不同实验室产生地球化学图的相似性—以Ag、Cs、Ga、Ge为例

编制中国76种元素地球化学图将使我们首次了解元素周期表上除氢，氧及惰性气体之外所有元素在中国大陆表层的分布，川滇黔桂76例元素地球化学图的编制是这一研究项目的试点，本文以不同实验室取得的Ag,Cs,Ga,Ge分析数据为例，探索，衡量不同实验室地球化学图相似性的方法，以优选实验室进行川滇黔桂4省区约4000件组合样76例元素的大规模分析工作。     

川滇黔桂76种元素地球化学图编制中分析方法与分析质量研究(二) 关于8个实验室对银元素分析的考核

国内8个实验室对川滇黔桂相同的76个泛滥平原沉积物样品的76种元素进行了分析测试,目的在于探索更有效的分析质量的评价方案,以便为编制相应的地球化学图优选不同元素的最佳分析方法。利用参考值、样本的统计学参数、相似性、密度分布函数、地球化学场的空间结构和地球化学异常的重合性等对Ag元素的分析数据作了评价,不但要求分析数据在绝对值方面有一定的精度,还强调了化探数据的空间属性,要求分析数据的空间分布方面也尽量与理想的地球化学图之间具有一致性。     

关于8个实验室对银元素分析的考核

国内8个实验室对川滇黔桂相同的76个泛滥平原沉积物样品的76种元素进行了分析测试,目的在于探索更有效的分析质量的评价方案,以便为编制相应的地球化学图优选不同元素的最佳分析方法,利用参考值,样本的统计学参数,相似性,密度分布函数,地球化学场的空间结构和地球化学异常的重合性对Ag元素的分析数据作了评价,不但要求分析数据在绝对值方面有一定的精度,还强调了化探数据的空间属性,要求分析数据的空间分布方面也尽量与理想的地球化学图之间具有一致性。     

国际地球化学填图样品分析方法和数据对比

以中国和世界发达国家或地区(欧洲、北美、澳大利亚与日本)过去10年内完成的或目前正在开展的全球性或国家性地球化学填图项目为例,总结了国际地球化学样品分析技术的新进展,并以中国实验室与欧洲实验室的分析数据的对比结果,剖析国际地球化学填图样品分析技术面临的挑战。研究表明:分析组成地壳所有元素的构想已被越来越多国家性、全球性地球化学填图项目所采纳;中国是世界上唯一具有填图样品76元素分析能力的国家;高水平的分析实验室(欧洲与中国)取得的数据大部分可以实现对比,但仍有10余个元素的分析数据存在明显偏差。实现所有分析元素数据的全球可对比,应是今后国际地球化学填图样品分析技术的主要发展方向。     

中国与欧洲全球尺度地球化学填图分析方法的对比

实施国际地球化学填图项目最关键的是分析问题。欧洲和中国在全球尺度地球化学填图做法上存在较大的差异。中国使用统一的采样介质,即泛滥平原沉积物,并使用几种大型设备作为骨干配合使用多方法分析系统,分析76种元素,这是人类历史上首次制作了元素周期表上除惰性气体元素和人工元素以外的几乎所有元素地球化学图。欧洲恰恰相反,欧洲在采样介质上趋向于多介质,而分析技术上只使用少数几种大型设备;分析方法的单一,使得很多关键元素没有分析出来,如贵金属元素Ag,Au,Ir,Os,Pd,Pt,Rh,Ru;卤族元素F,Cl,Br,I;分散元素Ge,In,Se,Te;与生命密切相关的元素K,N,S,B等。尽管欧洲强调以环境为目的,但很多与环境密切相关的元素都没有分析,所以欧洲的全球尺度地球化学填图的信息量大打折扣。这些不统一的做法,将会制约全球地球化学图的编制。     

《中国西南地区76种元素地球化学图集》出版发行

《中国西南地区76种元素地球化学图集》2008年5月由地质出版社出版发行。作者：谢学锦、程志中、张立生、冯济舟、叶家瑜、朱裕生。该书是据“我国西南五省市区76种元素区域化探图编制试点研究”项目成果编写而成。     

