Geochemical barriers: theory and practical applications

Geochemical barriers are zones in the Earth's crust with sharp physical or chemical gradients and they are often associated with concentrations of elements, sometimes to the extent of forming ore deposits. Four fundamental classes of geochemical barriers have been identified: (1) mechanical; (2) physico-chemical; (3) biochemical; (4) anthropogenic.Mechanical barriers are the simplest class and placer deposits are a good example. Physico-chemical barriers (the dominant class) are formed in zones characterized by sharp changes in the intensity of certain physico-chemical parameters of waters; tables of observed and predicted element associations have been prepared and these can be used to identify element concentrations which depend principally on the properties of waters. Biochemical barriers are specifically related to element concentrations brought about through reactions associated with life on Earth, for example, the accumulation of trace elements in effects are one variety. Although barriers consisting of combinations of several classes can occur, the main emphasis of this paper is on physico-chemical barriers with respect to ore deposits, soil geochemistry and groundwaters.     

The Soil Geochemical Atlas of Portugal: Overview and applications

The continental area of Portugal is now entirely covered by a soil geochemical survey (1 site/135 km²), taking as the sampling media topsoils (upper mineral horizons, A) and organic horizons (humus, O). Standard methods for sampling, sample preparation and analysis were used in order to achieve high quality and consistent data. Each sample was analyzed for 32 chemical elements, pH, electrical conductivity and organic matter content.The main purpose of the survey was to obtain baseline levels for various chemical elements. The compilation of all data (nearly 45,000 individual data) in an organised way, led to the production of the first Soil Geochemical Atlas of Portugal. In this Atlas it is possible to find for each chemical element a set of information statistics (basic statistical parameters, boxplots, cumulative frequency curves, etc.), maps of spatial distribution, among other information of geochemical and environmental interest. This paper gives an overview of the Soil Atlas and examples of application. The data were used to calculate reference values for 9 elements of environmental importance and to obtain empirical formulae allowing the estimation of elements in the coarse fraction of soils (< 2.00 mm) from known concentration in a finer fraction (< 0.18 mm).     

Archaean tonalitic gneiss of Finnish Lapland revisited: zircon ion-microprobe ages

We report single grain and grain-domain U–Pb zircon ages for the Tojottamanselkä tonalitic gneiss previously investigated by the whole-rock Rb–Sr, Pb–Pb and Sm–Nd methods, by conventional U–Pb zircon density/size fraction analysis and by Hf-isotopes (Kröner et al. 1981; Patchett et al. 1981; Jahn et al. 1984) and established as one of the oldest known rocks of the Baltic shield. Our data confirm the intrusive age as 3115±29 Ma (standard error), but we also found slightly older xenocrystic zircon cores with ²⁰⁷Pb/²⁰⁶Pb ages between 3161±19 and 3248±10 Ma that may either be derived from earlier phases of the tonalite melt or from pre-tonalite sialic crust. New magmatic zircon growth, probably during a metamorphic event that led to migmatization, is recorded by an age of 2836±30 Ma and may be coeval with widespread tonalite emplacement elsewhere in the northern Baltic shield at about this time.     

Geochemical Atlas of Slovakia and examples of its applications to environmental problems

