Thermal ionization instrumentation

In principle, all known ionization methods are suitable for mass spectrometric isotope ratio determinations. Today, those methods listed in Table 4 are applied for the isotope measurement of the elements in particular. With high precision thermal ionization instruments as well as with gas isotope mass spectrometers using electron impact ionization, relative standard deviations of the isotope ratio determination in the range of 0.1-0.001 % are available Using such types of mass spectro-... 

The first generation of MC-ICP-MS instruments employed the relatively low mass resolution ion optics found in thermal ionization instruments. As users... 

In contrast to thermal ionization methods, where the tracer added must be of the same element as the analyte, tracers of different elemental composition but similar ionization efficiency can be utilized for inductively coupled plasma mass spectrometry (ICPMS) analysis. Hence, for ICPMS work, uranium can be added to thorium or radium samples as a way of correcting for instrumental mass bias (e g., Luo et al. 1997 Stirling et al. 2001 Pietruszka et al. 2002). The only drawback of this approach is that small inter-element (e g., U vs. Th) biases may be present during ionization or detection that need to be considered and evaluated (e.g., Pietruszka et al. 2002). 

Kim Israel, a technician at LANL, Chemistry Division Bioassay Program, runs a thermal ionization mass spectrometry (TIMS) instrument. 

The relatively small mass differences for most of the elements discussed in this volume requires very high-precision analytical methods, and these are reviewed in Chapter 4 by Albarede and Beard (2004), where it is shown that precisions of 0.05 to 0.2 per mil (%o) are attainable for many isotopic systems. Isotopic analysis may be done using a variety of mass spectrometers, including so-called gas source and solid source mass spectrometers (also referred to as isotope ratio and thermal ionization mass spectrometers, respectively), and, importantly, MC-ICP-MS. Future advancements in instrumentation will include improvement in in situ isotopic analyses using ion microprobes (secondary ion mass spectrometry). Even a small increase in precision is likely to be critical for isotopic analysis of the intermediate- to high-mass elements where, for example, an increase in precision from 0.2 to 0.05%o could result in an increase in signal to noise ratio from 10 to 40. 

Units which are used in isotopic work depend on the precision of the measurements. Generally 5 units are used for stable isotopes and correspond to permil relative deviation. It is used occasionally also for non linear effects and then they are permil (%o) deviations without reference to mass differences between the isotopes. Since the beginning of the 70s (e.g., Papanastassiou and Wasserburg 1969) thermal ionization data are often given in e units which are fractional deviation from the normal in 0.01%. With the new generation of more precise instruments, results are sometimes given in ppm (parts per million) relative to a terrestrial standard sample. 

Iron. Fe has 4 isotopes of which the heaviest Fe has a very small abimdance of about 0.3%. The precision of thermal ionization mass spectrometers is around 10 s on this isotope and there is only a hint in some normal inclusions for an excess in 5 Fe (VoUcening and Papanastassiou 1989). Recent ICPMS measurements at the 2 s precision level display normal isotopic compositions for Fe in planetary materials but no Allende inclusion was reported in this study (Kehm et al. 2003). If excesses of similar magnitude to Ca, Ti, Cr were present they would not be clearly resolved in agreement with the observations. When Fe and Fe are used to correct for instrumental mass fractionation, Fe exhibits normal abundances, suggesting all three isotopes are present in solar relative abundances. 

Traditionally thermal ionization mass spectrometry was the instrument of choice for the isotopic analysis of metals because thermal ionization produced an ion beam with a very small kinetic energy spread ( 0.5 eV). Therefore only a magnetic mass analyzer is needed to resolve one isotope from another. Moreover, ionization of unwanted material, such as atmospheric contaminates, hydrocarbons from pump oil, or production of doubly ionized particles is almost non existent, thus background counts are minimized and signal-to-noise ratio is maximized. 

