Isotope spectrometry

Such an approach, termed LIBS-MLIF, may be very effective in certain cases, both for analytical purposes and for isotopic analysis. For example, recently laser-ablation molecular isotopic spectrometry (LAMIS) was proposed for boron isotope analysis (Russo et al. 2011 Mao et al. 2011). LIBS-MLIF was tested for this task and proved that an easy and confident detection of different boron isotopes using well known molecular emissions (MulUken 1925) is possible. Spectra of metallic boron with a natural concentration ratio of 4 between B and B isotopes were compared with corresponding spectra of an enriched boron sample with B isotope concentration more than 96 %. MLIF (0,n= 1,2...) transitions in the system for both samples were excited at the (0,0) transition at 233.13 and at 233.19 nm for BO molecules and molecules, respectively. Both isotopes have been found in boron bearing mineral, while under both excitations, the B isotope-enriched sample exhibited typical molecular emission bands characteristic for BO molecules and B molecular emission was not fotmd (Fig. 6.10)... 

Russo R, Bol shakov A, Mao X et al (2011) Laser ablation molecular isotopic spectrometry. Spectrochim Acta B 66 99-104... 

The first mass spectrometric investigation of the thiazole ring was done by Clarke et al. (271). Shortly after, Cooks et al., in a study devoted to bicydic aromatic systems, demonstrated the influence of the benzo ring in benzothiazole (272). Since this time, many studies have been devoted to the influence of various types of substitution upon fragmentation schemes and rearrangements, in the case of alkylthiazoles by Buttery (273) arylthiazoles by Aune et al. (276), Rix et al. (277), Khnulnitskii et al. (278) functional derivatives by Salmona el al. (279) and Entenmann (280) and thiazoles isotopically labeled with deuterium and C by Bojesen et al. (113). More recently, Witzhum et al. have detected the presence of simple derivatives of thiazole in food aromas by mass spectrometry (281). 

In this equation the red O signifies oxygen enriched in Its mass 18 isotope analysis of isotopic enrichment was performed by mass spectrometry... 

Isopropyl group (Section 2 13) The group (CH3)2CH— Isotactic polymer (Section 7 15) A stereoregular polymer in which the substituent at each successive chirality center is on the same side of the zigzag carbon chain Isotopic cluster (Section 13 22) In mass spectrometry a group of peaks that differ in m/z because they incorporate differ ent isotopes of their component elements lUPAC nomenclature (Section 2 11) The most widely used method of naming organic compounds It uses a set of rules proposed and periodically revised by the International Union of Pure and Applied Chemistry... 

Following the movement of airborne pollutants requires a natural or artificial tracer (a species specific to the source of the airborne pollutants) that can be experimentally measured at sites distant from the source. Limitations placed on the tracer, therefore, governed the design of the experimental procedure. These limitations included cost, the need to detect small quantities of the tracer, and the absence of the tracer from other natural sources. In addition, aerosols are emitted from high-temperature combustion sources that produce an abundance of very reactive species. The tracer, therefore, had to be both thermally and chemically stable. On the basis of these criteria, rare earth isotopes, such as those of Nd, were selected as tracers. The choice of tracer, in turn, dictated the analytical method (thermal ionization mass spectrometry, or TIMS) for measuring the isotopic abundances of... 

Two other techniques that depend only on base SI units are coulometry and isotope-dilution mass spectrometry. Coulometry is discussed in Chapter 11. Isotope-dilution mass spectroscopy is beyond the scope of an introductory text, however, the list of suggested readings includes a useful reference. 

Por a review of isotope dilution mass spectrometry see the following article. 

Eassett, J. D. Paulsen, P. J. Isotope Dilution Mass Spectrometry for Accurate Elemental Analysis, Anal. Chem. 1989, 61, 643A-649A. 

A further important use of El mass spectrometry lies in measuring isotope ratios, which can be used in estimating the ages of artifacts, rocks, or fossils. Electron ionization affects the isotopes of any one element equally, so that the true isotope ratio is not distorted by the ionization step. Further information on isotopes can be found in Chapter 46. 

Until about the 1990s, visible light played little intrinsic part in the development of mainstream mass spectrometry for analysis, but, more recently, lasers have become very important as ionization and ablation sources, particularly for polar organic substances (matrix-assisted laser desorption ionization, MALDI) and intractable solids (isotope analysis), respectively. 

