Isotopes, stable availability

Isotope dilution is applicable to any element for which an enriched isotope is available. Figure 1.1 of Chapter 1 indicates which elements are amenable to isotope dilution in most cases the natural element has at least two stable isotopes, but this is not necessarily the case. For example, 232Th, though radioactive (half-life of 1.4 X 1010 years), is present in the earth s crust 230Th (half-life of 7.5 X 104 years), an isotope present in nature at such low levels as to be negligible for most applications, is used as a spike for isotope dilution purposes in the author s laboratory. Another common example is the use of 233U (a synthetic isotope) as a spike for uranium analyses. The only elements not amenable to the technique are those, like cobalt and arsenic, that have only one stable isotope and all of whose radioactive isotopes have half-lives so short as to preclude their use. 

There are several disadvantages of using stable Isotopes as labels. They are more expensive than radioisotopes and the supply is limited. Analysis requires extensive, time-consuming sample preparation, and requires use of costly Instruments not readily available to all investigators. The cost and supply of stable Isotopes limits the quantities which can be used. One mg of 99.7% Zn costs 0.45. The same purity of Zn cost 155 per mg. The cost is expected to Increase in the near future, when a new batch of zinc Isotopes becomes available. Thus zinc Isotopes for use in a single human study may cost thousands of dollars. Specific Isotopes are sometimes out of stock and not available for several months or longer. 

The stable isotope of carbon, C , is obtained in the form of methane, cyanide or a carbonate. This isotope is available in larger quantities than are the radioactive carbons although highly enriched material is difficult to obtain. Measurements are readily and accurately made with a mass spectrometer. The usual procedure involves combustion of an organic substance containing by the wet oxidation procedure of Van Slyke and Folch or by the usual combustion methods followed by purification of the resulting CO2. The sample of CO2 is then analyzed by means of the mass spectrometer. It should be emphasized at this point that analyses of necessity must be carried out on analytically pure substances since most contaminants contain carbon. This is particularly true of biological substances which have to be isolated from natural sources. 

The common stable isotopes used in biosynthetic studies are H, N, and 0. Stable isotope-labeled precursors have replaced radiolabeled precursors in many biosynthetic studies for the following reasons 1) no appropriate radiolabeled isotope is available (e.g., N and O) 2) the detection methods frequently permit location of the label in the product directly and 3) radiocontamination and safety issues are reduced. The negative aspects of stable isotope studies... 

NMR Studies - The applications of stable isotopes coupled with NMR analysis have multiplied as higher field magnets and sophisticated computer techniques have increased sensitivity, A recent review which discussed NMR studies employing stable isotopes is available. ... 

Carrier addition is widely used, not only for yield determination, but because the added mass avoids problems of radiocolloidal behavior. Other advantages of added carrier are the ability to use precipitation for radionuclide separation and purification, and avoidance of unintended coprecipitation during scavenging. When carrier is not added because no stable isotope is available or the counting source must be very thin, radionuclide deposition on container walls or on suspended solids must be avoided by applying the techniques discussed in Section 4.4, notably use of nonisotopic carrier or low pH. 

Because copper has only two stable isotopes, only one tracer isotope is available, which limits the choice of techniques for metabolic studies substantially. In most human studies, Cu has been used to determine apparent absorption, as the difference between the amount of isotope ingested and the amount recovered in feces. To check for completeness of fecal collection, holmium has been suggested and successfully used as a non-absorbable, quantitative elemental marker in copper absorption studies [259]. Studies comparing copper absorption of foods intrinsically or extrinsicaUy labeled with Cu are limited. Johnson and co-workers [260, 261] found no statistically significant difference in copper absorption from intrinsically and extrinsicaUy labeled goose fiver, goose breast, peanut butter, and wheat. Harvey et al. [262] observed significant differences in copper absorption between intrinsically and extrinsicaUy labeled sunflower seeds and soy beans. 

Chloride presents a particularly difficult problem to accommodate. Not only does Cl have two high abundance isotopes ( Cl at 75.8% and Cl at 24.2%), it forms stable polyatomic molecules with both metals and non-metals. One of the most severe interferences is the direct overlap of the molecule " Ar Cl with the monoisotopic analyte element As. Because no alternate isotopes are available for As, either Cl must be absent or eliminated from the sample prior to analysis to ensure the most accurate determination. For modest concentrations of Cl in the sample, a mathematical correction can be made that results in a relatively accurate As determination. 

There are at least two mechanisms available for aziridine cis-trans isomerism. The first is base-catalyzed and proceeds via an intermediate carbanion (235). The second mechanism can be either thermally or photochemically initiated and proceeds by way of an intermediate azomethine ylide. The absence of a catalytic effect and interception of the 1,3-dipole intermediate provide support for this route. A variety of aziridinyl ketones have been found to undergo equilibration when subjected to base-catalyzed conditions (65JA1050). In most of these cases the cis isomer is more stable than the trans. Base-catalyzed isotope exchange has also been observed in at least one molecule which lacks a stabilizing carbonyl group (72TL3591). 

