AN ION PROBE CONTRIBUTION TO RARE EARTH ELEMENT INVESTIGATION OF GABBRO GOG-1 USING SECONDARY ION MASS SPECTROMETRY

An updated REE measurement of Gabbro GOG-1 was carried out by means of secondary ion mass spectrometry (SIMS). The availability of high amount of rock powder allowed the sample to be well ground and homogenized before analysis. Fused glass pellets were employed for SIMS investigations. REE data were compared with new ICP-AES and NAA analyses. REE results from all employed analytical techniques show good agreement and are consistent with in-situ SIMS measurements of REE in major mineral phases forming GOG-1. Extensive homogeneity tests seem to confirm the possibility to using this rock as a reference material for earth sciences.     

Determination of the Rare Earth Elements in Thirteen GSJ Silicate Rock Reference Samples by Secondary Ion Mass Spectrometry

Rare earth elements were determined by secondary ion mass spectrometry (SIMS) for 12 igneous rocks and one feldspar separate from the new rock reference samples of the Geological Survey of Japan. The study presents an expanded application of the SIMS facility.     

A Synthetic Germanium-Bismuth Glass for the Coarse Mass Calibration of SIMS Instruments

This short technical note describes a simple technique for synthesising an optimised binary glass for performing coarse mass table calibrations of secondary ion mass spectrometers. A Ge-Bi glass doped with five selected trace elements was used to anchor the entire mass table up to m/z ≥ 209 at an accuracy of < 0.5 dalton. Using this material it has been possible to calibrate coarsely the mass table of a Cameca ims 6f instrument in less than five minutes, thereby greatly simplifying the switch from low mass range to high mass range measurements. Although not suitable for the quantification of geological materials, the ease of synthesis and its utility for rapidly performing what is an otherwise time consuming process makes this material a useful tool for SIMS instruments which offer a multiple mass range capability.     

High-Resolution LA-ICP-MS for Accurate Determination of Low Abundances of K, Sc and Other Trace Elements in Geological Samples

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to determine K, Sc, Ti, V, Cr, Mn, Co, Ni and Zn in geological samples. Because the isotopes of these elements and the internal standard element (Ca) often have interferences from molecular ions when determined using quadrupole or sector-field ICP-MS in low mass resolution mode, ion intensities were measured at a high mass resolution of 4000. We investigated dynamic element fractionation, type and abundance of molecular ions using different geological reference materials. Highly resolved mass spectra were especially important for accurate low-abundance measurements. As a result, maximum "critical" concentration limits for each isotope were obtained, where a mass resolution of 4000 was necessary for reliable LA-ICP-MS analysis. To test the LA-ICP-MS technique, different international reference material glasses and powdered rock reference materials were analysed. Rock powders were fused to glass beads using an Ir-strip heater. Nearly all concentration values for the reference materials agreed with the reference values at the 95% confidence level. To demonstrate routine LA-ICP-MS analysis at a mass resolution of 4000, trace element data for Hawaiian basalts are also presented.     

Further Characterisation of the 91500 Zircon Crystal

This paper reports the results from a second characterisation of the 91500 zircon, including data from electron probe microanalysis, laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS), secondary ion mass spectrometry (SIMS) and laser fluorination analyses. The focus of this initiative was to establish the suitability of this large single zircon crystal for calibrating in situ analyses of the rare earth elements and oxygen isotopes, as well as to provide working values for key geochemical systems. In addition to extensive testing of the chemical and structural homogeneity of this sample, the occurrence of banding in 91500 in both backscattered electron and cathodoluminescence images is described in detail. Blind intercomparison data reported by both LA-ICP-MS and SIMS laboratories indicate that only small systematic differences exist between the data sets provided by these two techniques. Furthermore, the use of NIST SRM 610 glass as the calibrant for SIMS analyses was found to introduce little or no systematic error into the results for zircon. Based on both laser fluorination and SIMS data, zircon 91500 seems to be very well suited for calibrating in situ oxygen isotopic analyses.     

