The ideal mass analyzer: Fact or fiction?

Brunnée, Curt

doi:10.1016/0168-1176(87)80030-7

Cited by 97 publications

(26 citation statements)

References 194 publications

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“…The MS generally comprises an ion source, a mass analyzer, a detector (Faraday cup and/or multiplier), a detector amplifier (electrometer or ion-counting equipment), and a data recording system [82]. Mass bias can, in principle, occur at each of these stages.…”

Section: Mass Biasmentioning

confidence: 99%

High-temperature mass spectrometry: Instrumental techniques, ionization cross-sections, pressure measurements, and thermodynamic data (IUPAC Technical Report)

Drowart

Chatillon

Hastie

et al. 2005

Pure and Applied Chemistry

234

184

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An assessment of high-temperature mass spectrometry and of sources of inaccuracy is made. Experimental, calculated, and estimated cross-sections for ionization of atoms and inorganic molecules typically present in high-temperature vapors are summarized. Experimental cross-sections determined for some 56 atoms are generally close to theoretically calculated values, especially when excitation–autoionization is taken into account. Absolute or relative cross-sections for formation of parent ions were measured for ca. 100 molecules. These include homonuclear diatomic and polyatomic molecules, oxides, chalcogenides, halides, and hydroxides. Additivity of atomic cross-sections supplemented by empirical corrections provides fair estimates of molecular cross-sections. Causes of uncertainty are differences in interatomic distances and in shapes of potential energy curves (surfaces) of neutral molecules and of molecular ions and tendency toward dissociative ionization in certain types of molecules. Various mass spectrometric procedures are described that render the accuracy of measured thermodynamic properties of materials largely independent of ionization cross-sections. This accuracy is comparable with that of other techniques applicable under the conditions of interest, but often only the mass spectrometric procedure is appropriate at high temperatures.

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Section: Mass Biasmentioning

confidence: 99%

High-temperature mass spectrometry: Instrumental techniques, ionization cross-sections, pressure measurements, and thermodynamic data (IUPAC Technical Report)

Drowart

Chatillon

Hastie

et al. 2005

Pure and Applied Chemistry

234

184

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“…Aston alone detected 202 isotopes so that he become known as the father of isotope mass spectrometry. 1,2 Isotope ratio measurements are important in a number of different application fields (see Fig. 1): for the determination of stable isotopes and long-lived radionuclides by investigations of isotope variation in nature; in environmental monitoring; in geochronology; for quality assurance of fuel material; and for radioactive waste control.…”

Section: Introductionmentioning

confidence: 99%

State-of-the-art and progress in precise and accurate isotope ratio measurements by ICP-MS and LA-ICP-MS : Plenary Lecture

Becker

2002

J. Anal. At. Spectrom.

147

123

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The capability to determine isotope abundances is a main feature of mass spectrometry. The precise and accurate determination of isotope ratios is required for different application fields, such as: isotope ratio measurements of stable isotopes in nature, especially for the investigation of isotope variation in nature or age dating; determining isotope ratios of radiogenic elements in the nuclear industry; quality assurance of fuel material for reprocessing plants, nuclear material accounting and radioactive waste control; and tracer experiments using highly enriched stable isotopes or long-lived radionuclides in biological or medical studies. Inductively coupled plasma mass spectrometry and laser ablation ICP-MS (LA-ICP-MS) provides excellent sensitivity, precision and good accuracy for isotope ratio measurements with practically no restriction with respect to the ionization potential of the element investigated. Therefore both ICP-MS and LA-ICP-MS are increasingly replacing thermal ionization mass spectrometry (TIMS), which has been used as the dominant analytical technique for precise isotope ratio measurements for many decades. In the last few years instrumental progress for improving figures of merit in isotope ratio measurements in ICP-MS and LA-ICP-MS with a single ion detector has been achieved by the introduction of the collision cell interface, in order to dissociate disturbing argon-based molecular ions, to reduce the kinetic energy of ions and neutralize the disturbing argon ions of the plasma gas (Ar 1 ). The application of the collision cell in ICP-MS results in higher ion transmission, improved sensitivity and better precision of isotope ratio measurements compared to ICP-MS without the collision cell. The most important instrumental improvement for isotope analysis by sector field ICP-MS was the application of a multiple ion collector device (MC-ICP-MS) (developed about 10 years ago) in order to obtain better precision of isotope ratio measurements of up to 0.002%, RSD.

