿方法,采用地球化学资料和地质资料相结合,可有效地判断地质体的含矿性,确定有利的成矿部位。     

高分辨率等离子体质谱测定水提取相中59个元素的应用研究

金属活动态测量法是寻找隐伏矿的深穿透地球化学方法之一,目前有关金属活动态测量的应用研究较多,但对于活动态的提取和相态(包括水提取相)分析测定方法研究较少。传统的原子吸收光谱法只能测定单元素,而电感耦合等离子体质谱法(ICP-MS)最多同时测定水提取相中5个元素(Cr、Cu、Zn、Cd、Pb),已不能满足当前化探任务中金属活动态测量的需要。本文建立了高分辨率电感耦合等离子体质谱(HR-ICP-MS)测定水提取相中59个元素的方法。通过试验,确定了59个元素的最佳提取条件为:提取时间24 h,提取温度35℃,液固比15∶1,固液分离方法为离心分离。方法精密度(RSD,n=12)为3.11%~38.1%,其中RSD大于20%的数据只占全部试验结果的28.4%,表明该方法较为准确可靠,方法检出限满足元素活动态的分析要求。运用HR-ICP-MS测定水提取相中元素的方法,不仅增加了测定元素的数量,也降低了检出限,提高了精密度,可以为勘查地球化学研究提供更为全面的信息。     

利用全反射X射线荧光光谱法研究土壤中活动态元素提取动力学

活动态提取技术是深穿透地球化学研究隐伏矿的有效手段之一。提取时间是活动态提取技术的一个关键因子,由于提取剂与目标元素、赋存矿物的作用方式不同,提取时间对提取效果的影响会不同。本研究采用全反射X射线荧光光谱法(TXRF)测定土壤中Cu、Pb、Zn、Ni、Mn活动态提取量随提取时间的变化。结果表明,在1 h内,分析元素提取量随提取时间急速增长,在7 h内提取量增长速率较高,分析元素提取量基本在24 h达到平衡。对各元素的提取过程建立了两点动力学模型w_t=w_1exp(-k_1t)+w_2exp(-k_2t),模拟提取土壤中两种吸附形式的活动态元素,方程中k_1代表非专性吸附活动态(如离子态、静电吸附、以纳微颗粒形式存在)的提取速率常数,提取速率较快,k_2代表专性吸附的活动态(粘土吸附态、铁锰氧化物弱结合或有机络合态)的提取速率常数,提取速率相对较慢。     

河南卢氏夜长坪钼钨矿床成矿条件及找矿远景分析

夜长坪钼钨矿床是豫西地区进行隐伏矿预测并取得找矿成功的典型案例。通过对矿床特征及成矿控制条件的分析研究,认为该钼钨矿床位于地幔隆起与凹陷区之间的地壳厚度增大部位,受矿源层官道口群龙家园组白云岩,近东西向和北东向断裂构造交汇部位侵入的燕山期中酸性隐伏小岩体控制,矿体就位于隐伏小花岗斑岩体接触带的夕卡岩中,属(大型)斑岩-矽卡岩型钼钨矿床。在此基础上,结合矿区外围的地质物化探测量成果,提出夜长坪钼矿区外围南部十八盘-大角寺一带为钼钨找矿的远景区。     

