Comparison of Fused Glass Beads and Pressed Powder Pellets for the Quantitative Measurement of Al,Fe, Si and Ti in Bauxite by Laser‐Induced Breakdown Spectroscopy

Due to matrix interference and sample particle size effects, some of the most important and difficult issues in laser‐induced breakdown spectroscopy (LIBS) analysis are the calibration and quantitative measurement of a complex matrix. This study proposes the use of borate fusion as an alternative sample preparation procedure for the quantitative measurement of Al, Fe, Si and Ti in bauxite by LIBS. Analytical calibration curves were made using bauxite certified reference materials (CRM), and the precision and accuracy of the methods were evaluated by analysing an additional bauxite CRM, using two different approaches: pressed powder pellets and fused glass beads. The borate fusion method was the most suitable sample preparation technique, since particle size effects and matrix interference could be minimised, obtaining better linearity on the analytical calibration curves (r²), and more accurate and more precise results for bauxite analysis.     

定量分析宝石材料化学成分的激光诱导离解光谱方法研究

主要针对宝石材料进行了激光诱导离解光谱技术定量分析方法的总结以及对比研究。选择外标法、自由定标法和归一化的外标法三种较为适用于宝石材料分析的方法进行了介绍。选取陨石玻璃、绿辉石、紫色翡翠以及硅酸盐玻璃等成分较为均匀的样品作为分析对象,使用中国地质大学（武汉）珠宝学院自制的激光诱导离解光谱设备,分别运用三种方法对其进行了定量分析的计算。定量分析结果显示,外标法易受成分变化及结构差异而造成的基体效应的影响,分析的准确度不高;自由定标法在分析成分复杂的样品时,其影响因素十分复杂,会产生较大的误差;归一化的外标法可有效校正基体效应的影响,其定量分析结果要优于前两者,虽然在微量元素分析准确度上尚需改进,但不失为一种较好的快速定量分析宝石材料的定量分析方法。     

Laser Induced Breakdown Spectroscopy applications to meteorites: Chemical analysis and composition profiles

A fast procedure for chemical analysis of different meteorites is presented, based on LIBS (Laser Induced Breakdown Spectroscopy). The technique is applied to several test cases (Dhofar 019, Dhofar 461, Sahara 98222, Toluca, Sikhote Alin and Campo del Cielo) and can be useful for rapid meteorite identification providing geologists with specific chemical information for meteorite classification. Concentration profiles of Fe, Ni and Co are simultaneously detected across the Widmanstätten structure of the iron meteorite Toluca with a view to determining cooling rates. The LIBS analysis of meteorites is also used as a laboratory test for analogous studies on the respective parent bodies (Mars, asteroids) in space exploration missions where one clear advantage of the proposed technique is that no direct contact with the sample is required.     

Geological Applications of Laser‐Induced Breakdown Spectroscopy

Laser‐induced breakdown spectroscopy (LIBS) records light emitted from the decay of electrons to lower‐energy orbitals during cooling of laser‐induced ablation plasmas; the resultant spectra can be used in a variety of geoanalytical applications. Four aspects of LIBS analysis distinguish LIBS from traditional laboratory‐based analytical techniques: (i) the lack of necessary sample preparation, allowing rapid analysis of many samples, (ii) the ability to analyse both 20 to 100 μm‐diameter spots and whole rocks, (iii) the detailed chemical signature contained in a LIBS spectrum and (iv) the ability to take LIBS into the field in backpack portable instrumentation. Three case studies illustrate potential applications of LIBS in the geosciences. First, analysis of the Carrizozo basalt flow in New Mexico, USA, illustrated that LIBS spectra could discriminate between samples of similar composition within uncertainties typical of whole‐rock analysis by X‐ray fluorescence spectrometry. Second, spectra from four sets of rubies from Madagascar and Tanzania illustrate the use of LIBS and multivariate analysis to determine provenance with success rates of > 95%. This technique can also be applied to correlation of units. Finally, a chemical map of a copper ore from Butte, MT, USA, illustrates the use of spatially defined LIBS spectra to understand chemical variations within textural context.     

能谱仪PPA分析方法的实验研究: 以山西大同新生代玄武岩样品为例

以山西大同新生代玄武岩样品为例, 利用Quanta 200扫描电镜、GENESIS能谱仪对能谱仪PPA分析方法进行了实验研究, 该方法为粒度和物相自动分析方法.笔者首次把能谱仪PPA分析方法应用到地质学领域的岩石光薄片研究中, 快速得出了一系列不同物相的形态学数据及化学成分分析结果: 物相种类、每一种物相的颗粒数、每一个颗粒的平均直径、面积、周长、圆度、长宽比及化学成分等, 并得出了不同物相在该视域所占的面积百分比及每种物相颗粒的平均直径, 克服了传统光薄片粒度分析方法的所有缺点, 为矿物学、岩石学及矿床学研究提供了一套非常有意义的数据.      

