New Series of Rock and Sediment Geochemical Reference Materials

Certified or reference values for sixty six to sixty seven elements and element oxides are given for geochemical reference materials recently prepared by the Institute of Geophysical and Geochemical Exploration (IGGE), including limestone (GSR-13), granitic gneiss (GSR-14), amphibolite (GSR-15), lake sediment (GSS-9) and stream sediments (GSD-1a, GSD-13, GSD-14). These samples supplement the GSR 1-6, GSD1-8 and GSD 9-12 certified reference materials already prepared and characterized by the IGGE.     

GEOCHEMICAL STANDARD REFERENCE SAMPLES GSD 9–12, GSS 1–8 AND GSR 1–6

The 18 Chinese geochemical standard reference samples GSD 9-12 (stream sediments), GSS 1-8 (soils) and GSR 1-6 (rocks) were prepared after GSD 1-8 (stream sediments) for even wider and increasing needs of geology, exploration geochemistry and geochemical analysis. Usable values of 41 trace, minor and major elements of the 18 samples were published in 1984. In the following two years, efforts were concentrated on the determination of other elements, most of which are more difficult to determine accurately and hence not many data were available in the literature. At the same time, additional data on the 41 elements already evaluated were also submitted. In all, 155 234 results were available along with the 35 284 analytical data submitted. The processing of samples, the examination of sample homogeneity, the plan of collaborative analysis of the samples, and the criteria for defining the recommended values are described. The recommended or reference values of the 72 constituents, to-gether with the 35 284 analytical data of the 18 samples are published in this paper.     

Study and Application of Geochemical Reference Materials in the Institute of Geophysical and Geochemical Exploration (IGGE), China

In order to meet the needs of geochemical mapping and geochemical exploration, 125 geochemical reference materials have been successively prepared by the Institute of Geophysical and Geochemical Exploration (IGGE) since 1978. They include certified reference materials of stream sediments (GSD1-14), soils (GSS1-16; ASA 1–6, for analysis of available elements), various rocks (GSR1-6, GSR13-15), biological material (GSV1-4 and GSB 1–10), synthetic silicates (GSES I 1–11) and limestones (GSES II 1–9 for spectral analysis). They also include geochemical reference materials for ore analysis: Cu-Pb-Zn ores (GSO1-4), Cu-Pb-Zn concentrates (GSO5-7), platinum-group element (PGE) ores (GPt5-6 and GPt9-10), silver ores (GAg1-6) and geochemical reference materials for Au (GAu8-14) and PGE determination (GPt1-4, and GPt7-8). A multi-laboratory collaborative analysis scheme was adopted in the certification procedure of the IGGE. Dozens of competent laboratories with hundreds of senior analysts in China participated in the certification analysis. These samples have been supplied to more than thirty countries and more than 4000 customers from national industrial, agricultural, environmental, scientific and educational fields. Most of the geochemical reference materials are used for the calibration of measuring apparatus, evaluation of analytical methods, certification studies, quality control and laboratory accreditation programmes.     

岩石标准物质的研制

研制了霓霞正长岩，粗面岩，花岗闪长岩，辉长石，流纹岩及白云岩６种不同类型的岩石标准物质，对用Ｘ射线荧光光谱均匀性检验实际取样量进行了探讨，选择分析测试方法时，除采用了标准方法和长期应用的分析方法外，还采用了近年发展起来的新技术新方法，在定值中应用了多参数统计定值模式，给出了６９个元素的标准值和参考值，该批标准物质于１９９１年１月经国家技术监督局审核批准为国家一级标准物质，编号分别为ＧＢＷ０７１０９     

Determination of Mercury in Thirty‐three International Stream Sediment and Soil Reference Samples by Direct Mercury Analyser

Mercury was determined in thirty‐three international stream sediment and soil reference samples (eleven Chinese soils, GSS‐1 to GSS‐11; twelve Chinese stream sediments, GSD‐1A to GSD‐12; four Canadian stream sediments STSD‐1 to STSD‐4; South African stream sediments, SARM‐42, SARM‐46 and SARM‐47; Japanese stream sediments, JSd‐1 to JSd‐3) by direct mercury analyser. Samples were taken in 500 μl quartz boats, placed in an auto sampler and processed (drying time 60 s at 300 °C; decomposition time 120 s at 850 °C; waiting time 45 s). The instrument was calibrated in the low (0‐50 ng) and high ranges (50‐500 ng) with two reference materials GSS‐5 and GXR‐2 (USGS). Using the calibration line, reference samples were analysed for Hg. The results of the determinations agreed with the recommended values of RMs in all cases except JSd‐1. The RSD calculated for the RMs was found to be within 20%. The detection limit was 1 ng g^?1.     

