Secondary isotope mass spectrometry

Another interesting suite of approaches that undoubtedly wiU be further developed employs SIMS—secondary isotope mass spectrometry (also know as multiple-isotope imaging mass spectrometry (MIMS)). Orphan et al. (2001) applied FISH—SIMS or fluorescent in situ hybridization SIMS to detect isotopicaUy Ught carbon in archaeal ceUs, identifying the Archaea by FISH and using SIMS to quantify the isotopic composition of individual ceUs by ion microprobe. Finzi et al. (2006) applied nanoSIMS to visualize uptake of N2 and C02 by individual ceUs of a... 

The impact of an ion beam on the electrode surface can result in the transfer of the kinetic energy of the ions to the surface atoms and their release into the vacuum as a wide range of species—atoms, molecules, ions, atomic aggregates (clusters), and molecular fragments. This is the effect of ion sputtering. The SIMS secondary ion mass spectrometry) method deals with the mass spectrometry of sputtered ions. The SIMS method has high analytical sensitivity and, in contrast to other methods of surface analysis, permits a study of isotopes. In materials science, the SIMS method is the third most often used method of surface analysis (after AES and XPS) it has so far been used only rarely in electrochemistry. 

Finally, Chapters 14 16 deal with innovative applications in this field such as mass spectrometric compound-specific isotopic analysis, secondary ion mass spectrometry... 

The measurements that have been made at Rochester and the experience that has been gathered over the years on the operation of sputter ion sources [38] indicate that an analytical tool of unprecedented sensitivity and accuracy for isotopic ratio determinations can be constructed by coupling SIMS technology with the new accelerator technique. The only difference in principle between the experiments that have been conducted to date and the technique as it would be applied in secondary ion mass spectrometry is that the primary beam of cesium would be focussed to a fine probe of pm dimensions rather than the spot diameters of approximately 1 mm that have been used to date. 

Grignon N, Halpem S, Jeusset J, Briancon C, Fragu P. Localization of chemical elements and isotopes in the leaf of soybean (Glycine max) by secondary ion mass spectrometry critical choice of sample preparation procedure. JMicrosc 1997 186 51-66. 

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. 

Layne GD (2003) Advantages of secondary ion mass spectrometry (SIMS) for stable isotope microanalysis of the trace light elements. EOS Trans, Am Geophys Union 84 F1635 Lundstrom CC, Chaussidon M, Kelemen P (2001) A Li isotope profile in a dunite to Iherzolite transed within the Trinity Ophiolite evidence for isotopic fractionation by diffusion. EOS Trans, Am Geophys Union 82 991... 

In recent years, there have been several attempts to determine diffusion coefficients, mostly utilizing secondary ion mass spectrometry (SIMS), where isotope compositions have been measured as a function of depth below a crystal surface after exposing the crystal to solutions or gases greatly enriched with the heavy isotopic species. 

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. 

It is a remarkable feature of secondary ion mass spectrometry (SIMS) that considerable chemical information is accessible through the procedurally simple physical technique of sputtering. SIMS--espec ia 11 y under low primary ion flux conditions ("static SIMS," a 1 s o known as "molecular SIMS" when applied to compounds)—provides information on molecular weight and molecular structure and allows isotopic analysis. The surface sensitivity of SIMS permits its use in imaging, in monitoring of surface... 

Secondary Ion Mass Spectrometry Surface composition, isotope identification Ar+ Ar++0+ 0.5-10keV Secondary ions H-U 10 4-10"8... 

Figure 1 Studies published between 1988 and 1997 reporting use of secondary ion mass spectrometry (SIMS) in geochemistry and cosmochemistry. Papers are subdivided according to theme Hvy Iso, studies of heavy isotope ratios, principally for U-Pb dating Lt Iso, studies of light stable isotope ratios (H, B, C, O, S) Hvy El, studies primarily focused on analysis of elements >40 amu (e.g., rare earth elements) Lt El, studies primarily focused on analysis of elements <40 amu (e.g., water content) Prec Met, analysis of precious metal contents (e.g., Au, Ag, Pt) Expt, analysis of experimental run products Misc, other mis-cellanous studies utilizing SIMS.

Presolar grains are found in small quantities (with concentrations of ppb to several 100 ppm, see Table 2.1) in all types of primitive Solar System materials (Lodders Amari 2005 Zinner 2007). This includes primitive meteorites (the chondrites), IDPs, some of which might originate from comets, Antarctic micrometeorites (AMMs), and samples from comet Wild 2 collected by NASA s Stardust mission. Presolar grains are nanometer to micrometer in size. The isotopic compositions, chemistry, and mineralogy of individual grains with sizes >100 nm can be studied in the laboratory. Important analysis techniques are secondary ion mass spectrometry (SIMS) and resonance ionization mass spectrometry (RIMS)... 

In this review results from two surface science methods are presented. Electron Spectroscopy for Chemical Analysis (ESCA or XPS) is a widely used method for the study of organic and polymeric surfaces, metal corrosion and passivation studies and metallization of polymers (la). However, one major accent of our work has been the development of complementary ion beam methods for polymer surface analysis. Of the techniques deriving from ion beam interactions, Secondary Ion Mass Spectrometry (SIMS), used as a surface analytical method, has many advantages over electron spectroscopies. Such benefits include superior elemental sensitivity with a ppm to ppb detection limit, the ability to detect molecular secondary ions which are directly related to the molecular structure, surface compositional sensitivity due in part to the matrix sensitivity of secondary emission, and mass spectrometric isotopic sensitivity. The major difficulties which limit routine analysis with SIMS include sample damage due to sputtering, a poor understanding of the relationship between matrix dependent secondary emission and molecular surface composition, and difficulty in obtaining reproducible, accurate quantitative molecular information. Thus, we have worked to overcome the limitations for quantitation, and the present work will report the results of these studies. 

Several recent studies of elemental abundances in eclogite minerals have established the value of measuring elemental partitioning between minerals as indicators of mineral equilibrium. These studies mainly used secondary ion mass spectrometry (SIMS) and laser ablation ICP-MS. The data for the Maowu eclogite-pyroxenite body are used to illustrate this point, because the coherent U-Pb and Sm-Nd age data seem to indicate that REE in coexisting clinopyroxene and garnet attained chemical and Nd-isotopic equilibrium... 

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