‘Box‐Profile’ Ion Implants as Geochemical Reference Materials for Electron Probe Microanalysis and Secondary Ion Mass Spectrometry

Although electron probe microanalysis and secondary ion mass spectrometry are widely used analytical techniques for geochemical and mineralogical applications, metrologically rigorous quantification remains a major challenge for these methods. Secondary ion mass spectrometry (SIMS) in particular is a matrix‐sensitive method, and the use of matrix‐matched reference materials (RMs) is essential to avoid significant analytical bias. A major problem is that the number of available RMs for SIMS is extremely small compared with the needs of analysts. One approach for the production of matrix‐specific RMs is the use of high‐energy ion implantation that introduces a known amount of a selected isotope into a material. We chose the more elaborate way of implanting a so‐called ‘box‐profile’ to generate a quasi‐homogeneous concentration of the implanted isotope in three dimensions, which allows RMs not only to be used for ion beam analysis but also makes them suitable for EPMA. For proof of concept, we used the thoroughly studied mineralogically and chemically ‘simple’ SiO₂ system. We implanted either ⁴⁷Ti or ⁴⁸Ti into synthetic, ultra‐high‐purity silica glass. Several ‘box‐profiles’ with mass fractions between 10 and 1000 μg g^?1 Ti and maximum depths of homogeneous Ti distribution between 200 nm and 3 μm were produced at the Institute of Ion Beam Physics and Materials Research of Helmholtz‐Zentrum Dresden‐Rossendorf. Multiple implantation steps using varying ion energies and ion doses were simulated with Stopping and Range of Ions in Matter (SRIM) software, optimising for the target concentrations, implantation depths and technical limits of the implanter. We characterised several implant test samples having different concentrations and maximum implantation depths by means of SIMS and other analytical techniques. The results show that the implant samples are suitable for use as reference materials for SIMS measurements. The multi‐energy ion implantation technique also appears to be a promising procedure for the production of EPMA‐suitable reference materials.     

Analytical Developments in Secondary Ion Mass Spectrometry 2003

This annual review of secondary ion mass spectrometry (SIMS) highlights significant progress in the application of the technology for the following areas: U-Pb geochronology (notably in the fields of reference material zircons), sources of uncertainty during analysis and secondary ion yields. Major publications introduced a new zircon reference sample and dealt with an intercomparison study of a suite of established calibrators, some of which have been shown to have certain limitations. Another publication claimed that the principal uncertainty in U-Pb dating is related to variations in the Pb and U relative emission yields over a complete analytical session. 2003 saw the introduction of an automated particle identification procedure applied to the analysis of a chondritic meteorite, as well as new geometries of SIMS hardware (NanoSIMS) and techniques (time-of-flight SIMS). NanoSIMS allows a two to three order of magnitude reduction in sampling volume as a result of a reduced beam diameter, and time-of-flight SIMS allows the study of sample surfaces, and can provide data for elements concurrently.     

碳酸盐岩样品中镍和钪的电感耦合等离子体质谱分析与干扰校正方法

电感耦合等离子体质谱法(ICP-MS)已在碳酸盐岩微量元素测试中得到了广泛应用.然而,采用ICP-MS分析碳酸盐岩中含量较低的Ni(1.6～50.5μg/g)和Sc(0.3～6μg/g)时,信号值会受到高含量CaO(可高达56％)和MgO(可高达21％)的显著干扰,使测试值远高于真实值,从而无法获得准确的待测元素含量....     

The variability of chemical analyses as a function of sample heterogeneity,and the implications to the analyses of rock standards

The errors in the chemical analyses of a granodiorite rock powder for 6 constituents (K ₂O, Na₂O, CaO,∑Fe₂O₃, MgO, and MnO) have been determined by replicate analyses of the whole rock and of a series of different sieved fractions. Sample inhomogeneity is indicated. This is confirmed by analyses of the fused rock powder. Fusion to a glass is therefore recommended for the preparation of geochemical rock standards.     

Radiochemical Neutron Activation Trace Element Analysis Of Two USGS Ultrabasic Rock Reference Samples: Peridotite PCC-I and Dunite DTS-I

Most trace elements in ultrabasic rock samples are very often present in concentration levels of less than 10 ppm. In these cases, neutron activation analysis (NAA) is very useful. We have applied two different NAA procedures for the determination of 19 trace elements and CaO in two ultrabasic rock standards. Our values are compared with the preferred and published values, although the latter are not very abundant.     

