Secondary Ion Mass Spectrometry in Geochemistry and Cosmochemistry: Determination and Distribution of Carbon and Hydrogen in Silicate Samples

Based on a review of recent domestic and international literature, examples of using secondary ion mass spectrometry (SIMS) for the determination of carbon and hydrogen in solving particular problems of geochemistry and space chemistry are presented. Special attention is paid to problems arising in calibration procedures for the quantitative determination of carbon and hydrogen by SIMS. A summary of equipment currently used for SIMS analysis is given. Mass spectral imaging method based on mathematical processing of the recorded secondary ion currents of carbon and hydrogen for visualizing 3D distributions of elements is considered in detail.     

Quantitative analysis by thin-layer chromatography with secondary ion mass spectrometry

Summary A direct combination of thin-layer chromatography with secondary ion mass spectrometry (TLC/SIMS) provides a method for the quantitative analysis of thermally unstable compounds or compounds of low volatility such as nicergoline. The method is very simple and has excellent precision. The analysis was performed by using an aluminium TLC plate and a mixture of methylene chloride, acetone, and distilled water as a developing solvent. After development the portion of the plate with the nicergoline and the internal standard spots was cut off the TLC plate, and was attached to the SIMS holder directly. The amount of nicergoline was determined from the ratio of the fragment ion intensity of the nicergoline to the internal standard. The calibration curve was linear, and the detection limit was 10 ng at a signal-to-noise ratio of 5. This method should be considered for application to the determination of drugs in biological samples and also for the determination of possible impurities and decomposition products in drugs.     

Determination of nickel in standard rocks and glasses by photon activation analysis with 30-MeV bremsstrahlung

The determination of nickel in various silicate rocks and glasses by photon activation analysis with a linear electron accelerator is described. Simultaneous irradiation of the sample and comparative standards produces the ⁵⁸Ni(γ, n)⁵⁷Ni reaction, and a post-irradiation chemical separation is used in conjunction with Ge(Li) γ-spectrometry. Nickel abundances for ten standard silicate rocks and two elementally doped glasses are presented and compared with the data previously published. The method is quite simple and gives good reproducible results for nickel down to sub-p.p.m. levels.     

Determination of uranium in silicate rocks using laser induced fluorescence

A rapid method for fluorimetric estimation of uranium in silicate rocks is described. The fluorescence of uranyl complex is induced by laser beam in the ultraviolet region provided by nitrogen laser tube. The emission spectrum is quite intense and relatively persistent. For direct estimation of uranium in geological silicate materials without prior extraction, the interference of certain cations and anions that might be present in silicate rocks on uranium determination was studied. The limit of detection is 0.5 ppb.     

Feasibility study: fast liquid chromatography–mass spectrometry for the quantification of aspartic acid in an aspartate drug

We have studied the feasibility of fast high-performance liquid chromatography coupled to electrospray ionization mass spectrometry in the selected ion monitoring mode for the quantitative determination of aspartic acid in an aspartate drug. Internal standardization was required, but mass spectrometric detection allowed for very short retention times of approximately 0.5 min for the analyte and the internal standard without chromatographic separation. The analytical system was found stable, as demonstrated by multiple injections giving a coefficient of variation of 4% for the peak area ratio of aspartic acid and glutamic acid. Calibrations were linear between 0.5 ng and 150 ng aspartic acid injected, with accuracies between 99.8% and 102% found for the back-calculated amounts. Investigation of several drug batches gave reasonable results. Therefore, the method appeared feasible for the determination of aspartic acid in an aspartate drug from 0.3 wt% to 100 wt% aspartic acid.Abbreviations CV coefficient of variation - ESI electrospray ionization - HPLC high-performance liquid chromatography - HSGC headspace gas chromatography - KaFi Karl Fischer titration - MS mass spectrometry - MSD mass-selective detector - % m/m percentage by weight - PAR peak area ratio - r² coefficient of determination - RP reversed-phase - SIM selected ion monitoringThis work was originally presented as a poster at the Conference of the German Society for Mass Spectrometry, 9–12 March 2003, in Münster, Germany     

Determination of silicate in water by ion exclusion chromatography with conductivity detection

A novel method for the direct determination of silicate in water by ion exclusion chromatography with conductivity detection is reported. The method is simple and sensitive with good precision. The calibration graph was linear from 0.1000 micromol l(-1) to 1000.0 micromol l(-1) for silicate with a correlation coefficient of 0.997 (n=6). The detection limit was 0.02 micromol l(-1). The method was successfully applied to the determination of silicate in mineral water, tap water, distilled water and seawater. The recovery was from 93 to 104% and the relative standard deviation was in the range of 1.1 to 4.4%.     