双道氢化物原子荧光法同时测定地球化学样品中的微量砷和锑

已有大量研究工作表明砷是各种类型金矿床的极有效的探途元素,它也是许多热液多金属矿床的通用指示元素。锑作为指示元素做的工作比砷少,但是根据已有资料,它也是锑矿床、金矿床及多金属矿床的指示元素。我国最近发表的《苗龙金矿的发现》一文中很好地说明了砷及锑对找金矿的指示作用。     

地球化学标准物质的研制与应用

1978年以来,物化探研究所围绕我国地球化学调查和地质矿产勘查的需要,先后研制了多种地质物料的系列地球化学标准物质,包括水系沉积物、土壤(含全量和生物有效成份)、岩石、生物、光谱分析标准、多金属矿石与精矿、痕量铂族元素与铂矿石、痕量金与金矿石及银矿石标准物质,共计126个样品。具有系列性好和适用性强的特点,是我国地质测试质量体系的基本组成部分,其中GSD、GSS和GAu系列作为全国区域地球化学样品分析的量值和质量监控标准,保证了各省区不同时间、不同实验室的分析结果可以统一对比和成图。这些标准物质在我国地质矿产、冶金、农业、环境部门和科研院校中广泛应用,应用的国家达30余个。     

Geochemical Reference Samples, Drainage Sediment GSD 1 - 8 from China

A set of eight geochemical standard reference samples of stream sediments was prepared. The original purpose was to use these samples as primary standards for the data quality monitoring of a nation-wide regional geochemical survey program in China. But their use has been soon extended to other fields. Forty-one laboratories in China have joined in a collaborative venture to analyse these samples, using a variety of analytical procedures. Recommended values for over 50 trace and minor elements were derived by a method of repetitive elimination of outliers and calculation of central "tendency" from several central values.     

The Determination of Major Oxide and Trace Element Concentrations in Eighteen Chinese Standard Reference Samples by X-ray Fluorescence Spectrometry

Eighteen Chinese geologic reference samples (stream sediments GSD 9–12, soils GSS 1–8, and rocks GSR 1–6) were analyzed by wavelength-dispersive X-ray fluorescence spectrometry (XRFS) for major elements Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P, and by energy-dispersive XRFS for trace elements Ba, Ce, Cr, Cu, La, Nb, Ni, Rb, Sr, Y, Zn, and Zr. Major element analysis followed gravimetric determination of loss on ignition, and samples were prepared by fusion with Li₂B₄O₇. A loose-powder sample preparation was used for trace element analysis. The results reported in this study are, generally, in good agreement with concentrations compiled by X. Xie of the Geochemical Standard Reference Group and the Institute of Geophysical and Geochemical Exploration (People's Republic of China).     

CCD-1型平面光栅电弧直读发射光谱仪测定化探样品中硼锡银的含量

用WP-1米平面摄谱仪改造升级为CCD-1型平面光栅电弧直读发射光谱仪。天然地球化学标准物质系列基体与样品基体一致,采用国家一级土壤水系岩石地球化学标准物质作为标准系列,测定地球化学样品中硼锡银元素含量。检出限Ag:0.013×10^-6;Sn:0.26×10^-6;B:0.54×10^-6,精密度均小于7.6%(n=12)。检测数据经验证准确度精密度检出限合格率等各项指标均满足地质矿产实验室管理规范(DZ/T0130.4-2006)的要求。     

桂东鹰扬关地区1∶5万区域地质矿产调查成果与主要进展

桂东鹰扬关地区位于钦杭结合带西南段,通过开展该区1∶5万区域地质调查,以国际地层表(2015)为指南,对调查区地层进行了多重地层划分与对比研究。从岩石学、构造学、地球化学角度,对鹰扬关岩群进行了详细研究,明确了其为一套构造混杂岩,通过获得的变质火山碎屑岩锆石LA-ICP-MS U-Pb年龄,认为其主要形成于新元古代。根据岩性特征、野外接触关系及同位素年龄等将区内岩浆岩划分为8个岩体,16个填图单位,获得了各岩体的高精度测年数据,确定了岩浆岩年龄格架;研究了其岩石成因,探讨了岩浆源区以及形成的大地构造背景。建立了调查区构造格架,阐明了构造形成演化历史,划分了构造变形阶段,通过构造解析,于鹰扬关构造混杂岩中识别出5期构造变形,结合区域构造演化确定了相对时序。通过1∶5万水系沉积物测量,查明了1∶5万太保圩幅水系沉积物地球化学特征,编制了元素地球化学图等系列图件。     

