A statistical analysis of exploration geochemical data for uranium

This paper describes a statistical analysis of reconnaissance exploration geochemical data for uranium. Three sets of data were analyzed, as they related to: (a) Charlotte-Winston-Salem and (b) Charlotte two-degree NTMS quadrangles of the south-eastern U.S.A. The coefficient of variation for uranium in each of the three sets of data was less than unity and hence no transformation of the original variable was needed. These data were subjected to correlogram analysis. A first-order Markovian model of the type: Y₀ exp (-a |p|) was fit by the least-squares method to serial correlation coefficients of these data using the method proposed by Deming (1948). The model was tested by computing the variance-volume relationship for assumed individual blocks of unit length. The noise in the input (record) was eliminated by the application of an optimum bilateral exponential smoothing technique developed by Agterberg. A comparison of spectral density estimates obtained by a maximum entropy method employing Yule-Walker equations and the Burg algorithm was also made. The prediction error coefficients needed to determine the order of the autoregressive process and hence the spectral densities were determined in both cases for the three sets of data.On leave from National Geophysical Research Institute, Hyderabad-7, India.     

大兴安岭南部钠闪石流纹岩的岩石成因:年代学和地球化学证据

本文报道了在大兴安岭南部白音高老组新发现的钠闪石流纹岩的锆石U-Pb定年结果和岩石地球化学资料,以便揭示富碱钠闪石流纹岩的成因与区域构造演化.钠闪石流纹岩中锆石为自形-半自形的长柱状、短柱状,具有明显岩浆成因的震荡生长环带,结合其Th/U比值(1.2～1.9),暗示其为岩浆成因.锆石LA-ICP-MS U-Pb定年结果表明,其206Pb/238U年龄介于134 ～ 149Ma之间,其加权平均年龄为141Ma,表明钠闪石流纹岩形成于早白垩世早期.锆石εHf(t)=+9.07～+12.08,二阶段Hf模式年龄介于415 ～616Ma之间.岩石地球化学资料表明,钠闪石流纹岩以富硅、碱、铁质和贫钙、镁质为特征,在地球化学上,具有典型的A型流纹岩特征.该类岩石不仅具有高的稀土元素总量(REE=307×10-6～ 1395×10-6)、显著的Ce正异常(Ce/Ce* =6.52 ～ 18.6)和显著的Eu负异常(Eu/Eu*=0.007 ～0.009),而且表现出高场强元素(如Zr、Hf、Nb、Ta)的显著富集、大离子亲石元素(如Ba、Sr)的强烈亏损和很高的Ga/A1比值(104×Ga/Al =4.88～6.41).上述资料表明,钠闪石流纹岩的原始岩浆应是古俯冲蚀变洋壳部分熔融的产物,并形成于蒙古-鄂霍茨克缝合带闭合后的岩石圈伸展构造环境.     

The nature of the sub-continental mantle: constraints from the major-element composition of continental flood basalts

Many continental flood basalts (CFB) have isotope and trace-element signatures that differ from those of oceanic basalts and much interest concerns the extent to which these reflect differences in their upper mantle source regions. A review of selected data sets from the Mesozoic and Tertiary CFB confirms significant differences in their major- and trace-element compositions compared with those of basalts erupted through oceanic lithosphere. In general, those CFB suites characterised by low Nb/La, high (⁸⁷Sr/⁸⁶Sr)_i and low εNd_i tend to exhibit relatively low TiO₂, CaO/Al₂O₃, Na₂O and/or Fe₂O₃, and relatively high SiO₂. In contrast, those which have high Nb/La, low (⁸⁷Sr/⁸⁶Sr)_i and high εNd_i ratios, like the upper units in the Deccan Traps, have major- and trace-element compositions similar to oceanic basalts. It would appear that those CFB that have distinctive isotope and trace-element ratios also exhibit distinctive major-element contents, suggesting that major and trace elements have not been decoupled significantly during magma generation and differentiation.