Quantitative EGA analysis of H<Subscript>2</Subscript>O in silicate glasses

Summary The properties and quality of silicate glasses strongly depend on the amount of residual dissolved gases. Thus, the knowledge of the quantitative content of different volatile components is of great relevance within the technical production line. Several applications exist for the detection and quantification of a single gas in glass. Up to now no available technique provides simultaneous and quantitative information on different gases in a single run. We have developed a new technique to detect the most common volatiles (H₂O, CO₂, SO₂, O₂ and N₂) simultaneously and quantitatively in silicate glasses with the help of a modified Netzsch TG/MS system. One characteristic feature of this new method is the direct coupling of a thermo balance and a mass spectrometer without the use of any capillary or skimmer system.     

Quantitative analysis of films by ion microbeam methods. II: SIMS

The performance indicators for a quantitative analysis (random and systematic uncertainties) are defined, and their origin in SIMS (secondary ion mass spectrometry) is discussed. The different methods for quantitative SIMS analysis: calibration curve approach, implanted standard method, relative sensitivity factor (RSF) method, are discussed. Examples are given for successful quantitative SIMS analyses of epilayers, implanted depth profiles and interface (IF) impurity distribution. In conclusion, a comparison is made between SIMS and other advanced techniques for thin film analysis.     

Quantitative SIMS depth profiling of Al in AlGaN/AlN/GaN HEMT structures with nanometer‐thin layers

The possibilities of quantitative secondary ion mass spectrometry (SIMS) depth profiling of Al in AlxGa1 ? xN/AlN/GaN transistor heterostructures are shown. Using a series of test structures for a TOF.SIMS‐5 time‐of‐flight mass spectrometer, we obtained a refined linear calibration dependence of the secondary‐ion yield on the composition ×, namely, Y(CsAl+)/Y(CsGa+) = K × x/(1 ? x), with a high linear correlation coefficient, Rl = 0.9996, which permits quantitative SIMS analysis of relatively thick AlGaN barrier layers. The method of profile reconstruction with allowance for the main artifacts of ion sputtering has been first applied for the analysis of GaN/AlGaN/AlN/GaN high electron mobility transistor structure. This method permits to perform quantitative analysis of the thickness and composition of a nanometer‐thin AlN sublayer and to estimate the measurement error. For the structure being studied, the AlN sublayer is 1.2 ± 0.2 nm thick. Copyright © 2016 John Wiley & Sons, Ltd.     

Detection of peptides in high concentration of salts by electrospray droplet impact/secondary ion mass spectrometry

Electrospray droplet impact (EDI)/SIMS is a new desorption/ionization technique for mass spectrometry. EDI/SIMS utilizes large multiply charged water clusters produced by atmospheric pressure electrospray as primary projectiles. It was found to afford extremely soft desorption/ionization compared with conventional SIMS, and has been used for detection of peptides and proteins. In this study, EDI/SIMS was applied to the detection of peptide in a highly concentrated NaCl solution. The persistent appearance of peptide ions for 1 ppm peptides in NaCl is probably because of the segregation of peptides on the crystallized salts. The samples dried under vacuum gave better EDI/SIMS mass spectra than those under ambient atmospheric pressure. Copyright © 2011 John Wiley & Sons, Ltd.     

Determination of boron in silicon by SIMS with the matrix ion species ratio method

Summary In quantitative SIMS, the oxygen content of the sample surface proves to be a very important analytical parameter. The matrix ion species ratio method (MISR) was used to investigate the influence of the presence of oxygen on the determination of boron in silicon. By analysing standard samples at conditions of different oxygen coverage, the relation between the sensitivity of boron and the oxygen content of the sample surface, as indexed by the SiO⁺/Si³⁺ matrix ion species ratio, was established. The influence of the primary ion current density on this relation was investigated. The MISR procedure proves to be a suitable method to perform quantitative determinations (relative error < 10%) in conditions of changing oxygen content on the sample surface.

