Statistical precision of the intensities retrieved from constrained fitting of overlapping peaks in high-resolution mass spectra

Cubison, M. J.; Jimenez, José L.

doi:10.5194/amt-8-2333-2015

Cited by 63 publications

(93 citation statements)

References 33 publications

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“…For all ions, the limiting case of very high ion signals was simulated. The reader is referred to Cubison and Jimenez (2015) for a discussion of the effects of ion-counting uncertainties on fitting imprecision. Each probability distribution in Fig.…”

Section: Imprecision For Well-resolved Peaks With Known µ-Prediction mentioning

confidence: 99%

“…where σ h / h is approximately constant (on the order of a few percent) for a well-resolved peak within a given data set and may become much larger as peak overlap becomes important (Cubison and Jimenez, 2015). σ A is considered independent of the Poisson counting uncertainties σ p discussed in Sects.…”

Section: Overall Peak-integration Imprecision: Example For a Well-resmentioning

confidence: 99%

“…As these two ions are of similar m/z, but are nonetheless well resolved with a separation of ∼ 7 standard deviations (cf. Cubison and Jimenez, 2015), it was hypothesized that their µ-prediction biases may have Table 3. been approximately equal. Such approximate equality would have allowed µ-prediction biases to be fitted as a single free parameter during fitting of Eq.…”

Section: Estimation Of µ-Prediction (M/z) Errors From Single-peak Fitmentioning

confidence: 99%

“…They provided a parameterization for imprecision estimation in such a system while considering the lowest-achievable m/z-calibration uncertainty and, relative to this study, a large number of data points per peak. The present manuscript approaches the problem from the opposite direction to Cubison and Jimenez (2015), beginning from an empirical analysis and ending with a method for estimation which is not limited to just two peaks. The two approaches are compared in further detail in Sect.…”

Section: Introductionmentioning

confidence: 99%

“…2). Cubison and Jimenez (2015) used a PIKA-like approach to perform an extensive study of a two-peak system while assuming an ideal mass spectrometer. They provided a parameterization for imprecision estimation in such a system while considering the lowest-achievable m/z-calibration uncertainty and, relative to this study, a large number of data points per peak.…”

Section: Introductionmentioning

confidence: 99%

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Peak-fitting and integration imprecision in the Aerodyne aerosol mass spectrometer: effects of mass accuracy on location-constrained fits

et al. 2015

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Abstract. The errors inherent in the fitting and integration of the pseudo-Gaussian ion peaks in Aerodyne high-resolution aerosol mass spectrometers (HR-AMSs) have not been previously addressed as a source of imprecision for these or similar instruments. This manuscript evaluates the significance of this imprecision and proposes a method for their estimation in routine data analysis.In the first part of this work, it is shown that peakintegration errors are expected to scale linearly with peak height for the constrained-peak-shape fits performed in the HR-AMS. An empirical analysis is undertaken to investigate the most complex source of peak-integration imprecision: the imprecision in fitted peak height, σ h . It is shown that the major contributors to σ h are the imprecision and bias inherent in the m/z calibration, both of which may arise due to statistical and physical non-idealities of the instrument. A quantitative estimation of these m/z-calibration imprecisions and biases show that they may vary from ion to ion, even for ions of similar m/z.In the second part of this work, the empirical analysis is used to constrain a Monte Carlo approach for the estimation of σ h and thus the peak-integration imprecision. The estimated σ h for selected well-separated peaks (for which m/z-calibration imprecision and bias could be quantitatively estimated) scaled linearly with peak height as expected (i.e. as n 1 ). In combination with the imprecision in peak-width quantification (which may be easily and directly estimated during quantification), peak-fitting imprecisions therefore dominate counting imprecisions (which scale as n 0.5 ) at high signals. The previous HR-AMS uncertainty model therefore underestimates the overall fitting imprecision even for wellresolved peaks. We illustrate the importance of this conclusion by performing positive matrix factorization on a synthetic HR-AMS data set both with and without its inclusion.In the third part of this work, the Monte Carlo approach is extended to the case of an arbitrary number of overlapping peaks. Here, a modification to the empirically constrained approach was needed, because the ion-specific m/z-calibration bias and imprecision can generally only be estimated for well-resolved peaks. The modification is to simply overestimate the m/z-calibration imprecision in all cases. This overestimation results in only a slight overestimate of σ h , while significantly reducing the sensitivity of σ h to the unknown, ion-specific m/z-calibration biases. Thus, with only the meaPublished by Copernicus Publications on behalf of the European Geosciences Union. J. C. Corbin et al.: AMS peak-integration errorssured data and an approximate estimate of the order of magnitude of m/z-calibration biases as input, conservative and unbiased estimates of peak-integration imprecisions may be obtained for each peak in any ensemble of overlapping peaks.