The previous discussion has centered on how to obtain as much molecular mass and chemical structure information as possible from a given sample. However, there are many uses of mass spectrometry where precise isotope ratios are needed and total molecular mass information is unimportant. For accurate measurement of isotope ratio, the sample can be vaporized and then directed into a plasma torch. The sample can be a gas or a solution that is vaporized to form an aerosol, or it can be a solid that is vaporized to an aerosol by laser ablation. Whatever method is used to vaporize the sample, it is then swept into the flame of a plasma torch. Operating at temperatures of about 5000 K and containing large numbers of gas ions and electrons, the plasma completely fragments all substances into ionized atoms within a few milliseconds. The ionized atoms are then passed into a mass analyzer for measurement of their atomic mass and abundance of isotopes. Even intractable substances such as glass, ceramics, rock, and bone can be examined directly by this technique. 

Plasma torches and thermal ionization sources break down the substances into atoms and ionized atoms. Both are used for measurement of accurate isotope ratios. In the breakdown process, all structural information is lost, other than an identification of elements present (e.g., as in inductively coupled mass spectrometry, ICP/MS). 

The upper part of the figure illustrates why the small difference in mass between an ion and its neutral molecule is ignored for the purposes of mass spectrometry. In mass measurement, has been assigned arbitrarily to have a mass of 12.00000, All other atomic masses are referred to this standard. In the lower part of the figure, there is a small selection of elements with their naturally occurring isotopes and their natural abundances. At one extreme, xenon has nine naturally occurring isotopes, whereas, at the other, some elements such as fluorine have only one. 

Recently, it has become possible to create isotopes that do not exist naturally. These are the artificial isotopes, and all are radioactive. For example, 13 artificially created isotopes of iodine are known, as well as its naturally occurring monoisotopic form of mass 127. Mass spectrometry is able to measure m/z values for both natural and artificial isotopes. 

This example can be used in reverse to show the usefulness of looking for such isotopes. Suppose there were an unknown sample that had two molecular ion peaks in the ratio of 3 1 that were two mass units apart then it could reasonably be deduced that it was highly likely the unknown contained chlorine. In this case, the isotope ratio has been used to identify a chlorine-containing compound. This use of mass spectrometry is widespread in general analysis of materials, and it... 

This accurate measurement of the ratio of abundances of isotopes is used for geological dating, estimation of the ages of antiquities, testing athletes for the use of banned steroids, examining fine details of chemical reaction pathways, and so on. These uses are discussed in this book under various headings concerned with isotope ratio mass spectrometry (see Chapters 7, 14, 15, 16, 17, 47, and 48). 

A common mistake for beginners in mass spectrometry is to confuse average atomic mass and isotopic mass. For example, the average atomic mass for chlorine is close to 35.45, but this average is of the numbers and masses of Cl and Cl isotopes. This average must be used for instruments that cannot differentiate isotopes (for example, gravimetric balances). Mass spectrometers do differentiate isotopes by mass, so it is important in mass spectrometry that isotopic masses be used... 

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. 

This is the basic process in an inductively coupled plasma discharge (ICP). The excited ions can be examined by observing the emitted light or by mass spectrometry. Since the molecules have been broken down into their constituent atoms (as ions) including isotopes, these can be identified and quantified by mass spectrometry, as happens with isotope ratio measurements. 

The three isotopes of hydrogen are almost indistinguishable for most chemical purposes, but a mass Spectrometer can see them as three different entities of mass 1, 2, and 3 Da. Isotopes of other elements can also be distinguished. Mass spectrometry is important for its ability to separate the isotopes of elements. 

A few natural isotopes are radioactive. Of the three isotopes of hydrogen, only that of mass 3 (tritium) i.s radioactive. Radioactive isotopes can be examined by other instrumental means than mass spectrometry, but these other means cannot see the nonradioactive isotopes and are not as versatile as a mass Spectrometer. 

Routine mass spectrometry can be used to identify many elements from their approximate ratios of isotope abundances. For example, mercury-containing compounds give ions having the seven isotopes in an approximate ratio of 0.2 10.1 17.0 23.1 13.2 29.7 6.8. 

FTICR. Fourier-transform ion cyclotron resonance GC/IRMS. gas chromatography isotope ratio mass spectrometry... 

GD/IRMS. glow discharge isotope ratio mass spectrometry HPLC. high-pressure liquid chromatography... 

IKES. ion kinetic energy spectroscopy IRMS. isotope ratio mass spectrometry ISDMS. isotope dilution mass spectrometry ITMS. ion trap mass spectrometry LA. laser ablation... 

Platzner, I.T., Modem Isotope Ratio Mass Spectrometry, Wiley, Chichester, U.K., 1997. 

For marble provenance studies, the most successful technique seems to be the measurement, through mass spectrometry, of the abundance ratios of the stable isotopes of carbon and oxygen (116). However, no single technique appears to provide unequivocal results, especially in cases such as the different Mediterranean sources, and a combination is often necessary to arrive at an approximate place of origin (117). 

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