Isotope abundancies analysis

Uranium with isotopic abundances different from that of natural uranium is the primary signature for HEU production activities. In any separation technology some enriched uranium will inevitably be released to the environment. Environmental samples taken at or near an enrichment facility can contain some of the enriched material altering the uranium isotopic abundance. Analysis of samples of vegetation, water and soil for uranium isotopic content using a sensitive analytical technique, such as thermal ionization mass spectrometry is recommended as the primary technique for the detection of HEU production. 

C1477. (2008). Standard test method for isotopic abundance analysis of uranium hexafluoride by Multi-Collector, Inductively Coupled Plasma-Mass Spectrometry. West Conshohocken, PA ASTM. 

A major example of isotope-dilution analysis lies in the procedure itself, which does not require any quantitative isolation of the elements being investigated. The relation between the abundance of the element under investigation and the spike is such that, once the spike has been intimately mixed with the sample, any losses of sample have no effect on the result (Figure 48.14). 

It is not necessary that there be two isotopes in both the sample and the spike. One isotope in the sample needs to be measured, but the spike can have one isotope of the same element that has been produced artificially. The latter is often a long-lived radioisotope. For example, and are radioactive and all occur naturally. The radioactive isotope does not occur naturally but is made artificially by irradiation of Th with neutrons. Since it is commercially available, this last isotope is often used as a spike for isotope-dilution analysis of natural uranium materials by comparison with the most abundant isotope ( U). 

This book presents a unified treatment of the chemistry of the elements. At present 112 elements are known, though not all occur in nature of the 92 elements from hydrogen to uranium all except technetium and promethium are found on earth and technetium has been detected in some stars. To these elements a further 20 have been added by artificial nuclear syntheses in the laboratory. Why are there only 90 elements in nature Why do they have their observed abundances and why do their individual isotopes occur with the particular relative abundances observed Indeed, we must also ask to what extent these isotopic abundances commonly vary in nature, thus causing variability in atomic weights and possibly jeopardizing the classical means of determining chemical composition and structure by chemical analysis. 

Applications Table 8.58 shows the main fields of application of inorganic mass spectrometry. Mass-spectrometric techniques find wide application in inorganic analysis, and are being used for the determination of elemental concentrations and of isotopic abundances for speciation and surface characterisation for imaging and depth profiling. Solid-state mass spectrometry is usable as a quantitative method only after calibration by standard samples. 

Barrie, A., Bricout, J. and Koziet, J. (1984) Gas chromatography stable isotope ratio analysis at natural abundance levels. Biomedical Mass Spectrometry 11, 439 447. 

This new edition includes results from recent space missions, including WMAP and FUSE, new material on abundances from stellar populations, nebular analysis and meteoric isotopic anomalies, and abundance analysis of X-ray gas, and several extra problems at the end of chapters. 

Wiedmeyer (1998). One method of testing for interference is to examine the survey data. In this type of analysis a large number of points are recorded across the mass range, rather than a single measurement taken at a particular mass number for each element. Figure 9.5 shows survey data (dashed line) for masses 203 to 210 on a sample believed to contain lead. The natural lead isotopic abundance is superimposed, shown by filled columns. The proximity of the survey data to the actual abundance of lead indicates that lead is present, and that no interfering elements are present. In this case, a single measurement at mass 208 (which is used for most analyses of lead) is sufficient to quantify lead in the sample. 

Stable-isotope dilution analysis is an analytical technique in which a known quantity of a stable-labelled isotope is added to a sample prior to extraction, in order to quantitate a particular compound. The ratio of the naturally abundant and the stable-labelled isotope is a measure of the naturally abundant compound and can be determined only by gas chromatography-mass spectrometry since the naturally abundant and the stable-labelled isotope cannot be completely separated gas chromatographically. 

The first example of a dynamic flux analysis was a study performed in the 1960s [269]. In the yeast Candida utilis, the authors determined metabolic fluxes via the amino acid synthesis network by applying a pulse with 15N-labeled ammonia and chasing the label with unlabeled ammonia. Differential equations were then used to calculate the isotope abundance of intermediates in these pathways, with unknown rate values fitted to experimental data. In this way, the authors could show that only glutamic acid and glutamine-amide receive their nitrogen atoms directly from ammonia, to then pass it on to the other amino acids. 