国际地球化学填图新进展

欧洲和中国在国际地球化学填图中起着积极而重要的作用,而且进展也是最显著的。欧洲地球化学基准值填图计划于1996年被欧洲26个国家地质调查局长论坛(FOREGS)正式批准。经过近10年的工作,于2005年出版了电子版欧洲地球化学图集。中国不仅自己开展了多层次地球化学填图计划,而且还与发展中国家合作开展了全球尺度和成矿带尺度地球化学填图合作。欧洲和中国无论是在全球尺度,还是在区域尺度地球化学填图做法上都存在较大的差异。在采样介质上中国使用统一的采样介质,在分析技术上中国使用几种大型设备作为骨干配合使用多方法分析系统;欧洲恰恰相反,欧洲在采样介质上趋向于多介质,而分析技术上只使用少数几种大型设备。欧洲的做法尽管使用多介质采样获得了元素在更多天然介质中的分布信息,但使用单一分析技术,使得很多关键元素没有分析出来,如贵金属元素Ag,Au,Ir,Os,Pd,Pt,Rh,Ru;卤族元素F,Cl,Br,I;分散元素Ge,In,Se,Te;与生命密切相关的元素N,S,B等。尽管欧洲强调以环境为目的,但很多与环境密切相关的元素都没有分析,所以欧洲的全球尺度地球化学填图的信息量大打折扣。这些不统一的做法,特别是在全球尺度地球化学填图不统一的做法,会影响到以后全球地球化学图的编制。     

中国东部大陆岩石地球化学图揭示的信息

根据中国东部各省(区、市)区域地质志、1∶50万地质图和中国东部地壳与岩石元素丰度研究成果首次编制的中国东部60种元素的岩石地球化学图,基本反映了与特定岩性有关的区域岩石地球化学元素含量分布特征和与大地构造单元有关的区域地球化学元素含量分布特征,直观表达了中国东部空间地理上元素背景含量的宏观分布与变化,以及不同大地构造单元元素背景含量的变化趋势。这一成果为勘查地球化学、环境地球化学,特别是区域化探扫面水系沉积物资料的定量解释提供了基本依据,为基础地质、大地构造、区域成矿研究提供了重要资料,也为地球化学块体理论及其形成机制的研究提供了强有力的支持。     

中国东部大陆岩石地球化学图揭示的信息

根据中国东部各省(区、市)区域地质志、1:50万地质图和中国东部地壳与岩石元素丰度研究成果首次编制的中国东部60种元素的岩石地球化学图,基本反映了与特定岩性有关的区域岩石地球化学元素含量分布特征和与大地构造单元有关的区域地球化学元素含量分布特征,直观表达了中国东部空间地理上元素背景含量的宏观分布与变化,以及不同大地构造单元元素背景含量的变化趋势.这一成果为勘查地球化学、环境地球化学,特别是区域化探扫面水系沉积物资料的定量解释提供了基本依据,为基础地质、大地构造、区域成矿研究提供了重要资料,也为地球化学块体理论及其形成机制的研究提供了强有力的支持.     

因子分析在编制多元素地球化学图中的应用

为了形象地表达地球化学测量所取得的成果,需要编制各种类型的地球化学图。目前用于编图的方法很多,移动平均分析、趋势面分析及常被采用的勾绘等含量线的方法等,多用于单元素地球化学图的编制。而各种形象地用符号、图式表示含量变化的编图方法,虽然也用于多元素     

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.     

深部矿井水煤共采水文地质数值分析

针对兖州煤田下组煤深部开采受奥灰高承压水威胁以及当地大型煤化工企业生产用水量大的现状,在已进行的水文地质勘探及放水试验基础上,评价奥灰富水性,并采用有限差分法进行奥灰疏水降压数值模拟研究,提出水煤共采观点。研究结果表明:兖州煤田深部奥灰水压高,合理布置水煤共采孔,可以实现奥灰水位的有效疏降,疏降中心区水位最大降深可达110 m,突水系数显著下降,提高了下组煤开采的安全性;同时可提供煤化工43200 m3/d的供水量,能达到可持续的、水资源保护性的供水效果,实现下组煤的水煤共采。     

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.     

Partition coefficients of Hf,Zr, and REE between zircon,apatite, and liquid

Concentration ratios of Hf, Zr, and REE between zircon, apatite, and liquid were determined for three igneous compositions: two andesites and a diorite. The concentration ratios of these elements between zircon and corresponding liquid can approximate the partition coefficient. Although the concentration ratios between apatite and andesite groundmass can be considered as partition coefficients, those for the apatite in the diorite may deviate from the partition coefficients. The HREE partition coefficients between zircon and liquid are very large (100 for Er to 500 for Lu), and the Hf partition coefficient is even larger. The REE partition coefficients between apatite and liquid are convex upward, and large (D=10–100), whereas the Hf and Zr partition coefficients are less than 1. The large differences between partition coefficients of Lu and Hf for zircon-liquid and for apatite-liquid are confirmed. These partition coefficients are useful for petrogenetic models involving zircon and apatite.     

