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An in-depth evaluation of accuracy and precision in Hg isotopic analysis via pneumatic nebulization and cold vapor generation multi-collector ICP-mass spectrometry

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Abstract
Mercury (Hg) isotopic analysis via multi-collector inductively coupled plasma (ICP)-mass spectrometry (MC-ICP-MS) can provide relevant biogeochemical information by revealing sources, pathways, and sinks of this highly toxic metal. In this work, the capabilities and limitations of two different sample introduction systems, based on pneumatic nebulization (PN) and cold vapor generation (CVG), respectively, were evaluated in the context of Hg isotopic analysis via MC-ICP-MS. The effect of (i) instrument settings and acquisition parameters, (ii) concentration of analyte element (Hg), and internal standard (Tl)-used for mass discrimination correction purposes-and (iii) different mass bias correction approaches on the accuracy and precision of Hg isotope ratio results was evaluated. The extent and stability of mass bias were assessed in a long-term study (18 months, n = 250), demonstrating a precision a parts per thousand currency sign0.006 % relative standard deviation (RSD). CVG-MC-ICP-MS showed an approximately 20-fold enhancement in Hg signal intensity compared with PN-MC-ICP-MS. For CVG-MC-ICP-MS, the mass bias induced by instrumental mass discrimination was accurately corrected for by using either external correction in a sample-standard bracketing approach (SSB) or double correction, consisting of the use of Tl as internal standard in a revised version of the Russell law (Baxter approach), followed by SSB. Concomitant matrix elements did not affect CVG-ICP-MS results. Neither with PN, nor with CVG, any evidence for mass-independent discrimination effects in the instrument was observed within the experimental precision obtained. CVG-MC-ICP-MS was finally used for Hg isotopic analysis of reference materials (RMs) of relevant environmental origin. The isotopic composition of Hg in RMs of marine biological origin testified of mass-independent fractionation that affected the odd-numbered Hg isotopes. While older RMs were used for validation purposes, novel Hg isotopic data are provided for the latest generations of some biological RMs.
Keywords
Mass spectrometry, ICP-MS, DISCRIMINATION, METHYLMERCURY, CONTAMINATION, MATRIX, Biological samples, Metals, Heavy metals, Reference materials, Geochemistry, Geology, RATIO MEASUREMENTS, MERCURY ISOTOPES, BIAS CORRECTION, MULTICOLLECTOR ICPMS, MS, FRACTIONATION