穿透性地球化学在干旱戈壁荒漠覆盖区的应用 ——甘肃花牛山铅锌矿试验实例

干旱戈壁荒漠区地处我国西北部地区,天山、北山、祁连山三大多金属成矿带横贯其中,成矿条件优越,找矿尤其是找隐伏矿的潜力巨大,但受风成砂土的影响,很难获知覆盖层下方的矿化信息.穿透性地球化学已被证实是有效寻找隐伏矿的方法,其被定义为能探测深部隐伏矿体发出的直接信息的勘查地球化学理论与方法技术.笔者在花牛山铅锌矿开展土壤微细粒全量测量、金属活动态测量(水溶态测量、黏土吸附态测量、铁锰氧化物态测量)和地电化学测量多种穿透性地球化学勘查方法实测工作,结果表明,5种测量方法分析数据主成矿元素(铅、锌)异常衬度高,变异系数大,富集成矿可能性大,地球化学异常与深部隐伏矿体位置吻合,相比较而言,土壤微细粒全量测量效果最好,黏土吸附态测量、铁锰氧化物态测量和地电化学测量效果较好,水溶态测量效果稍差;所选方法技术针对干旱戈壁荒漠区寻找隐伏铅锌矿是有效的.气固介质中内生条件下的纳米金属微粒的发现为利用土壤作为采样介质的穿透性地球化学方法技术(土壤微细粒测量、金属活动态测量)提供了理论基础.电提取泡塑载体中大量的微米级的黏土矿物颗粒发现,以及微量元素异常与铁、铝等常量元素异常高度一致,初步推断地电化学测量提取过程是对黏土矿物颗粒选择性吸附过程.     

东秦岭钼铅锌银多金属矿集区地球物理场特征及综合信息找矿模型

东秦岭地区是我国重要的钼矿资源产地,已查明大型、超大型斑岩型钼(钨)矿床十多处;在这些钼(钨)矿床外围,近年又找到了许多达中大型规模的脉型铅锌银(金)矿床,形成钼(钨)铅锌银(金)多金属矿集区。区内众多的矿集区均分布于重磁推断的隐伏岩体(基)区及其边部附近,矿床的形成严格受隐伏岩体的侵入形态、顶面深度和所处构造的控制,二者具有非常明显的时空关系。研究矿集区地球物理场特征,推定隐伏岩体和断裂构造的分布,是深部找矿工作的有效途径。通过研究矿集区和典型矿床的地质特征和重、磁、电异常特征,建立了矿田和矿床的地质成矿模型和综合信息找矿模型。地质成矿模型描述了隐伏岩体、小花岗斑岩体和钼(钨)铅锌银(金)矿床的顺序约束,即隐伏岩体控制小花岗斑岩体的形成,小花岗斑岩体控制钼(钨)铅锌银(金)矿床的形成;综合信息找矿模型包括隐伏岩体、小花岗斑岩体和矿体(矿化体)的重、磁、电异常标志。根据找矿模型进行了深部找矿预测。研究成果对在东秦岭地区进行深部找矿工作具有重要意义。     

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.     

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.     

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).     

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.     

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.     

Alkaline rocks of Samchampi-Samteran, District Karbi-Anglong, Assam, India

The Samchampi-Samteran alkaline igneous complex (SAC) is a near circular, plug-like body approximately 12 km² area and is emplaced into the Precambrian gneissic terrain of the Karbi Anglong district of Assam. The host rocks, which are exposed in immediate vicinity of the intrusion, comprise granite gneiss, migmatite, granodiorite, amphibolite, pegmatite and quartz veins. The SAC is composed of a wide variety of lithologies identified as syenitic fenite, magnetite ± perovskite ± apatite rock, alkali pyroxenite, ijolite-melteigite, carbonatite, nepheline syenite with leucocratic and mesocratic variants, phonolite, volcanic tuff, phosphatic rock and chert breccia. The magnetite ± perovskite ± apatite rock was generated as a cumulus phase owing to the partitioning of Ti, Fe at a shallow level magma chamber (not evolved DI = O1). The highly alkaline hydrous fluid activity indicated by the presence of strongly alkalic minerals in carbonatites and associated alkaline rocks suggests that the composition of original melt was more alkalic than those now found and represent a silica undersaturated ultramafic rock of carbonated olivine-poor nephelinite which splits with falling temperature into two immiscible fractions—one ultimately crystallises as alkali pyroxenite/ijolite and the other as carbonatite. The spatial distribution of varied lithotypes of SAC and their genetic relationships suggests that the silicate and carbonate melts, produced through liquid immiscibility, during ascent generated into an array of lithotypes and also reaction with the country rocks by alkali emanations produced fenitic aureoles (nephelinisation process). Isotopic studies (δ¹⁸O and δ¹³C) on carbonatites of Samchampi have indicated that the δ¹³C of the source magma is related to contamination from recycled carbon.