Application of Laser‐Induced Breakdown Spectroscopy and Hyperspectral Images for Direct Evaluation of Chemical Elemental Profiles of Coprolites

This study demonstrates the application of laser‐induced breakdown spectroscopy (LIBS) and hyperspectral imaging to the investigation of coprolite and fossil samples. Solid samples from the Permian (seven coprolites and one fossil), Cretaceous (one coprolite) and Oligo‐Miocene (two coprolites) periods were directly analysed, and emission spectra from 186 to 1042 nm were obtained in several areas covering coprolite/fossil and rock material. Initial exploratory analyses were performed using principal component analysis with the data set normalised by the norm (Euclidean norm = 1). After identification and selection of emission lines of eleven elements (Al, Ca, Cr, Fe, K, Mg, Mn, Na, Ni, P and Si), the signals were normalised again by the relative intensity of the selected element. Phosphorus was identified mainly in the coprolites, while K and Na were primarily found in the rock material. In several cases, there was a positive correlation between Ca and P. A sample from the Oligo‐Miocene series was also analysed using inductively coupled plasma‐optical emission spectrometry (ICP‐OES) (rock and coprolites were analysed separately). Based on the quantitative results from ICP‐OES, it was confirmed that the tendency was the same as that observed with the results obtained from LIBS directly in the solid sample.     

Development of a Matrix‐Matched Sphalerite Reference Material (MUL‐ZnS‐1) for Calibration of In Situ Trace Element Measurements by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Sphalerite (ZnS) is an abundant ore mineral and an important carrier of elements such as Ge, Ga and In used in high‐technology applications. In situ measurements of trace elements in natural sphalerite samples using LA‐ICP‐MS are hampered by a lack of homogenous matrix‐matched sulfide reference materials available for calibration. The preparation of the MUL‐ZnS1 calibration material containing the trace elements V, Cr, Mn, Co, Ni, Cu, Ga, Ge, As, Se, Mo, Ag, Cd, In, Sn, Sb, Tl and Pb besides Zn, Fe and S is reported. Commercially available ZnS, FeS, CdS products were used as the major components, whereas the trace elements were added by doping with single‐element ICP‐MS standard solutions and natural mineral powders. The resulting powder mixture was pressed to pellets and sintered at 400 °C for 100 h using argon as an inert gas. To confirm the homogeneity of major and trace element distributions within the MUL‐ZnS1 calibration material, measurements were performed using EPMA, solution ICP‐MS, ICP‐OES and LA‐ICP‐MS. The results show that MUL‐ZnS‐1 is an appropriate material for calibrating trace element determination in sphalerite using LA‐ICP‐MS.     

A Comparative Study of Five Reference Materials and the Lombard Meteorite for the Determination of the Platinum‐Group Elements and Gold by LA‐ICP‐MS

A range of independently characterised reference materials (RMs) for LA‐ICP‐MS, used for the determination of the platinum‐group elements (PGE) and Au in a sulfide matrix, were analysed and compared: 8b, PGE‐A, NiS‐3, Po727‐T1, Po724‐T and the Lombard meteorite. The newly developed RM NiS‐3 was used as the RM for the calibration of all LA‐ICP‐MS analyses and the measured concentrations of the other RMs compared against their published concentrations. This data were also used to assess the consistency of concentrations calibrated against the different RMs. It was found that Po727‐T1 and 8b produced results that were comparable, within uncertainty, for all elements. Po727‐T1 also produced consistent results with NiS‐3 for all elements. All other RMs showed differences for some elements, especially Ru in Po724‐T, and Os, Ir and Au in PGE‐A. The homogeneity of the PGE and Au in each RM was assessed, by comparing the precision of multiple LA‐ICP‐MS spot analyses with the average uncertainty of the signal. Po724‐T, Po727‐T1 and the Lombard meteorite were found to be homogeneous for all elements, but 8b, PGE‐A and NiS‐3 were heterogeneous for some elements. This is the first direct comparison between a range of independently characterised PGE and Au LA‐ICP‐MS RMs.     