Distribution of Cu,Co, As,and Fe in mine waste,sediment, soil,and water in and around mineral deposits and mines of the Idaho Cobalt Belt,USA

The distribution of Cu, Co, As and Fe was studied downstream from mines and deposits in the Idaho Cobalt Belt (ICB), the largest Co resource in the USA. To evaluate potential contamination in ecosystems in the ICB, mine waste, stream sediment, soil, and water were collected and analyzed for Cu, Co, As and Fe in this area. Concentrations of Cu in mine waste and stream sediment collected proximal to mines in the ICB ranged from 390 to 19,000 μg/g, exceeding the USEPA target clean-up level and the probable effect concentration (PEC) for Cu of 149 μg/g in sediment; PEC is the concentration above which harmful effects are likely in sediment dwelling organisms. In addition concentrations of Cu in mine runoff and stream water collected proximal to mines were highly elevated in the ICB and exceeded the USEPA chronic criterion for aquatic organisms of 6.3 μg/L (at a water hardness of 50 mg/L) and an LC50 concentration for rainbow trout of 14 μg/L for Cu in water. Concentrations of Co in mine waste and stream sediment collected proximal to mines varied from 14 to 7400 μg/g and were highly elevated above regional background concentrations, and generally exceeded the USEPA target clean-up level of 80 μg/g for Co in sediment. Concentrations of Co in water were as high as in 75,000 μg/L in the ICB, exceeding an LC50 of 346 μg/L for rainbow trout for Co in water by as much as two orders of magnitude, likely indicating an adverse effect on trout. Mine waste and stream sediment collected in the ICB also contained highly elevated As concentrations that varied from 26 to 17,000 μg/g, most of which exceeded the PEC of 33 μg/g and the USEPA target clean-up level of 35 μg/g for As in sediment. Conversely, most water samples had As concentrations that were below the 150 μg/L chronic criterion for protection of aquatic organisms and the USEPA target clean-up level of 14 μg/L. There is abundant Fe oxide in streams in the ICB and several samples of mine runoff and stream water exceeded the chronic criterion for protection of aquatic organisms of 1000 μg/L for Fe. There has been extensive remediation of mined areas in the ICB, but because some mine waste remaining in the area contains highly elevated Cu, Co, As and Fe, inhalation or ingestion of mine waste particulates may lead to human exposure to these elements.     

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.     

Partitioning of Hf,Lu, Ti,and Mn between olivine,clinopyroxene and basaltic liquid

The crystal/liquid partition coefficients of Lu, Hf, Ti, Mn and Ca have been measured between olivine, clinopyroxene and basaltic melt. The Ti, Mn, and Ca partition coefficients were determined at natural abundance levels. The Lu and Hf partition coefficients were determined at doping levels ranging from 0.5 to 1.5 wt% “trace element” as oxide in order to allow analysis by electron microprobe. Olivine/liquid partition coefficients for Lu, Hf, Ti, Mn, and Ca were determined at 1 bar and temperatures from 1150 to 1177° C. Clinopyroxene/liquid partition coefficients were determined for Lu, Hf, Ti, and Mn at pressures of 10, 15, and 20 kbars and temperatures from 1250 to 1290° C. The olivine/liquid partition coefficients of Hf, Lu, Ti, and Ca are small. D(Hf-ol) is zero within the analytical uncertainty. Both D(Lu-ol) and D(Mn-ol) decrease with increasing temperature, but D(Ti-ol) and D(Ca-ol) are constant over the narrow temperature range studied. The partition coefficient results are summarized below.

Distribution of copper,cobalt and nickel in ores and host-rocks,Ingladhal, Karnataka,India

Stratiform quartz-sulphide lodes in Ingladhal occur in a typical Precambrian green-stone-belt environment comprising metabasalts, tuff, chert and cherty iron-sulphide formation. Unusually high cobalt contents of metavolcanics and of sulphide minerals in orebodies suggest a consanguinity between ores and rocks. 90% of total nickel, 70% of total cobalt but only 30% of total copper in rocks occur in silicate phases and thus indicate an early separation of copper from cobalt and nickel. Unusually high non-sulphide copper in barren bedded cherts implies availability of Cu-rich solution prior to their lithification. Pyrite in sediments, in volcanics, and in orebodies is characterized by a distinctive pattern of Co-Ni distribution in each case. Partitioning of Co and Ni between coexisting sulphide pairs is complex, but gross equilibrium is indicated. Very high trace metal content of orebody pyrite sharply contrasts with very low such values in pyrite from adjacent sediments and points to a higher temperature of formation of orebodies.