Isobaric, mass spectrometry

An alternative to the bridge technique was recently reported for thorium analysis in silicate rocks for which both Th and Th are measured on a single lon-counting detector (Rubin 2001). With careful chemistry and mass spectrometry, °Th/ Th ratios of igneous rocks can be measured with this technique with a precision that is similar to the bridge method. The disadvantage of this technique is that °Th ion-count rates are extremely low (around 10 cps) with normal silicate thorium ratios and are therefore subject to perturbations from background variation and low-level isobaric interferences in normal samples. 

Noticeable trends in inorganic mass spectrometry are speed, simultaneity, and fewer problems from isobars and tuned plasma conditions. Inorganic MS techniques used for inorganic trace analysis have been reviewed [350]. Various monographs deal with inorganic mass spectrometry [351,352] and plasma-source mass spectrometry in particular [353,354]. 

Resolution (or resolving power) plays an important role in mass spectrometry for applications requiring the characterization of very similar chemical species. The ability to detect and accurately measure the m/z ratio of a particular ion depends directly on the resolving power of the mass analyzer. For example, if a sample contains two isobaric compounds (i.e., having the same nominal molecular mass but different elemental formulae) the difference in the exact masses of the molecular ions will be much less than 1 m/z unit. Any mass analyzer possessing a nominal resolving power (e.g., RP< 1000) will register only one peak in the mass spectrum of such a binary mixture. Attempts to measure the... 

As mentioned above, gas-phase coordination of unsaturated C—C bonds to metal cations constitutes another means for double-bond localization. Peake and Gross260 determined the fragmentation of Fe+/olefin complexes by CID spectrometry and reported highly characteristic differences for several constitutional octadiene isomers. High-resolution mass spectrometry proved to be necessary in certain cases due to the isobaric masses of Fe and even two units of C2H4 and/or CO261. Although not based on gas-phase ion/molecule... 

Several samarium and neodymium isotopes are isobars (Table 4.2) and cannot be separated by mass spectrometry. Thus, samarium and neodymium must be completely separated by chemical procedures prior to measuring them in a mass spectrometer. The ion-exchange chemistry necessary to separate these elements is now well developed (see Appendix). Isotope measurements can be done either by TIMS or ICPMS (inductively... 

Resonance-ionization mass-spectrometry is still in the development stage in terms of its application to cosmochemistry. The Charisma instrument, which is operated by Argonne National Laboratories, uses multiple lasers to resonantly ionize only the elements of interest, which are then analyzed with a time-of-flight mass spectrometer. The Charisma instrument has made isotopic measurements of molybdenum, zirconium, strontium, ruthenium, barium and other elements in presolar grains. These measurements are made possible by the high ionization efficiency of the RIMS technique and its ability to completely eliminate isobaric interferences. Work is now underway to build a RIMS instrument that can be operated by an individual investigator in a university laboratory. If this succeeds, RIMS will play an increasing role in analysis of extraterrestrial materials. 

Operation of quadrupole mass filters operated in higher zones of stability is described with an emphasis on the potential of elemental mass spectrometry by Du et al.19 These quadrupole mass filters allow a mass resolution in the second stability region of up to 9000 and make it possible to resolve a multitude of isobaric interferences. 

Part of a mass spectrum for the determination of Fe and Cr contamination in boron nitride contaminated with carbon measured by LIMS is shown in Figure 6.9. The analyte ions 53Cr+ and 54Fe+ due to different masses of isobaric atomic and cluster ions are clearly separated from boron and boron carbide cluster ions as demonstrated in Figure 6.9. Cluster ion formation has been studied by laser ionization mass spectrometry (LIMS) on a boron nitride target.10... 

Am with a half-life of ti = 432 a has to be determined in waste and environmental samples by mass spectrometry. The determination of 238Pu (ti 88 a) at the trace level is difficult in the presence of uranium due to isobaric interference with 238 U+ in mass spectra measured by ICP-MS or LA-ICP-MS. Therefore the application of a sensitive and selective technique such as RIMS or AMS is advantageous. The determination of 238Pu for plutonium isotope analysis in irradiated... 

A major topic in isotope mass spectrometry is the determination of the half-lives of long-lived radionuclides. De Bievre and Verbruggen34 determined the half-life of 241 Pu for 3-decay in the isobaric radionuclide 241 Am on material from Oak Ridge that had initially been about 93% isotopically enriched. Due to the isobaric interference of 241 Pu and 241 Am radionuclides during mass spectrometric measurements by TIMS, Am had to be removed by chemical separation immediately (less than 48 h) prior to measurements as described in reference 34. On the basis of all the measurements performed over an extended period of more than 20 years and after considering the possible effects of systematic errors during these measurements, a half-life for the 3 decay of 241 Pu of (ti/2 = 14.290 0.006 a) was reported.34... 

Resonant and non-resonant laser post-ionization of sputtered uranium atoms using SIRIS (sputtered initited resonance ionization spectroscopy) and SNMS (secondary neutral mass spectrometry) in one instrument for the characterization of sub-pm sized single microparticles was suggested by Erdmann et al.94 Resonant ionization mass spectrometry allows a selective and sensitive isotope analysis without isobaric interferences as demonstrated for the ultratrace analysis of plutonium from bulk samples.94 Unfortunately, no instrumental equipment combining both techniques is commercially available. 

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