A New Digestion and Chemical Separation Technique for Rapid and Highly Reproducible Determination of Lu/Hf and Hf Isotope Ratios in Geological Materials by MC-ICP-MS

A new digestion procedure and chemical separation technique has been developed for measurement of Lu/Hf and Hf isotope ratios that does not require high‐pressure bombs or use of HF or HClO₄ acids. Samples are digested in dilute HCl or HNO₃ after flux‐fusion at 110 0 °C in the presence of lithium metaborate. High field strength elements (HFSE) and rare earth elements (REE) are separated from this solution by co‐precipitation with iron hydroxide. The dissolved precipitate (in 2 mol l^?1 HCl) is loaded directly onto a standard cation exchange column which separates remaining sample matrix from the heavy REE (Lu+Yb), and the middle‐light REE and HFSE (Hf). The middle‐light REE and individual HFSE are then separated (10.5, 9 and 6 mol l^?1 HCl) using a miniaturized column containing TEVA spec resin which provides a REE‐, Ti‐ and Zr‐free Hf cut. This chemical separation scheme can also be readily adapted for isotopic analysis of the Sm‐Nd system and/or the other HFSE (Ti, Zr). Total procedural blanks for this technique are < 10 0 pg and < 2 pg for Hf and Lu, respectively, even when digesting large (0.5 g) samples. We present data from replicate digestions of international rock reference materials which demonstrate this technique routinely reproduces Lu/Hf ratios to < 0.2% (2s) and ¹⁷⁶ Hf/¹⁷⁷ Hf isotope ratios to < 30 ppm (2s). Moreover, the technique is matrix‐independent and has been successfully applied to analysis of diverse materials including basalts, meteorites, komatiites, kimberlites and carbonatites. The relative simplicity of this technique, coupled with the ease of digestion (and sample‐spike equilibration) of large difficult‐to‐dissolve samples, and the speed (2 days) with which samples can be digested and processed through the chemical separation scheme makes it an attractive new method for preparing samples for Lu‐Hf isotopic investigation.     

QUANTITATIVE ANALYSIS OF TRACE ELEMENTS IN GEOLOGICAL MATERIALS BY LASER ABLATION ICPMS: INSTRUMENTAL OPERATING CONDITIONS AND CALIBRATION VALUES OF NIST GLASSES

A UV laser ablation microprobe coupled to an ICPMS has been used to determine trace element concentrations in solids with a spatial resolution of 50 microns and detection limits ranging from 2 μg/g for Ni to 50 ng/g for the REE, The, and U. Experiments designed to optimize laser operating conditions show that pulse rates of 4 Hz produce a steady state signal with less inter-element fractionation per unit time than higher pulse rates (10–20 Hz). Comparisons of laser microprobe analyses of garnets and pyroxenes using the NIST 610 and 612 glasses as calibration standards, with proton microprobe, solution ICPMS, INAA and XRF data show no significant matrix effects. Laser microprobe analyses of the NIST 610 and 612 glasses have a precision and accuracy of 2–5%, and error analysis shows that counting statistics and the precision on the internal standard concentration accounts for the analytical uncertainty. The NIST glasses appear to be useful calibration materials for trace element analysis of geological materials by laser microprobe.     

Laser Ablation and Solution ICP-MS Determination of Rare Earth Elements in USGS BIR-1G, BHVO-2G and BCR-2G Glass Reference Materials

Data are reported for rare earth elements (REE) in three geological glass reference materials (BIR-1G, BHVO-2G and BCR-2G) using a UV (266 nm) laser ablation ICP-MS system and the classical (HF-HClO₄) acid decomposition method, followed by conventional nebulisation ICP-MS. External calibration of laser ablation analyses was performed using NIST SRM reference materials with internal standardisation using ²⁹Si and ⁴⁴Ca. Replicate analyses of reference basaltic glasses yielded an analytical precision of 1-5% (RSD) for all the elements by solution ICP-MS and 1-8% (RSD) by laser ablation ICP-MS. The relative differences between the REE concentrations measured by solution and laser ablation ICP-MS compared with the reference values were generally less than 11 % for most elements. The largest deviations occurred for La determined by solution ICP-MS in BIR-1G. The results of both solution and laser ablation ICP-MS agreed well, generally better than 7%, with the exception of La, Pr and Sm in BIR-1G. The measured REE laser ablation data for BIR-1G, BHVO-2G and BCR-2G agreed with the previously published data on these basaltic reference glasses, within a range of 0-10% for most elements. No significant influences were observed for the predicted spectral interferences on some REE isotopes in the analysis of basaltic glasses.     

