T e c h n i c a l N o t e

ICP-Mass Spectrometry
The 30-Minute Guide
to ICP-MS

First...a little history

ICP-MS (Inductively Coupled Plasma-Mass Spectrometry) is not a new technique. In fact, it is over 25 years old!

The first papers on ICP-MS were published in the 1980s and PerkinElmer SCIEX™ introduced the first commercially available
ICP-MS instrument in 1983. Since that time, many improvements and refinements have been made to each generation of ICP-
MS instrumentation. Today, ICP-MS is a technique used daily by many laboratories as a routine analytical tool.

ICP-MS offers many benefits to laboratories performing trace metal determinations.

• ICP-MS offers detection limits equal to or better than those attainable using Graphite Furnace Atomic Absorption (GFAA)
with much higher productivity.

• ICP-MS can easily handle both simple and complex sample matrices.

• ICP-MS has detection limit capabilities that are superior to those obtained in Inductively Coupled Plasma-Optical Emission
Spectrometry (ICP-OES).

ELAN 9000 Detection Limit Atomic Symbol

ELAN DRC II Detection Limit Isotopic Abundance
(in Class 100 clean room)
Most Abundant Isotope

Detection Limit Ranges

Figure 1. Elements determined by ICP-MS and approximate detection capability.

 What can be measured with an ICP-MS? • Interface – links the atmospheric pressure ICP ion source
For laboratories using flame or furnace AA or ICP-OES, and the high vacuum mass spectrometer
ICP-MS offers the opportunity to achieve higher productivity • Lens – focuses ions into a beam for transmission into
and obtain lower detection limits. Let’s look at what an the Quadrupole Collision Cell and/or Reaction Cell;
ICP-MS instrument can do and how it operates. employs user defined gases to reduce or remove inter-
The ICP-MS instrument measures most of the elements in ferences that may impact the detection limit achieved
the periodic table. The elements shown in color in Figure 1 for a specified element
can be analyzed by ICP-MS with detection limits at or below • Quadrupole – acts as a mass filter to sort ions by their
the parts per trillion (ppt) range. Elements that are in white mass-to-charge ratio (m/z)
are either not measurable by ICP-MS (the upper right-hand
side) or do not have naturally occurring isotopes. The lines • Vacuum system – provides high vacuum for ion optics,
shown for each element in Figure 1 depict the number and quadrupole, and detector
relative abundance of the natural isotopes for that element • Detector – counts individual ions passing through the
– this is sometimes referred to as the isotopic fingerprint of quadrupole
the element. The naturally occurring isotopes of each element
all have the same atomic number (number of protons in the • Data handling and system controller – controls all aspects
nucleus), but differ by the atomic mass. This is the result of of instrument control and data handling to obtain final
the different number of neutrons present in the nucleus of concentration results
each isotope. Most samples analyzed by ICP-MS are liquids. However,
ICP-MS shares some components, including the quadrupole solid samples can be analyzed using lasers or heated cells
mass spectrometer, vacuum system, and detector, with to vaporize the sample. Gas samples can be measured by
other types of mass spectrometers such as LC/MS and GC/MS. direct introduction into the instrument. The most common
However, the plasma ion source used in ICP-MS is much sample introduction system used on an ICP-MS consists of
different than the lower-energy ion sources used in LC/MS a nebulizer and spray chamber. The nebulizer converts the
and GC/MS instruments. The extreme high temperature of liquid samples into very small droplets. These droplets are
the plasma ion source completely breaks apart the molecules carried through the spray chamber and into the tube or
present in a sample. As a result, the ICP-MS detects only injector that is the center channel of the torch and then into
elemental ions. This makes ICP-MS much more comparable the plasma. The plasma ionizes the elements present in the
to other inorganic techniques, such as AA and ICP-OES, for droplets. These ions then pass through the interface and the
elemental analysis. In addition, the standard and sample ion lens. After being focused by the ion lens, the ions are
preparation techniques, sample introduction systems, and separated by their mass-to-charge ratio in the mass spec-
potential interferences are all very similar to those in AA trometer and measured by the detector. Once the detector
and ICP-OES. One advantage of ICP-MS over these other measures the ions, the computerized data system is used to
inorganic techniques for elemental determination is that convert the measured signal intensities into concentrations
ICP-MS can determine the individual isotopes of each of each element and generate a report of the results. The
element. This allows ICP-MS to perform isotope ratio next few pages briefly describe the function of each part of
and isotope dilution measurements. the ICP-MS in more detail.