When compared (at 8% MgO) with oceanic basalt trends, the displacement of many CFB to lower Na₂O, Fe₂O₃^*, TiO₂ and CaO/Al₂O₃, but higher SiO₂, at similar Mg#, is not readily explicable by crustal contamination. Rather, it reflects source composition and/or the effects of the melting processes. The model compositions of melts produced by decompression of mantle plumes beneath continental lithosphere have relatively low SiO₂ and high Fe₂O₃^*. In contrast, the available experimental data indicate that partial melts of peridotite have low TiO₂, Na₂O and Fe₂O₃^*CaO/Al₂O₃, if the peridotite has been previously depleted by melt extraction. Moreover, melting of hydrated, depleted peridotite yields SiO₂-rich, Fe₂O₃- and CaO-poor melts. Since anhydrous, depleted peridotite has a high-temperature solidus, it is argued that the source of these CFB was variably melt depleted and hydrated mantle, inferred to be within the lithosphere. Isotope data suggest these source regions were often old and relatively enriched in incompatible trace elements, and it is envisaged that H₂O±CO₂ were added at the same time as the incompatible elements. An implication is that a significant proportion of the new continental crust generated since the Permian reflected multistage processes involving mobilization of continental mantle lithosphere that was enriched in minor and trace elements during the Proterozoic.     

用AutoCAD二次开发系统绘制化探图

将地球化学测量的分析数据按照每条测线上的测点位置以一定的顺序依次输入Microsoft Excel、Microsoft Word或其他数据库软件编制的多元素分析数据表，并对各元素分别建立成纯文本数据文件。根据制图比例尺、测线数目和间距、测线上测点数目和点距、测区的某一角点坐标等已知参数，分别计算出各测点在图纸上的坐标值，将纯文本数据文件中各元素的分析结果标注在图纸上对应的测点位置，以绘制原始数据图并根据如上的参数以及化验数据计算编绘平面剖面图，最后再根据测线方位角使整个图形旋转，从而完成图件的制作。按照上述方法，以VisualLISP为工具，利用AutoCAD2000二次开发技术编制相应的处理程序，从而实现地球化学原始数据图和平面剖面图的微机制图。     

Multidimensional statistical technique for detection of low contrast geochemical anomalies

In this article we propose an advanced technique for detecting low contrast geochemical anomalies using a set of features. There are three principal elements in this technique: (1) a statistical measure of the contrast of the anomaly, denoted as τ; (2) selection of a background population; and (3) reduction of the dimensionality of the feature space. In the frame of the model, which describes the statistical distribution of geochemical background as a multidimensional normal distribution of logarithms of concentrations, the index, τ, is a powerful test statistic for the hypothesis of abnormality of an observation. Maps of τ anomalies can be rigorously interpreted on the basis of statistical inferences. Under all equal conditions this technique allows the detection of geochemical anomalies with at least the same contrast (if the chemical elements in a background population are correlated, then even the better) as using selective extractions of metals from soil or other techniques for data processing. The advantages of the proposed technique are demonstrated both theoretically and on examples of rare-metal and copper–nickel mineral deposits.     

Sulfur gases produced by the decomposition of sulfide minerals: Application to geochemical exploration

We have evaluated the potential application of sulfur gas analysis to exploration for buried sulfide mineral deposits by: (1) calculating by use of equilibrium thermodynamics, the relative abundances of gases that should be given off by decomposing sulfide minerals; and (2) determining experimentally the abundances of gases that are actually given off. The calculations indicate that the gases that should be given off by decomposing sulfide minerals are (in order of decreasing abundance) H₂S, COS, CS₂, CH₃SH, (CH₃)₂S₂ or SO₂ or S₂ (depending on Eh and pH). In contrast, our experiments show that decomposing sulfide minerals evolve only CS₂ and COS, in order of decreasing abundance. Pyrite produces the largest amounts of sulfur gas. Moist (rather than saturated) and non-sterile (rather than sterile) conditions enhance gas generation from pyrite, although no large difference appeared between sterile and non-sterile experiments for other sulfide minerals. These experiments indicate that the sulfur gases CS₂ and COS could be useful indicators of buried metal sulfide deposits.     