Determination of Zirconium, Niobium, Hafnium and Tantalum at ng g-1 Levels in Geological Materials by Direct Nebulisation of Sample HF Solution into FI-ICP-MS

We have developed a rapid and accurate method to determine Zr, Nb, Hf and Ta (denoted as HFSE) in geological samples by inductively coupled plasma-mass spectrometry fitted with a flow injection system (FI-ICP-MS). The method involves sample decomposition by HF followed by HF dissolution of HFSE coprecipitated with insoluble M and Ca fluoride residues formed during the initial HF attack. This HF solution was directly nebulized into an ICP mass spectrometer. An external calibration curve method and an isotope dilution method (ID) were applied for the determination of Nb and Ta, and of Zr and Hf, respectively. Recovery yields of HFSE were > 96% for peridotite, basalt and andesite compositions, apart from Zr and Hf for peridotite (> 85%). No matrix effects for either signal intensities of HFSE or isotope ratios of Zr and Hf were observed in basalt, andesite and peridotite solutions down to a dilution factor of 100. Detection limits in silicate rocks were 40, 2, 1 and 0.1 ng g-1 for Zr, Nb, Hf and Ta, respectively. This technique required only 0.1 ml of sample solution, and thus is suitable for analysing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates. We also present newly determined data for the Zr, Nb, Hf and Ta concentrations in USGS silicate reference materials DTS-1, PCC-1, BCR-1, BHVO-1 and AGV-1, GSJ reference materials JB-1, -2, -3, JA-1, -2 and -3, and the Smithsonian reference Allende powder.     

Determination of Rare Earth Elements in Geological Reference Materials: A Comparative Study by INAA and ICP-MS

Data was obtained for the rare earth elements (REE) by instrumental neutron activation analysis (INAA) and inductively coupled plasma-mass spectrometry (ICP-MS) in twenty geological reference materials. In general, the precision obtained by ICP-MS is better for the light REE, decreasing with increasing atomic number. This is partly a result of the occurrence of the heavy REE at low concentrations. The precision of the data obtained by INAA is good (5% RSD). The data obtained also showed that for the elements determined by both methods, the accuracy is similar for the light REE and better for the middle and heavy REEs by INAA. Higher uncertainty is achieved by ICP-MS mainly for elements at very low concentrations, occurring at about ten times the chondritic values.     

Rapid and highly reproducible analysis of rare earth elements by multiple collector inductively coupled plasma mass spectrometry

A method has been developed for the rapid chemical separation and highly reproducible analysis of the rare earth elements (REE) by isotope dilution analysis by means of a multiple collector inductively coupled plasma mass spectrometer (MC-ICP-MS). This technique is superior in terms of the analytical reproducibility or rapidity of analysis compared with quadrupole ICP-MS or with thermal ionization mass spectrometric isotope dilution techniques. Samples are digested by standard hydrofluoric-nitric acid-based techniques and spiked with two mixed spikes. The bulk REE are separated from the sample on a cation exchange column, collecting the middle-heavy and light REE as two groups, which provides a middle-heavy REE cut with sufficient separation of the light from the heavier REE to render oxide interferences trivial, and a Ba-free light REE cut. The heavy (Er-Lu), middle (Eu-Gd), and light REE (La-Eu) concentrations are determined by three short (1 to 2 min) analyses with a CETAC Aridus desolvating nebulizer introduction system. Replicate digestions of international rock standards demonstrate that concentrations can be reproduced to <1%, which reflects weighing errors during digestion and aliquotting as inter-REE ratios reproduce to ≤0.2% (2 SD). Eu and Ce anomalies reproduce to <0.15%. In addition to determining the concentrations of polyisotopic REE by isotope dilution analysis, the concentration of monoisotopic Pr can be measured during the light REE isotope dilution run, by reference to Pr/Ce and Pr/Nd ratios measured in a REE standard solution. Pr concentrations determined in this way reproduce to <1%, and Pr/REE ratios reproduce to <0.4%. Ce anomalies calculated with La and Pr also reproduce to <0.15% (2 SD). The precise Ce (and Eu) anomaly measurements should allow greater use of these features in studying the recycling of materials with these anomalies into the mantle, or redox-induced effects on the REE during recycling and dehydration of oceanic lithosphere, partial melting, metamorphism, alteration, or sedimentation processes. Moreover, this technique consumes very small amounts (subnanograms) of the REE and will allow precise REE determinations to be made on much smaller samples than hitherto possible.     