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Section: Imprecision For Well-resolved Peaks With Known µ-Prediction mentioning

confidence: 99%

Section: Overall Peak-integration Imprecision: Example For a Well-resmentioning

confidence: 99%

Section: Estimation Of µ-Prediction (M/z) Errors From Single-peak Fitmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Peak-fitting and integration imprecision in the Aerodyne aerosol mass spectrometer: effects of mass accuracy on location-constrained fits

et al. 2015

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Semi-differential analysis of irreversible voltammetric peaks

Grdeń

2016

J Solid State Electrochem

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Voltammetric peaks obtained by simulation of electrochemical reactions under conditions of linear semi-infinite diffusion with an irreversible electron transfer process are analysed using a semi-differentiation procedure. Obtained semi-derivative peaks, separated or overlapped, are fitted with appropriate mathematical functions. The functions used for data fitting include a function describing symmetrical peaks, proposed by several authors for fitting irreversible semiderivative peaks, and two alternative functions that express asymmetric shape of the irreversible semi-derivative signals. When applied to the overlapped irreversible semi-derivative peaks, the latter two functions allow calculating certain electrochemical parameters with a better accuracy as compared with the function derived for the symmetrical peaks.

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Application of Calorimetric Low-Temperature Detectors for the Investigation of Z-Yield Distributions of Fission Fragments

et al. 2018

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In recent experiments, the new concept of calorimetric lowtemperature detectors (CLTDs) was applied for the first time for the investigation of isotopic yields of fission fragments. Fragments from neutron-induced fission sources were mass-separated by the LOHENGRIN spectrometer at the ILL Grenoble and, after passing silicon nitride membranes used as degraders, detected in a CLTD array. The new detector concept of a thermal detector provides a fundamental advantage over conventional ionization-mediated detectors, in particular for heavier particle masses at low energies. Using fissile targets of 235 U, 239 Pu and 241 Pu, nuclearcharge separation was studied in the mass region 82 ≤ A ≤ 139. For light fragments, the Z resolution matches historically best values with conventional techniques, while for heavier masses substantial improvement was attained. We have gained first LOHENGRIN data on the isotopic yields in the light-mass group of 241 Pu. Towards mass-symmetry, known Z-yield data were supplemented in the range A = 110 to 113 for 241 Pu and 239 Pu. Extended data sets were cumulated for A = 92 and 96 due to a recent request from studies on the reactor anti-neutrino spectrum. Furthermore, considerable progress was achieved to extend isotopic yield measurements up to the heavy-mass region, hardly accessible until now.

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Statistical precision of the intensities retrieved from constrained fitting of overlapping peaks in high-resolution mass spectra

Cited by 63 publications

References 33 publications

Peak-fitting and integration imprecision in the Aerodyne aerosol mass spectrometer: effects of mass accuracy on location-constrained fits

Peak-fitting and integration imprecision in the Aerodyne aerosol mass spectrometer: effects of mass accuracy on location-constrained fits

Semi-differential analysis of irreversible voltammetric peaks

Application of Calorimetric Low-Temperature Detectors for the Investigation of Z-Yield Distributions of Fission Fragments

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