催化光度法测定化探样品中的痕量钯

本文对催化（Ce^＋4～Hg2^＋2体系）光度法测定钯的测定条件进行了实验和探讨。实验发现,在文献的基础上,改变试剂的加入顺序（先加Ce^＋4、后加Hg2^＋2）,延长催化反应时间到60min,可使该体系的检测下限降到0．18ng／g,因此,本文制定的分析方法可满足新地球化学研究对钯的测定要求（要求测定下限为0．2ng／g）用本文所制定的方法对含钯为：0．26、2．3、4．6、60．0ng／g的标样分别进行9次测定、其测定结果与标准值相符,相对标准偏差分别为：11．7％、10．4％、7．8％、4．8％。     

Petrological and geochemical evolution of the Kymi stock, a topaz granite cupola within the Wiborg rapakivi batholith, Finland

The 6×3 km Kymi monzogranite stock represents the apical part of an epizonal late-stage pluton that was emplaced within the 1.65 to 1.63 Ga Wiborg rapakivi batholith. The stock has a well-developed zonal structure, from the rim to the center: stockscheider pegmatite, equigranular topaz granite, porphyritic topaz granite. The contact between the two granites is usually gradational within a few centimeters, but local inclusions of the porphyritic granite in the equigranular granite indicate that the latter solidified later. Hydrothermal greisen and quartz veins, some of which contain genthelvite, beryl, wolframite, cassiterite, and sulfides, cut the granites of the stock and the surrounding country rocks. The equigranular granite contains 1 to 4 vol.% topaz, and its biotite is lithian siderophyllite; the porphyritic granite has 0 to 3 vol.% topaz, and the mica is siderophyllite. The equigranular granite is geochemically highly evolved with elevated Li, Rb, Ga, Ta, and F, and very low Ba, Sr, Ti, and Zr. The REE patterns show deep negative Eu anomalies and tetrad effects indicating extreme magmatic fractionation and aqueous fluid–rock interaction. The zonal structure of the stock is interpreted as a result of differentiation within the magma chamber. Internal convection in the crystallizing magma chamber and upward flow of residual melt as a boundary layer along sloping contacts resulted in accumulation of a layer of highly evolved, volatile-rich magma in the apical part of the chamber. Crystallization of this apical magma produced the stockscheider pegmatite and the equigranular granite; the underlying crystal mush solidified as the porphyritic granite. Much of the crystallization took place from volatile-saturated melt, and episodic voluminous degassing expelled fluids into opened fractures where they or their derivatives reacted with country rocks and caused alteration and mineralization.     

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop—Zones A–C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite–smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.     

Discriminating four tectonic settings: Five new geochemical diagrams for basic and ultrabasic volcanic rocks based on log — ratio transformation of major-element data

We present five new discriminant function diagrams based on an extensive database representative of basic and ultrabasic rocks from four tectonic settings of island arc, continental rift, ocean-island, and mid-ocean ridge. These diagrams were obtained after log_e-transformation of concentration ratios of major-elements — a technique recommended for a correct statistical treatment of compositional data. Higher % success rates (overall values from ∼ 83 to 97%) were obtained for proposing these new diagrams as compared to those (∼82 to 94%) obtained from the discriminant analysis of the raw major-element concentration data (i.e., without the log_e-transformation and without taking ratios of the compositional data, but using exactly the same database to provide an unbiased comparison), suggesting that such a data transformation constitutes a statistically correct and recommended technique. The new diagrams also resulted in less mis-classification of basic and ultrabasic rocks from known tectonic settings than the diagrams obtained from the raw data. The use of these highly successful new discriminant function diagrams is illustrated using Miocene to Recent basic and ultrabasic rocks from three areas of Mexico with complex or controversial tectonic settings (Mexican Volcanic Belt, Los Tuxtlas volcanic field, and Eastern Alkaline Province), as well as older rocks from three areas (Deccan, Malani, and Bastar) of India. Additionally, the major-element data from two ‘known’ continental arc settings are used to show that they are similar to those from the island arc setting. Continental rift setting is inferred for all Mexican cases and for one cratonic area of India (Malani) and an IAB setting for the Bastar craton. The Deccan flood basalt province of India is used to warn against an indiscriminate use of those discrimination diagrams that do not explicitly include the likely setting of the area under evaluation. An Excel template is also provided for an easy application of these new diagrams for discriminating the four settings considered in this work.     