Importance of Skewness and Kurtosis Statistical Tests for Outlier Detection and Elimination in Evaluation of Geochemical Reference Materials

A common characteristic of concentration data compilations for geochemical reference materials (GRM) is a skewed frequency distribution because of aberrant analytical data. Rejection of outlying results usually is required to obtain a better estimate of mean concentration values. The present work describes the application of an approach, based on skewness and kurtosis statistical tests, to establish reliable concentration values in study of rare-earth element compilations for GRM. Frequency histograms of initial concentrations for these elements differ significantly from a normal distribution, as deduced from their skewness and kurtosis coefficients. The statistical procedure shows that rejection of outliers yields normal distributions which can be used to provide mean concentrations with smaller standard deviations for a large number of cases, although for many elements our %RSD are similar (within 5%) to literature values. This procedure has been applied to derive new concentration data for rare-earth elements in 26 GRM, which are compared with earlier compilations to show that the statistical procedure proposed here provides mean values with greater quality value. Although most present mean concentrations are similar (within 5%) to those reported in previous literature, some of them are significantly different (with differences of up to 40%) in a few GRM.     

胶东金青顶金矿床成矿流体来源的黄铁矿微量元素及He-Ar同位素证据

金青顶金矿床是目前国内最大的石英单脉型金矿,其金储量超过50 t,规模为大型。对该矿床成矿流体性质和来源的研究十分必要。笔者通过Ⅱ号矿体主要载金矿物黄铁矿微量元素的研究发现,其Co/Ni为2.317～11.734(平均7.17),显示主要为热液成因;高场强元素(HFSE)特征显示,成矿早期以富F流体为主,主成矿期以富Cl流体为主;稀土配分模式显示成矿物质并不是直接来源于围岩昆嵛山二长花岗岩。对黄铁矿流体包裹体He、Ar同位素特征的研究表明,3He/4He、40Ar/36Ar分别为0.1～2.2 Ra(平均值0.60 Ra),462.7～1 507.5(平均值831),显示成矿流体主要源自地壳,并与深部幔源流体发生了不同程度的混合,且上升过程中有少量大气降水加入。     

Trace element mobility in dolomitic argillites of the Mesoproterozoic Belt-Purcell Supergroup, Western North America

