Measurements of isotopic ratios

Precise measurement of isotope ratios can be obtained by comparing the yields of isotopic ions desorbing from a sample placed on a strongly heated filament that is generally made from platinum, tantalum, rhenium, or tungsten. 

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. 

Thermal ionization has three distinct advantages the ability to produce mass spectra free from background interference, the ability to regulate the flow of ions by altering the filament temperature, and the possibility of changing the filament material to obtain a work function matching ionization energies. This flexibility makes thermal ionization a useful technique for the precise measurement of isotope ratios in a variety of substrates. 

If samples are introduced batchwise, then the sample enters the flame as a plug and the elements are measured transiently. If the samples are introduced continuously, then the measurement of isotope ratios can also be continuous as long as sample is flowing into the flame. 

Isotope ratios are very useful for (a) identifying elements from their pattern of isotopes in a spectrum obtained on an ordinary mass spectrometer or (b) obtaining detailed information after accurate measurement of isotope ratios from special isotope ratio instruments. 

More precise estimates come from accurate measurements of isotope ratios. Three pairs of radioactive isotopes and their products are abundant enough for such ratios to be measured ... 

Precise measurement of isotopic ratios requires a special type of mass spectrometer. There are important differences between the IRMS and a regular organic mass spectrometer. 

As for all trace-level analyses, sample preparation and handling are of crucial importance. In addition to all the usual problems of GC-MS, measurements of isotope ratios must ensure that none of these steps introduce any isotope discrimination. Any chemical reactions, including conversion of the organic sample molecules to the simple gases which are those actually analyzed, must be quantitative (100% conversion) to avoid kinetic isotope effects [627]. Until relatively recently, all gas IRMS experiments employed a dual-inlet system to permit switching between sample and standard C02 contained in two bellows containers. The pressures in the two bellows are adjusted to be equal and,... 

While competitive methods to determine KIE s are free from errors due to differences in reaction conditions (impurities, temperature, pH, etc.) they do require access to equipment that allows high precision measurements of isotope ratios. The selection of an appropriate analytical technique depends on the type of the isotope and its location in the molecule. For studies with stable isotopes the most commonly used technique (and usually the most appropriate) is isotope ratio mass spectrometry (IRMS). 

To avoid the kind of problems which trouble whole-molecule mass spectrometry it is better to use instrumentation especially designed for high precision measurements of isotope ratios isotope-ratio mass spectrometry (IRMS). 

Shortly after the development of the early mass spectrometers, Li isotopes were identified by Francis Aston (1932). Although mass spectrometric techniques are those most commonly applied to the measurement of isotope ratios in geochemistry, attempts to quantify Li isotopes have been made using non-mass based emission methods (e.g., atomic absorption Zaidel and Korennoi 1961 various nuclear methods Kaplan and Wilzbach 1954 Brown et al. 1978 ... 

Due to the relative uniform isotope abundances in the mass range o Hg to o Hg, several possibilities exist for the measurement of isotope ratios, thus far 5-values are generally presented as ratios. 

Also important is the effect of detector dead time. When ions are detected using a pulse counting (PC) detector, the resultant electronic pulses are approximately 10 ns long. During and after each pulse there is a period of time during which the detector is effectively dead (i.e. it cannot detect any ions). The dead time is made up of the time for each pulse and recovery time for the detector and associated electronics. Typical dead times vary between 20 and 100 ns. If dead time is not taken into account there will be an apparent reduction in the number of pulses at high count rates, which would cause an inaccuracy in the measurement of isotope ratios when abundances differ markedly. However, a correction can be applied as follows ... 

The highly precise measurement of isotope ratios has a long tradition in organic geochemistry. Nowadays, the elucidation of stable isotope distributions is highly desirable in view of fundamental studies in biochemistry, nutrition, drug research and also in the authenticity assessment of food ingredients. 

A dual ion beam collector developed by Nier2 is illustrated in Figure 4.1 b. Both collectors are connected to two amplifiers for the simultaneous and direct measurement of ion currents in the dual mode. Amplifier 1 works with degeneration whereas amplifier 2 works without. Such a dual ion beam collector is applied, for example, for precise and accurate measurements of isotope ratios, especially of gases in commercial stable isotope ratio mass spectrometers.2... 

Further details of different strategies in solution calibration are described in the literature.1 29 76 79 Precise and accurate measurements of isotope ratios, which is one of the major advantages of mass spectrometric techniques, are a requirement for the application of isotope dilution techniques in trace analysis, which is also the main goal of the application of isotope dilution in solution based calibration in LA-ICP-MS. 

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... 

S. Gas source mass spectrometry (GSMS) with electron impact (El) ion source produces nearly mono-energetic ions (similar to TIMS) and is an excellent tool for the high precision isotope analysis of light elements such as H, C, N and O, but also for S or Si.7,100,101 Precise and accurate measurements of isotope ratios have been carried out by gas source mass spectrometers with multiple ion collectors by a sample/standard comparison and the 8 values of isotope ratios were determined (see Equation 8.4). Electron impact ionization combined with mass spectrometry has been applied for elements which readily form gaseous compounds (e.g., C02 or S02) for the isotope analysis of carbon and sulfur, respectively). 