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MLA
Rua Ibarz, Ana Maria, et al. “An In-Depth Evaluation of Accuracy and Precision in Hg Isotopic Analysis via Pneumatic Nebulization and Cold Vapor Generation Multi-Collector ICP-Mass Spectrometry.” ANALYTICAL AND BIOANALYTICAL CHEMISTRY, vol. 408, no. 2, 2016, pp. 417–29, doi:10.1007/s00216-015-9131-2.
APA
Rua Ibarz, A. M., Bolea Fernandez, E., & Vanhaecke, F. (2016). An in-depth evaluation of accuracy and precision in Hg isotopic analysis via pneumatic nebulization and cold vapor generation multi-collector ICP-mass spectrometry. ANALYTICAL AND BIOANALYTICAL CHEMISTRY, 408(2), 417–429. https://doi.org/10.1007/s00216-015-9131-2
Chicago author-date
Rua Ibarz, Ana Maria, Eduardo Bolea Fernandez, and Frank Vanhaecke. 2016. “An In-Depth Evaluation of Accuracy and Precision in Hg Isotopic Analysis via Pneumatic Nebulization and Cold Vapor Generation Multi-Collector ICP-Mass Spectrometry.” ANALYTICAL AND BIOANALYTICAL CHEMISTRY 408 (2): 417–29. https://doi.org/10.1007/s00216-015-9131-2.
Chicago author-date (all authors)
Rua Ibarz, Ana Maria, Eduardo Bolea Fernandez, and Frank Vanhaecke. 2016. “An In-Depth Evaluation of Accuracy and Precision in Hg Isotopic Analysis via Pneumatic Nebulization and Cold Vapor Generation Multi-Collector ICP-Mass Spectrometry.” ANALYTICAL AND BIOANALYTICAL CHEMISTRY 408 (2): 417–429. doi:10.1007/s00216-015-9131-2.
Vancouver
1.
Rua Ibarz AM, Bolea Fernandez E, Vanhaecke F. An in-depth evaluation of accuracy and precision in Hg isotopic analysis via pneumatic nebulization and cold vapor generation multi-collector ICP-mass spectrometry. ANALYTICAL AND BIOANALYTICAL CHEMISTRY. 2016;408(2):417–29.
IEEE
[1]
A. M. Rua Ibarz, E. Bolea Fernandez, and F. Vanhaecke, “An in-depth evaluation of accuracy and precision in Hg isotopic analysis via pneumatic nebulization and cold vapor generation multi-collector ICP-mass spectrometry,” ANALYTICAL AND BIOANALYTICAL CHEMISTRY, vol. 408, no. 2, pp. 417–429, 2016.
@article{7171441,
  abstract     = {Mercury (Hg) isotopic analysis via multi-collector inductively coupled plasma (ICP)-mass spectrometry (MC-ICP-MS) can provide relevant biogeochemical information by revealing sources, pathways, and sinks of this highly toxic metal. In this work, the capabilities and limitations of two different sample introduction systems, based on pneumatic nebulization (PN) and cold vapor generation (CVG), respectively, were evaluated in the context of Hg isotopic analysis via MC-ICP-MS. The effect of (i) instrument settings and acquisition parameters, (ii) concentration of analyte element (Hg), and internal standard (Tl)-used for mass discrimination correction purposes-and (iii) different mass bias correction approaches on the accuracy and precision of Hg isotope ratio results was evaluated. The extent and stability of mass bias were assessed in a long-term study (18 months, n = 250), demonstrating a precision a parts per thousand currency sign0.006 % relative standard deviation (RSD). CVG-MC-ICP-MS showed an approximately 20-fold enhancement in Hg signal intensity compared with PN-MC-ICP-MS. For CVG-MC-ICP-MS, the mass bias induced by instrumental mass discrimination was accurately corrected for by using either external correction in a sample-standard bracketing approach (SSB) or double correction, consisting of the use of Tl as internal standard in a revised version of the Russell law (Baxter approach), followed by SSB. Concomitant matrix elements did not affect CVG-ICP-MS results. Neither with PN, nor with CVG, any evidence for mass-independent discrimination effects in the instrument was observed within the experimental precision obtained. CVG-MC-ICP-MS was finally used for Hg isotopic analysis of reference materials (RMs) of relevant environmental origin. The isotopic composition of Hg in RMs of marine biological origin testified of mass-independent fractionation that affected the odd-numbered Hg isotopes. While older RMs were used for validation purposes, novel Hg isotopic data are provided for the latest generations of some biological RMs.},
  author       = {Rua Ibarz, Ana Maria and Bolea Fernandez, Eduardo and Vanhaecke, Frank},
  issn         = {1618-2642},
  journal      = {ANALYTICAL AND BIOANALYTICAL CHEMISTRY},
  keywords     = {Mass spectrometry,ICP-MS,DISCRIMINATION,METHYLMERCURY,CONTAMINATION,MATRIX,Biological samples,Metals,Heavy metals,Reference materials,Geochemistry,Geology,RATIO MEASUREMENTS,MERCURY ISOTOPES,BIAS CORRECTION,MULTICOLLECTOR ICPMS,MS,FRACTIONATION},
  language     = {eng},
  number       = {2},
  pages        = {417--429},
  title        = {An in-depth evaluation of accuracy and precision in Hg isotopic analysis via pneumatic nebulization and cold vapor generation multi-collector ICP-mass spectrometry},
  url          = {http://dx.doi.org/10.1007/s00216-015-9131-2},
  volume       = {408},
  year         = {2016},
}

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