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.     

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.     

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.     

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.     

应用激光诱导离解光谱自由定标法测定黄金首饰成分初探

利用激光诱导离解光谱自由定标法对一系列高纯度黄金样品进行定量分析与研究,初步证明了将此方法应用于黄金首饰成分测定的可行性。采用波长1 064nm的Nd∶YAG脉冲激光器激发黄金样品,波长范围为200～760nm的4CCD光纤光谱仪采集发射光谱,对Au元素质量分数范围为85.0%～99.6%的6件黄金标准样品进行激光诱导离解光谱测试。对所得黄金样品光谱中的Au,Cu,Ag三种元素分别选择合适的原子（离子）谱线代入自由定标法模型,通过所得参数拟合得到了所有元素原子（离子）的二维波尔兹曼平面曲线,并以此为基础进行元素的质量分数计算。激光诱导离解光谱自由定标法定量分析黄金样品中Au元素的质量分数与标准值的相对误差〈3%。     

KArMars: A Breadboard Model for In Situ Absolute Geochronology Based on the K–Ar Method Using UV‐Laser‐Induced Breakdown Spectroscopy and Quadrupole Mass Spectrometry

We present a breadboard prototype to perform in situ dating applicable to planetary exploration. Based on the K–Ar dating method and using instruments inspired by flight‐proven analytical components, ‘KArMars’ ablated a geological sample under high vacuum with a quadrupled ultraviolet (UV at 266 nm) Nd:YAG laser. During ablation, the K content of the target material was given by laser‐induced breakdown spectroscopy and the released ⁴⁰Ar was measured with a quadrupole mass spectrometer. Because K was measured as a concentration and ⁴⁰Ar as a count of atoms, these values were converted using the ablated mass given by the product of the density and the ablated volume. The uncertainties of the age measurement were < 15%. The quality of the K–Ar measurements was enhanced by the advantages of UV laser ablation such as the minimisation of thermal effects on argon diffusion. This work demonstrates that a specialised instrument inspired by this set‐up could provide in situ absolute geochronology with sufficient precision for scientific investigations, particularly where the crater density counting provides higher uncertainties on Mars.     

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。     

基于预分类策略的激光诱导击穿光谱技术用于岩石样品定量分析

岩石样品中复杂的基质效应严重影响激光诱导击穿光谱（LIBS）定量分析的准确性,其原因是目标元素的发射特性会受到基质的影响,导致其发射强度偏离理想的规律。为提高定量分析准确性,本文提出一种基于岩性基质特性的预分类定量分析方法。该方法首先构建基于k近邻（kNN）与支持向量机（SVM）算法的多层分类模型识别样品的岩性进行分类,通过kNN算法将样品分成碳酸盐和硅酸盐两大类,再利用SVM算法将大类细分成6类,而后针对不同岩性样品分别构建元素定量模型。通过采用预分类方法,可以确保分析的样品具有相似的化学成分,更好地确定分析时的基准线和校准曲线,从而减少分析中的不确定度,提高定量准确性。kNN算法通过交叉验证选取最优的k值,同时使用网格寻优方法确定了SVM算法中关键惩罚参数C和RBF宽度参数γ,利用该分类模型对来自6类岩性的39个国标岩石样品和国标岩石混合样品中的Si、Ca、Mg和K元素进行分析,岩性识别的准确率达100%,保证了后续定量分析的准确性,并针对不同岩性中的不同元素采用了合适的预处理方式提升光谱数据的稳定性。相比于传统标准曲线定量方法,采用预分类方法可以减少不同岩性基质之间的相互影响,从而减小样品基质非均匀性带来的误差。对比两种方法进行数据分析,测试集样品的预测值与参考值相关性分析系数从0.231～0.664提高至0.994～0.999,平均相对标准偏差从38.2%降低至8.6%。与传统定量分析方法相比较,采用预分类定量分析方法所构建模型对上述4种元素定量分析结果准确性有着明显的提高,为提高岩石元素定量分析准确性提供新的思路,拓宽了LIBS技术的实际应用范围。     

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.     

Rare Earth Element Determination in Olivine by Laser Ablation‐Quadrupole‐ICP‐MS: An Analytical Strategy and Applications

Olivine offers huge, largely untapped, potential for improving our understanding of magmatic and metasomatic processes. In particular, a wealth of information is contained in rare earth element (REE) mass fractions, which are well studied in other minerals. However, REE data for olivine are scarce, reflecting the difficulty associated with determining mass fractions in the low ng g^?1 range and with controlling the effects of LREE contamination. We report an analytical procedure for measuring REEs in olivine using laser ablation quadrupole‐ICP‐MS that achieved limits of determination (LOD) at sub‐ng g^?1 levels and biases of ~ 5–10%. Empirical partition coefficients (D values) calculated using the new olivine compositions agree with experimental values, indicating that the measured REEs are structurally bound in the olivine crystal lattice, rather than residing in micro‐inclusions. We conducted an initial survey of REE contents of olivine from mantle, metamorphic, magmatic and meteorite samples. REE mass fractions vary from 0.1 to double‐digit ng g^?1 levels. Heavy REEs vary from low mass fractions in meteoritic samples, through variably enriched peridotitic olivine to high mass fractions in magmatic olivines, with fayalitic olivines showing the highest levels. The variable enrichment in HREEs demonstrates that olivine REE patterns have petrological utility.     