The Belt-Purcell Supergroup comprises dolomite-rich stratigraphic units in a dominantly siliciclastic succession, where sedimentation spans 1400-1470 Ma. Dolomitic units are variable mixtures of co-sedimented argillite and primary carbonate post-depositionally converted to secondary dolomite. Based on rare earth element (REE) relationships three distinct REE patterns are identified in the dolomite-rich units: Type 1 (T1d; d = dolomitic sample) with REE patterns parallel to post-Archean Upper Continental Crust (PA-UCC), albeit at lower absolute abundances due to dilution by carbonate content; Type 2 (T2d) with Heavy REE (HREE) enrichment but Light REE (LREE) depletion relative to T1d; and Type 3 (T3d) with enrichment in LREE and HREE relative to T1d, but erratic Middle REE (MREE) patterns. There is a progressive increase of ΣREE from T1d through T2d to T3d, whereas for ΣLREE/ΣHREE T2d < T1d < T3d. T1d-T2d and T3d represent three different “snapshots” of a continuous process.In terms of timing, dolomitization of calcite primary sediment in all samples likely took place broadly during burial diagenesis, as inferred for most Proterozoic dolomites. T1d is easily explained by provenance: however, T2d and T3d cannot be related to provenance, weathering or sedimentary sorting processes to explain higher concentrations of HREE referenced to PA-UCC and consequently developed in the sediment from a T1d precursor. The same three REE signatures have been described in previous studies in counterpart siliciclastic counterparts throughout the Belt-Purcell Supergroup at three different locations. Mobility of normally stable REE is accompanied by mobility of normally isochemical high field strength elements (HFSE) in T2d and T3d to give REE/REE, HFSE/HFSE, REE/HFSE and Y/HREE fractionations. No specific REE-HFSE signatures are apparent in the carbonate-rich units as compared to their non-dolomitic siliciclastic counterparts. This unusual mobility of REE and HFSE reflected in T2d and T3d is attributed to alkaline oxidizing post-depositional brines. Salinity was derived from seawater-sediment reactions, dissolution of evaporite minerals, and the smectite-illite transformation, whereas alkaline oxidizing conditions were promoted by groundwater interaction with mafic units in the basin, CO₂ introduced into the system during episodic rifting with mantle degassing, and interaction of syn-sedimentary mafic intrusions with carbonate units at early stages of BPS deposition. Intermittent brine activity, inducing T2d and T3d patterns, spanned >1 Ga as recorded by secondary monazite grains with age distributions that correspond to large scale tectono-thermal events in Laurentia.Post-depositional processes and redistribution of carbonate can have an impact on transitional stratigraphic contacts between dolomitic and siliciclastic units which may have been incorrectly described as primary due to sedimentary environment changes.     

Reference Materials for Geochemical Studies: New Analytical Data by ICP-MS and Critical Discussion of Reference Values

Abundances of twenty four trace elements, including Y and fourteen rare earth elements (REE), are reported for eighty six geological reference materials and four proficiency testing samples. Analytical data were obtained by ICP-MS using solution nebulisation after mixed acid digestion (HF-HClO₄) under pressure. Analysed samples cover a wide range of element concentrations and mineralogical compositions, including samples for which there are few previously published data. Precision for elemental determinations in nearly 90% of the samples analysed is better than 5%. Accuracy, estimated by comparison with data from compilations is better than 6% for well characterized reference materials. Results obtained for samples that are low in trace elements are often significantly lower than compiled reference values. A critical discussion of the compiled data sets, especially for Y and the REEs, indicates that some reference values seem to be erroneous.     

UV Laser Ablation ICP-MS: Some Applications in the Earth Sciences

This study reports a series of applications of UV laser ablation ICP-MS in the geological sciences. The advantages and disadvantages of the PQ "S" option and the use of nitrogen in the carrier gas are discussed. A general problem common to all ablation techniques is the calibration technique and experiments involving synthetic calibration samples are covered. Zircon geochemistry and geochronology by LA-ICP-MS are discussed and data are presented for REE, Hf and U for a standard zircon (91500) as well as a series of zircons from Zimbabwe. The potential of using Ce and Eu anomalies in petrologic studies is illustrated by zircons from a fractionated gabbroic-granite in the Urals. The potential of the LA-ICP-MS method to utilise standard X-ray fluorescence glass discs is demonstrated as a useful semi-quantitative tool in determining REE patterns. LA-ICP-MS is a powerful tool in the analysis of the platinum group elements (and Re) and some examples are given in the successful application of the technique to partitioning in iron meteorites.     

富氟花岗岩体系岩浆流体内稀土元素演化规律的实验研究

高温高压实验结果表明，随着富氟过铝花岗质岩浆分离结晶作用的进行，在与熔体相共存的流体相中，REE浓度呈有规律地变化：当温度从750℃下降至接近固相线（570℃）时，流体相中REE浓度逐渐降低，这一规律与REE在稀有金属花岗岩体上部岩相带中REE含量贫化的地质事实相一致。在富氟过铝质花岗岩体系中，REE易于分散进入某些造岩矿物（如黑云母等）和副矿物（如萤石和锡石等）中，从而不利于REE形成热液矿床。     

