Isotopic dilution analysis advantage

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... 

Discuss the advantages and disadvantages associated with isotope dilution analysis. 

Isotope dilution analysis is now internationally regarded as a reference or highly qualified primary method thanks to all these advantages. 

One of the key steps in any isotope dilution analysis concerns the isolation and purification of the diluted activity, plus the measurement of its specific activity. Two techniques are usually preferred for the separation precipitation and solvent extraction. As a purification step, precipitation has the advantage that the precipitate can easily be weighed at the time of separation, thereby allowing a quick determination of the specific activity. The main problem with the use of precipitation techniques involves the occurrence of co-precipitation phenomena, in which unwanted materials are precipitated along with the desired substance, thus altering the sample specific activity. Precipitation techniques are used for the isolation of inorganic components. 

The principle of the isotope dilution analysis (IDA) is described in Section 6.4. Due to its advantages as a definitive and accurate analytical method for the determination of element concentration via isotope ratio measurements, IDA is being increasingly applied in mass spectrometry, especially in ICP-MS and LA-ICP-MS as one of the most frequently used techniques. For example, the isotope dilution technique is employed in species analysis in biological systems, " e.g., for the determination of mercury species in tuna material,or in aquatic systems. Further applications of the isotope dilution technique are the determination of selenomethionine in human blood serum by capillary HPLC-ICP (ORC) MS ° or sulfur speciation in gas oil, diesel or heating fuel by LA-ICP-MS. Evans and co-workers have reported on the high accuracy analysis of sulfur in diesel fuel by IDA. ICP-SFMS has been employed for Si species analysis in biological or clinical samples and... 

The main and unique advantage of this method is the fact that quantitative separation of the element or compound to be determined is not necessary. It is substituted by measuring any fraction. This advantage is most clearly illustrated by an example from biology if the blood volume of an animal is to be determined, it is obvious that the animal will not survive the extraction of the whole amount of blood to be measured. By application of isotope dilution analysis, a small measmed volume V of a solution is injected that contains a measured activity of a radionuclide of low radiotoxicity. Mixing is effected by blood circulation. After some minutes, a small volume of blood is taken and the activity is measured. In analogy to eq. (17.15), the unknown volume is... 

ICP-MS offers unique advantages including element specificity, wide linear dynamic range, low detection limits and, ability to perform isotope dilution analysis. ... 

The inherent sensitivity of these isotopic methods is especially attractive when a specific reaction is to be studied in detail. Furthermore, the formation of a radioactive product enables isotope dilution analysis to be applied to establishing the specificity of the reaction. A wide range of substrate and enzyme concentrations can be used and it is often possible to measure low enzymatic activity in crude homogenates without the need for extensive purification of the enzyme. This undoubtedly has constituted one of the major practical advantages of the radiochemical techniques. 

Differentiation between labeled and unlabeled flavor compounds is based on the difference in nuclear masses of the isotopes and on employment of the mass spectrometry method. One of the main advantages of isotope dilution analysis is the high selectivity of the gas chromatography/mass spectrometry combination. The selectivity and the sensitivity of the determination can be further enhanced by the use of different ionization techniques. In most cases, differentiation between the internal standard and the analyte is achieved with the aid of chemical ionization with reactant gases, with the intensities of the molecular ions typically being measured by selective ion monitoring (SIM mode). 

Radiochemical methods of analysis take advantage of the decay of radioactive isotopes. A direct measurement of the rate at which a radioactive isotope decays may be used to determine its concentration in a sample. For analytes that are not naturally radioactive, neutron activation often can be used to induce radioactivity. Isotope dilution, in which a radioactively labeled form of an analyte is spiked into the sample, can be used as an internal standard for quantitative work. 

Table 8.62 shows the main characteristics of ICP-MS, which is widely used in routine analytical applications. The ICP ion source has several unique advantages the samples are introduced at atmospheric pressure the degree of ionisation is relatively uniform for all elements and singly charged ions are the principal ion product. Theoretically, 54 elements can be ionised in an ICP with an efficiency of 90 % or more. Even some elements that do not show ionic emission lines should be ionised with reasonable efficiency (namely, As, 52 % and P, 33%) [381]. This is one of the advantages of ICP-MS over ICP-AES. Other features of ICP-MS that make it more attractive than ICP-AES are much lower detection limits ability to provide isotopic ratio information and to offer isotope dilution capabilities for quantitative analysis and clean and simple spectra. The... 

One of the advantages of the isotope dilution technique is that the quantitative recovery of the analytes is not required. Since it is only their isotope ratios that are being measured, it is necessary only to recover sufficient analyte to make an adequate measurement. Therefore, when this technique is used in conjunction with graphite furnace atomic absorption spectrometry, it is possible to determine the efficiency of the preconcentration step. This is particularly important in the analysis of seawater, where the recovery is very difficult to determine by other techniques, since the concentration of the unrecovered analyte is so low. In using this technique, one must assume that isotopic equilibrium has been achieved with the analyte, regardless of the species in which it may exist. 

A logical approach which serves to minimise such uncertainties is the use of a number of distinctly different analytical methods for the determination of each analyte wherein none of the methods would be expected to suffer identical interferences. In this manner, any correspondence observed between the results of different methods implies that a reliable estimate of the true value for the analyte concentration in the sample has been obtained. To this end Sturgeon et al. [21] carried out the analysis of coastal seawater for the above elements using isotope dilution spark source mass spectrometry. GFA-AS, and ICP-ES following trace metal separation-preconcentration (using ion exchange and chelation-solvent extraction), and direct analysis by GFA-AS. These workers discuss analytical advantages inherent in such an approach. 

Another GC method, isotope dilution GC-MS, involves the addition of an isotopomer of the analyte of interest to the sampling manifold (e.g., see Bandy et al., 1993 and Blomquist et al., 1993). In the case of S02, where the ambient S02 consists mainly of K 0 and 32S, S02 containing the 34S isotope is used. This labeled S02 at mass 66 is used as internal standard and has a number of additional advantages such as minimizing the loss of the analyte in the sampling system (Bandy et al., 1993). The air with the added isotopomer is trapped cryogenically and then sampled into a GC-MS for analysis. 

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. 

Isotope dilution in combination with the substoichiometric principle is applied in various ways. The most important examples are radioimmunoassay for protein analysis and DNA analysis. In radioimmunoassay, radionuclides are used as tracers and immunochemical reactions for isolation. Radioimmunoassay was first described in 1959 by Yalow and Berson, and since then has found very broad application in clinical medicine, in particular for the measurement of serum proteins, hormones, enzymes, viruses, bacterial antigens, drugs and other substances in blood, other body fluids and tissues. Only one drop of blood is needed, and the analysis can be per-fonned automatically. Today more than 10 immunoassays are made annually in the United States. The most important advantages of the method are the high sensitivity and the high specificity. In favourable cases quantities down to 10 g can... 

In clinical chemistry the determination of stable elements by radiochemical methods offers no outstanding advantages over alternative methods, but the use of radioisotopes for determining organic compounds is developing rapidly. In isotope dilution methods (G6), a pure but radioactive form of the compound to be measured is mixed with the sample, a fraction is isolated, and its activity is determined. In radio-metric or derivative analysis (W14), a radioactive reagent is allowed to react with the analyte the labeled compound is separated and its activity is measured. The isotopes commonly used are C,... 

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