Accurate and Precise Silicon Isotope Analysis of Sulfur‐ and Iron‐Rich Samples by MC‐ICP‐MS

Silicon isotope determination of sulfur‐rich samples by MC‐ICP‐MS can be challenging because cation‐exchange chromatography used for Si purification does not efficiently remove anionic sulfur species. Results for pure Si standard solutions with addition of sulfate showed shifts of up to +1.04 ± 0.10‰ (2s) in δ³⁰Si. Doping of both standard solutions and samples with S to a fixed S/Si ratio can eliminate the relative change in instrumental mass fractionation due to variable S/Si in samples and also boosts the relative sensitivity of Si by up to 66%. Moreover, Fe hydroxide precipitation during sample processing adsorbs Si resulting in isotopic fractionations. Tests using Fe‐rich samples showed that this could be a major factor for observed shifts in δ³⁰Si. Acidification of the sample and standard solutions to a pH < 1 aggressively dissolved any Fe hydroxide precipitates, even in relatively Fe‐rich samples such as chondrite meteorites. The pH values of the sample solutions were subsequently adjusted to a range of 2–3 by adding ultra‐pure NaOH solutions. The combination of sulfur doping and the pH adjustment protocol ensured a full recovery of Si and proved to be an efficient and reliable method for Si isotope determination of S‐ and Fe‐rich materials.     

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.      

In Situ U‐Th‐Pb Dating and Sr‐Nd Isotope Analysis of Bastnäsite by LA‐(MC)‐ICP‐MS

Bastnäsite is the end member of a large group of carbonate–fluoride minerals with the common formula (REE) CO₃F·CaCO₃. This group is generally widespread and, despite never occurring in large quantities, represents the major economic light rare earth element (LREE) mineral in deposits related to carbonatite and alkaline intrusions. Since bastnäsite is easily altered and commonly contains inclusions of earlier‐crystallised minerals, in situ analysis is considered the most suitable method to measure its U‐Th‐Pb and Sr‐Nd isotopic compositions. Electron probe microanalysis and laser ablation (multi‐collector) inductively coupled plasma‐mass spectrometry of forty‐six bastnäsite samples from LREE deposits in China, Pakistan, Sweden, Mongolia, USA, Malawi and Madagascar indicate that this mineral typically has high Th and LREE and moderate U and Sr contents. Analysis of an in‐house bastnäsite reference material (K‐9) demonstrated that precise and accurate U‐Th‐Pb ages could be obtained after common Pb correction. Moreover, the Th‐Pb age with its high precision is preferable to the U‐Pb age because most bastnäsites have relatively high Th rather than U contents. These results will have significant implications for understanding the genesis of endogenous ore deposits and formation processes related to metallogenic geochronology research.     

Rapid U‐Pb Geochronology by Laser Ablation Multi‐Collector ICP‐MS

Detrital zircon (DZ) U‐Pb laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) has revolutionised the way geologists approach many Earth science questions. Although recent research has focused on rapid sample throughput, acquisition rates are limited to 100–300 analyses h^?1. We present a method to acquire zircon U‐Pb dates at rates of 120, 300, 600 and 1200 analyses h^?1 (30, 12, 6 and 3 s per analysis) by multi‐collector LA‐ICP‐MS. We demonstrate the efficacy of this method by analysing twelve zircon reference materials with dates from ~ 3465 to ~ 28 Ma. Mean offset from high‐precision dates increases with faster rates from 0.9% to 1.1%; mean random 1s uncertainty increases from 0.6% to 1.3%. We tested this new method on a sandstone sample previously characterised by large‐n DZ geochronology. Quantitative comparison shows increased correspondence among age distributions comprising > 300 dates. This new method holds promise for DZ geochronology because (a) it requires no major changes to hardware, but rather modifications to software; (b) it yields robust age distributions well‐suited for quantitative analysis and maximum depositional age calculations; (c) there is only a minor sacrifice of accuracy and measurement uncertainty; and (d) there is less burden to researchers in terms of time investment and analytical cost.     

Non‐Matrix‐Matched Calibration for the Multi‐Element Analysis of Geological and Environmental Samples Using 200 nm Femtosecond LA‐ICP‐MS: A Comparison with Nanosecond Lasers

LA‐ICP‐MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non‐matrix‐matched calibration. We therefore investigated matrix‐related effects with a new 200 nm femtosecond (fs) laser ablation system (NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer (ESI NWR 193) and a 213 nm Nd:YAG (NWR UP‐213) laser. The ion intensity of the 200 nm fs laser ablation was much lower than that of the 213 nm Nd:YAG laser, because the ablation rate was a factor of about 30 lower. Our experiments did not show significant matrix dependency with the 200 nm fs laser. Therefore, a non‐matrix‐matched calibration for the multi‐element analysis of quite different matrices could be performed. This is demonstrated with analytical results from twenty‐two international synthetic silicate glass, geological glass, mineral, phosphate and carbonate reference materials. Calibration was performed with the certified NIST SRM 610 glass, exclusively. Within overall analytical uncertainties, the 200 nm fs LA‐ICP‐MS data agreed with available reference values.     

