Mass isotope dilution

A mass-isotope dilution method for determining the gamma isomer of benzene hexachloride, in which gamma-hexadeuterobenzene hexachloride is used as a tracer molecule and the dilution is determined by use of infrared spectrophotometry, has been developed by Trenner et al. (52). Impurities have no effect on the accuracy of this method. 

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. 

Isotope Dilution Another important quantitative radiochemical method is isotope dilution. In this method of analysis a sample of analyte, called a tracer, is prepared in a radioactive form with a known activity. Ax, for its radioactive decay. A measured mass of the tracer, Wf, is added to a sample containing an unknown mass, w, of a nonradioactive analyte, and the material is homogenized. The sample is then processed to isolate wa grams of purified analyte, containing both radioactive and nonradioactive materials. The activity of the isolated sample, A, is measured. If all the analyte, both radioactive and nonradioactive, is recovered, then A and Ax will be equal. Normally, some of the analyte is lost during isolation and purification. In this case A is less than Ax, and... 

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

ICPMS is uniquely able to borrow a quantitation technique from molecular mass spectrometry. Use of the isotope dilution technique involves the addition of a spike having a different isotope ratio to the sample, which has a known isotope ratio. This is usefiil for determining the concentration of an element in a sample that must undergo some preparation before analysis, or for measuring an element with high precision and accuracy. ... 

The isotope dilution principle, first employed by Hevesy and Hobbie (133) in 1932 for the determination of lead in ores, was applied by Schoenheimer et al. (241) to the determination of amino acids. [Shemin and Foster (248) have reviewed this topic.] An N15-amino acid derivative was added to a protein hydrolyzate, a sample of the amino acid to be determined was isolated and purified, the excess N15 in this product was estimated with the mass spectrograph, and the grams of amino acid originally present were calculated from Equation 2. 

MAZUR W, FOTSIS T, WAHALA K, OJALA S, SALAKKA A and ADLERCREUTZ H (1996) Isotope dilution gas chromatographic-mass spectrometric method for the determination of isoflavonoids, coumestrol and lignans in food samples. Biochem. 233 (2) 169-80. 

Dizdaroglu, M. (1993). Quantitative determination of oxidative base damage in DNA by stable isotope-dilution mass spectrometry. FEBS Lett. 315, 1-6. 

Separation and detection methods The common methods used to separate the Cr(III)/(VI) species are solvent extraction, chromatography and coprecipitation. In case of Cr(VI) from welding fumes trapped on a filter, a suitable leaching of the Cr(VI) from the sample matrix is needed, without reducing the Cr(VI) species. The most used detection methods for chromium are graphite furnace AAS, chemiluminescence, electrochemical methods, ICP-MS, thermal ionization isotope dilution mass spectrometry and spectrophotometry (Vercoutere and Cornelis 1995)- The separation of the two species is the most delicate part of the procedure. 

Cohen A, Hertz HS, Mandel J, Paule RC, Schaffer R, Sniegoski LT, Sun T, Welch MJ, and White E V (1980) Total serum cholesterol by isotope dilution mass spectrometry A candidate definitive method. Chn Chem 26 854-860. 

Creed JT, and Brockhoff CA (1999) Isotope dilution analysis of bromate in drinking water matrixes by ion chromatography with inductively coupled plasma mass spectrometric detection. Anal Chem 71 722-726. 

Ellerbe P, Cohen A, Welch MJ, and White V E (1990) Determination of serum uric acid by isotope dilution mass spectrometry as a candidate definitive method. Anal. Chem 62 2173-2177. 

Ellerbe PM, Sniegoski LT, and Welch MJ (1995) Isotope dilution mass spectrometry as a candidate definitive method for determining total glycerides and triglycerides in serum. Clin Chem 41 397-404. 

Ellerbe, P, Meiselman S, Sniegoski LT, Welch MJ, and White E V (1989) Determination of serum cholesterol by a modification of the isotope dilution mass spectrometric definitive method. Anal Chem 61 1718-1723. 

Kingston HMS, Huo D, Lu Y, and Chalk S (1998) Accuracy in spedes analysis spedated isotope dilution mass spectrometry (SIDMS) exemplified by the evaluation of chromium species. Spectrochim Acta 536 299-309. 