Results of comprehensive geochemical mapping and thematic studies of the Slovak territory (rocks, soils, stream sediments, groundwaters, biomass, and radioactivity) in the first half of the 1990s led to several new research programmes in Slovakia, within the frame of which new methodologies for geochemical data evaluation and map visualization were elaborated. This study describes the application and elaboration of data from the Geochemical Atlas of the Slovak Republic at national and regional levels. Based on the index of environmental risk (I_ER = ΣPEC/PNEC), the level of contamination for the geological component of the environment in Slovakia was evaluated. Approximately 10.5% of Slovakia’s territory was characterized as being environmentally disturbed to highly disturbed. In the areas where environmental loadings have accumulated, 14 regions where environmental risks existed due to high element concentrations were defined. The model calculations of health risk estimates based on the databases of the Geochemical Atlas for groundwater and soils indicate that the possible risk occurrence of carcinogenic diseases from groundwater arsenic contents is high in more than 10% of Slovakia, whereas the chronic risk is negligible. To determinate the background and threshold levels a combined statistical–geochemical approach was developed and applied as an example for groundwater at the national level as well as for single groundwater bodies. The results of statistical method application for the whole groundwater body (GBW) were compared with the background values for anthropogenically non-influenced areas in GBW. Final background value took into account time variations and spatial distribution of the element in GBW. Furthermore, based on the database from the Geochemical Atlas for groundwater, groundwater bodies potentially at qualitative risk were delineated for the whole of Slovakia. From a total of 101 groundwater bodies 17 were characterized as being at risk and 22 as being at possible risk.     

U/Th dating by SHRIMP RG ion-microprobe mass spectrometry using single ion-exchange beads

We present a new analytical method for U-series isotopes using the SHRIMP RG (Sensitive High mass Resolution Ion MicroProbe) mass spectrometer that utilizes the preconcentration of the U-series isotopes from a sample onto a single ion-exchange bead. Ion-microprobe mass spectrometry is capable of producing Th ionization efficiencies in excess of 2%. Analytical precision is typically better than alpha spectroscopy, but not as good as thermal ionization mass spectroscopy (TIMS) and inductively coupled plasma multicollector mass spectrometry (ICP-MS). Like TIMS and ICP-MS the method allows analysis of small samples sizes, but also adds the advantage of rapidity of analysis. A major advantage of ion-microprobe analysis is that U and Th isotopes are analyzed in the same bead, simplifying the process of chemical separation. Analytical time on the instrument is ∼60 min per sample, and a single instrument-loading can accommodate 15-20 samples to be analyzed in a 24-h day. An additional advantage is that the method allows multiple reanalyses of the same bead and that samples can be archived for reanalysis at a later time. Because the ion beam excavates a pit only a few μm deep, the mount can later be repolished and reanalyzed numerous times. The method described of preconcentrating a low concentration sample onto a small conductive substrate to allow ion-microprobe mass spectrometry is potentially applicable to many other systems.     

Geochemical fingerprinting: 40 years of analytical development and real world applications

Geochemical fingerprinting is a rapidly expanding discipline in the earth and environmental sciences. It is anchored in the recognition that geological processes leave behind chemical and isotopic patterns in the rock record. Many of these patterns, informally referred to as geochemical fingerprints, differ only in fine detail from each other. For this reason, the approach of fingerprinting requires analytical data of very high precision and accuracy.     

辽宁省草河掌—桓仁地区铜矿资源量地球化学定量预测

矿产资源地球化学模型建立与定量预测研究以成矿成晕地质、地球化学理论为指导,以各尺度勘查地球化学数据为基础,以现代GIS信息技术为手段,通过研究总结典型矿田(矿集区)、矿床的异常特征,建立成矿带内典型矿床地球化学找矿模型,为预测区的地球化学定量预测提供类比依据,从而进行资源量预测。在资源量预测过程中加入了相似度、剥蚀程度、衬值等要素,有效地加大了预测靶区遴选的可信度,通过类比法与面金属量法两种预测方法的加权平均,使预测资源量合理。文章对草河掌—桓仁地区铜矿资源量进行了估算,共新增预测铜资源量21 812.9t。     