鲁西中、新生代镁铁质岩浆作用与地幔化学演化

镁铁质火成岩作为分布最为广泛的典型幔源岩石, 已成为探索地幔化学性状及示踪岩石圈深部过程的主要研究对象.通过对典型样品元素-同位素组成的系统测定, 并结合前人已有资料, 综合研究了鲁西中生代和新生代镁铁质岩石的地质与地球化学特征.研究结果表明, 中生代镁铁质火成岩总体具有富轻稀土和大离子亲石元素、贫高场强元素、I_Sr值变化范围大(0.70396~0.71247)、ε_Nd (t) 值显著偏低(-9.20~-21.21) 的地球化学特征, 但该区南部和北部的中生代镁铁质岩石在元素-同位素组成上仍存在一定差别, 主要表现在南部较之北部镁铁质岩石具有更高的稀土总量(ΣREE为325.52×10-6~555.75×10-6)和轻、重稀土比值(LREE/HREE=17.75~25.97), 以及更高的LILE/HFSE比值(如La/Nb=6.37~13.85, Th/Nb=0.52~1.53).南部镁铁质岩石较之北部镁铁质岩石也更富放射成因锶, I_Sr值分别为0.70844~0.71247和0.70396~0.70598.元素-同位素综合示踪指示鲁西中生代地幔总体具有因岩石圈大规模拆沉作用形成的EMⅠ型富集地幔特征, 但其南部叠加了因深俯冲而进入地幔的扬子陆壳的影响, 因而表现出EMⅠ和EMⅡ组分混合的富集地幔特征.新生代玄武岩具有类似于大洋玄武岩的地球化学特征, 其源区应为亏损的软流圈地幔, 但在部分熔融形成岩浆之前遭受了近期的交代作用.自中生代至新生代, 华北克拉通地幔具有由富集向亏损演变的趋势, 这一化学性状的演变最可能是中生代以来岩石圈大规模拆沉作用, 导致软流圈地幔上涌并对原有岩石圈地幔再改造所致.      

Formation Process of Zircon Associated with REE‐Fluorocarbonate and Niobium Minerals in the Nechalacho REE Deposit,Thor Lake,Canada

The two drill holes, which penetrated sub‐horizontal rare earth element (REE) ore units at the Nechalacho REE in the Proterozoic Thor Lake syenite, Canada, were studied in order to clarify the enrichment mechanism of the high‐field‐strength elements (HFSE: Zr, Nb and REE). The REE ore units occur in the albitized and potassic altered miaskitic syenite. Zircon is the most common REE mineral in the REE ore units, and is divided into five types as follows: Type‐1 zircon occurs as discrete grains in phlogopite, and has a chemical character similar to igneous zircon. Type‐2 zircon consists of a porous HREE‐rich core and LREE–Nb–F‐rich rim. Enrichment of F in the rim of type‐2 zircon suggests that F was related to the enrichment of HFSE. The core of type‐2 zircon is regarded to be magmatic and the rim to be hydrothermal in origin. Type‐3 zircon is characterized by euhedral to anhedral crystals, which occur in a complex intergrowth with REE fluorocarbonates. Type‐3 zircon has high REE, Nb and F contents. Type‐4 zircon consists of porous‐core and ‐rim, but their chemical compositions are similar to each other. This zircon is a subhedral crystal rimmed by fergusonite. Type‐5 zircon is characterized by smaller, porous and subhedral to anhedral crystals. The interstices between small zircon grains are filled by fergusonite. Type‐4 and type‐5 zircon grains have low REE, Nb and F contents. Type‐1 zircon is only included in one unit, which is less hydrothermally altered and mineralized. Type‐2 and type‐3 zircon grains mainly occur in the shallow units, while those of type‐4 and type‐5 are found in the deep units. The deep units have high HFSE contents and strongly altered mineral textures (type‐4 and type‐5) compared to the shallow units. Occurrences of these five types of zircon are different according to the depth and degree of the hydrothermal alteration by solutions rich in F and CO₃, which permit a model for the evolution of the zircon crystallization in the Nechalacho REE deposit as follows: (i) type‐1 (discrete magmatic zircon) is formed in miaskitic syenite. (ii) LREE–Nb–F‐rich hydrothermal zircon formed around HREE‐rich magmatic zircon (type‐2). (iii) type‐3 zircon crystallized through the F and CO₃‐rich hydrothermal alteration of type‐2 zircon which formed the complex intergrowth with REE fluorocarbonates; (iv) the CO₃‐rich hydrothermal fluid corroded type‐3, forming REE–Nb‐poor zircon (type‐4). Niobium and REE were no longer stable in the zircon structure and crystallized as fergusonite around the REE–Nb‐leached zircon (type‐4); (v) type‐5 zircon is formed by the more CO₃‐rich hydrothermal alteration of type‐4 zircon, suggested by the fact that type‐4 and type‐5 zircon grains are often included in ankerite. Type‐3 to type‐5 zircon grains at the Nechalacho REE deposit were continuously formed by leaching and/or dissolution of type‐2 zircon in the presence of F‐ and/or CO₃‐rich hydrothermal fluid. These mineral associations indicate that three representative hydrothermal stages were present and related to HFSE enrichment in the Nechalacho REE deposit: (i) F‐rich hydrothermal stage caused the crystallization of REE–Nb‐rich zircon (type‐2 rim and type‐3), with abundant formation of phlogopite and fluorite; (ii) F‐ and CO₃‐rich hydrothermal stage led to the replacement of a part of REE–Nb–F‐rich zircon by REE fluorocarbonate; and (iii) CO₃‐rich hydrothermal stage resulted in crystallization of the REE–Nb–F‐poor zircon and fergusonite, with ankerite. REE and Nb in hydrothermal fluid at the Nechalacho REE deposit were finally concentrated into fergusonite by way of REE–Nb–F‐rich zircon in the hydrothermally altered units.     

