Isotope ratio mass spectrometry species

The additional measurement of 13c/l2C ratios in carbonaceous aerosols by isotope ratio mass spectrometry provides information concerning fractionation during chemical conversion of carbon-containing atmospheric species. However, 13c/l2C ratios, expressed in terms of the del value, 513c,... 

The Faraday cup was widely used in the beginning of mass spectrometry but all the characteristics of this detector mean that it is now generally used in the measurement of highly precise ratios of specific ion species as in isotopic ratio mass spectrometry (IRMS) or in accelerator mass spectrometry (AMS). To obtain a highly accurate ratio in such relative abundance measurements, the intensities of the two stable beams of specific ions are measured simultaneously with two Faraday cups. 

Different protein-based methods have been reviewed for species identification in milk and dairy products, and for characterization of cheese maturity, such as electrophoretic, chromatographic, and immunological techniques (11, 12). In addition to new developments in these techniques, the interdisciplinary and dynamic nature of milk product analysis is being enhanced by the application of disciplines already used to analyze other foodstuffs. Among them, capillary electrophoresis (CE), polymerase chain reaction, and isotope ratio mass spectrometry are just gaining popularity for solving dairy authenticity problems (13-15). 

FIGURE 35.13 C18 0 and C16 0 fatty acids formed via hydrolysis of triacylglycerides are ubiquitous archaeological residues indicative of the presence of animal fats and often identified using GC-MS. Natural abimdance isotope ratio mass spectrometry can be used to distingmsh between species via differences in 5 C content ([117] figure reproduced with kind permission). 

Special mass spectrometry systems are built for isotope ratio measurements. Most isotope ratio mass spectrometers consist of a single-focusing magnetic sector instrument and a multiple Faraday cup detection system. Because the Faraday cup exhibits a stable response, it is an ideal detector for isotope ratio measurements. Simultaneous collection of relevant ion beams from all isotopes provides high-precision isotopic measurements. A three-Faraday cup detection system is shown in Figure 7.9. The multicup assembly is placed at the focal plane of the mass analyzer and can be used for the simultaneous detection of each isotopic form of the analyte species (e.g., m/z 44, 45, and 46 from CO2). Commercial instruments with up to nine collectors are available. 

Few of the naturally occurring elements have significant amounts of radioactive isotopes, but there are many artificially produced radioactive species. Mass spectrometry can measure both radioactive and nonradioactive isotope ratios, but there are health and safety issues for the radioactive ones. However, modem isotope instmments are becoming so sensitive that only very small amounts of sample are needed. Where radioactive isotopes are a serious issue, the radioactive hazards can be minimized by using special inlet systems and ion pumps in place of rotary pumps for maintaining a vacuum. For example, mass spectrometry is now used in the analysis of Pu/ Pu ratios. 

Quantitative mass spectrometry, also used for pharmaceutical appHcations, involves the use of isotopicaHy labeled internal standards for method calibration and the calculation of percent recoveries (9). Maximum sensitivity is obtained when the mass spectrometer is set to monitor only a few ions, which are characteristic of the target compounds to be quantified, a procedure known as the selected ion monitoring mode (sim). When chlorinated species are to be detected, then two ions from the isotopic envelope can be monitored, and confirmation of the target compound can be based not only on the gc retention time and the mass, but on the ratio of the two ion abundances being close to the theoretically expected value. The spectrometer cycles through the ions in the shortest possible time. This avoids compromising the chromatographic resolution of the gc, because even after extraction the sample contains many compounds in addition to the analyte. To increase sensitivity, some methods use sample concentration techniques. 

Secondary isotope effects are small. In fact, most of the secondary deuterium KIEs that have been reported are less than 20% and many of them are only a few per cent. In spite of the small size, the same techniques that are used for other kinetic measurements are usually satisfactory for measuring these KIEs. Both competitive methods where both isotopic compounds are present in the same reaction mixture (Westaway and Ali, 1979) and absolute rate measurements, i.e. the separate determination of the rate constant for the single isotopic species (Fang and Westaway, 1991), are employed (Parkin, 1991). Most competitive methods (Melander and Saunders, 1980e) utilize isotope ratio measurements based on mass spectrometry (Shine et al., 1984) or radioactivity measurements by liquid scintillation (Ando et al., 1984 Axelsson et al., 1991). However, some special methods, which are particularly useful for the accurate determination of secondary KIEs, have been developed. These newer methods, which are based on polarimetry, nmr spectroscopy, chromatographic isotopic separation and liquid scintillation, respectively, are described in this section. The accurate measurement of small heavy-atom KIEs is discussed in a recent review by Paneth (1992). 

CAI s that were once molten (type B and compact type A) apparently crystallized under conditions where both partial pressures and total pressures were low because they exhibit marked fractionation of Mg isotopes relative to chondritic isotope ratios. But much remains to be learned from the distribution of this fractionation. Models and laboratory experiments indicate that Mg, O, and Si should fractionate to different degrees in a CAI (Davis et al. 1990 Richter et al. 2002) commensurate with the different equilibrium vapor pressures of Mg, SiO and other O-bearing species. Only now, with the advent of more precise mass spectrometry and sampling techniques, is it possible to search for these differences. Also, models prediet that there should be variations in isotope ratios with growth direction and Mg/Al content in minerals like melilite. Identification of such trends would verify the validity of the theory. Conversely, if no correlations between position, mineral composition, and Mg, Si, and O isotopic composition are found in once molten CAIs, it implies that the objects acquired their isotopic signals prior to final crystallization. Evidence of this nature could be used to determine which objects were melted more than once. 

Mass spectrometry is based upon the separation of charged ionic species by their mass-to-charge ratio, m/z. Within the general chemical context however, we are not used to taking into concern the isotopes of the elemental species involved in a reaction. The molecular mass of tribromomethane, CHBrs, would therefore be calculated to 252.73 g mol using the relative atomic masses of the elements as listed in most periodic tables. In mass spectrometry we have to leave this custom behind. Because the mass spectrometer does not separate by elements but by isotopic mass, there is no signal at m/z 252.73 in the mass spectmm of tribromomethane. Instead, major peaks are present at m/z 250, 252, 254 and 256 accompanied by some minor others. 

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. 

The isotopic dilution method can be extended to non-radioactive tracers by using mass spectrometry or NMR to determine the variation in isotopic ratios. This method can be used for the measurement of molecules or elemental species (about 60 elements have stable isotopes). This approach allows ultra-trace analysis because, contrary to radioactive labelling where the measurement relies on detecting atoms that decompose during the period of measurement, all labelled atoms are measured. Isotopic mass spectrometers are well suited for these measurements. 

Mass Spectrometry. Mass spectrometric detection was used in early laboratory studies of H02 (103, 104) and has also been used in more recent investigations (105). The H02 peak at the mass-to-charge ratio mle = 33 is useful in laboratory identification and quantification, but in the atmosphere, most likely multiple species will interfere because of, for example, fragmentation of hydrocarbons, hydrogen peroxide, or oxygen isotopes. 

---