Isotope ratios internal

Roehl, R., Gomez,]., and Woodhouse, L. R. (1995). Correction of mass bias drift in inductively coupled plasma mass spectrometry measurements of zinc isotope ratios using gallium as an isotope ratio internal standard./. Ana/. Xt. Spectrom. 10(1), 15. 

Because variations in accurate isotope ratio measurements typically concern only a few parts per 1000 by mass and there are no universal absolute ratios, it is necessary to define some standards. For this purpose, samples of standard substances are produced and made available at two major centers IAEA (International Atomic Energy Authority, U.K.) and NIST (National Institute for Standards and Technology, U.S.). Standards from other sources are also available. These primary standards can be used as such, or alternative standards can be employed if the primary ones are not available. However, any alternative standards need to be related accurately to the primary ones (see formulae below). For example, the material PDB (PeeDee belemnite), used particularly as a standard for the ratio of isotopes, is no longer readily available, and a new standard, VPDB,... 

Differences in measured isotope ratios (R) can be compared for two substances by using a new ratio a. The two substances may constitute part of a series of measurements on a sample, which are to be internally compared, or they may constitute results from a series that is compared with an external value from a standard substance. 

Two further expressions are used in discussions on isotope ratios. These are the atom% and the atom% excess, which are defined in Figure 48.6 and are related to abundance ratios R. It has been recommended that these definitions and some similar ones should be used routinely so as to conform with the system of international units (SI). While these proposals will almost certainly be accepted by mass spectrometrists, their adoption will still leave important data in the present format. Therefore, in this chapter, the current widely used methods for comparison of isotope ratios are fully described. The recommended Sl-compatible units such as atom% excess are introduced where necessary. 

All values of the IRMM Isotopic Reference Materials are traceable to the SI (the international system of base quantities and base units). Isotopic measurement results corrected by means of these Isotope Ratio Reference Materials have reduced (ISO/BIPM) uncertainties. Isotopic measruements carried out against these Spike Reference Materials are traceable to the SI, if carried out properly. Further details are available from IRMM website see Chapter 8. 

White, J. W. (1992). Internal standard stable carbon isotope ratio method for determination of C-4 plant sugars in honey Collaborative trial study, and evaluation of improved protein preparation procedure. J. Assoc. Ojfic. Anal. Chem. 75,543-548. 

Residues of isoxaflutole, RPA 202248 and RPA 203328 are extracted from surface water or groundwater on to an RP-102 resin solid-phase extraction (SPE) cartridge, then eluted with an acetonitrile-methanol solvent mixture. Residues are determined by liquid chromatography/tandem mass spectrometry (LC/MS/MS) on a Cg column. Quantitation of results is based on a comparison of the ratio of analyte response to isotopically labeled internal standard response versus analyte response to internal standard response for calibration standards. 

For precise measurement of isotopic composition by mass spectrometry, it is also common to use either a natural, known isotopic ratio to correct for instrumental mass fractionation (e g., internal normalization) or to add a tracer for this purpose. For example for natural uranium samples, one can use the natural U/ U of 137.88 to correct for fractionation. Alternatively, one can use an added double spike of ratio -unity... 

Accuracy for all thorium measurements by TIMS is limited by the absence of an appropriate normalization isotope ratio for internal correction of instrumental mass fractionation. However, external mass fractionation correction factors may be obtained via analysis of suitable thorium standards, such as the UC-Santa Cruz and IRMM standards (Raptis et al. 1998) for °Th/ Th, and these corrections are usually small but significant (< few %o/amu). For very high precision analysis, the inability to perform an internal mass fractionation correction is probably the major limitation of all of the methods for thorium isotope analysis discussed above. For this reason, MC-ICPMS techniques where various methods for external mass fractionation correction are available, provide improved accuracy and precision for Th isotope determinations (Luo et al. 1997 Pietruszka et al. 2002). 

However, thorium has only two naturally occurring long-lived isotopes, and all Th measurements by TIMS are limited by the absence of a well-constrained isotope ratio that can be used for internal normalization purposes to correct for instrumental mass fractionation. In this regard, one of the most important advantages of MC-ICPMS over MC-TIMS is the ability to admix two elements with overlapping mass ranges and use the... 

Using internal or within-run TIMS/ICP-MS isotope-ratio errors without evaluating the magnitude of the external (run to run) error ... 

Both absolute quantitation and relative quantitation of species in mixtures is of interest in some circumstances. Quantitation in a 5-minute analysis can be achieved by addition of an internal standard, ideally the target microorganism grown in special media to incorporate heavy isotopes92-95 and determination of the relative peak heights of pairs of proteins from the analyte and the standard. Isotope-labeled proteins or peptides, selected to match proteins or peptides characteristic of target microorganisms, can also serve as internal standards for isotope ratio measurement. The addition of unmatched proteins or peptides is less reliable for either ESI or MALDI measurements because of unpredictable suppression in the variable mixture. 

The production of 13CC>2 from [13C]-deca-BDE degradation was analyzed using the technique of gas chromatography coupled to mass spectrometer for isotope ratio (GC-EMRI). This technique measures the isotopic ratio 13C/12C of CO2 in the gas phase with respect to an international standard V-PDB (Vienna Pee Dee Belem-nite). This isotopic ratio is reported in 8 notation relative to an international standard per mil (%o) ... 