本世纪初我国油气化探的发展方向

在油气化探工作中,稠环芳烃含量对区域油气异常有着重要的指示作用。对于稠环芳烃的测定,诸多前处理条件对稠环芳烃的提取效率有显著的影响。本文研究了油气化探样品振荡提取法的多种前处理条件（提取溶剂、样品粒径、振荡时间和静置时间、提取温度）对荧光强度测定结果的影响。实验结果表明,提取溶剂不同,测定结果存在较大差异,各提取溶剂的提取效率大小依次为：二氯甲烷>正己烷>乙酸乙酯>石油醚。综合考虑溶剂背景值对测定结果的影响,选择以正己烷为提取溶剂进行条件实验。在研究的粒径范围内,荧光强度随样品粒径的减小而增大,但粒径过小荧光强度反而降低,粒径在0.125~0.090 mm之间的样品荧光强度最高;荧光强度随着振荡时间和静置时间的增加而增强,其中静置时间的影响较大,静置9 h后荧光强度提高不显著;振荡时间的影响相对较小,振荡20 min后提取效率提高不显著;提取温度对荧光强度的影响最为显著,在相同条件下,提取温度越高荧光强度越大,且提取温度是影响稠环芳烃测定结果重现性的关键因素。油气化探样品前处理的最优化条件为：采用粒径在0.090~0.177 mm之间的样品,以色谱纯正己烷为溶剂,提取温度25℃,振荡时间20 min,静置时间12 h。     

Multipurpose geochemical maps produced by integration of geochemical exploration data sets in The Paraná Shield, Brazil

Old geochemical datasets from the Paraná Shield of southern Brazil have been integrated into a new geochemical database and the results are presented as a series of multipurpose geochemical maps. Although the 24 datasets retrieved were analysed by three different laboratories, the maps produced correlate surprisingly well with bedrock geological features.The retrieval of old geochemical exploration data sets for the purpose of generating maps showing element depletions and enrichments is a powerful tool with a wide range of applications: trace elements such as Zn, Cu and Mo can significantly affect crop productivity; areas with high abundances of harmful elements such as As and F can be delineated in order to identify public health hazards; heavy metals such as Cd, Pb and Hg can be measured in order to better constrain knowledge of chemical background levels for environmental monitoring. The integration and manipulation of different data sets can however be complicated by the heterogeneity in sampling and analytical procedures.     

Pebble cards — a record of the coarse fraction of stream sediments for geochemical exploration

Recording the coarse fraction of stream sediments on cardboard cards is suggested as an aid in geological interpretation of geochemical anomalies.     

纳米金属微粒的采集观测及其对地球化学勘查的意义

近几年纳米地球化学的研究为成矿元素在覆盖层中的迁移机理研究提供了直接的微观证据,同时为将其应用于未来覆盖区找矿奠定了基础。通过详细介绍地气、土壤和矿石样品中纳米金属微粒的采集和观测方法,展示两个研究实例,并对不同介质中纳米金属颗粒的可对比性、对覆盖区隐伏矿勘查的意义进行讨论,认为地气和土壤中的纳米金属微粒可作为地球化学示踪物质。     

Application of multi-element statistical analysis for regional geochemical mapping in Central Japan

Some 434 stream sediment samples were collected in Central Japan for a nationwide geochemical mapping project. The resulting geochemical maps are compared with geological, mineral resource and land use maps. Spatial distribution patterns of elemental concentrations in stream sediments are determined mainly by surface geology. Elevated elemental concentrations of alkali elements, Be, Ga, Y, Cs, Ba, lanthanide (Ln), Tl, Th, and U are consistent with outcrop areas of granite, felsic volcanic rock, and accretionary complexes. High concentrations of MgO, Al₂O₃, P₂O₅, CaO, 3d transition metals, Zn, and Sr are present in sediments supplied from mafic volcanic rock, high pressure metamorphic rocks, and mafic-ultramafic rocks in accretionary complexes.A procedure is established and guidelines are set for a statistical test suite for geochemical mapping. Analysis of variance (ANOVA) and multiple comparison tests are effective for comparing means among the data subsets that are classified by parent lithological materials. Among the many procedures that have been proposed for multiple comparison tests, the Holm procedure was selected for this study. Multiple comparison statistically confirmed the correspondence of elemental abundance in stream sediments with surface geologies. However, visual interpretation of some elements is inconsistent with results of multiple comparison. According to the Holm procedure, the U content in stream sediments is affected not by granite, but by felsic volcanic rock. The Holm procedure clarifies that As, Sb, and Bi, that are not explained by the presence of mineral deposits, are enriched significantly in samples derived from accretionary complexes. Hydrothermal activity on the ocean floor might affect their levels of enrichment. Significant enrichment of Cu, Zn, Cd, Sn, Sb, Hg, and Pb observed in urban areas are also supported by the Holm procedure. The authors inferred that these sediment samples had been contaminated.     