Glasses in the D'Orbigny angrite

The angrites are a small and heterogeneous group of achondritic meteorites with highly unusual chemical and mineralogical features. The abundant presence of glasses in D'Orbigny makes this rock a unique member of the angrite group. Glasses fill open spaces, form pockets, and occur as inclusions in olivines. Their physical settings exclude an incorporation from an external source. Major and trace element (rare earth elements [REE], Li, B, Be, transition elements, N and C) contents of these glasses and host olivines were measured combining laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), secondary-ion mass spectrometry (SIMS), Nuclear Reaction Analysis (NRA), and EMP techniques. Based on the major element composition, glasses filling voids could represent either a melt formed by melting an angritic rock or a melt from which angrites could have crystallized. Trace element contents of these glasses strongly indicate a direct link to the D'Orbigny bulk meteorite. They are incompatible with the formation of the glasses by partial melting of a chondritic source rock or by shock melting. The refractory elements (e.g., Al, Ti, Ca) have about 10 × CI abundances with CaO/TiO₂ and FeO/MnO ratios being approximately chondritic. Trace element abundances in the glasses appear to be governed by volatility and suggest that the refractory elements in the source had chondritic relative abundances. Although the glasses (and the whole rock) lack volatile elements such as Na and K, they are rich in some moderately volatile elements such as B, V, Mn, Fe (all with close to CI abundances), and Li (about 3-5 × CI). These elements likely were added to the glass in a sub-solidus metasomatic elemental exchange event. We have identified a novel mechanism for alteration of glass and rock compositions based on an exchange of Al and Sc for Fe and other moderately volatile elements in addition to the well-known metasomatic exchange reactions (e.g., Ca-Na and Mg-Fe).Because glass inclusions in olivine were partly shielded from the metasomatic events by the host crystal, their chemical composition is believed to be closer to the original composition than that of any other glasses. The relative trace element abundances in glasses of glass inclusions in olivine and glass pockets are also unfractionated and at the 10 to 20 × CI level. These glasses are chemically similar to the common void-filling glasses but show a much wider compositional variation. Inclusion glasses demonstrate that at least olivine grew with the help of a liquid. In analogy to olivines in carbonaceous chondrites, initial formation could also have been a vapor-liquid-solid condensation process. At that time, the glass had a purely refractory composition. This composition, however, was severely altered by the metasomatic addition of large amounts of FeO and other moderately volatile elements. The presence of volatile elements such as carbon and nitrogen in glasses of glass inclusions is another feature that appears to give these glasses a link with those hosted by olivines of carbonaceous chondrites. All these features point to an origin from a vapor with relative abundances of condensable elements similar to those in the solar nebula.     

中条山地区绛县群和中条群沉积时限:夹层斜长角闪岩SIMS锆石U-Pb年代学证据

中条山地区出露大量早前寒武纪岩石,是认识华北克拉通晚太古代至早元古代大地构造演化的关键地区。绛县群变质陆缘碎屑-火山岩及中条群变质陆缘碎屑-碳酸盐岩建造是该区最主要的地层单元,同时也是一系列铜矿床的赋矿围岩。目前,对于二者的形成时代仍缺乏直接证据。本文通过高精度的二次离子质谱锆石U-Pb定年,厘定了绛县群和中条群中的斜长角闪岩夹层分别形成于~2189Ma和~2086Ma。结合已有同位素资料,我们认为绛县群变质沉积-火山岩系可能形成于ca.2160~2190Ma,而中条群中段的大理岩和黑色片岩系(余元下组和篦子沟组)形成于ca.2059~2086Ma之间。另外,岩石组合和矿化类型指示,中条山地区在ca.2090~2190Ma可能经历了两次裂谷事件。     

Ultra-Trace Element Analysis of NIST SRM 616 and 614 using Laser Ablation Microprobe-Inductively Coupled Plasma-Mass Spectrometry (LAM-ICP-MS): a Comparison with Secondary Ion Mass Spectrometry (SIMS)