Figure 1. Schematic representation of the calcium mass spectrum in (a) natural materials, (b) a Ca- Ca tracer solution used for separating natural mass dependent isotopic fractionation from mass discrimination caused by thermal ionization, and (c) a typical mixture of natiwal calcium and tocer calcium used for analysis. The tracer solution has roughly equal amounts of Ca and Ca. In (c) the relative isotopic abundances are shown with an expanded scale. Note that in the mixed sample, masses 42 and 48 are predominantly from the tracer solution, and masses 40 and 44 are almost entirely from natural calcium. This situation enables the instrumental fractionation to be gauged from the Ca/ Ca ratio, and the natural fractionation to be gauged from the sample Ca/ Ca ratio.

Ireland TR, Fahey AJ, Zinner EK (1991) Hibonite-bearing microspherules a new type of refractory inclusions with large isotopic anomalies. Geochim Cosmochim Acta 55 367-379 Johnson CM, Beard BL (1999) Correction of instrumentally produced mass fractionation during isotopic analysis of Fe by thermal ionization mass spectrometry. Int J Mass Spect 193 87-99 Jungck MHA, Shimamura T, Lugmair GW (1984) Calcium isotope variations in Allende. Geochim Cosmochim Acta 48 2651-2658... 

A water-cooled sampling probe of internal diameter 1 mm and external diameter 5 mm with a 3-meter long heated line was used to measure concentrations of unburned hydrocarbon (flame ionization detector, Analysis Automation, 520) and NOj (chemiluminescence analyzer, Thermal Environment Instruments, 42) at the combustor exit on a wet basis. The former, measured to a precision of the order of 1 ppm, was used to ensure complete consumption of fuel within the duct, and the latter with a precision of around 0.2 ppm was used to quantify the effect of oscillations on NOj. emissions. 

Johnson, C.M. and Beard, B.L., 1999. Correction of instrumentally produced mass fractionation during isotopic analysis of Fe by thermal ionization mass spectrometry. International J. Mass Spectrometry, 193 87-99. 

Sr). Over the past 30 years, lead and strontium isotope ratios have been measured with thermal ionization mass spectrometry (TIMS). Elemental salts are deposited on a filament heated to produce ionized particles, which are then sent into a mass spectrometer where they are detected by multiple Faraday cups arrayed such that ions of several masses are collected simultaneously. TIMS is capable of high precision isotope discrimination, but the instruments tend to be large and expensive, and extensive sample preparation is required prior to sample introduction. Newer ICP-MS-based technologies like multi-collector ICP-MS (especially laser ablation) circumvent some of the sample preparation issues while exploiting the precision of simultaneous mass discrimination, but they are still limited by the number and configuration of ion collectors. 

The tail of the plasma formed at the tip of the torch is the spectroscopic source, where the analyte atoms and their ions are thermally ionized and produce emission spectra. The spectra of various elements are detected either sequentially or simultaneously. The optical system of a sequential instrument consists of a single grating spectrometer with a scanning monochromator that provides the sequential detection of the emission spectra lines. Simultaneous optical systems use multichannel detectors and diode arrays that allow the monitoring of multiple emission lines. Sequential instruments have a greater wavelength selection, while simultaneous ones have a better sample throughput. The intensities of each element s characteristic spectral lines, which are proportional to the number of element s atoms, are recorded, and the concentrations are calculated with reference to a calibration standard. 

Accuracy of isotope ratio measurement is critically dependent on having the instrument properly calibrated and following correct analytical protocol. Mass bias is present to some degree in all thermal ionization analyses, and a lot of ingenuity has been invested in mitigating its effect. Mass bias arises from a... 

The ideal internal standard is the same element as the analyte because it has similar mass, ionization energy, and chemical properties. Therefore, isotope dilution based calibration provides high accuracy as long as isotope equilibration is attained and the measured isotopes are free of spectral overlaps [192,193]. Standards do not need to be matrix-matched. Quadrupole-based ICP-MS instruments can typically provide isotope ratio precision of 0.1% to 0.5%. Much better isotope ratio precision can be obtained by using simultaneous MS detection, such as a multicollector-based instrument or perhaps time-of-flight MS. In comparison to thermal ionization mass spectrometry, ICP-MS provides much higher sample throughput and simpler, faster sample preparation. 

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