Platinum-Group Element Geochemical Certified Reference Materials (GPt1-7)

Unlike the situation for other elements, few reference materials certified for the platinum-group elements are currently available. Therefore, the GPt1-7 series of PGE geochemical CRMs, prepared by the IGGE, represent an important addition and comprise a range of matrix types, including a soil, stream sediment, Mg-rich ultramafic rock, Fe-rich ultramafic rock, platinoid ore depleted in Cu, Ni and Fe, and a chromitite. The concentration of PGE in these samples ranges over 4-5 orders of magnitude and the samples were shown to have good homogeneity as assessed by a variance test. Analytical methods based on different principles were used in sample certification, including several fire assay and wet chemical procedures used for decomposition and preconcentration. Certified values for the elements Pt, Pd, Os, Ru, Ir, Rh and Au were determined by AAS, catalytic colourimetry (COL), catalytic polarography (POL), atomic emission spectrometry (AES), ICP-MS and NAA. Recently, the GPt1-7 samples were approved as national primary CRMs by the State Bureau of Technical Supervision of China.     

Geochemical Atlas of the Slovak Republic at a scale of 1:1,000,000

The Geochemical Atlas of Slovak Republic (49,036 km²) at a scale of 1 : 1,000,000 was compiled during 1991–1995 together with maps of associated geochemical and ecological features at a scale of 1 :200,000. Investigations were aimed at the evaluation of concentrations and distributions of Al, As, Ba, Be, Ca, Ce, Co, Cd, Cs, Cr, Cu, Fe, Ga, Hg, K, La, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, Sb, Se, Sn, Sr, Th, U, V, W, Y, Zn, Zr in groundwater (16,359 samples), stream sediments (24,422 samples), rocks (3839 samples), soils (9892 samples from 4946 profiles; A and C horizons of each profile were sampled) and forest biomass (the foliage of the forest tree species from 3063 plots was sampled). In groundwater field measurements of temperature, pH, conductivity, dissolved O₂, acidity, alkalinity were done. The evaluation was oriented to the natural radioactivity of the Slovak territory as follows: rocks (K, U, Th, U_tot and dose rate, 15,573 reference spectrometric points), radon risk and water (U_nat, ²²⁶Ra, ²²²Rn; 5271 samples). The main objective of the Geochemical Atlas was to construct single-component maps showing concentrations of chemical elements, compounds and measured parameters in the researched media of Slovakia at a scale of 1 : 1,000.000 and to create interactive databases of chemical composition and/or measured parameters of groundwater, biomass, rocks, soils, stream sediments and natural radioactivity, for the entire territory of the Slovak Republic. The single-component maps are not constructed in the part ‘Rocks’, where all the main rocks types of Slovakia are presented in the ‘Map of lithogeochemical rock types of Slovakia at a scale of 1: 500,000’. The edition of six atlases has been planned. In 1997 the first three atlases will appear (Groundwater, Biomass, Natural Radioactivity). Publishing of last three atlases (Rocks, Soils, Stream Sediments) is planned for 1998. Since the analytical works on stream sediments were finished during 1997, it was not possible to present here the results of that part of the Geochemical Atlas.     

Mineralogical and Chemical Composition of International Carbon and Oxygen Isotope Calibration Material NBS 19, and Reference Materials NBS 18, IAEA-CO-1 and IAEA-CO-8

International carbon and oxygen isotope calibration material NBS 19 and reference materials NBS 18, International Atomic Energy Agency (IAEA)-CO-1 and IAEA-CO-8 are prepared from naturally occurring rock specimens of marble and carbonatite. Mineralogical and chemical analysis showed that only NBS 19 and IAEA-CO-1 represent essentially pure samples of calcite containing < and minimal (< 1%) quantities of quartz. In contrast, both NBS 18 and IAEA-CO-8, although primarily composed of calcite, are contaminated by a range of additional phases. NBS 18 was estimated to contain 1% Fe-dolomite and trace (< 1%) quantities of apatite and quartz. IAEA-CO-8 was estimated to contain at least 4% non-carbonate material (including apatite, barite, biotite and magnetite). NBS 18 and IAEA-CO-8 are both derived from samples of carbonatite and the calcite component of each material is characterised by appreciable substitution of Mg + Mn + Sr ± Fe ± Ba (Σ ≈ 14000–15000 μg g^-1) for Ca. The observations reported in this study complement data in the literature detailing significant grain-scale isotopic heterogeneity in NBS 18 and IAEA-CO-8. Both data sets highlight the need for careful characterisation of calibration materials prior to distribution.     

