Isotope ratio mass spectrometry general

The purpose of this paper was to briefly describe fundamentals of isotope ratio mass spectrometry (IRMS), review the analytical systems currently available both for traditional dual-inlet (DI-IRMS) and the newer continuous-flow (CF-IRMS) and describe the specialized instruments that are in general use for isotopic measurements. 

The Faraday cup was widely used in the beginning of mass spectrometry but all the characteristics of this detector mean that it is now generally used in the measurement of highly precise ratios of specific ion species as in isotopic ratio mass spectrometry (IRMS) or in accelerator mass spectrometry (AMS). To obtain a highly accurate ratio in such relative abundance measurements, the intensities of the two stable beams of specific ions are measured simultaneously with two Faraday cups. 

Stable isotope ratio mass spectrometers that interface directly to a gas chromatograph are commercially available. This type of analysis is known variously as gas chromatography-isotope ratio mass spectrometry (GC-IRMS), gas chromatography-combustion isotope ratio mass spectrometry, or compound-specific isotope analysis. The same principle of operation has also been used for more general isotope ratio analyses, where the components of interest are combusted as bulk samples. This type of arrangement, known as continuous flow-isotope ratio mass spectrometry, allows rapid automated analyses of and... 

Isotope ratio mass spectrometry (IR-MS) is used with GC for the high-precision measurement of isotopic ratios of D/H, C/ C, and from organic mixtures. In general, gas chromatography is coupled to isotope ratio mass spectrometry via a combustion furnace [9]. 

The extent to which isotope fractionation is observed for a given element is determined by both the relative mass difference between its isotopes and the extent to which the element participates in physical processes and/or chemical reactions. For the light elements H, C, N, O, and S, variations in their isotopic composition caused by mass-dependent isotope fractionation have been extensively studied using gas source isotope ratio mass spectrometry. For most of the metallic and metalloid elements (except Li and B), the relative mass difference between the isotopes is more limited, such that the variation in isotopic composition thus created is considerably more limited. The high precision with which isotope ratios can be measured nowadays however, not only allows the small isotope fractionations to be revealed, but also quantified. Even for the heaviest naturally occurring element U, variation in its isotopic composition due to the occurrence of isotope fractionation has been demonstrated [13]. As a general rule, elements that can occur in the environment in several oxidation states tend to show more pronounced isotope fractionation. 

The use of carbon isotopes to study DOC is becoming more prevalent due to technological advances in mass spectrometry. DOC generally occurs in natural waters in low concentrations, typically ranging between 0.5 ppm and 10 ppm carbon (Thurman, 1985 see Chapter 5.10). Thus, several liters to tens of liters of water were once necessary to extract enough DOC for conventional dual gas-inlet isotopic analysis. Today, automated total organic carbon analyzers (TOCs) are commercially available, and have been successfully interfaced with continuous flow isotope ratio mass spectrometers (CF-IRMS) for stable isotopic measurements of samples containing ppb concentrations of DOC (e.g., St-Jean, 2003). 

It is seen that also in the general polyisotopic case the ratio of sample and spike amounts can be determined solely from isotope ratio measurements. Isotope dilution mass spectrometry measures the change in the ratio of two isotopes of the element of interest, induced by the addition of a known amount of the same eiement with an artificially altered isotope ratio of the same isotopes to a weighed aliquot of a sample. Since only isotope ratios in the different materials are measured, it follows that sample treatment or recoveries for chemical separations need not be quantitative once isotopic equilibration after spiking has been achieved. Also variability of chemical separation recovery is generally not important. 

Aramendfa,M., Resano, M., Vanhaecke, F. (2010) Isotope ratio determination by laser ablation-single collector-inductively conpled plasma-mass spectrometry. General capabiUties and possibilities for improvement. Journal of Analytical Atomic Spectrometry, 25,390-404. 

This example can be used in reverse to show the usefulness of looking for such isotopes. Suppose there were an unknown sample that had two molecular ion peaks in the ratio of 3 1 that were two mass units apart then it could reasonably be deduced that it was highly likely the unknown contained chlorine. In this case, the isotope ratio has been used to identify a chlorine-containing compound. This use of mass spectrometry is widespread in general analysis of materials, and it... 

As discussed earlier, the production ratio Pgi/P83 cani in general, reliably be obtained from equation (1) and, therefore, the 81Kr-Kr method avoids much of the uncertainty arising from unknown production rates or production ratios. The method derives exposure ages from Kr isotopic ratios as obtained from mass spectrometry and does not require a knowledge of the concentration of spallation Kr, which makes the method inherently more precise. 

Using the three measured ratios, Ca/ Ca, Ca/ " Ca and Ca/ " Ca, three unknowns can be solved for the tracer/sample ratio, the mass discrimination, and the sample Ca/ Ca ratio (see also Johnson and Beard 1999 Heuser et al. 2002). Solution of the equations is done iteratively. It is assumed that the isotopic composition of the Ca- Ca tracer is known perfectly, based on a separate measurement of the pure spike solution. Initially it is also assumed that the sample calcium has a normal Ca isotopic composition (equivalent to the isotope ratios listed in Table 1). The Ca/ Ca ratio of the tracer is determined based on the results of the mass spectrometry on the tracer-sample mixture, by calculating the effect of removing the sample Ca. This yields a Ca/ Ca ratio for the tracer, which is in general different from that previously determined for the tracer. This difference is attributed to mass discrimination in the spectrometer ion source and is used to calculate a first approximation to the parameter p which describes the instrumental mass discrimination (see below). The first-approximation p is used to correct the measured isotope ratios for mass discrimination, and then a first-approximation tracer/sample ratio and a first-approximation sample CeJ Ca... 

Mass spectrometry is based upon the separation of charged ionic species by their mass-to-charge ratio, m/z. Within the general chemical context however, we are not used to taking into concern the isotopes of the elemental species involved in a reaction. The molecular mass of tribromomethane, CHBrs, would therefore be calculated to 252.73 g mol using the relative atomic masses of the elements as listed in most periodic tables. In mass spectrometry we have to leave this custom behind. Because the mass spectrometer does not separate by elements but by isotopic mass, there is no signal at m/z 252.73 in the mass spectmm of tribromomethane. Instead, major peaks are present at m/z 250, 252, 254 and 256 accompanied by some minor others. 

These same six samples were also analyszed by inductively coupled plasma-mass spectrometry (ICP-MS) to determine if the same element patterns detected in the EMPA analysis could be observed with a less labor intensive method. ICP-MS works in a similar manner as TIMS, expect the sample is dissolved and injected into a plasma flame in order to atomize and ionize the sample. Isotopes ratios can be determined in this manner, but generally the precision is less than with TIMS. 

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