Automated Extraction of a Five‐Year LA‐ICP‐MS Trace Element Data Set of Ten Common Glass and Carbonate Reference Materials: Long‐Term Data Quality,Optimisation and Laser Cell Homogeneity

LA‐ICP‐MS is increasingly applied to obtain quantitative multi‐element data with minimal sample preparation, usually achieved by calibration using reference materials (RMs). However, some ubiquitous RMs, for example the NIST SRM 61× series glasses, suffer from reported value uncertainties for certain elements. Moreover, no long‐term data set of analyses conducted over a range of ablation and tuning conditions exists. Thus, there has been little rigorous examination of the extent to which offsets between measured and reported values are the result of error in these values rather than analytically induced fractionation. We present new software (‘LA‐MINE’), capable of extracting LA‐ICP‐MS data with no user input, and apply this to our system, yielding over 5 years of data (~ 5700 analyses of ten glass and carbonate RMs). We examine the relative importance of systematic analytical bias and possible error in reported values through a mass‐specific breakdown of fourteen of the most commonly determined elements. Furthermore, these data, obtained under a wide range of different ablation conditions, enable specific recommendations of how data quality may be improved, for example the role of diatomic gas, the effect of differential inter‐glass fractionation factors and choice of transport tubing material. Finally, these data demonstrate that the two‐volume Laurin ablation cell is characterised by no discernible spatial heterogeneity in measured trace element ratios.     

Li2B4O7熔融玻璃-激光剥蚀等离子体质谱法测定水系沉积物国家标准定值样品中微量元素

建立了激光剥蚀等离子体质谱法直接测定Li2B4O7熔融玻璃中微量元素的分析方法。详细讨论了内标元素的选择及Li2B4O7熔融玻璃的均一性、背景空白对分析测定的影响。以Li2B4O7熔融玻璃中低同位素丰度的6Li作内标，水系沉积物国家标准参考物质熔融玻璃建立多元素标准校正曲线，用于标准参考物质及水系沉积物定值样品的分析，测定值与标准值或溶液雾化等离子体质谱结果比较，具有较好的一致性。     

Quantification of turbate microstructures through a subglacial till: dimensions and characteristics

Despite extensive study and debate regarding the significance of turbate (also known as ‘rotational’) microstructures in glacially deformed sediments, characteristics regarding the dimensions of these features remain unresolved. This study presents the first explicitly quantitative measurement and analysis of turbate microstructure dimensions, and their relation to till texture through thin section analysis. Samples were taken from coarse‐resolution horizontal and vertical transects of a macroscopically homogenous subglacial till, with subset areas of each thin section (30 mm²) analysed. The frequency and apparent a‐axes and b‐axes of both coreless and cored turbate structures (and their corestones) were measured, and simple univariate statistical methods used to establish the (in‐)variability of these dimensions through the till profile. Summarizing findings, (i) the dimensions of both cored and coreless turbate populations display log‐normal distributions when all measurements are analysed together, although not all individual sample populations possess these same distributions; (ii) turbate dimension populations are inconsistent within a sample block, precluding evaluation of turbate variability through a profile from single thin sections; (iii) analysis of turbate morphology and variability provisionally indicate that the three‐dimensional structure of turbates are likely to be cylindrical or flared, while weak relationships are also observed amongst till texture, turbate dimensions and frequency.     

Potential Orthopyroxene,Clinopyroxene and Olivine Reference Materials for In Situ Lithium Isotope Determination

Over 1400 electron probe and 700 ion probe microanalyses were performed on eleven mineral separates to evaluate their potential as reference materials for in situ Li isotopic determination. Our results suggest the homogenous distributions of major elements, Li and its isotopes for each sample. Hence, these samples are suitable to be used as reference materials for in situ measurements of Li abundance and Li isotopes by secondary ion mass spectrometry (SIMS) or laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). These samples have the advantage of mitigating probable matrix effects during calibration owing to the wide range of compositions. The effect of composition on the δ⁷Li of olivine measured by SIMS is a linear function of composition, with δ⁷Li increasing by 1.0‰ for each mole per cent decrease in forsterite component.     

Geochemical Fingerprinting by Handheld Laser‐Induced Breakdown Spectroscopy

A broad suite of geological materials was studied a using a handheld laser‐induced breakdown spectroscopy (LIBS) instrument. Because LIBS is simultaneously sensitive to all elements, the full broadband emission spectrum recorded from a single laser shot provides a ‘chemical fingerprint’ of any material – solid, liquid or gas. The distinguishing chemical characteristics of the samples analysed were identified through principal component analysis (PCA), which demonstrates how this technique for statistical analysis can be used to identify spectral differences between similar sample types based on minor and trace constituents. Partial least squares discriminant analysis (PLSDA) was used to distinguish and classify the materials, with excellent discrimination achieved for all sample types. This study illustrates through four examples (carbonate minerals and rocks, the oxide mineral pair columbite–tantalite, the silicate mineral garnet and native gold) how portable, handheld LIBS analysers can be used for real‐time chemical analysis under simulated field conditions for element or mineral identification, plus such applications as stratigraphic correlation, provenance determination and natural resource exploration.     