青岛大珠山高分异花岗岩地球化学特征与含矿性分析

青岛大珠山位于莱州湾南西,小珠山南西侧,属于中生代晚燕山期酸性侵入花岗岩体,岩性以中粗粒钾长花岗岩和花岗斑岩为主。前人对小珠山地球化学特征已有研究,但大珠山花岗岩地球化学研究尚处空白阶段。对所取的十件样品进行岩相学、全岩主微量及稀土元素、Li同位素、锆石U-Pb测年、斜长石电子探针原位分析。结果显示：岩相学表明研究区花岗岩含有锂辉石,有明显伟晶岩脉,岩石类型为I—S型花岗岩;样品为高硅花岗岩(SiO₂=66.97%～74.97%);全碱含量高(Na₂O+K₂O=8.70%～10.73%),属于过铝质高钾钙碱性系列;Eu负异常明显(δEu=0.25～0.56)。计算高分异花岗岩常见指数：铝饱和指数(A/CNK=0.91～1.01);分异指数(DI)为87.07～96.65;锆饱和温度为836.3～862.6℃;锆石Ti温度计反映岩浆结晶温度为698.5～738.9℃。年代学表明样品年龄为113.1±0.36 Ma,为早白垩世崂山期花岗岩。研究区花岗岩具有明显稀土元素四分组效应(TE_{1, 3}=1.04～...     

地球化学填图与地球化学勘查

在中国与西方国家，地球化学填图的目的与做法并不相同，西方的地球化学填图是由研究机构开展的，使用等离子焰光量计、X射线荧光光谱仪等大型仪器进行多元素分析，目的是取得多种元素在地球表层分布的基础性资料。地球化学勘查则由矿业公司主要分析少量成矿元素，目的是为了找矿。而中国的地球化学填图计划却做出了巨大努力，使地球化学填图取得的资料既有学术价值又对矿产勘查具有重大的实用意义。本文详细讨论了西方国家与中国地球化学填图与地球化学勘查的思路、方法与技术的演变，并瞻望了地球化学填图在21世纪的巨大发展前景。     

Unlocking the applications of automated mineral analysis

Identifying and quantifying the relative abundance of minerals is a fundamental part of many aspects of both pure and applied geology. Historically, quantitative mineralogy could be achieved using optical microscopy and point counting. This is a slow and operator dependent process, and practically impossible to achieve in, for example, very fine grained samples. Over the last decade a range of automated mineralogy technologies have arisen from the global mining industry and are being increasingly used in other branches of geology. These technologies, based on scanning electron microscopy with linked energy dispersive spectrometers, have the potential to revolutionise how we quantify mineralogy. In addition, during measurement, the sample textures are also captured, providing a wealth of valuable data for the geologist. In this article we review the current state of automated mineralogy and highlight the many areas of application for this technology.     

Location and quantitative analysis of OH in coesite

 The incorporation of hydrogen (deuterium) into the coesite structure was investigated at pressures from 3.1 to 7.5 GPa and temperatures of 700, 800, and 1100 °C. Hydrogen could only be incorporated into the coesite structure at pressures greater 5.0 GPa and 1100 °C . No correlation between the concentration of trace elements such as Al and B and the hydrogen content was observed based on ion probe analysis (1335 ± 16 H ppm and 17 ± 1 Al ppm at 7.5 GPa, 1100 °C). The FTIR spectra show three relatively intense bands at 3575, 3516, and 3459 cm⁻¹ (ν₁ to ν₃, respectively) and two very weak bands at 3296 and 3210 cm⁻¹ (ν₄ and ν₅, respectively). The band at 3516 cm⁻¹ is strongly asymmetric and can be resolved into two bands, 3528 (ν_2a) and 3508 (ν_2b) cm⁻¹, with nearly identical areas. Polarized infrared absorption spectra of coesite single-crystal slabs, cut parallel to (0 1 0) and (1 0 0), were collected to locate the OH dipoles in the structure and to calibrate the IR spectroscopy for quantitative analysis of OH in coesite (ɛ _{i ,tot}=190 000 ± 30 000 l mol⁻¹ _H2O cm⁻²). The polarized spectra revealed a strong pleochroism of the OH bands. High-pressure FTIR spectra at pressures up to 8 GPa were performed in a diamond-anvil cell to gain further insight into incorporation mechanism of OH in coesite. The peak positions of the ν₁, ν₂, and ν₃ bands decrease linearly with pressure. The mode Grüneisen parameters for ν₁, ν₂, and ν₃ are −0.074, −0.144 and −0.398, respectively. There is a linear increase of the pressure derivatives with band position which follows the trend proposed by Hofmeister et al. (1999). The full widths at half maximum (FWHM) of the ν₁, ν₂, and ν₃ bands increase from 35, 21, and 28 cm⁻¹ in the spectra at ambient conditions to 71, 68, and 105 in the 8 GPa spectra, respectively. On the basis of these results, a model for the incorporation of hydrogen in coesite was developed: the OH defects are introduced into the structure by the substitution Si^4+(Si2)+4O²⁻= ^[4]□^(Si2) + 4OH⁻, which gives rise to four vibrations, ν₁, ν_2a, ν_2b, and ν₃. Because the OH(D)-bearing samples do contain traces of Al and B, the bands ν₄ and ν₅ may be coupled to Al and/or B substitution. Received: 19 December 2000 / Accepted: 23 April 2001     