关于冀西北孔达岩系时代的新认识

<正> 八十年代下半期前,在我国对早前寒武系地层(>1850Ma),如“太华群”、“登封群”、“胶东群”、“阜平群”和“桑干群”等常笼统地划归太古宙,从而造成早元古宙(2550—1850Ma)地层的“空缺”和混乱。如果我们将富有特征和能反映大气圈、水圈、生物圈以     

Accurate Measurement of Rare Earth Elements by ICP‐MS after Ion‐Exchange Separation: Application to Ultra‐Depleted Samples

This study reports precise and accurate data for rare earth elements (REE) measured on eight geological reference materials, five enriched in REE (BE‐N, BHVO‐2, BR, BR‐24 and RGM‐1) and three very depleted in REE (BIR‐1, UB‐N and DTS‐2). Data were acquired by quadrupole ICP‐MS after isolation of the REE using an ion‐exchange chromatography procedure. All the measured REE abundances were similar within ≈ 5% (10% for the most REE‐depleted sample DTS‐2) to the high‐quality measurements previously published in the literature. We also show that by using an internal Tm spike, the reproducibility of the data was improved to ～ 1%. Applying this technique to the analysis of ultra‐depleted rock samples (sub ng g^?1), we show that significant improvements were obtained relative to the routine trace element measurement method. The chondrite‐normalised patterns were smooth instead of displaying irregularities. Although the classical method gives excellent results on REE‐rich samples, we believe that our technique improves the precision and accuracy of measurements for highly REE‐depleted rocks.     

Rare earth element mobility during prograde granulite facies metamorphism: significance of fluorine

