Isotope ratio measurement

Lasers can be used in either pulsed or continuous mode to desorb material from a sample, which can then be examined as such or mixed or dissolved in a matrix. The desorbed (ablated) material contains few or sometimes even no ions, and a second ionization step is frequently needed to improve the yield of ions. The most common methods of providing the second ionization use MALDI to give protonated molecular ions or a plasma torch to give atomic ions for isotope ratio measurement. By adjusting the laser s focus and power, laser desorption can be used for either depth or surface profiling. 

Gases and vapors of volatile liquids can be introduced directly into a plasma flame for elemental analysis or for isotope ratio measurements. Some elements can be examined by first converting them chemically into volatile forms, as with the formation of hydrides of arsenic and tellurium. It is important that not too much analyte pass into the flame, as the extra material introduced into the plasma can cause it to become unstable or even to go out altogether, thereby compromising accuracy or continuity of measurement. 

Since detailed chemical structure information is not usually required from isotope ratio measurements, it is possible to vaporize samples by simply pyrolyzing them. For this purpose, the sample can be placed on a tungsten, rhenium, or platinum wire and heated strongly in vacuum by passing an electric current through the wire. This is thermal or surface ionization (TI). Alternatively, a small electric furnace can be used when removal of solvent from a dilute solution is desirable before vaporization of residual solute. Again, a wide variety of mass analyzers can be used to measure m/z values of atomic ions and their relative abundances. 

The use of accurate isotope ratio measurement is exemplified here by a method used to determine the temperature of the Mediterranean Sea 10,000 years ago. It is known that the relative solubility of the two isotopic forms of carbon dioxide COj) in sea water depends on temperature... 

Because variations in accurate isotope ratio measurements typically concern only a few parts per 1000 by mass and there are no universal absolute ratios, it is necessary to define some standards. For this purpose, samples of standard substances are produced and made available at two major centers IAEA (International Atomic Energy Authority, U.K.) and NIST (National Institute for Standards and Technology, U.S.). Standards from other sources are also available. These primary standards can be used as such, or alternative standards can be employed if the primary ones are not available. However, any alternative standards need to be related accurately to the primary ones (see formulae below). For example, the material PDB (PeeDee belemnite), used particularly as a standard for the ratio of isotopes, is no longer readily available, and a new standard, VPDB,... 

For example, if a carbonaceous sample (S) is examined mass spectrometrically, the ratio of abundances for the carbon isotopes C, in the sample is Rg. This ratio by itself is of little significance and needs to be related to a reference standard of some sort. The same isotope ratio measured for a reference sample is then R. The reference ratio also serves to check the performance of the mass spectrometer. If two ratios are measured, it is natural to assess them against each other as, for example, the sample versus the reference material. This assessment is defined by another ratio, a (the fractionation factor Figure 48.2). 

From a series of isotope ratio measurements, the precision of measurement can be assessed statistically, as shown here. Precision reveals the reproducibility of the measurement method, but it does not provide information on the accuracy of the measurement (see also Figures 48.8 and 48.9). 

Almost any type of analyzer could be used to separate isotopes, so their ratios of abundances can be measured. In practice, the type of analyzer employed will depend on the resolution needed to differentiate among a range of isotopes. When the isotopes are locked into multielement ions, it becomes difficult to separate all of the possible isotopes. For example, an ion of composition CgHijOj will actually consist of many compositions if all of the isotopes ( C, C, H, H, 0, O, and 0) are considered. To resolve all of these isotopic compositions before measurement of their abundances is difficult. For low-molecular-mass ions (HjO, COj) or for atomic ions (Ca, Cl), the problems are not so severe. Therefore, most accurate isotope ratio measurements are made on low-molecular-mass species, and resolution of these even with simple analyzers is not difficult. The most widely used analyzers are based on magnets, quadrupoles, ion traps, and time-of-flight instruments. 

Almost any kind of ion source could be used, but, again, in practice only a few types are used routinely and are often associated with the method used for sample introduction. Thus, a plasma torch is used most frequently for materials that can be vaporized (see Chapters 14-17 and 19). Chapter 7, Thermal Ionization, should be consulted for another popular method in accurate isotope ratio measurement. 

Accurate, precise isotope ratio measurements are important in a wide variety of applications, including dating, examination of environmental samples, and studies on drug metabolism. The degree of accuracy and precision required necessitates the use of special isotope mass spectrometers, which mostly use thermal ionization or inductively coupled plasma ionization, often together with multiple ion collectors. 

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. 

Thermal or surface emission of ions is one of the oldest ionization techniques used for isotope ratio measurements. 

Accurate, precise isotope ratio measurements are used in a variety of applications including dating of artifacts or rocks, studies on drug metabolism, and investigations of environmental issues. Special mass spectrometers are needed for such accuracy and precision. 

Becker JS, Dietze H-J (2000) Precise and accurate isotope ratio measurements by ICP-MS. Fresenius J Anal Chem 368 23-30... 