LIBS analysis of geomaterials: Geochemical fingerprinting for the rapid analysis and discrimination of minerals

Laser-induced breakdown spectroscopy (LIBS) is a simple atomic emission spectroscopy technique capable of real-time, essentially non-destructive determination of the elemental composition of any substance (solid, liquid, or gas). LIBS, which is presently undergoing rapid research and development as a technology for geochemical analysis, has attractive potential as a field tool for rapid man-portable and/or stand-off chemical analysis. In LIBS, a pulsed laser beam is focused such that energy absorption produces a high-temperature microplasma at the sample surface resulting in the dissociation and ionization of small amounts of material, with both continuum and atomic/ionic emission generated by the plasma during cooling. A broadband spectrometer-detector is used to spectrally and temporally resolve the light from the plasma and record the intensity of elemental emission lines. Because the technique is simultaneously sensitive to all elements, a single laser shot can be used to track the spectral intensity of specific elements or record the broadband LIBS emission spectra, which are unique chemical ‘fingerprints’ of a material. In this study, a broad spectrum of geological materials was analyzed using a commercial bench-top LIBS system with broadband detection from ∼200 to 965 nm, with multiple single-shot spectra acquired. The subsequent use of statistical signal processing approaches to rapidly identify and classify samples highlights the potential of LIBS for ‘geochemical fingerprinting’ in a variety of geochemical, mineralogical, and environmental applications that would benefit from either real-time or in-field chemical analysis.     

Geochemical fingerprinting of oceanic basalts with applications to ophiolite classification and the search for Archean oceanic crust

Two geochemical proxies are particularly important for the identification and classification of oceanic basalts: the Th–Nb proxy for crustal input and hence for demonstrating an oceanic, non-subduction setting; and the Ti–Yb proxy for melting depth and hence for indicating mantle temperature and thickness of the conductive lithosphere. For the Th–Nb proxy, a Th/Yb–Nb/Yb projection demonstrates that almost all oceanic basalts lie within a diagonal MORB–OIB array with a principal axis of dispersion along the array. However, basalts erupted at continental margins and in subduction zones are commonly displaced above the MORB–OIB array and/or belong to suites with principal dispersion axes which are oblique to the array. Modelling of magma–crust interaction quantifies the sensitivity of the Th–Nb proxy to process and to magma and crustal compositions. For the Ti–Yb proxy, the equivalent Ti/Yb–Nb/Yb projection features a discriminant boundary between low Ti/Yb MORB and high Ti/Yb OIB that runs almost parallel to the Nb/Yb axis, reflecting the fact that OIB originate by melting beneath thicker lithosphere and hence by less melting and with residual garnet. In the case of volcanic-rifted margins and oceanic plume–ridge interactions (PRI), where hot mantle flows toward progressively thinner lithosphere (often becoming more depleted in the process), basalts follow diagonal trends from the OIB to the MORB field. Modelling of mantle melting quantifies the sensitivity of the Ti–Nb proxy to mantle potential temperature and lithospheric thickness and hence defines the petrogenetic basis by which magmas plot in the OIB or MORB fields. Oceanic plateau basalts lie mostly in the centre of the MORB part of that field, reflecting a high degree of melting of fertile mantle. Application of the proxies to some examples of MORB ophiolites helps them to be further classified as C (contaminated)-MORB, N (normal)-MORB, E (enriched)-MORB and P (plume)-MORB ophiolites, which may add a useful dimension to ophiolite classification. In the Archean, the hotter magmas, higher crustal geotherms and higher Th contents of contaminants all result in widespread crustal input that is easy to detect geochemically with the Th–Nb proxy. Application of this proxy to Archean greenstones demonstrates that almost all exhibit a crustal component even when reputedly oceanic. This indicates, either that some interpretations need to be re-examined or that intra-oceanic crustal input is important in the Archean making the proxy less effective in distinguishing oceanic from continental settings. The Ti–Yb proxy is not effective for fingerprinting Archean settings because higher mantle potential temperatures mean that lithospheric thickness is no longer the critical variable in determining the presence or absence of residual garnet.     

