Isotope dilution ratios

It is obvious that, no matter what kind of mass spectrometer or ionization method is used, correction for isotopic bias is mandatory for successful application of isotope dilution. The basis of the whole technique rests on trustworthy measurement of the isotope dilution ratio [Rm in Eq. (5.7)], which necessitates application of a bias correction. Accuracy of the final result is critically dependent upon accurate calibration of the instrumentation, and, as always, it is important to have analysis of reference materials mimic as closely as possible that of samples. 

Equation (1) makes clear that the uncertainty of an IDMS assay consists of the sum of the relative uncertainty of the "spike" and the relative uncertainty of the measurement of an isotope dilution ratio Rb- This statement is valid for both the uncertainty generated by the imprecision (or reproducibility) of the measurement of "spike" and Rb as well as by the systematic error(s) in the measurement of the "spike" and of the isotope dilution ratio Rb-... 

We will now see that this is equally valid for IDMS of bi-isotopic elements (Eq. 4 and Fig. 2) and in the poly-isotopic case (Eq. 5 and Fig. 3). We note that R can be chosen 2 ways the major isotope abundance being in the denominator or in the nominator of Rx or Ry. We arbitrarily choose the latter, hence Ry 1 and quite different from Rb ( 1). We note that Ry is then little affected by Rb- Also because Ry appears in both nominator and denominator of Eq. 4, any uncertainty on Ry, will have very little effect on the uncertainty of Wx/A/y. On the other hand Rx will be small (the major isotope abundance will now be in the denominator of Rx) with respect to Rb or to 1, so any uncertainty on Rx will not contribute to the uncertainty of A/x/Wy. Consequently only the uncertainty of Rb in the denominator will largely determine the uncertainty of N /Ny and hence of the IDMS result. The precision with which an isotope dilution ratio can be measured, determines the precision of an IDMS determination as far as the isotopic measurement is concerned. Further limitations are, or may be ... 

For some applications, such as isotope dilution/ratio studies, high precision is also a very important data quality objective. However, to understand what is realistically achievable, we have to be aware of the practical limitations of measuring a signal and counting ions in ICP-MS. Counting statistics tell us that the standard deviation of the... 

Isotopic dilution analysis is widely used to determine the amounts of trace elements in a wide range of samples. The technique involves the addition to any sample of a known quantity (a spike) of an isotope of the element to be analyzed. By measuring isotope ratios in the sample before and after addition of the spike, the amount of the trace element can be determined with high accuracy. The method is described more fully in Figure 48.13. 

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. ... 

Without isotope dilution, the simultaneous measurement of U and Th is essential in LA-MC-ICPMS, although large (10-100% level) elemental, matrix-dependent fractionation effects can still be observed between U and Th (e g., Stirling et al. 2000). As a result, Th/U ratios can be systematically lower, and apparent U- Th-ages... 

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.

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... 

Isotope dilution (ID) is a technique for the quantitative determination of element concentrations in a sample, on the basis of isotope ratios [382]. An important prerequisite for isotope dilution is the availability of two stable isotopes, although in some cases the use of long-lived radionuclides allows the application range to be further extended [420]. 

Isotope dilution mass spectrometry (IDMS) can be applied with most of the ionisation methods used in mass spectrometry to determine isotope ratios with greater or lesser accuracy. For calibration by means of isotope dilution, an exactly known amount of a spike solution, enriched in an isotope of the element(s) to be determined, is added to an exactly known amount of sample. After isotopic equilibration, the isotope ratio for the mixture is determined mass spectrometrically. The attraction of IDMS is its potential simplicity it relies only on the measurement of ratios. The... 

In isotope dilution inductively coupled plasma-mass spectrometry (ID-ICP-MS) the spike, the unspiked and a spiked sample are measured by ICP-MS in order to determine the isotope ratio. Using this technique, more precise and accurate results can be obtained than by using a calibration graph or by standard addition. This is due to elimination of various systematic errors. Isotopes behave identically in most chemical and physical processes. Signal suppression and enhancement due to the matrix in ICP-MS affects both isotopes equally. The same holds for most long-term instrumental fluctuations and drift. Accuracy and precision obtained with ID-ICP-QMS are better than with other ICP-QMS calibration... 