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“…Isotope ratio measurements require fast scanning across masses of interest and thus, since the magnetic field cannot be changed quickly enough, it is kept constant while varying the acceleration voltage and the voltage applied to the electrostatic filter instead ("E-scan" mode). However, according to the Liouville's theorem [18], the reduction of the acceleration voltage (to increase the monitored mass) leads to an expansion of the ion beam size. This effect might, in turn, lead to a reduction of the ion transmission rate and the apparition of a mass discrimination effect in favor of the lightest ions that is specific to the Element2 [17,19].…”

Section: Icp-ms Isotope Ratio Measurements and Correction For Mass DImentioning

confidence: 99%

Low uncertainty reverse isotope dilution ICP-MS applied to certifying an isotopically enriched Cd candidate reference material: A case study

Trešl

Quétel

2005

J. Am. Soc. Mass Spectrom.

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An analytical method is presented based on reverse isotope dilution single detector inductively coupled plasma magnetic sector mass spectrometry (ID-ICP-SMS) and applied to the specific case of the certification of a 111 Cd enriched candidate Cd spike calibration material (nominal mass fraction 10 mg kg Ϫ1 in 5% HNO 3 solution). Uncertainty propagation was used as a tool for both determining the analytical approach and validating it. The robustness of close to "exact matching" reverse IDMS to correction of measured isotope intensities for multiplicative (mass discrimination) and (semi)additive effects (dead time, instrumental background, and isobaric interference) is discussed. The very low experimental relative standard deviation of the mean (0.08%) of eight replicate determinations indicated that all significant sources of uncertainty had probably been taken into account for the estimation of the final combined uncertainty statement (U c ϭ 0.17%, k ϭ 1). IRMM-621 was used as comparator. Uncertainties on IUPAC isotopic abundances of 111 Cd and 112 Cd, for the natural Cd solution involved between the two enriched materials, formed nearly 60% of U c . The repeatability of the isotope ratio measurements contributed less than 10%. Correction for procedural blank necessitated somewhat unusual calculations (potential contamination of an enriched material with natural Cd). The procedure also involved a quadrupole based ICP-MS judged to be appropriate for the characterization of the isotopic composition. For comparison purposes, direct IDMS results are simulated using identical experimental input data. Finally, a significant background signal in the 106 -116 mass region, observed only with the magnetic sector instrument, was attributed to argon based isobaric interferences. I sotope dilution mass spectrometry (IDMS) was recognized as having the potential to be a primary ratio method of measurement [1]. When applied correctly, it can be of "practical use in establishing traceability to the SI unit system" [2] and accurate results with sufficiently small uncertainties can be achieved. The advantages and disadvantages of the IDMS method have been discussed [3,4] since its invention nearly 50 years ago. One of the significant advantages over other approaches is that the analyte recovery does not have to be quantitative, providing that isotopic equilibration has been achieved between all of the analyte and added spike material. Commonly there is the reverse IDMS (or two-way IDMS) whereby the spike material is calibrated against a well-characterized assay material. The alternative is direct IDMS (or one-way IDMS) which is faster but requires a spike material already reliably certified "once for all" for the element content and isotopic composition. Direct IDMS has the potential to lead to relative combined uncertainties on the amount content determination of ϳ1% (k ϭ 2) even with quadrupole ICP-MS (inductively coupled plasma mass spectrometry) instrumentation [5]. In many cases this is entirely fit for the purpose and a bett...

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The ideal mass analyzer: Fact or fiction?

Cited by 97 publications

References 194 publications

High-temperature mass spectrometry: Instrumental techniques, ionization cross-sections, pressure measurements, and thermodynamic data (IUPAC Technical Report)

High-temperature mass spectrometry: Instrumental techniques, ionization cross-sections, pressure measurements, and thermodynamic data (IUPAC Technical Report)

State-of-the-art and progress in precise and accurate isotope ratio measurements by ICP-MS and LA-ICP-MS : Plenary Lecture

Low uncertainty reverse isotope dilution ICP-MS applied to certifying an isotopically enriched Cd candidate reference material: A case study

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