CHAPTER

Introduction

Inductively coupled plasma—mass spectrometry (referred to in this book as

ICP-MS), a technique for the elemental chemical characterization of virtu-
ally any material, evolved during the late 1990s into a mature analytical
procedure. This technique has a variety of characteristics that make it
uniquely suited for the solution of chemical analysis problems in many
applications. These characteristics include the ability to precisely identify
and measure (quantitate) all elements in the periodic table including the
often difficult to analyze refractory elements. In addition to this wide scope
of elemental analysis, the technique has the inherent capability to perform
these determinations in a multielement analysis mode, efficiently providing
comprehensive elemental compositional characterization. The technique
also has the powerful ability to measure individual isotopes of the analyte
elements, providing a capability that has many useful applications ranging
from isotope dilution quantitation to stable isotope tracer studies.
Another equally important characteristic is the ability to detect and mea-
sure concentrations of analyte elements at very low levels. State-of-the-art
2 Chapter 1 Introduction

instrumentation is currently capable of quantitatively measuring analytes

down to 1-10 ng of analyte element per liter, in solution. This direct high
measurement sensitivity across the periodic table exceeds the capability of
most other modern instrumental methods of analysis. Indeed, even non-
metallic elements can be determined with sufficient sensitivity to serve as a
useful trace analytical tool. Additional advantageous characteristics, includ-
ing a large linear dynamic working range, high accuracy and precision of
measurement, and minimal interferences, make this a pov^erful and useful
trace analysis tool.
The wide availability of commercial instrumentation, utilizing a variety
of approaches to the ICP-MS technology, provides the chemist with sever-
al alternatives for the solution of analytical problems. The effective combi-
nation of types of spectrometers (or ion measurement technology) cou-
pled with many approaches to sample introduction makes techniques
available that can be customized for a specific sample type or form of ana-
lyte. This book summarizes the operational characteristics of this technol-
ogy, the various configurations and types of instrumentation currently
available, characteristics and relative advantages of different types of sample
introduction, procedures and techniques for attaining and interpreting
results, and potential problems with data acquisition and interpretation for
specific applications.

1.1 HISTORY

The roots of ICP-MS began in the mid-1960s with the advent of a tech-
nique called inductively couple plasma-atomic emission spectrometry
(ICP-AES). For decades, prior to this, atomic emission spectrometry (flame,
direct current-arc, and controUed-waveform spark) was the predominant
method used for elemental analysis. The work of Greenfield et al. (1964)
and work done essentially simultaneously by Wendt and Fassel (1965) intro-
duced an emission spectrometric technique that provided high sensitivity
trace element analysis with a multielement detection capability. This tech-
nique is still widely used today and can be studied in publications by
Boumans (1987) and Montaser and GoHghtly (1992).
The most advantageous and unique feature of this technique is the use of
the atmospheric pressure argon inductively coupled plasma (ICP) for sample
atomization and efficient atomic excitation.This plasma is a highly energetic
media consisting of inert ionized gas. Its high equivalent temperature
(7000—10,000 K) provides exceptional atomization (i.e., decomposition of
 1,2 Overview 3

complex materials in a sample to individual atoms) followed by highly effi-

cient atomic excitation. This characteristic of the plasma results in the abili-
ty to analyze very refractory materials (those difficult to atomize) and those
w^ith high excitation potentials that are difficult to excite by other atomic
emission sources. The result is a very satisfactory trace elemental analytical
technique.
Houk et al. (1980) demonstrated the advantages that could be realized by
using the ICP as an ionization source. They coupled the ICP with a mass
spectrometer and identified the ion species found in the plasma and meas-
ured their quantitative concentrations. They also discovered that the result
was a much simpler spectrum than that obtained in atomic emission spec-
trometry, potentially reducing interelement interferences, while providing
significantly higher quantitative sensitivity. It soon became apparent that
measuring ion currents by this instrumental approach produced much
higher signal-to-background ratios, yielding significantly higher analytical
sensitivity, which resulted in much improved detection limits.
Soon commercial instrumentation became available, with the first
equipment being offered by a Canadian company called Sciex (which sub-
sequently merged with Perkin Elmer). Sciex delivered an instrument called
the Elan to customer laboratories in 1984. As with most highly sophisticat-
ed instrumentation, the early models often exhibited design deficiencies
that were corrected by an evolutionary process as nev^ models w^ere intro-
duced into the marketplace and as users developed techniques and
methodologies that required specialized apparatus. Models of instrumenta-
tion that were available in 2000 are listed in Table 1.1.