The method of partial extraction of metals in a constant current electrical field for geochemical exploration

The method of partial extraction of metals (PEM) was invented by a group of Leningrad researchers in the late 60's to early 70's. It is based on the leaching of minerals and rocks under the influence of an electric field, on the migration of metal compounds in this field and on their accumulation in specially equipped receiver-electrodes. The quantity of extracted metals and the speed of accumulation is correlated with the composition of ore bodies and the distance of the sample sites from them. It is possible to use the PEM method for geochemical exploration in areas of thick overburden and for drill logging. The main features of the PEM method are good sensitivity and the possibility of determining the position of maximum concentrations for different metals. A number of techniques for field observations and several examples of their successful applications are described.     

A review of indicator minerals and sample processing methods for geochemical exploration

Geochemical exploration based on the analysis of indicator minerals (IMs) is becoming increasingly used as an effective method for mineral exploration for many types of mineral deposits. The types of IMs used or recommended for exploration for different types of deposits, their properties suitable for concentrating them, as well as those of other common minerals from which they must be separated are listed.     

基于深地勘探的化探新方法发展现状分析

矿产资源是人类社会经济发展的重要物质基础,我国目前处于经济大发展时期,对矿产资源的需求量日益增大。然而随着已知矿、露头矿及浅部矿的日渐枯竭,未来的勘探工作重点势必将由地表浅部转向地下深部的隐伏矿勘查。国内外找矿实践证明,化探在寻找深部及隐伏矿床方面是一种直接、快速、有效的方法技术,而且随着"深穿透地球化学"概念的提出及发展,通过对穿透能力很强的气体、纳米级微粒、离子提取技术和植物地球化学测量技术的研究,提出了相关的深穿透地球化学勘探方法技术,本文对其异常形成机制进行了分析,并就其在寻找深部及隐伏矿床中的成效进行了探讨。     

催化极谱法连续测定化探样品中的钨、钼

本方通过催化极谱法连续测定化探样品中的的钨、钼的试验,研究了测量过程的共存干扰离子的消除、指示剂用量的选择、酸度影响、底液各组分用量等主要影响因素,选择了最佳实验条件．．并确定了钨、钼的质量浓度与电流呈线性关系的范围。在进行回收率、精密度、栓出限试验,均能满足化探找矿的要求,测定结果经国家一级标准物质验证,测定结果与标准值相符。     

川西义敦岛弧中部图姆沟组流纹岩年代学、地球化学特征及其对岩浆成因的限定

【研究目的】 义敦岛弧是三江特提斯复合造山带的重要组成部分。区域现有的研究较多集中在弧花岗质侵入岩及其成矿作用上,而对区内流纹岩的研究则相对匮乏。【研究方法】 本文在详细野外填图的基础上,对图姆沟组流纹岩进行岩石学、地球化学和同位素年代学研究。【研究结果】 流纹岩锆石U-Pb成岩年龄216.5 Ma,为晚三叠世。岩石SiO₂含量为73.24%~74.72%,全碱含量为5.26%~6.27%,为钙碱性系列,富集大离子亲石元素Rb、Th、U、K和轻稀土元素,亏损高场强元素Nb、Ta、Ti、P和重稀土元素,具典型的岛弧火山岩特征。【结论】 图姆沟组流纹岩是印支期甘孜—理塘洋壳向西俯冲环境下地壳部分熔融的产物。