Determination of Trace Element Mass Fractions in Ultramafic Rocks by HR‐ICP‐MS: A Combined Approach Using a Direct Digestion/Dilution Method and Preconcentration by Coprecipitation

A procedure is described for the determination of thirty‐seven minor and trace elements (LILE, REE, HFSE, U, Th, Pb, transition elements and Ga) in ultramafic rocks. After Tm addition and acid sample digestion, compositions were determined both following a direct digestion/dilution method (without element separation) and after a preconcentration procedure using a double coprecipitation process. Four ultramafic reference materials were investigated to test and validate our procedure (UB‐N, MGL‐GAS [GeoPT12], JP‐1 and DTS‐2B). Results obtained following the preconcentration procedure are in good agreement with previously published work on REE, HFSE, U, Th, Pb and some of the transition elements (Sc, Ti, V). This procedure has two major advantages: (a) it avoids any matrix effect resulting from the high Mg content of peridotite, and (b) it allows the preconcentration of a larger trace element set than with previous methods. Other elements (LILE, other transition elements Cr, Mn, Co, Ni, Cu, Zn, as well as Ga) were not fully coprecipitated with the preconcentration method and could only be accurately determined through the direct digestion/dilution method.     

Multi-methodological investigation of kunzite, hiddenite, alexandrite, elbaite and topaz, based on laser-induced breakdown spectroscopy and conventional analytical techniques for supporting mineralogical characterization

Gem-quality alexandrite, hiddenite and kunzite, elbaite and topaz minerals were characterized through a multi-methodological investigation based on EMPA-WDS, LA-ICP-MS, and laser-induced breakdown spectroscopy (LIBS). With respect to the others, the latter technique enables a simultaneous multi-elemental composition without any sample preparation and the detection of light elements, such as Li, Be and B. The criteria for the choice of minerals were: (a) the presence of chromophore elements in minor contents and/or as traces; (b) the presence of light lithophile elements (Li, Be and B); (c) different crystal chemistry complexity. The results show that LIBS can be employed in mineralogical studies for the identification and characterization of minerals, and as a fast screening method to determine the chemical composition, including the chromophore and light lithophile elements.     

基于数字图像处理技术的砂土颗粒级配分析研究

砂土颗粒级配是影响砂土工程性质的重要参数之一，传统的颗分试验方法由于试验原理不同而具有不同的适用范 围。为更加方便、准确地获取砂土颗粒级配，提出了一种基于数字图像处理技术来获取SEM照片中的砂颗粒粒径参数及级 配特征的新方法。将准备好的砂土样品打磨成薄片放在扫描电镜下拍照，然后利用Photoshop软件对照片进行拼接，并采用 自主研发的SMAS数字图像分析系统对拼接好的照片进行定量分析处理，获取样品的微观结构参数，将获得的“土颗粒等 效直径”和“土颗粒面积”分别等效为实际土颗粒粒径和土颗粒质量，进而换算得到砂土的颗粒级配曲线；然后将通过数 字图像技术获得的砂土颗粒级配曲线与通过传统筛分法和激光粒度分析法得到的颗粒级配曲线进行对比，验证了提出的数 字图像处理方法的有效性和可靠性，同时分析了两种方法之间存在的差异及其原因，并对数字图像处理方法和传统颗分方 法各自的优缺点进行了讨论。     

基于数字图像处理技术的砂土颗粒级配分析研究

砂土颗粒级配是影响砂土工程性质的重要参数之一,传统的颗分试验方法由于试验原理不同而具有不同的适用范 围。为更加方便、准确地获取砂土颗粒级配,提出了一种基于数字图像处理技术来获取SEM照片中的砂颗粒粒径参数及级 配特征的新方法。将准备好的砂土样品打磨成薄片放在扫描电镜下拍照,然后利用Photoshop软件对照片进行拼接,并采用 自主研发的SMAS数字图像分析系统对拼接好的照片进行定量分析处理,获取样品的微观结构参数,将获得的“土颗粒等 效直径”和“土颗粒面积”分别等效为实际土颗粒粒径和土颗粒质量,进而换算得到砂土的颗粒级配曲线;然后将通过数 字图像技术获得的砂土颗粒级配曲线与通过传统筛分法和激光粒度分析法得到的颗粒级配曲线进行对比,验证了提出的数 字图像处理方法的有效性和可靠性,同时分析了两种方法之间存在的差异及其原因,并对数字图像处理方法和传统颗分方 法各自的优缺点进行了讨论。     