1.2 OVERVIEW

The first ICP-MS instruments employed a conventional crystal-controlled

(27-MHz) radio-frequency ICP operating at between 1 and 2 kW of incident
power. They, as well as subsequent models, utilize atmospheric pressure argon
gas flowing through a concentric quartz torch. A sample, usually in the form of
an aqueous solution, is converted to an aerosol by a nebulization process and
transported to the plasma by an argon gas stream. In the plasma the analyte
elements are atomized, followed immediately by ionization. The composition
of the ion population in the plasma is proportional to the concentration of the
analyte species in the original sample solution. Ions that are produced by the
ICP are representatively sampled and extracted from the plasma, v^here they
are separated and measured by a quadrupole mass spectrometer.The key to the
 Chapter 1 Introduction

TABLE 1.1 Commercial ICP-MS Instrumentation Available in 2000

Manufacturer Model Type

Finnigan MAT Corp. Element2 Magnetic

Finnigan MAT Corp. Neptune Multiple collector
GBC Scientific Equip. Optimass 8000 Time-of-flight
Hewlett Packard Corp.'' HP4500 Series Quadrupole
JEOL JMS-Plasmax 2 Magnetic
LECO Corp. Renaissance Time-of-flight
Micromass Inc. Platform ICP Collision cell quadrupole
Micromass Inc. Plasma Trace 2 Magnetic
Micromass Inc. Iso-Plasma Trace Multicollector
N u Instruments Nu Plasma MulticoUector
Perkin Elmer/Sciex Elan 6100 Quadrupole
Perkin Elmer/Sciex Elan 6100 D R C Reaction cell quadrupole
Seiko Instruments SPQ 9000 Quadrupole
Spectro Analytical Inst. SpectroMass 2000 Quadrupole
Thermo-Jarrell Ash POEMS II Combination AES/MS
Varian Corp. Ultramass 700 Quadrupole
VG Elemental PlasmaQuad 3 Quadrupole
VG Elemental P Q Excell Collision cell quadrupole
VG Elemental Axiom SC Magnetic
VG Elemental Axiom M C Multicollector

'^Yokogawa Anal. Inst.

technology is a cleverly engineered interface to sample ions from the atmos-

pheric pressure argon plasma and transport them into the low-operating pres-
sure (10'"^ - 10~^ torr) of the mass spectrometer without modifying their com-
positional distribution. This interface allows the marriage of two
well-developed technologies in the field of analytical chemistry—the induc-
tively coupled plasma from the atomic emission spectrometry community, and
the quadrupole mass spectrometer from the organic compound analysis field.
As the nature of the technique evolved, modification and improvements
in both technologies increased the versatility and performance of the sys-
tem. These improvements in the ICP included changes in the radio-fre-
quency (RF) power generator, utihzing various frequencies other than 27
MHz, improved tuning and R F coupling networks between the generator
and the plasma torch, and the utilization of mixed-gas plasmas (N2, O^,
etc.). At the spectrometer end, high-resolution magnetic sector mass
spectrometers and, more recently, time-of-flight mass spectrometers, have
greatly enhanced the performance characteristics of the instrumentation.
 1.2 Overview 5

However, the conventional quadrupole argon ICP-MS still provides the

operating analytical chemist with sufficient utility to solve the majority of
elemental analysis problems at a reasonable equipment investment cost.
Several reference sources are available that summarize the characteristics
of this technique. These references should be consulted for additional
details regarding specific topics.Table 1.2 lists these references in alphabeti-
cal order.

TABLE 1.2 Selected References

Author/editor Tide Publisher Year

Adams, F, Gijbels, R . Inorganic Mass Spectrometry Wiley 1988

and Van Grieken, R.
Date, A.R. and Gray, A.L. Applications of Inductively Blackie 1989
Coupled Plasma Mass
Spectrometry
Evans, E.H., Giglio, J.J., Inductively Coupled and Royal Society 1995
Castillano,T.M. Microwave Induced Plasma of Chemistry
and Caruso, J.A. Sources for Mass
Spectrometry
Hill, Steve J. Inductively Coupled Plasma Sheffield 1999
Spectrometry and Its Academic Press
Applications
Holland, G. and Applications of Plasma Source Royal Society 1991
Eaton, A.N. Mass Spectrometry of Chemistry
HoUand, G. and Applications of Plasma Source Royal Society 1993
Eaton, A.N. Mass Spectrometry II of Chemistry

Jarvis,K.E., Gray, A.L. Handbook of Inductively Blackie 1992

and Houk, R.S. Coupled Plasma Mass
Spectrometry
Montaser, A. and Inductively Coupled Plasmas VCH 1992
Golightly D.W. in Analytical Atomic
Spectroscopy, 2nd ed.
Montaser, A. Inductively Coupled Plasma Wiley-VCH 1998
Mass Spectrometry