Abundances of lUPAC (the International Union of Pure and Applied Chemistry). Their most recent recommendations are tabulated on the inside front fly sheet. From this it is clear that there is still a wide variation in the reliability of the data. The most accurately quoted value is that for fluorine which is known to better than I part in 38 million the least accurate is for boron (1 part in 1500, i.e. 7 parts in [O ). Apart from boron all values are reliable to better than 5 parts in [O and the majority arc reliable to better than I part in 10. For some elements (such as boron) the rather large uncertainty arises not because of experimental error, since the use of mass-spcctrometric measurements has yielded results of very high precision, but because the natural variation in the relative abundance of the 2 isotopes °B and "B results in a range of values of at least 0.003 about the quoted value of 10.811. By contrast, there is no known variation in isotopic abundances for elements such as selenium and osmium, but calibrated mass-spcctrometric data are not available, and the existence of 6 and 7 stable isotopes respectively for these elements makes high precision difficult to obtain they are thus prime candidates for improvement. 

In addition to the 4 stable isotopes sulfur has at least 9 radioactive isotopes, the one with the longest half-life being which decays by activity (Kmax 0.167 MeV, 87.5 d). can be prepared by Cl(n,p), S(n,> ) or S(d,p) and is commercially available as SeicmcQt H2S, SOCb and KSCN. The radiation has a similar energy to that of C ( mav 0.155 MeV) and similar counting techniques can be used (p. 276). The maximum range is 300 min in air and 0.28 mm in water, and effective shielding is provided by a perspex screen 3-10 mm thick. The preparation of many - S-containii compounds has been... 

For quantitative work, it is necessary to estimate the concentration of 5-amino-l-(P-D-ribofuranosyl)imidazole in aqueous solution. It seems that the only available method is the Bratton-Marshall assay, which was originally developed for the estimation of arylamines in biological fluids. The principle of the method is the spectrometric estimation of a salmon-pink colored dyestuff obtained by diazotation in situ, followed by coupling with /V-( 1 -naphthyl)ethyl-enediamine.65 The only remaining problem then is to know the molar extinction of this dye because pure samples of AIRs are not available. A value of 16800 at 520 nM was obtained for the dyes prepared from a model compound, 5-amino-l-cyclohexylimidazole-4-carboxylic acid (54), which is crystalline. A comparable molar extinction can be expected for the dye prepared from imidazole 55, if the carboxyl group does not exert too much influence on the chromophore. Actually, its influence is perceptible even with the naked eye, the dyestuff prepared from 53 having a somewhat different, wine-red color, with max>520 nM. The molar extinction for 55 is 17400 at 500 nM. When the decarboxylation of 54 was conducted under mild acidic conditions (pH 4.8, 50°C, 1 hour), estimation of 5-aminoimidazole 55 by the Bratton-Marshall method led to the conclusion that the reaction was almost quantitative.66 Similar conditions for the final decarboxylation were adopted in the preparation of samples of AIRs labeled with stable isotopes.58... 

The natural occurrence of the group-IIA elements ranges from common to rare e.g., Ca is 5th in the order of atomic abundance of the elements in the earth s crust. Mg is 7th, Ba and Sr are 21st and 22nd, respectively, and Be is 32nd . Radium is of extremely limited availability. It does occur naturally, although it has neither stable nor long-lived radioaetive isotopes it is found in association with U, since ll/2... 

A smaller number of individuals, 132 samples, was analyzed for stable isotopes of nitrogen. There were two objectives to the nitrogen isotope analysis 1) to determine the amount of animal protein in the diet and to look for variation between the sexes and 2) to determine when infants were weaned from the breast. These objectives were addressed by selecting at least ten individuals, when available, from a number of age classes. Figure 1.1 illustrates the age distribution of the sample. Table 1.3 shows the results of these analyses. Individual 5 N values are provided in Herring et al. (1998). 

Bones of 19 individuals were analyzed for strontium, rubidium and zinc. The number of samples was limited by the availability of bone after the stable isotope analyses were completed. Strontium was analyzed in order to test for trophic level, and to compare to other results obtained in the region on prehistoric peoples (Katzenberg 1984). Rubidium is not expected in human bone, so its presence acts as a measure of contamination. The use of zinc as a paleodi-etary indicator has been questioned recently (Ezzo 1994) and we were interested to see if there was any relationship between zinc content in food and bone. 

Numerous geochemical data (fluid inclusions, stable isotopes, minor elements) on the epithermal vein-type deposits in Japan are available and these data can be used to constrain geochemical environment of ore deposition (gas fugacity, temperature, chemical compositions of ore fluids, etc.) and origin of ore deposits. 

RMsfor Radioisotopes, Stable Isotopes and Rodiopharmaceuticals 145 Tab. 4.6 Overview of available reference materials for "Am, and °Sr... 

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