In the analysis of seawater, isotope dilution mass spectrometry offers a more accurate and precise determination than is potentially available with other conventional techniques such as flameless AAS or ASV. Instead of using external standards measured in separate experiments, an internal standard, which is an isotopically enriched form of the same element, is added to the sample. Hence, only a ratio of the spike to the common element need be measured. The quantitative recovery necessary for the flameless atomic absorption and ASV techniques is not critical to the isotope dilution approach. This factor can become quite variable in the extraction of trace metals from the salt-laden matrix of seawater. Yield may be isotopically determined by the same experiment or by the addition of a second isotopic spike after the extraction has been completed. 

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. 

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. 

Relative error on isotope dilution measurements is minimum whenever the mixture isotopic ratio is the square root of spike and sample isotopic ratios. 

Stable-isotope dilution analysis is an analytical technique in which a known quantity of a stable-labelled isotope is added to a sample prior to extraction, in order to quantitate a particular compound. The ratio of the naturally abundant and the stable-labelled isotope is a measure of the naturally abundant compound and can be determined only by gas chromatography-mass spectrometry since the naturally abundant and the stable-labelled isotope cannot be completely separated gas chromatographically. 

The isotope dilution gas chromatography-mass spectrometry method described by Lopez-Avila et al. [16] and discussed in section 5.3.1.3 has been applied to the determination of Atrazine in soil. In this method known amounts of labelled Atrazine were specked into soil samples before extraction with acetone-hexane. The ratio of the naturally abundant compound and the stable-labelled isotope was determined by high-resolution gas chromatography-mass spectrometry with the mass spectrometer in the selected ion monitoring mode. Detection limits of 0.1-l.Oppb were achieved. Accuracy was >86% and precision better than 8%. 

In Section III.D various methods were mentioned for determination of the 15N to 14N isotope ratio. Some applications to amines that appeared in the recent literature are presented here. Isotope dilution with a known aliquot of labelled compound allows solving some of the problems related to nonquantitative recovery yields of analyte in the analytical processing of a sample. However, the possibility of isotopic fractionation has to be taken into consideration. 

Isotope dilution mass spectrometry (IDMS) is another method to overcome the problem of sample recovery [370-372]. The 13C-labeled isotope of the analyte is added to the sample at the commencement of the analysis and the ratio of the labeled and unlabeled compound is measured by MS. This technique eliminates the need for recovery measurements and automatically accounts for any losses in the determination [373]. The two major limitations of this method are the cost and availability of the labeled compounds and the need to use the MS as a detector. 

An isotope dilution mass spectrometric method involves the addition of a known quantity of Tc followed by chemical separation, purification, and measurement of the Tc/ Tc isotopic ratio . An improved technique has been developed for the analysis of Tc in environmental samples. After spiking with Tc the isolated technetium is concentrated onto anion exchange beads. Determination of as little as 1 pg has been achieved through the enhanced ionization efficiency afforded by the resin bead source ... 

In the previous section, the role of solvent extraction was limited to preparing the analyte for subsequent analysis. A large majority of procedures that use solvent extraction in chemical analysis are used in this fashion. However, the extraction itself, or rather the distribution ratio characterizing it, may provide an appropriate measured signal for analysis. Examples of this use of solvent extraction are found in spectroscopy, isotope dilution radiometry, and ion-selective electrodes using liquid membranes. In the latter case, electrochemical determinations are possible by controlling the local concentration of specific ions in a solution by extraction. 

Flow-injection sample introduction has been successfully applied in the analysis of standard reference materials and in the measurement of accurate and precise isotope ratios, and, hence, isotope dilution analysis. The rapid sample throughput possible with FI should allow a four-fold increase in the sampling rate compared with conventional nebufization techniques. Also, the amount of sample consumed per analytical measurement by FI is considerably less than continuous nebufization. TTiese considerations are of particular importance for the cost-effective operation of ICP-MS. 

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