 Mafic gneisses occur as lenses or thin layers in spatial association with tonalitic leucosomes in a granulite zone of the Quetico subprovince of the Superior Province, Ontario, Canada, and exhibit concentric zoning with a biotite-rich margin, orthopyroxene-rich outer zone, clinopyroxene-rich central zone, and, occasionally, patches of relict amphibolites within the clinopyroxene-rich zone. The granulites (biotite-, orthopyroxene- and clinopyroxene-rich zones) in the mafic gneisses are characterized by significant amounts of rare earth element (REE)-bearing fluorapatite (1–10 vol.%) and other REE-rich minerals (allanite, monazite and zircon). Fluorapatite shows an increase in modal abundance from the biotite- and orthopyroxene-rich zones to the clinopyroxene-rich zone, but is rare in the relict amphibolites. Textural evidence and element partitioning indicate that fluorapatite (and other REE-rich minerals) was part of the peak metamorphic assemblages. Whole-rock geochemical analyses confirm that the granulites in the mafic gneisses contain anomalously high contents of REE and high field strength elements (HFSE), whereas the relict amphibolites are geochemically typical of tholeiitic basalts. Mass-balance calculations reveal that REE and HFSE were introduced into the mafic gneisses during the prograde granulite facies metamorphism, pointing to REE mobility under granulite facies metamorphic conditions. The presence of high F contents in the REE-rich minerals and their associated minerals (e.g. biotite and hornblende) suggests that REE and HFSE may have been transported as fluoride complexes during the granulite facies metamorphism. This conclusion is supported by previously published results of hydrothermal experiments on the partitioning of REE between fluorapatite and F-rich fluids at 700°C and 2 kbar. Received: 2 May 1995 / Accepted: 28 September 1995     

Study on the multi-sources of ore-forming materials and ore-forming fluids in the Huize lead-zinc ore deposit

TheHuizelarge sizedPb ZndepositinYunnan ProvinceislocatedinthecenteroftheSichuan Yun nan GuizhouPb Zn Agpolymetalmineralizationzone(SYGPb ZnMMD)inwesternYangtzePlateandis oneofthefamousPb Zn GebasesinChina(Wang Jiangzhenetal.,2003;WangXiaochunetal.,2000).Thisdeposit,whichischaracterizedbylarge scale(Pb+Znmetallicreservesarehigherthan5mil liontons),highPb+Zngrade(thePb+Zngradesof mostoresare25%-35%),highabundanceofuseful associatedelements(Ag,Ge,Cd,Ga,etc.)and someimportantbreakt…     

Rare Earth and High Field‐Strength Elements in the Multani Mitti Clay: A Study Using INAA

Instrumental neutron activation analysis was used to determine nine rare earth elements (REE), Sc and five high field‐strength elements (HFSE) in the Multani Mitti (MM) clay. Chondrite‐normalised rare earth element patterns for the MM clay compared with those for the Post‐Archaean Australian Shale (PAAS), Upper Continental Crust (UCC) and North American Shale Composite (NASC) showed enrichment of light REEs and depletion of heavy REEs with a slight negative Eu anomaly. The Multani Mitti clay showed close resemblance to PAAS and NASC in its average REE and HFSE contents. Positive correlations between La/Ce, La/Sm, La/Yb, Zr/Hf, Th/U and Th/Ta ratios predict enrichment of LREEs, Zr and Th and depletion of HREEs. A parent source of felsic origin for the MM clay is also endorsed through the high La/Th and low Th/Sc ratios observed.     

偏振能量色散X射线荧光光谱法测定硫化物矿石中的铜铅锌

X射线荧光光谱法用于分析矿石主成分的常规制样方法有粉末压片法与玻璃熔融法,但分析硫含量高的地质样品时,前者存在矿物效应和粒度效应问题、后者可能腐蚀贵金属坩埚。为满足矿产勘查的需要,急需一种适应于硫化物矿石主成分分析的制样方法。本文建立了一种硝酸+氢氟酸封闭消解试样,标准溶液校准,偏振能量色散X射线荧光光谱(PE-EDXRF)同时测定硫化物样品中铜、铅、锌三种元素的分析方法。用GBW 07162~GBW 07168等7种矿石国家一级标准物质进行精密度和准确度实验。结果表明,当样品中铜、铅、锌元素含量大于1%时,几乎所有样品中的铜、铅、锌元素的精密度(RSD,n=6)优于5%,检测结果与标准值一致性良好。本方法通过样品消解、直接液体进样等技术的应用,消除了粒度效应和矿物效应等基体效应对分析结果的影响,解决了因缺乏基体匹配的标准物质而造成的含量校准的问题,使PE-EDXRF技术可以在硫化物矿石分析中得到比较方便的应用。这种分析方法为实验室矿石分析提供了新手段,也为野外现场PE-EDXRF分析高矿化度样品提供了新途径。