White V E, Welch MJ, Sun T, Sniegoski LT, Schaffer R, Hertz HS, and Cohen A (1982) The accurate determination of serum glucose by isotope dilution/mass spectrometry - two methods. Biomed Mass Spectrom 9 395-405. 

Kessler A, Siekmann L (1999) Measurement of urea in human serum by isotope dilution mass spectrometry. A reference procedure. Clin Chem 45 1523-1529. 

SlEKMANN L (1979) Determination of steroid hormones by the use of isotope dilution mass spectrometry a definitive method in clinical chemistry. J Steroid Biochem 11 117-123. 

Calcium exists in the human body as Ca(II) protein-bound and free Ca (II) ions (Dilana et al. 1994). For total extracellular Ca in plasma, serum and urine a definitive isotope dilution-mass spectrometry (ID-MS) method exist. Free Ca(II) in plasma/serum can be determined with PISE, but no definitive and reference methods exist. For Ca in faeces, tissue and blood flame atomic absorption (FAAS) is used widely. 

McCann MT, Thompson MM, Gueron IC et al. (1996) Methyl malonic acid quantification by stable isotope dilution gas chromatography-mass spectrometry from filter paper urine samples. Clin Chem 42 9io-9i4. 

The development of new fiber coatings in the near future should further improve the specificity of SPME and overcome some of the observed matrix effects. Quantification by stable isotope dilution gas chromatography/mass spectrometry (GC/MS) may assist in improving analytical performance. Along with the possible application of micro LC and capillary LC columns to in-tube SPME, the development of novel derivatization methods and the potential for the analysis of fumigant pesticides, SPME appears to be a technique with a future in the analysis of pesticide residues in food. 

In most alpha and mass spectrometric methods for which sample preparation is extensive and chemical recoveries can vary considerably from sample to sample, precise elemental concentrations are determined by isotope dilution methods (e.g., Faure 1977). This method is based on the determination of the isotopic composition of an element in a mixture of a known quantity of a tracer with an unknown quantity of the normal element. The tracer is a solution containing a known concentration of a particular element or elements for which isotopic composition has been changed by enrichment of one or more of its isotopes. 

Table 1 lists MORE studies to date and Figures 2 and 3 present data from different areas of ridge. The first study of U-series disequilibria in MORE was the pioneering work of Condomines et al. (1981) (Fig. 2A). These workers analyzed samples having a relatively wide range in composition (Mg 72 to 57) from the FAMOUS region of the Mid-Atlantic Ridge (MAR 37°N) by combined alpha spectrometry (for U and Th isotopic ratios) and mass spectrometry (isotope dilution measurements for U and Th... 

Figure 5. Histogram Th/U for clinopyroxenes in peridotites and pyroxenites from the Ronda peridotite massif Concentrations were measured by isotope dilution mass spectrometry in acid-leached clinopyroxenes. This histogram shows that pyroxenites do not have larger Th/U ratios than peridotites. Thus, the correlation found between ( °Th/ U) and Th/U cannot be explained by mixing of peridotite and pyroxenite melts as advocated in Sigmarsson et al. (1998). Data from Hauri et al. (1994) and Bourdon and Zindler (unpublished). It can be shown with a simple Student t-test that the two populations are indistinguishable.

Crowley, J.R., Yarasheski, K., Leeuwenburgh, C., Turk, J., and Heinecke, J.W., Isotope dilution mass spectrometric quantification of 3-nitrotyrosine in proteins and tissues is facilitated by reduction to 3-aminotyrosine, Anal. Biochem., 259, 127, 1998. 

Conventional calibration MDRD equation [used only with those creatinine methods that have not been recalibrated to be traceable to isotope dilution mass spectrometry (IDMS)]... 

The main advantages of plasma-source mass spectrometry (PS-MS) over other analytical techniques, such as PS-AES and ETAAS, are the possibilities of quantitative isotope determination and isotope dilution analysis the rapid spectral scanning capability of the mass spectrometer and semiquantitative determinations to within a factor of two or three. Several labelling methods are used for the quantification of analytes present in complex mixtures. In these methods, the sample is spiked... 

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