An analytical procedure has been proposed for precise uranium isotope ratio measurements in a thin uranium layer on a biological surface by LA-ICP-MS using a cooled laser ablation chamber.125 One drop of uranium isotope standard reference materials NIST, 350, NIST 930, of our isotopic laboratory standard CCLU 500 (20p.l, U concentration 200 ng 1) and of uranium with natural isotopic pattern were deposited on the leaf surface and analyzed by LA-ICP-MS at well defined laser crater diameters of 10, 15, 25 and 50 p.m. A precision for measurements of isotope ratios in the range of 2.1-1.0% for 235U/238U in selected isotope standards was observed whereby the precision and the accuracy of isotope ratios compared to the non-cooled laser ablation chamber was improved.125... 

Van den Boom et al.150 have reported on the determination of silicon isotope ratio measurements in silicate materials by MC-ICP-MS (at a mass resolution of 2500 to resolve isobaric interferences) after sodium hydroxide sample digestion and purification of silicon. 829Si and 830Si have been determined for several silicon isotope standard reference materials. A precision for 830Si of 0.18-0.41 %o was achieved. Precise and accurate measurements of isotope ratios on transient signals by HPLC-MC-ICP-MS for nuclear application was performed by Giinther-Leopold et al.151... 

Geochronology for age dating of minerals is a major field in earth sciences, includes measurements of isotope ratios and requires advanced sensitive, precise and accurate mass spectrometric techniques. The determination of the age of the Earth has been of significant interest for hundreds... 

Data acquisition parameters. Precision and accuracy in the measurement of isotope ratios can be improved if the number of measurements is increased (e.g. if the measurement time is increased). Various measurement protocols can be applied and those whereby the time actually spent on measuring the isotope ratios of interest is maximised are preferable. The data acquisition parameters of an ICP-MS device that can be changed to improve the isotope ratio precision... 

Inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) is a well-known analytical technique based on the measurement of isotope ratios in samples where their isotopic composition was altered by the addition of a known amount of an isotopically enriched element. 

I. Gunther-Leopold, B. Wernli, Z. Kopajtic and D. Gunther, Measurement of isotope ratios on transient signals by MC-ICP-MS, Anal. Bioanal. Chem., 378, 2004, 241-249. 

Acceleration mass spectrometry (AMS) - The precise measurement of isotopic ratios for very low abundance isotopes is beyond the capability of conventional mass spectrometers. In these cases of isotopes at minute trace levels, some 50 mass spectrometers exist worldwide. The tendetrons used for these types of analyses are derived from Van de Graaff-type particle accelerators. These instruments are based on tandem mass spectrometry. 

Work by Catanzaro et al. in 1968 (6) led to a new analytical procedure permitting the measurement of isotopic ratios to about 0.05% (95% L.E.) this resulted in the availability of three standard reference materials, so that results could be placed on an absolute basis. This procedure, still the most precise and accurate one available, requires about 1 mg of lead for an analysis. A second procedure (7) has been developed which utilizes silica gel as an ionization enhancer. This method permits the measurement of isotopic ratios to about 0.1% (95% L.E.), but it requires only 0.1 /xg of lead per analysis. In addition, the instrumentation and data handling have been vastly improved so that many samples can be studied quickly and conveniently. 

The ionization energy of Ar is 15.8 electron volts (eV), which is higher than those of all elements except He, Ne, and F. In an Ar plasma, analyte elements can be ionized by collisions with Ar+, excited Ar atoms, or energetic electrons. In atomic emission spectroscopy, we usually observe the more abundant neutral atoms, M. However, the plasma can be directed into a mass spectrometer (Chapter 22), which separates and measures ions according to their mass-to-charge ratio.17 For the most accurate measurements of isotope ratios, the mass spectrometer has one detector for each desired isotope.18... 

Most isotope ratio measurements have been performed using sector mass spectrometers. Some work has been reported, notably by Heumann [35], in which a quadrupole-based system was used. Instruments used for measurement of isotope ratios are most often dedicated to that purpose. In most instances only a relatively small mass range needs to be monitored, just enough to encompass the isotopes of the analyte element. Without the ability to scan the entire elemental mass range [usually from mlz = 6 (Li) through mfc = 238 (U) for elemental analysis], mass spectrometers designed to measure isotope ratios cannot readily be adapted for other purposes. See Chapter 2 for a discussion of instrumentation required for elemental analysis of solid materials and Chapter 3 for a treatment of the in-strumenation needed for elemental analysis of solutions. 

There are many instances in which it is highly desirable to analyze the smallest possible sample. This is of obvious importance when radioactive species are involved, but it is also advantageous when analyzing smaller samples means processing smaller amounts of material for an analysis, as is often the case in geological applications, among others. Measurement of isotopic ratios from pico-gram or smaller quantities of analyte has been reported for technetium [70,71], actinide elements [72], and rare earth elements [73]. 

Thermal ionization has widespread application in areas where measurement of isotope ratios is the goal of the analysis. Each area has its unique problems and challenges, and there is considerable cross-fertilization among disciplines. Exhaustive treatment would require a book of its own no attempt has been made here to cover all areas addressed by thermal ionization. Rather, a few areas of current and historical interest have been selected these should give the reader a good idea of the versatility of the technique. 

Simultaneous secondary ion detection is limited to the number of detectors placed in the transmission plane of the magnetic sector. Quasi-simultaneous detection of two or more ions may be achieved by programming electrostatic deflection plates to switch ions rapidly within a fairly narrow mass range (see Fig. 4.6). Simultaneous or quasisimultaneous collection of ions is especially helpful for measurement of isotopic ratios. 

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