四川盆地华蓥山峨眉玄武岩地球化学特征及其成因分析

四川盆地华蓥山玄武岩出露于茅口组顶部,夹于龙潭组底部的杂色泥岩、页岩之间,岩性为灰黑色粗玄岩,底部致密块状,顶部见气孔—杏仁状构造。TAS图解显示玄武岩属于碱性与偏碱性过渡带上的拉斑玄武岩系列,TiO₂含量介于2.92%～3.63%之间,Ti/Y值为465～567,属于高钛玄武岩（HT）。岩石LREE/HREE=3.25～3.96,轻稀土略富集,具有右倾平滑型稀土分配模式。华蓥山玄武岩与云南宾川,贵州赫章等地峨眉山玄武岩的地球化学特征相似,反映了相同的幔源性质。结合野外地质特征,认为华蓥山玄武岩应属峨眉地幔柱的一部分,是沿着华蓥山基底断裂发生裂隙式喷发的产物。研究区的高钛玄武岩Ce/Yb介于22.65～27.93,与前人报道的高钛玄武岩Ce/Yb比值范围基本一致,处于石榴石稳定区与尖晶石稳定区的过渡带,Th/Ta、Nb/U、La/Ta等比值反映出岩石受壳源物质的混染程度很低,可能是地幔柱轴部的产物。     

粒度分析理论技术进展及其应用

粒度分析在区分沉积环境、判定物质输运方式、判别水动力条件和分析粒径趋势等方面具有重要作用。本文主要介绍粒径测试技术方法及其新进展,包括传统的直接测量法、筛析法、沉降法和以计算机为依托的激光粒度测试仪法;评述沉积物分类命名方法理论及其在区分沉积环境、判定物质输运方式和判别水动力条件等方面的应用,以及粒度分析在研究海洋环境中沉积物输运方向、即粒径趋势分析方面的重要作用。随着计算机技术的快速发展,粒度分析测试技术正朝向自动化和测试内容多样化方向发展,其在实践中的应用也将更加广泛。     

Geochemical features of aerosols in Santiago de Chile from time series analysis

Santiago, the capital of Chile, suffers from high air pollution levels, especially during winter. An extensive particulate matter (PM) monitoring and analysis program was conducted to quantify elemental concentrations of PM. Size-resolved PM samples (PM_2.5 and PM_10–2.5) from the La Paz and Las Condes stations in Santiago (2004–2005) were analyzed using ICP-MS. Most trace element concentrations (Cu, Pb, Zn, Mn, V, Sb, Pb and As) were higher during winter than during summer and were also higher at the La Paz station than at the Las Condes station. During the highest pollution events, As concentrations in PM_2.5 (16 ng m^?3) exceeded the annual average standard value (6 ng m^?3). A 10-year time series showed decreasing Pb and As concentrations and slightly increasing Zn, Cu and Mn concentrations. Concentrations of Cr and Ni remained relatively constant. The implementation of new public policies in 1998 may explain the decreasing concentrations of Pb and As. Enrichment factor (EF) calculations identified two principal groups: elements with EF < 10 (Mg, Y, Zr, U Sr, Ca, Ti, and V) and EF > 10 (Rb, K, Cs, Fe, P, Ba, Mn, Ni, Cr, Co, Zn, Sn, Pb, Cu, Mo, Cd, As, Ag, and Sb), which were related to natural and anthropogenic PM sources, respectively. Three main PM sources were identified using factor analysis: a natural source (crustal matter and marine aerosol), combustion and copper smelting. Three other sources were identified using rare earth elements: fluid catalytic crackers, oil-fired power production and catalytic converters.     