Chemical Analysis of Iron Meteorites by Inductively Coupled Plasma-Mass Spectrometry

Iron meteorites were analysed for nineteen siderophile and chalcophile elements by conventional inductively coupled plasma-mass spectrometry with the specific aim of demonstrating that this technique is an effective alternative to the more routine, yet complex, methodologies adopted in this field such as instrumental or radiochemical neutron activation analysis. Two aliquots of each meteorite sample, in the form of small shavings, were dissolved, one in 6 mol l^-1 HNO₃ and the other in aqua regia , and diluted to a final concentration of 1 mg sample per 1 ml of solution, without pre-concentrating the analytes. Nitric acid solutions were used for the determination of the elements Cr, Co, Ni, Cu, Ga, Ge and As; aqua regia solutions were analysed for the elements Mo, Ru, Rh, Pd, In, Sn, Sb, W, Re, Ir, Pt and Au. Samples were analysed by external calibration, carried out using synthetic multi-elemental solutions, and internal standardisation (with Be, Rb and Bi selected as internal standards). The results obtained from the analyses of nine geochemically well-characterized iron meteorites (Canyon Diablo, Odessa, Toluca, Coahuila, Sikhote-Alin, Buenaventura, Tambo Quemado, Gibeon, NWA 859) with widely variable chemical compositions are in good agreement with literature values for most elements. Detection limits were generally below the lowest concentration observed in iron meteorites. The most notable exception is for Ge, which cannot be successfully determined in the low-Ge meteorites of groups IVA, IVB and IIIF and a number of ungrouped irons. A test of the overall reproducibility of the adopted method, undertaken by repeatedly analysing the same Odessa IAB meteorite specimen, yielded relative standard deviations (1 s ) of between 1 and 6% for all elements except Cr (40%).     

基于pXRF的荞麦山铜多金属矿床元素富集规律研究

大数据技术在地学领域的应用越来越广泛,大数据思维为地学研究开辟了新的思路。从数据出发,以数据驱动模式去分析地质问题,在元素分布特征分析、矿床地化异常识别等方面较传统地学分析方法有着明显的优势。文章基于便携式X荧光分析仪（pXRF）测试的原位、无损、快捷、多元素分析等优点,对宣城矿集区内的荞麦山铜多金属矿床岩芯进行高密度的全数据原位采集,使用主成分分析（PCA）、多元逐步线性回归等方法进行量化分析。2种方法均表明,荞麦山铜多金属矿床中元素Mg、Ca、Mn、Co、As、Se、Ag、Hg、U和成矿元素Cu、Fe、S、W存在正相关关系;钻孔矿化和蚀变特征、铜硫矿石、钨矿石、石英砂岩均表现出不同的元素组合,特别是主成分综合得分（PCA）和第一主成分（PC1）元素对钻孔成矿区具有较好的指示效果;逐步多元线性回归分析进一步量化了元素富集规律,对成矿元素的拟合能够较好地与钻孔信息形成对应。因此,pXRF高密度的原位测量能够快速获取全面、准确的元素数据,分析结果能够直观反映荞麦山铜多金属矿床各元素的深度空间分布情况及量化相关关系,对深部地球化学特征的恢复和找矿提供帮助。     

New CGSP Carbonate Matrix Reference Materials for LA-ICP-MS Analysis

Four CGSP (Chinese Geological Standard Powders) carbonate matrix element reference materials were prepared by a coprecipitation method. The major and trace elements were dissolved from natural rare earth carbonate raw materials in strong acid and precipitated with ammonium bicarbonate or ammonia to form carbonate matrix phases. The carbonate reference materials were ground and pressed into tablets for microanalysis. The element homogeneity and stability in CGSP reference materials were tested by LA-ICP-MS using a calibration strategy without an internal standard element and evaluated mainly following ISO Guide 35: 2017 and JJF 1343-2012. Although the homogeneity of most of elements in the CGSP series were comparable to the repeatability obtained from homogeneous glasses, some elements (e.g., Mo, Se, Ga, Ge, Cd, Ni, Co, U) were found to have some degree of heterogeneity. All of elements passed the t-test evaluation in a 32-month stability examination except for Mo in CGSP-A, Na, Ge, Mo in CGSP-B, Ni, Cd, Sn in CGSP-C, and Al, P, Tb, Ho in CGSP-D. The certified element mass fraction values and uncertainties were determined with the characterisation of a non-operationally defined measurand using various bulk analysis methods in eight laboratories. GGSPs will provide a new carbonate calibration reference option for microanalysis.