The microanalytical capability of laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS) to determine ultra trace elemental concentrations has been demonstrated by the analysis of two low concentration glass standard reference materials, NIST SRM 614 and 616. Results for fifty two elements at concentrations in the low ng g^-1 range are compared with those determined using secondary ion mass spectrometry (SIMS). Both techniques provide results at these concentrations that generally agree within 95% confidence limits, demonstrating the accuracy for ultra-trace level of in situ determinations by the two techniques. At concentrations of less than 20 ng g^-1 in NIST SRM 616, an accuracy and precision of better than 10% has been obtained for most mono-isotopic rare earth elements, when a spot size of 50 μm is used. Limits of detection for selected elements were as low as 0.5 ng g^-1.     

二次离子质谱微区原位牙形石氧同位素分析及其在古海表水温记录中的应用

利用生物成因磷灰石的氧同位素信息能够重建古海水温度,尤其是牙形石,结合其在生物地层学上的研究,它的数据解释具有明确的古环境意义。牙形石微小的个体一直是其精确地球化学分析的限制因素。作为对牙形石微区原位氧同位素测试方法的探索研究,本文利用Cameca IMS--1280 型二次离子质谱仪对牙形石进行了微区原位氧同位素组成测试,通过分析得到可靠的古表层海水温度 ( SST) 记录,表明从晚二叠世到早三叠世SST 存在明显的上升过程。相比常规Ag3PO4 实验方法,牙形石微区原位氧同位素分析方法更加快速,而且能够有效避免牙形石易受到污染的部位,获得更为可靠的牙形石氧同位素组成的测定结果。     

Ni partitioning between diopside and silicate melt: A redetermination by ion microprobe and recognition of an experimental complication

The ion probe is uniquely suited for measurement of element partitioning between phases in experimental and natural systems. A redetermination of the partitioning of Ni between diopside and quenched silicate melt using samples previously measured by β-track mapping gives 1.87 (weight ratio of ⁶²Ni in diopside/melt), slightly lower than the β-track value of 2.05. Critical to the accurate determination of distribution coefficients are: (1) a secondary ion signal that is linear with concentration in the range measured, and (2) a calibration using known concentrations to correct for differential secondary ion yields from different phases. In the present case the secondary ion signal is linear with Ni concentrations below ~ 1 wt% in both diopside and glass, but nonlinear above. Differential yields were corrected by calibrating the secondary ion signal against compositions determined by electron microprobe.Partition coefficients measured using ⁵⁸Ni and ⁶⁰Ni, in contrast to ⁶²Ni, are not constant with concentration in these samples probably due to Ni migration during crystallization. Measurements using these isotopes (or bulk Ni) show a change of partition coefficient with Ni concentration.     

飞行时间二次离子质谱(TOF-SIMS)在矿物包裹体研究中的应用

矿物包裹体的化学成分研究在地质学、矿床学和油气勘探等方面具有重要意义。目前对包裹体化学成分分析的主要分析方法有激光烧蚀电感耦合等离子体质谱(LA-ICP-MS)、电子探针(EPMA)、显微激光拉曼光谱(LRS)、傅里叶变换红外光谱(FTIR)、质子诱发X射线光谱分析(PIXE)、同步辐射X射线荧光光谱(SXRF)和(传统的)二次离子质谱分析(SIMS)等。本文在对上述方法的分析特点进行简单介绍的基础上,重点阐述了对于矿床学样品表征具有广泛应用潜力的飞行时间二次离子质谱(TOF-SIMS)的原理、特点和技术优势,总结了国内外学者应用TOF-SIMS对矿物包裹体化学成分分析的研究进展与存在问题,并做了相关领域的展望。     

Organic Geochemical Microanalysis by Time‐of‐Flight Secondary Ion Mass Spectrometry (ToF‐SIMS)

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) is a powerful method for the chemical analysis of solid surfaces. In this paper, the capabilities and limitations of this technique and the potential for its use in geochemical research are outlined. Using ToF‐SIMS, the chemical composition of sample structures down to 10–100 μm can be determined, without the need for pre‐selection or labelling of the analysed substances. In addition, the lateral distribution of organic and inorganic compounds can be mapped in geochemical samples at a resolution in the micrometre range. The capabilities of the technique in geochemistry are illustrated by two examples. In the first example, it is shown that ToF‐SIMS can be used to detect biomarkers in oil samples, making it a promising method for the analysis of biomarkers in fluid inclusions. In the second example, a number of specific lipid biomarkers were identified and mapped on the surface of a microbial mat cryosection surface. Post‐measurement optical microscopy correlated the localisation of the lipids with the presence of methanotrophic archaea in the microbial mat.     