油气盆地储层构造裂缝定量预测研究方法及其应用

构造裂缝预测研究的基本方法有岩石破裂法、主曲率法、能量法、统计学方法.针对不同类型致密油气(田)藏,可采用不同方法或多方法综合处理.以川西新场气田为例,采用统计法和岩石破裂法相结合,预测了新场晚侏罗统蓬莱镇组中、上砂层组(J3p1、J3p2)、中侏罗统沙溪庙组(J 2 s)"A"和"C"砂岩层和千佛岩组(J 2q)砂砾岩层中裂缝发育状况.结果表明,研究区大部分高产气井和产气井与预测的喜马拉稚期构造运动形成的裂缝发育区一次发育区有很好的对应关系,具有两层以上裂缝发育区的叠合区,是天然气聚集最有利区块.     

小波分析的原理及其在电磁感应仪EM38数据分析中的应用

利用小波变换对澳大利亚新南威尔士Mandamah地区所测得EM38数据进行全局阈值消噪处理,通过分解与重构,从中提取有效信息,去除干扰,得到去噪后的数据。将去噪后的数据与地球化学铜元素的异常特征和已知的铜矿化区域进行分析与对比,推测出该地区的铜矿化预测区。该方法能有效地去除噪声,又不会损失有用信息。实际资料处理结果表明：小波分析方法在EM38数据处理中可以起到独特的作用与效果。     

小波分析的原理及其在电磁感应仪EM38数据分析中的应用

利用小波变换对澳大利亚新南威尔士Mandamah地区所测得EM38数据进行全局阈值消噪处理,通过分解与重构,从中提取有效信息,去除干扰,得到去噪后的数据。将去噪后的数据与地球化学铜元素的异常特征和已知的铜矿化区域进行分析与对比,推测出该地区的铜矿化预测区。该方法能有效地去除噪声,又不会损失有用信息。实际资料处理结果表明：小波分析方法在EM38数据处理中可以起到独特的作用与效果。     

坦桑尼亚水系沉积物地球化学特征及金资源前景

坦桑尼亚地形景观丰富,大部分地区基岩出露条件较好,水系发育。在坦桑尼亚开展国家尺度（1：100万）水系沉积物地球化学调查,首次查明了坦桑尼亚全国地球化学背景,明确了各元素分布区特定的地质地球化学意义。共采集4258件水系沉积物样品,采用ICP-MS、XRF等13种配套分析方法分析71种元素（化合物）的含量。分析结果表明,Au异常主要位于维多利亚湖区绿岩带内,在周边的活动带中存在富金地体的延伸。中温和中—高温成矿元素Ag、Cu、Pb、Zn和W、Sn、Mo、Nb、Ta异常主要分布在基巴拉锡成矿带、玛拉嘎拉西台地和新生代裂谷火山岩中;Ni、Co、Cr、V等元素异常主要分布于西部的玛拉嘎拉西台地、乌本迪带和新生代裂谷火山岩中,主要与基性—超基性岩体有关。共圈定金地球化学块体31处,金成矿远景区8处,采用地球化学块体法初步评价了金的资源潜力,为进一步在坦桑尼亚开展金矿及其他矿产勘查和基础研究提供了有利信息。