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Inductively coupled plasma mass spectrometry

Nature Reviews Methods Primers volume 3, Article number: 52 (2023) Cite this article

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Abstract

Inductively coupled plasma mass spectrometry (ICP-MS) combines plasma chemistry, which produces singly charged elemental ions, with mass spectrometric detection. Unlike other mass spectrometry ionization sources, the ICP can efficiently handle liquid, solid and gaseous samples. Nuclides of metals, metalloids and some non-metals — such as sulfur, phosphorus and halogens — can be ionized, with an ionization degree that depends on the intrinsic properties of the element and sample matrix. As a stand-alone technique, ICP-MS excels in (ultra-)trace multi-elemental analysis and isotopic analysis. Combined with chromatographic separations, molecules are assessed as elemental species, whereas laser ablation-ICP-MS enables direct sampling from solid surfaces, either in the imaging modality or for bulk analysis. Scanning-type mass analysers, such as quadrupole-based mass spectrometers and sector field mass spectrometers, dominate the field. Time-of-flight ICP mass spectrometers are considered the go-to instruments for multi-elemental analysis of microscale and nanoscale particles and single cells as discrete entities in a time-resolved manner. This Primer covers the major analytical applications of ICP-MS — multi-element, single-particle, single-cell, laser ablation, speciation and isotopic analysis — and outlines the underlying measurement strategies, challenges and example applications.

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Fig. 1: Types of ICP mass spectrometers.
Fig. 2: Calibration strategies and limits of detection for ICP-MS analysis.
Fig. 3: Analytical variants of ICP-MS analysis.
Fig. 4: Applications of ICP-MS across research fields.

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Acknowledgements

T.V.A. thanks the Research Foundation Flanders for support from a postdoctoral research fellowship (FWO.3E0.2022.0048.01). F.V. thanks BOF-UGent for financial support from a GOA grant. E.B.-F. acknowledges financial support from the Ramón y Cajal programme (RYC2021-031093-I) funded by MCIN/AEI/10.13039/501100011033 and the European Union (NextGenerationEU/PRTR).

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Authors and Affiliations

  1. Atomic and Mass Spectrometry Research Unit (A&MS), Department of Chemistry, Ghent University, Ghent, Belgium

    Thibaut Van Acker, Eduardo Bolea-Fernandez & Frank Vanhaecke

  2. Institute of Analytical Chemistry, Faculty of Chemistry, University of Vienna, Vienna, Austria

    Sarah Theiner & Gunda Koellensperger

  3. University of Zaragoza, Aragón Institute of Engineering Research (I3A), Department of Analytical Chemistry, Zaragoza, Spain

    Eduardo Bolea-Fernandez

Authors
  1. Thibaut Van Acker
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  2. Sarah Theiner
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  3. Eduardo Bolea-Fernandez
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  4. Frank Vanhaecke
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  5. Gunda Koellensperger
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Contributions

Introduction (E.B.-F., F.V. and G.K.); Experimentation (T.V.A., S.T., E.B.-F., F.V. and G.K.); Results (T.V.A., S.T., E.B.-F., F.V. and G.K.); Applications (T.V.A., S.T., E.B.-F., F.V. and G.K.); Reproducibility and data deposition (T.V.A., S.T., F.V. and G.K.); Limitations and optimizations (T.V.A.); Outlook (T.V.A.); Overview of the Primer (all authors).

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Correspondence to Frank Vanhaecke or Gunda Koellensperger.

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Glossary

Dwell times

Periods of time an instrument collects signals for one or more points on a peak.

Faraday cup detectors

Metal hollow collectors, open at one end and closed at the other, used to collect beams of charged particles (ions) in vacuum. The electric current measured is used to determine the total number of ions collected during a specific time period.

Laser ablation

The process of removing material from a solid or liquid surface upon irradiation with a highly energetic laser beam.

Limit of detection

The lowest analyte concentration or quantity that can be detected in a matrix with reasonable certainty (3s.d. criterion).

Limit of quantification

The lowest analyte concentration or quantity that can be quantified in a matrix with reasonable certainty (10s.d. criterion).

M+ atomic ions

Singly positively charged metal ions that are created in the inductively coupled plasma and analysed via the mass analyser.

Mass discrimination

The bias between the experimental and true isotope ratio obtained via inductively coupled plasma mass spectrometry caused by differences in ion extraction, transmission and detection efficiency as a function of the mass-to-charge ratio.

Multi-collector ICP-MS instrument

A type of double-focusing sector field inductively coupled plasma (ICP) mass spectrometer in Nier–Johnson geometry with multiple detectors enabling high-precision isotopic analysis.

Quadrupole

A type of mass spectrometer that separates ions as a function of their mass-to-charge ratio (m/z) by transmitting ions with a m/z within a narrow range (1 amu). Ions with a desired m/z follow a stable path under the effect of a static and high-frequency electric field. Ions with a different m/z follow an unstable path and are rejected from the ion beam.

Scanning-type instruments

Inductively coupled plasma mass spectrometers that scan each nuclide sequentially.

Sector field-type instruments

Mass spectrometers comprising a static electric and magnetic sector that separates the ions in space as a function of their mass-to-charge ratio.

Supersonic expansion

Adiabatic gas expansion upon transition from a high-pressure to low-pressure region via a small orifice.

Tandem mass spectrometry

A method using a mass spectrometer equipped with two quadrupole mass filters and a collision/reaction cell in between that provides enhanced capabilities to overcome spectral overlap via chemical resolution.

Time of flight

A method using a mass spectrometer that separates ions in time in a field-free flight tube as a function of their mass-to-charge ratio. Ion packages are accelerated to the same kinetic energy and subsequently introduced in the flight tube. Lighter ions travel faster than heavier ions and arrive at the detector faster.

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Van Acker, T., Theiner, S., Bolea-Fernandez, E. et al. Inductively coupled plasma mass spectrometry. Nat Rev Methods Primers 3, 52 (2023). https://doi.org/10.1038/s43586-023-00235-w

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