微区原位普通铅同位素分析技术及其地质应用进展

应用激光剥蚀-多接收器电感耦合等离子体质谱(LA-MC-ICP-MS)和二次离子质谱(SIMS)等分析技术进行微区原位普通Pb同位素分析是微区地球化学研究的重要内容之一.综述了矿物、熔体包裹体和沉积结核的微区原位普通Pb同位素分析技术及其地质应用的新进展.这些研究资料表明该分析技术在岩浆岩成因、沉积物物源示踪、地幔地球化学、古海洋学以及矿床学等的研究中提供了常规的全岩Pb同位素分析方法难以获得的重要信息,充分展示了该分析技术在地球科学研究中的应用前景.     

Accurate quantification of melt inclusion chemistry by LA-ICPMS: a comparison with EMP and SIMS and advantages and possible limitations of these methods

Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) has recently emerged as a powerful in situ microanalytical technique for major to trace elements in heterogeneous samples such as fluid and melt inclusions. Here, a rigorous comparison of melt inclusion (MI) data acquired by electron microprobe (EMP), ion microprobe (the secondary ion mass spectrometry, SIMS) and LA-ICPMS is used to evaluate the applicability and advantages/drawbacks of these approaches. We are specifically interested in determining if LA-ICPMS data on entire, unexposed, crystallized MI that cannot be homogenized in the lab are accurate and of a useful precision.

Quantification of LA-ICPMS MI signals requires the use of an internal standard, i.e., the concentration of one element, or an element ratio, at the time of MI entrapment must be known independently, in order to derive the pure MI composition from the MI plus host mixed signal. Analysis of plagioclase-hosted glassy MI of a mid-ocean ridge basalt (MORB) sample from the East Pacific Rise illustrates that melt inclusion chemistry can be accurately quantified by LA-ICPMS, including the correction for postentrapment sidewall crystallisation of the host mineral without prior reheating in the lab.

The LA-ICPMS data obtained on crystallized MI demonstrate agreement with the EMP and SIMS data on exposed glassy MI at the 1 standard deviation uncertainty level except for a few elements close to their limits of detection. LA-ICPMS data reduction schemes include the quantification of analytical uncertainty on each element of single MI. Therefore, weighted average element concentrations can be obtained for MI assemblages, at precisions that compare well with those of average element concentrations obtained by EMP and SIMS.

Simple sample preparation minimizing inclusion loss through polishing combined with the analytical efficiency of 50 inclusions plus neighbouring host mineral at up to 40 elements per day enable the collection of statistically relevant datasets by LA-ICPMS. These allow to recognize nonrepresentative MI (e.g., heterogeneous entrapment). Application to individual clinopyroxene crystals from the AD79 pumice horizon of Mt. Somma-Vesuvius reveals chemical variability that exceeds the analytical precision on single melt inclusions. This variability was not obvious from the limited data set obtained by SIMS and EMP.

The largest source of nonquantifiable error for EMP and SIMS data stems from the requirement of reheating the melt inclusions in the lab in order to reverse postentrapment crystallisation onto inclusion walls or growth of crystallites. For LA-ICPMS analysis of unexposed MI, the reliability with which the internal standard (IS) element concentration is known determines the quality of the data. LA-ICPMS, however, cannot analyse H₂O, F, S and Cl reliably, has higher limits of detection (LODs) than SIMS for some elements for MI below 25 μm, has lower spatial resolution than both EMP and SIMS and consumes much more sample per analysis. Therefore, EMP, SIMS and LA-ICPMS are complementary in MI research, and the type of application will determine the analytical method or methods of choice.     

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.