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Title: Fundamental and methodological investigations for the improvement of elemental analysis by inductively coupled plasma mass soectrometry

Abstract

This dissertation describes a variety of studies meant to improve the analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation (LA) ICP-MS. The emission behavior of individual droplets and LA generated particles in an ICP is studied using a high-speed, high frame rate digital camera. Phenomena are observed during the ablation of silicate glass that would cause elemental fractionation during analysis by ICP-MS. Preliminary work for ICP torch developments specifically tailored for the improvement of LA sample introduction are presented. An abnormal scarcity of metal-argon polyatomic ions (MAr{sup +}) is observed during ICP-MS analysis. Evidence shows that MAr{sup +} ions are dissociated by collisions with background gas in a shockwave near the tip of the skimmer cone. Method development towards the improvement of LA-ICP-MS for environmental monitoring is described. A method is developed to trap small particles in a collodion matrix and analyze each particle individually by LA-ICP-MS.

Authors:
 [1]
+ Show Author Affiliations
  1. Ames Lab., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1082957
Report Number(s):
IS-T 3073
DOE Contract Number:
AC02-07CH11358
Resource Type:
Thesis/Dissertation
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ebert, Christopher Hysjulien. Fundamental and methodological investigations for the improvement of elemental analysis by inductively coupled plasma mass soectrometry. United States: N. p., 2012. Web. doi:10.2172/1082957.
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Ebert, Christopher Hysjulien. Fundamental and methodological investigations for the improvement of elemental analysis by inductively coupled plasma mass soectrometry. United States. doi:10.2172/1082957.
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Ebert, Christopher Hysjulien. Sun . "Fundamental and methodological investigations for the improvement of elemental analysis by inductively coupled plasma mass soectrometry". United States. doi:10.2172/1082957. https://www.osti.gov/servlets/purl/1082957.
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@article{osti_1082957,
title = {Fundamental and methodological investigations for the improvement of elemental analysis by inductively coupled plasma mass soectrometry},
author = {Ebert, Christopher Hysjulien},
abstractNote = {This dissertation describes a variety of studies meant to improve the analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation (LA) ICP-MS. The emission behavior of individual droplets and LA generated particles in an ICP is studied using a high-speed, high frame rate digital camera. Phenomena are observed during the ablation of silicate glass that would cause elemental fractionation during analysis by ICP-MS. Preliminary work for ICP torch developments specifically tailored for the improvement of LA sample introduction are presented. An abnormal scarcity of metal-argon polyatomic ions (MAr{sup +}) is observed during ICP-MS analysis. Evidence shows that MAr{sup +} ions are dissociated by collisions with background gas in a shockwave near the tip of the skimmer cone. Method development towards the improvement of LA-ICP-MS for environmental monitoring is described. A method is developed to trap small particles in a collodion matrix and analyze each particle individually by LA-ICP-MS.},
doi = {10.2172/1082957},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2012},
month = {Sun Jan 01 00:00:00 EST 2012}
}
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Thesis/Dissertation:
View Thesis/Dissertation (2.41 MB)
DOI:  10.2172/1082957
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  • Particle size effects and elemental fractionation in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) are investigated with nanosecond and femtosecond laser ablation, differential mobility analysis, and magnetic sector ICP-MS. Laser pulse width was found to have a significant influence on the LA particle size distribution and the elemental composition of the aerosol and thus fractionation. Emission from individual particles from solution nebulization, glass, and a pressed powder pellet are observed with high speed digital photography. The presence of intact particles in an ICP is shown to be a likely source of fractionation. A technique for the online detection ofmore » stimulated elemental release from neural tissue using magnetic sector ICP-MS is described. Detection limits of 1 μg L -1 or better were found for P, Mn, Fe, Cu, and Zn in a 60 μL injection in a physiological saline matrix.« less

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  • The fundamental and practical aspects are described for extracting ions from atmospheric pressure plasma sources into an analytical mass spectrometer. Methodologies and basic concepts of inductively coupled plasma mass spectrometry (ICP-MS) are emphasized in the discussion, including ion source, sampling interface, supersonic expansion, slumming process, ion optics and beam focusing, and vacuum considerations. Some new developments and innovative designs are introduced. The plasma extraction process in ICP-MS was investigated by Langmuir measurements in the region between the skimmer and first ion lens. Electron temperature (T e) is in the range 2000--11000 K and changes with probe position inside an aerosolmore » gas flow. Electron density (n e) is in the range 10 8--10 10 -cm at the skimmer tip and drops abruptly to 10 6--10 8 cm -3 near the skimmer tip and drops abruptly to 10 6--10 8 cm -3 downstream further behind the skimmer. Electron density in the beam leaving the skimmer also depends on water loading and on the presence and mass of matrix elements. Axially resolved distributions of electron number-density and electron temperature were obtained to characterize the ion beam at a variety of plasma operating conditions. The electron density dropped by a factor of 101 along the centerline between the sampler and skimmer cones in the first stage and continued to drop by factors of 10 4--10 5 downstream of skimmer to the entrance of ion lens. The electron density in the beam expansion behind sampler cone exhibited a 1/z 2 intensity fall-off (z is the axial position). An second beam expansion originated from the skimmer entrance, and the beam flow underwent with another 1/z 2 fall-off behind the skimmer. Skimmer interactions play an important role in plasma extraction in the ICP-MS instrument.« less