Once geological samples are dissolved, a mixed Ca- Ca tracer is added to the sample ( Ca/ Ca 1). The isotopic abundances in the mixed sample-tracer solution are illustrated in Figure 1. When the mixed solution has roughly equal amounts of the isotopes Ca, Ca, and Ca, then a near-optimal situation is achieved with regard to the corrections for the presence of the tracer (cf Johnson and Beard 1999 for a detailed analysis of spike-sample ratios). The... 

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.

Brand W (2002) Mass spectrometer hardware for analyzing stable isotope ratios. In P de Groot (ed.) Handbook of stable isotope analytical techniques. Elsevier, Amsterdam Brandriss ME, O Neil JR, Edlund MB, Stoermer EF (1998) Oxygen isotope fractionation between diatomaceous silica and water. Geochim Cosmochim Acta 62 1119-1125 Bremner JM, Keeney DR (1966) Determination and isotope ratio analysis of different forms of nitrogen in soils. III. Soil Sci Soc Am Proc 30 577-582 Brenninkmeijer CAM (1993) Measurement of the abundance of CO in the atmosphere and the and 0/ 0 ratio of atmospheric CO with applications in New Zealand and Australia. J Geophys Res 98 10595-10614... 

To perform the isotope dilution analysis we will use an enriched Cd solution which has the isotopic abundances shown in Table B.3. We will use the lo Cdi iiCd isotopic pair for the analysis. 

Isotope ratio analysis, 131-134 abundance, 131 correction factor, 131 detector dead time, 132-133 mass bias, 131. 132(f) precision of, 133... 

Applications to Biological Samples. - Methods of distance measurements were compared for four doubly spin-labelled derivatives of human carbonic anhydrase.53 The distances between the spin labels were obtained from continuous wave spectra by analysis of the relative intensity of the half-field transition, Fourier deconvolution of the line-shape broadening, and computer simulation of line-shape changes. For variants with interspin distances greater than 18 A, the DEER method also was used. For each variant, at least two methods were applicable and reasonable agreement between distances obtained by different methods was obtained. The useful distance ranges for the techniques employed at X-band with natural isotope abundance spin labels were estimated to be half-field transition (5-10 A), line-shape simulation (up to 15 A), Fourier deconvolution (8 - 20 A), and four-pulse DEER (> 18 A).53... 

Another combination of magnetic and electric sector fields, together with a tandem accelerator, is realized in different types of accelerator mass spectrometers (AMS)17 applied for carbon-14 dating and extreme ultratrace analysis of long-lived radionuclides at natural isotope abundances (see Chapter 5). 

An outstanding feature of inorganic mass spectrometry is its determination of precise and accurate isotopic abundances and isotope ratios. Isotopes of the same element (of the same number of protons or atomic number of element, Z) are, by definition, nuclides with different mass m and mass number A (A = Z + N) due to the different number of neutrons (N) in the nucleus. Isotope analyses are of special interest for characterizing the composition of samples with respect to stable and unstable isotopes in quite different concentration ranges - from the analysis of matrix elements down to the trace and ultratrace concentration level.1-9 Of 1700 isotopes, nearly 16 % (264 isotopes) are stable. The chemical elements Tc, Pm, Th, U and the transuranic elements do not possess stable isotopes. 

For measurements of isotope ratios or isotope abundances, any of the mass spectrometers discussed in the previous chapters, such as SSMS, LIMS, GDMS56 and LA-ICP-MS,6 are of benefit for the direct isotope analysis of solid samples. SSMS and LIMS are rarely applied in isotope analysis due to their relatively low precision. Several applications of the isotope dilution technique as a calibration strategy in SSMS, mostly on geological samples, are known.57-59 GDMS has been mostly applied in multi-element trace analysis and depth profiling and plays only a minor role... 

Figure 9.49 Comparison of isotope abundances of metallic Os and natural highly enriched 187Os samples (a) results of isotope analysis on metallic osmium (lohnson Matthey Chemicals) (b) isotope analysis on natural 187Os enriched samples due to /3 decay of 187Re.108...

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