Elemental analyzer-isotope ratio mass spectrometry

Elflein, L. and Raezke, KP. (2008) Improved detection of honey adulteration by measuring drSerences between C-13/C-12 stable carbon isotope ratios of protein and sugar compounds with a combination of elemental analyzer-isotope ratio mass spectrometry and liquid chromatography—isotope ratio mass spectrometry (delta C-13-EA/LC-IRMs). Apidologie, 39 (5), 574-587. 

Of all the different mass spectrometric techniques for isotope analysis (such as ICP-MS, LA-ICP-MS, TIMS, GDMS, AMS, SIMS, RIMS and isotope ratio mass spectrometry of gases), the greatest proportion of pubhshed papers today concern ICP-MS with single and multiple ion collection.19 Due to its benefits, ICP-MS has now become a widely accepted method for isotope analysis and allows isotope ratios to be measured in a short time with good accuracy and precision.9,19,75 78 As discussed above, as a powerful and universal tool, ICP-MS has opened up new applications for isotope ratio measurements of elements with a high first ionization potential, which are difficult to analyze with TIMS (such as Mo, Hf, Fe). Of all the heavy metals studied, uranium was favoured by ICP-MS and LA-ICP-MS. 

The nuclear area is one that has been heavily dependent upon isotope ratio mass spectrometry performed by thermal ionization. Applications in this area are among the major reasons for the continued push to analyze smaller and smaller samples. There are two primary reasons for this (1) maximum practicable reduction of the hazards associated with radioactivity and (2) presence of often only a very small amount of the target element available. Areas addressed include evaluation of uranium enrichment processes [86], isotopic analysis of transuranium elements (all elements through einsteinium have been analyzed) [87], and environmental monitoring for release of uranium and other actinides [88,89]. This last area has received renewed emphasis in the wake of the Gulf War [90]. 

CF-IRMS Continuous flow-isotope ratio mass spectrometry. A procedure that uses an instrument that is capable of repeatedly and rapidly measuring the masses of selected gases (e.g., carbon dioxide, hydrogen, nitrogen) delivered in a continuous gas stream from another instrument, such as an elemental analyzer or a gas chromatograph, to determine their isotopic compositions. 

FIGURE 15.7 Schematic showing a flash combustion EA in series with an interface and IRMS for the analysis of bulk nitrogen and carbon isotope values (based on a ThermoFinnigan Flash Elemental Analyzer [31]). Reprinted from Benson, S., Fennard, C, Maynard, R, Roux, C. (2006) Forensic applications of isotope ratio mass spectrometry—a review. Forensic Sci. Int., 157(1), 1-22, with permission from Elsevier [1]. 

Accoe, E, Berglund, M., Geypens, B., Taylor, P. (2008) Methods to reduce interference effects in thermal conversion elemental analyzer/continuous flow isotope ratio mass spectrometry 5 180 measurements of nitrogen-containing compounds. Rapid Communications in Mass Spectrometry, 22(14), 2280-2286. 

The steady-state operation of the ICP source is beneficial for the correction of instrumental mass bias by standard-sample bracketing, where the raw (measured and uncorrected) isotope ratio data of a sample are referenced to the results obtained for an isotopic standard, which is preferentially analyzed before and after each sample [27, 35]. This technique is similar to the standardization method commonly used in gas source isotope ratio mass spectrometry. To account best for drifts in instrumental mass bias, which can be particularly severe for light elements such as Li and B, data collection often utilizes multiple but short analytical measurements for samples that are each bracketed by standard analyses. Switching between samples and standards can be very rapid, if long washout protocols are not required, and mass spectrometric measurements of about 5 min or less have been used to optimize the precision of Li and Mg isotope ratio measurements by MC-ICP-MS [111, 112]. 

TI is a very precise and accurate method in stable isotope ratio measurements and quantification of inorganic elements, for example, by isotope dilution mass spectrometry [8]. Because TI is a continuous ion source, it could be coupled to any analyzer that is suitable for such sources. However, because the strength of TI lies in the quantitative precision and accuracy, sector analyzers are preferred to ensure maximum quality. 

To analyze element distribution, isotope ratios and species in single cells, development of advanced inorganic mass spectrometric techniques in combination with biomolecular mass spectrometry is required for future applications. 

Isotope dilution mass spectrometry (ID-MS) is widely accepted as a quantification procedure of proven accuracy in elemental analysis and isotope ratio measurements [4]. Several areas of research in nuclear science, geochronology, medicinal chemistry, environmental science, and agricultural science have benefited from this technique. ID-MS is applicable to all elements that have at least two stable isotopes. Monoisotopic elements can be analyzed only if they have a long-lived natural or artificial radioisotope. For example, iodine and thorium have been determined with spikes of the long-lived isotopes 29i and 25 Th, respectively [44]. TI-MS and ICP-MS are the methods of choice for accurate ID-MS analysis. ICP-MS has the advantage that several elements can be analyzed simnltaneously under the same experimental conditions. Other ionization techniqnes discussed in this chapter have also been coupled with ID-MS. 

Mass spectrometric techniques are based on the measurement or counting of ions produced at high temperatures. An ion can be identified on the basis of its mass-to-charge ratio (m/z), characteristic of a certain isotope. In addition, quantification is based on the dependence between the number of ions and the concentration of a given isotope in the sample. Mass spectrometers consist of an ion source, a mass analyzer, and an ion detector. The ion source is typically the basis for the different types of mass spectrometric techniques. Plasmas are the most common ion sources for Mass spectrometric elemental determinations, and it is mass spectrometry (MS) using this ion source that will now be described. Complete details of this technique can be found in published monographs.29,30... 

---