内蒙古中东部浅覆盖区化探岩屑测量方法研究及靶区优选应用

内蒙古自治区中东部二连浩特-东乌珠穆沁旗（东乌旗）一带草原区,地貌景观多为平缓山丘类型.因水系沉积物、风积物以及风化残积物等共存,采样介质的不同将直接影响到地球化学测量效果.在东乌旗的阿太乌拉地区和阿巴嘎旗的莫若格钦两地,对比不同粒度的样品,发现金属矿物微颗粒以物理状态不均匀地混合在岩屑介质内.与小于80目的细粒样品相比,小于4目至大于20目之间粒度的岩屑,化探异常的衬值更大,提取的异常也更准确.采用MapInfo软件提供的IDW插值法成图,得到非常清楚的各种元素之间的空间分布关系,直观地显示出找矿有利地段,对找矿靶区的筛选具有良好的指导意义.笔者通过研究,在工作区内发现几处Cu-Au及Ag-Pb-Zn-Cu异常区,并且初步证实存在带状分布的矿化体,找矿前景良好.实践证明,化探岩屑测量为在浅覆盖地区快速锁定矿产普查范围起到了非常重要的作用.     

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.     

Provisional Elemental Values for Eight New Geochemical Lake Sediment and Stream Sediment Reference Materials LKSD-1, LKSD-2, LKSD-3, LKSD-4, STSD-1, STSD-2, STSD-3 and STSD-4*

The collection and preparation of four lake and four stream sediment reference materials are described. Provisional values related to both total concentrations and concentrations derived from partial extraction procedures are presented for major, minor and trace element constituents. As large amounts of samples (160–200 kg) have been prepared, they should be of interest to soil analysts.     

A contribution to geochemical prospecting for fluorite

With fluorine as indicator, eight different extraction methods were tested for their suitability in geochemical prospecting for fluorite in stream sediments. Since this material can be regarded as coarse-grained, clastic fragments derived from the bedrock - i.e. granites, gneisses, and fluorite veins as well - it was concluded that the fluorine content of the stream sediments comes mostly from fluorine-bearing bedrock minerals. Anomalous samples contain fluorine predominantly as fluorite from fluorspar mineralization.Five of the commonest fluorine-bearing minerals - fluorite, mica, apatite, amphibole and tourmaline - were treated with the different extractants and with various times of reaction and mineral grain size. Fluorine analysis was by ion-selective electrode. The ratio cx-F (fluorite) vs. cx-F (mica, apatite) was found to be a useful measure of the applicability of the respective method.In order to test this conclusion 41 stream sediment samples (−177 microns −80 mesh) from the area under investigation were treated with eight different extractants.The most suitable extraction solution - boric acid solution - was used for the reconnaissance stream sediment survey in an area of 400 km² in the southeastern part of the Black Forest (F.R. Germany).     

中国西南滇黔桂关键资源远景新区锂地球化学时空分布特征及找矿预测

锂因其在新能源领域的应用广泛性和不可替代性而备受关注。以往锂矿勘查主要集中于盐湖型和硬岩型锂矿,针对沉积型锂矿开展工作较少。本文聚焦于中国西南滇黔桂地区,以岩石和水系沉积物中锂的时空分布特征为基础,分析区域内沉积型锂矿成矿潜力。结果显示,中国西南滇黔桂地区水系沉积物锂含量平均值为46. 7×10-6,显著高于全国背景值32×10-6。以57. 0×10-6为异常下限,共圈定9个锂地球化学省,与已知的沉积型锂矿床分布具有良好的对应性。同时,锂异常浓集区与某些特定时代和岩性的地层分布密切相关。区内水系沉积物中锂元素含量受到岩石锂含量制约,以碳酸盐岩为主的构造单元水系沉积物中的锂显著次生富集,以陆源碎屑岩为主的构造单元内水系沉积物中锂富集程度较弱。综合分析认为,西南滇黔桂地区锂异常带的形成受区域岩石类型、次生富集作用和气候条件等多重因素制约。该研究对了解西南滇黔桂地区锂元素次生聚集就位机制和指导沉积型锂资源的找矿勘查具有重要的参考意义。