Towards a Method for Quantitative LA‐ICP‐MS Imaging of Multi‐Phase Assemblages: Mineral Identification and Analysis Correction Procedures

Here, we present an approach to laser ablation ICP‐MS mapping of multi‐phase assemblages that permits the use of different internal standard elements, concentration values and reference materials for each mineral. In this way, we obtain not only broad pictures of elemental distributions within samples but can also extract high accuracy concentration data for any user‐selected region. This is accomplished by assigning regions of an image to corresponding mineral phases on a pixel‐by‐pixel basis. In this way, accurate trace element concentrations can be determined for each mineral phase, despite potential variations in their ablation characteristics. We present an example where elemental maps are constructed from ablation of a gabbroic sample that includes the phases apatite, amphibole and plagioclase. This work represents an important first step towards development of a method to produce highly accurate LA‐ICP‐MS elemental maps of multi‐phase samples.     

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.     

Determination of Thallium in the USGS Glass Reference Materials BIR‐1G,BHVO‐2G and BCR‐2G and Application to Quantitative Tl Concentrations by LA‐ICP‐MS

Here, we present determinations of thallium (Tl) concentrations in the USGS reference materials BIR‐1G, BHVO‐2G and BCR‐2G measured by solution ICP‐MS. The Tl content in these three glasses spans a range of about 2–230 ng g^?1, which is similar to the values published for the respective powder materials. The determined range of Tl concentrations in these three glass reference materials makes them ideal for investigating Tl concentrations in basaltic and andesitic volcanic glasses. We also performed a series of laser ablation ICP‐MS measurements on the three samples, which show that this technique is able to determine Tl concentrations in glass samples with concentrations as low as 2 ng g^?1.     

High‐Precision Fe and Mg Isotope Ratios of Silicate Reference Glasses Determined In Situ by Femtosecond LA‐MC‐ICP‐MS and by Solution Nebulisation MC‐ICP‐MS

In this study, a technique for high precision in situ Fe and Mg isotope determinations by femtosecond‐laser ablation‐multi collector‐ICP‐MS (fs‐LA‐MC‐ICP‐MS) was developed. This technique was employed to determine reference values for a series of common reference glasses that may be used for external standardisation of in situ Fe and Mg isotope determinations in silicates. The analysed glasses are part of the MPI‐DING and United States Geological Survey (USGS) reference glass series, consisting of basaltic (BIR‐1G, BCR‐2G, BHVO‐2G, KL2‐G, ML3B‐G) and komatiitic (GOR128‐G and GOR132‐G) compositions. Their Fe and Mg isotope compositions were determined by in situ fs‐LA‐MC‐ICP‐MS and by conventional solution nebulisation multi‐collector ICP‐MS. We determined δ⁵⁶Fe values for these glasses ranging between ‐0.04‰ and 0.10‰ (relative to IRMM‐014) and δ²⁶Mg values ranging between ‐0.40‰ and ‐0.15‰ (relative to DSM‐3). Our fs‐LA‐MC‐ICP‐MS results for both Fe and Mg isotope compositions agreed with solution nebulisation analyses within analytical uncertainties. Furthermore, the results of three USGS reference glasses (BIR‐1G, BHVO‐2G and BCR‐2G) agreed with previous results for powdered and dissolved aliquots of the same reference materials. Measurement reproducibilities of the in situ determinations of δ⁵⁶Fe and δ²⁶Mg values were usually better than 0.12‰ and 0.13‰ (2s), respectively. We further demonstrate that our technique is a suitable tool to resolve isotopic zoning in chemically‐zoned olivine crystals. It may be used for a variety of different applications on isotopically‐zoned minerals, e.g., in magmatic or metamorphic rocks or meteorites, to unravel their formation or cooling rates.     

U‐Pb Detrital Zircon Analysis – Results of an Inter‐laboratory Comparison

Inter‐laboratory comparison of laser ablation ICP‐MS and SIMS U‐Pb dating of synthetic detrital zircon samples provides an insight into the state‐of‐the art of sedimentary provenance studies. Here, we report results obtained from ten laboratories that routinely perform this type of work. The achieved level of bias was mostly within ± 2% relative to the ID‐TIMS U‐Pb ages of zircons in the detrital sample, and the variation is likely to be attributed to variable Pb/U elemental fractionation due to zircon matrix differences between the samples and the reference materials used for standardisation. It has been determined that ~ 5% age difference between adjacent age peaks is currently at the limit of what can be routinely resolved by the in situ dating of detrital zircon samples. Precision of individual zircon age determination mostly reflects the data reduction and procedures of measurement uncertainty propagation, and it is largely independent of the instrumentation, analytical technique and reference samples used for standardisation. All laboratories showed a bias towards selection of larger zircon grains for analysis. The experiment confirms the previously published estimates of the minimum number of grains that have to be analysed in order to detect minor zircon age populations in detrital samples.