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Bestimmung von Bor in Silicium durch SIMS mit der Matrix Ion Species Ratio Method

     

Micelle mediated extraction of titanium and its ultra-trace determination in silicate rocks

A highly sensitive method for extractive spectrophotometric determination of titanium in silicate rocks is described. Titanium in the range 0-10 microg as TiO2 is extracted into benzene or toluene by the formation of a ternary complex of the metal with thiocyanate (SCN-) and cetyltrimethylammonium bromide (CTA) in the ratio 1:2:2. A deep yellowish-orange ternary complex thus formed is suitable for the determination of titanium at wavelength 421 nm. The optimum colour intensity of this ternary complex was attained when the complex was extracted from an aqueous solution having concentrations of thiocyanate and HCl, in the range, 1.5-2.5 and 1-5 mol L(-1), respectively. The molar absorptivity and Sandell's sensitivity of the extracted species were found to be 1.1-1.0x10(5) L mol(-1) cm(-1) and 0.47 ng cm(-2) (referred to titanium), respectively, at lambda(max) of 421 nm. Except Fe3+, Nb5+ and V5+, no interference was encountered in the estimation of titanium. While up to 10 mg L(-1) Nb and V did not interfere in the determination of titanium, the interference of Fe(3+) was eliminated by reducing it to Fe2+ using SnCl2 solution. The method is highly sensitive and selective. The results obtained for titanium estimation in a host of silicate rock samples have been found to be highly reproducible, accurate and favourably comparable with certified values of reference materials and those obtained from standard methods.     

Glass of the past: The degradation and deterioration of medieval glass artifacts

Medieval artifacts made of glass are at a serious disadvantage concerning the chemical stability compared with ancient or common modern glasses. The total amount of silica and other network formers such as alumina is very low and potassium instead of sodium was introduced into the silicate structure by using local raw material. By means of scanning electron microscopy (SEM), secondary ion mass spectrometry (SIMS) and nuclear reaction analysis (NRA) a weathering mechanism governed by an ion exchange process could be determined for medieval glass paintings exposed to the ambient air for centuries. Additionally, the leached glass surface of medieval hollow glass artifacts found in a well and exposed to moist earth show a brown discoloring due to the oxidation of Mn(II) to Mn(IV) oxide. That process can be converted by a treatment of the glass objects in an aqueous hydrazine solution.     

热电离质谱法超高精度测定~(142)Nd/~(144)Nd同位素比

142Nd/144Nd比值的超高精度测定技术对于研究太阳系早期演化及月球-地球早期硅酸盐分异具有重要应用价值.本实验利用热电离质谱(TIMS)开展142Nd/144Nd比值的超高精度测试研究,并对比了动态多接收和静态多接收两种测量方式.结果表明,动态模式具有更高的准确度和精密度.讨论了影响测试精度的各种因素,在此基础上通过优化测试条件,对国际标准(Jndi-1)的142Nd/144Nd测试结果为1.1418348,外部精度优于5×10-6(2SD), 完全满足146Sm-142Nd体系研究的技术要求.     

Isolation and Characterization of Wax Esters in Fennel and Caraway Seed Oils by SPE-GC

A rapid method for the isolation and quantitative determination of wax esters in vegetable oils was developed. For the first time wax esters in oils were separated from the triglyceride matrix by means of solid-phase extraction, which allows rapid sample preparation in parallel and therefore a high sample throughput. The thus obtained wax ester fractions of fennel and caraway seed oils were analyzed by high temperature gas chromatography. GC-MS analyses were carried out using electron impact ionization in order to characterize the wax ester fraction. With respect to the results of the GC-MS analyses different isomers of saturated wax esters with the same carbon number were observed. Additional monounsaturated wax esters with an unsaturated fatty acid moiety were identified.     

The automatic determination of silicate-silicon in natural waters with special reference to sea water

An automatic method using a Technicon AutoAnalyzer is described for the determination of silicate in natural waters in the range 0–4 mg Si/l. It is based on the conversion of silicate to β-silicomolybdic acid which is reduced by means of a metolsulphite reagent to molybdenum blue. Interference of phosphate is prevented by oxalic acid. The relationship between silicate concentration and optical density is linear in both fresh waters and sea water. With sea water the salt error of the method is ca. 5% at a salinity of 35‰ A coefficient of variation of 0.8% was found at a silicate concentration of 1 mg Si/l with both fresh and sea waters.     