Figure 14.1 Stylised diagram illustrating the inputs and outputs that determine analyte isotope ratios. The analyte can be a compound, a position in a compound, or a bulk mixture. Inputs 1 and 2 and outputs 3 and 4 are internal to the system (e.g. an organism). Inputs 1A, 1B, 2A, and 2B are external contributors to inputs 1 and 2, respectively. The isotope ratios of inputs 1 and 2 depend on relative flux (e.g. diet) from the outside. axare fractionation factors between precursors and products. The isotope ratio of the analyte (RAnalyte) is a composite of the relative contributions of inputs I and 2 and degradation to outputs 3 and 4. Adapted from Brenna (2001)...

Flegal and Stukas [406] described the special sampling and processing techniques necessary for the prevention of lead contamination of seawater samples, prior to stable lead isotopic ratio measurements by thermal ionisation mass spectrometry. Techniques are also required to compensate for the absence of an internal standard and the presence of refractory organic compounds. The precision of the analyses is 0.1 -0.4% and a detection limit of 0.02 ng/kg allows the tracing of lead inputs and biogeochemical cycles. 

Natural abundance data are nearly always reported as delta values, 5 in units of per mil ( mil = 1000), written %o. This is a relative measurement made against a laboratory s own reference material, a working standard , calibrated against an international standard. Delta values are calculated from measured isotope ratio as ... 

Stichler, W. 1995. Interlaboratory comparison of new materials for carbon and oxygen isotope ratio measurements. Pp. 67-74 in Reference and Intercomparison Materials for Stable Isotopes of Light Elements, Vienna International Atomic Energy Agency, LAEA-TECDOC-825. 

In principle, the three isotope method may be widely applied to new isotope systems such as Mg, Ca, Cr, Fe, Zn, Se, and Mo. Unlike isotopic analysis of purified oxygen, however, isotopic analysis of metals that have been separated from complex matrices commonly involves measurement of several isotopic ratios to monitor potential isobars, evaluate the internal consistency of the data through comparison with mass-dependent fractionation relations (e.g., Eqn. 8 above), or use in double-spike corrections for instrumental mass bias (Chapter 4 Albarede and Beard 2004). For experimental data that reflect partial isotopic exchange, their isotopic compositions will not lie along a mass-dependent fractionation line, but will instead lie along a line at high angle to a mass-dependent relation (Fig. 10), which will limit the use of multiple isotopic ratios for isobar corrections, data quality checks, and double-spike corrections. 

The accuracy with which absolute isotope abundances can be measured is substantially poorer than the precision with which relative differences in isotope abundances between two samples can be determined. Nevertheless, the determination of absolute isotope ratios is very important, because these numbers form the basis for the calculation of the relative differences, the 5-values. Table 1.6 sununarizes absolute isotope ratios of primary standards used by the international stable isotope community. 

Table 1.6 Absolute isotope ratios of international standards. (After Hayes 1983)...

By using internal correction, isotopic ratios can be obtained at a very... 

The carbonate shells of foraminifera preserve this isotope ratio when they are incorporated into sediments, and mass spectrometry can be used to measure the ratio. So the oaygen isotope record of deep-sea sediments tells us about past changes in the extent of the ice sheets. In an international initiative in the early 1970s called... 

Isotope ratios are given as deviations, in relation to a defined primary standard (zero point). The polyethylene foils CH 7 and NBS 22-oil are commercially available secondary standards, certificated and managed by the International Atomic Energy Agency. However, GC-lRMS systems cannot be calibrated without the aid of alternative peripheries like an elemental analyser (EA) or a dual inlet, owing to the lack of commonly accepted reference materials applicable in GC-IRMS techniques (Fig. 17.11). 

If an internal isochron cannot be generated, a model age can be determined from the measured 207pb /206Pb of the sample and the assumed initial lead isotopic ratios. For studies of the early solar system, this initial lead composition is assumed to be that measured in troilite (FeS) from the Canyon Diablo meteorite. Troilite is a uranium-free mineral and its host meteorite formed very early in the history of the solar system. Because the U/Pb ratio of the solar system is low, the lead incorporated into the troilite should not have evolved significantly from the initial composition in the solar system. 

Three types of isochron diagrams are used in discussions of short-lived radionuclides. An internal isochron is one based entirely on measurements from the object being dated. By measuring several minerals with different parent/daughter elemental ratios, one can obtain an array of data that gives both the initial ratio (NR/Ns)a and the initial isotopic ratio of the daughter element Figure 8.25 shows an example of an internal isochron for an... 

Volkening, J., Koppe, M., and Heumann, K. G. (1991) Tungsten isotope ratio determinations by negative thermal ionization mass spectrometry. International Journal of Mass Spectrometry and Ion Processes, 107, 361-368. 

Following extractive deproteinization of the plasma, the amino acids (and their stable-isotope-labeled internal standards) are separated by HPLC and introduced into the mass spectrometer. Electrospray ionization results in the formation of electrically charged molecules, which are separated on the basis of their mass/charge (m/z) ratio in the first quadrupole. Following fragmentation in the collision cell, the characteristic fragment for each amino acid is selected in the second quadrupole. This process is named multiple reaction monitoring. 

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