Cochran JK, Masque P (2003) Short-lived U/Th-series radionuclides in the ocean tracers for scavenging rates, export fluxes and particle dynamics. Rev Mineral Geochem 52 461-492 Cohen AS, O Nions RK (1991) Precise determination of femtogram quantities of radium by thermal ionization mass spectrometry. Anal Chem 63 2705-2708 Cohen AS, Belshaw NS, O Nions RK (1992) High precision uranium, thorium, and radium isotope ratio measurements by high dynamic range thermal ionization mass spectrometry. Inti J Mass Spectrom Ion Processes 116 71-81... 

Neder H, Heusser G, Laubenstein M (2000) Low-level y-ray germanium-spectrometer to measure veiy low primordial radionuclide concentrations. ApplRadiat Isot 53 191-195 Palacz ZA, Freedman PA, Walder AJ (1992) Thorium isotope ratio measurements at high abundance sensitivity using a VG 54-30, an energy-filtered thermal ionization mass spectrometer. Chem Geol 101 157-165... 

Platzner IT, Becker JS, Dietze H-J (1999) Stability study of isotope ratio measurements for uranium and thorium by ICP-QMS. At Spectrosc 20 6-12... 

Walder AJ, Freedman PA (1992) Isotopic ratio measurement using a double focusing magnetic sector mass analyser with an inductively coupled plasma as an ion somce. J Anal At Spectrom 7 571-575... 

Walder AJ, Roller D, Reed NM, Hutton RC, Freedman PA (1993) Isotope ratio measurement by inductively coupled plasma multiple collector mass spectrometry incorporating a high efficiency nebulization system. J Anal At Spectrom 8 1037-1041... 

Data on mineral s arates in present day volcanic rocks. Since every dating method (including the K-Ar or C systems) can be affected by several geochemical perturbations which may lead to erroneous ages, the best test for the °Th- U mineral isochrons consists in the analysis of presently erupted lavas or historic lavas of well known eruption dates. Rather surprisingly the data obtained on such samples are not so numerous (some examples are illustrated in Fig. 10). Early data showed that, in some cases, there were interlaboratory analytical discrepancies, especially in Th isotope ratios measured on mineral separates extracted from the same lava flows (this was the case for the 1971 lava from Mt. Etna and 1944 lava from Mt. Vesuvius Capaldi and Pece 1981 Hemond and Condomines 1985 Capaldi et al. 1985). This emphasizes the fact that °Th- U mineral analyses... 

For measurements by AS, the errors of the isotope ratio will be dominated by counting statistics for each isotope. For measurements by TIMS or ICP-MS, the counting-statistic errors set a firm lower limit on the isotopic measurement errors, but more often than not contribute only a part of the total variance of the isotope-ratio measurements. For these techniques, other sources of (non-systematic) error include ... 

Applications Sector instruments are applied for niche applications such as high-resolution measurements and fundamental ion chemistry studies. Magnetic sector mass spectrometers remain the instrument of choice in areas of target compound trace analysis, accurate mass measurement and isotope ratio measurement. 

Heumann et al. [420,423] have recently given overviews of plasma MS for isotope ratio measurements. A review of the ID-SSMS method can also be found in the literature [422],... 

Both absolute quantitation and relative quantitation of species in mixtures is of interest in some circumstances. Quantitation in a 5-minute analysis can be achieved by addition of an internal standard, ideally the target microorganism grown in special media to incorporate heavy isotopes92-95 and determination of the relative peak heights of pairs of proteins from the analyte and the standard. Isotope-labeled proteins or peptides, selected to match proteins or peptides characteristic of target microorganisms, can also serve as internal standards for isotope ratio measurement. The addition of unmatched proteins or peptides is less reliable for either ESI or MALDI measurements because of unpredictable suppression in the variable mixture. 

Flegal and Stukas [406] described the special sampling and processing techniques necessary for the prevention of lead contamination of seawater samples, prior to stable lead isotopic ratio measurements by thermal ionisation mass spectrometry. Techniques are also required to compensate for the absence of an internal standard and the presence of refractory organic compounds. The precision of the analyses is 0.1 -0.4% and a detection limit of 0.02 ng/kg allows the tracing of lead inputs and biogeochemical cycles. 

Figure 26. Deuterium isotope ratio vs. oxygen isotope ratio measured in our sequence of German oaks and Japanese C. japonica.

In principle to all elements at low (ppb) concentrations. Valuable for first look analysis, at solid samples. Isotopic ratio measurements can distinguish between sources of elements in tracer studies and environmental samples. Use in geological dating based upon isotopic ratios. 

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. 

T. Walczyk. Iron Isotope Ratio Measurements by Negative Thermal Ionisation Mass Spectrometry using FeF Molecular Ions. Int. J. Mass Spectrom. Ion Proc., 161(1997) 217-227. 

J. S. Becker and H. J. Dietze. Precise and Accurate Isotope Ratio Measurements by ICP-MS. Fresenius J. Anal. Chem., 368(2000) 23-30. 

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