Micro X-ray absorption near edge structure at the sulfur and iron K-edges in natural silicate glasses

Both sulfur and iron chemical environments were studied in natural compounds; sulfides, sulfates and silicate basaltic glasses which are supposed to have variable oxidation states, using XANES (X-ray absorption near edge structure) spectroscopy. Although X-ray absorption methods are well suited for such investigations, the size of natural glass inclusions trapped in volcanic minerals, ranging from a few micrometers to several tenths of micrometers, makes micro-spectroscopy necessary. Hence, we present the μ-XANES spectra at the sulfur and iron K-edges of olivine-hosted glass inclusions containing from 1000 to 1650 ppm S, and between 5.5 and 7.8 wt.% Fe. By combining both high energy and spatial resolutions, we demonstrate the ability of the μ-XANES to produce quantitative determination of sulfur and iron valence states. We have identified various species for sulfur, specifically S^II−, S^VI and possibly S^IV, in basaltic glass inclusions hosted in olivine grains. We propose a method to calibrate the proportion of Fe dissolved as Fe³⁺ in basaltic glasses for which the Fe³⁺/ΣFe ratio varies between 0.05 and 0.48 with a relative precision of less than 10%.     

气相色谱法测定碳酸二甲酯的含量

选用HP-INNOWAX毛细管色谱柱及氢火焰离子化检测器(FID)，采用二阶程序升温，以正丁醇为内标物，建立了测定碳酸二甲酯(DMC)含量的气相色谱法。当DMC的体积分数(X)为0．02％～0．64％时，DMC与正丁醇的峰面积比(Y)与DMC的体积分数(X)有良好的线性关系，线性回归方程为Y=0．4427X-0．0406，相关系数r=0．9994．检出限为0．1nL。对实际样品进行测定，加标回收率为93．7％～97．0％，相对标准偏差为0．84％～1．27％。方法适用于DMC的含量分析。     

Carbon nanotubes as adsorbent of solid-phase extraction and matrix for laser desorption/ionization mass spectrometry

A method with carbon nanotubes functioning both as the adsorbent of solid-phase extraction (SPE) and the matrix for matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) to analyze small molecules in solution has been developed. In this method, 10 microL suspensions of carbon nanotubes in 50% (vol/vol) methanol were added to the sample solution to extract analytes onto surface of carbon nanotubes because of their dramatic hydrophobicity. Carbon nanotubes in solution are deposited onto the bottom of tube with centrifugation. After removing the supernatant fluid, carbon nanotubes are suspended again with dispersant and pipetted directly onto the sample target of the MALDI-MS to perform a mass spectrometric analysis. It was demonstrated by analysis of a variety of small molecules that the resolution of peaks and the efficiency of desorption/ionization on the carbon nanotubes are better than those on the activated carbon. It is found that with the addition of glycerol and sucrose to the dispersant, the intensity, the ratio of signal to noise (S/N), and the resolution of peaks for analytes by mass spectrometry increased greatly. Compared with the previously reported method by depositing sample solution onto thin layer of carbon nanotubes, it is observed that the detection limit for analytes can be enhanced about 10 to 100 times due to solid-phase extraction of analytes in solution by carbon nanotubes. An acceptable result of simultaneously quantitative analysis of three analytes in solution has been achieved. The application in determining drugs spiked into urine has also been realized.     

Metallurgical applications of SIMS

Summary This paper reviews the unique advantages provided by Secondary Ion Mass Spectrometry (SIMS) for the characterization of heterogeneous conducting metallurgical samples: detection and imaging of the lateral distribution of every element (H-U), even at very low concentration and excellent depth resolution in the nanometer range. The advantages brought by coupling SIMS with other conventional microscopical and microanalytical techniques (SEM, EPMA, TEM/STEM) are illustrated by examples taken from the author's laboratory: quantitative analysis of the solid solution and within phases, surface, thin film and interface analysis by depth profiles. Special attention will be brought to the advantages of Ion Microscopy and the importance of high mass resolution. The difficulties associated with the variations of sputtering rate and ionization probability in multiphase systems will also be discussed.

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Anwendungen von SIMS in der Metallurgie