A quick overview Sample introduction

An ICP-MS consists of the following components: The sample introduction system on an ICP-MS is very similar
to that used on a flame AA or ICP-OES. When measuring
• Sample introduction system – consists of the peristaltic metal content in a liquid sample, the liquid must be in a
pump, nebulizer and spray chamber, and provides the form acceptable to the instrument’s plasma. This is achieved
means of getting samples into the instrument by introducing the sample to a nebulizer such as a cross-
• ICP torch – generates the plasma which serves as the ion flow type shown in Figure 2. A cross-flow nebulizer works
source of the ICP-MS, converting the analyte atoms to ions on the same principle as the old hand-pumped insecticide
sprayer:

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1. A flow of gas is passed at right angles over the end of a The interface – sampling ions
tube containing a liquid. Placing a plasma, operating at 6000 °C, near an ion focusing
2. The flow of gas shears the liquid into very small droplets device operating near room temperature, is like placing the
forming an aerosol. earth about a half-mile away from the sun. In addition to a
large temperature difference, the plasma operates at a pressure
3. The droplets then pass through a spray chamber that that is much higher than the vacuum required by the ion
eliminates all droplets except those that are the right size lens and mass spectrometer portions of the instrument. The
and velocity for introduction into the plasma. interface allows the plasma and the ion lens system to coexist
Other types of nebulizers are also useful for introducing the and the ions generated by the plasma to pass into the ion
liquid sample to the ICP-MS instrument. The specific type lens region. The interface (shown in Figure 4) consists of
of nebulizer used can be selected based on the sample type two inverted funnel-like devices called cones. The sampler
and volume. cone is located next to the plasma and the skimmer cone is
located several millimeters behind the sampler cone. Each
The ICP torch – making ions cone has an opening of approximately one-millimeter in
diameter at the apex that permits the ions to pass through.
The plasma generated in the ICP torch creates a very hot
The cones are typically made of nickel or platinum and are
zone that serves a variety of functions. At a temperature of
mounted into a water-cooled metal housing to prevent
approximately 6000 °C, the plasma is about 10 times hotter
damage from the heat of the plasma. The region between
than a pizza oven, three times hotter than a welding torch,
the two cones is evacuated to a pressure of a few Torr by a
and equal to the temperature at the surface of the sun. The
mechanical roughing pump. The holes in the cones or orifices
plasma is generated by passing argon through a series of
must be large enough to prevent deposited materials from
concentric quartz tubes (the ICP torch) that are wrapped at
clogging them. The orifices must also be small enough to
one end by a radio frequency (RF) coil. Energy supplied to
maintain a consistent vacuum on the other side of the interface.
the coil by the RF generator couples with the argon to
As samples pass through an ICP-MS instrument, materials
produce the plasma.
will eventually deposit on these cones and will need to
During their voyage into the plasma, shown in Figure 3, be removed by occasional cleaning. How often the cones
the liquid droplets containing the sample matrix and the require cleaning is an important maintenance item that must
elements to be determined are dried to a solid and then be considered when selecting an ICP-MS. Some systems use
heated to a gas. As the atoms travel through the plasma, an additional cone or cones to help guide the ions toward
they absorb more energy from the plasma and eventually the lens system.
release one electron to form a singly charged ion. The singly
charged ions exit the plasma and enter the interface region. The lens system – focusing ions
Similar processes occur in the flame or plasma of AA and The ion lens is positioned immediately behind the inter-
ICP instruments, respectively. The difference is that ICP-MS face. It is responsible for focusing ions into the quadrupole
measures the ions themselves and the other techniques region. Since the ions generated in the plasma are nearly
measure light instead. all positively charged, they have a natural tendency to repel
each other. In order to get as many of the ions as possible
into the quadrupole for mass separation and eventual
Aerosol (fine droplets) measurement, it is necessary to keep the ion beam from
Argon diverging. This is achieved by passing the ions through a
Nebulizer Flow
charged device that acts as a focusing lens.

Liquid Sample

Figure 2. Cross-flow nebulizer.

Figure 3. Form of sample in ICP-MS.

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 Photons from the plasma can create high signal backgrounds more frequently with the inert atom when compared to
if they are permitted to pass through the spectrometer and the analyte ion. Each of these collisions removes a certain
onto the detector. Additionally, species not fully ionized in amount of the kinetic energy possessed by the ion. It makes
the plasma – frequently called neutrals – can impact system sense, then, that at the end of the ions’ journey through this
stability if they are permitted to pass into the spectrometer. cloud of inert atoms, the analyte ion will retain more of its
For these two reasons, it is most important that a device energy when compared to the interferent ion. If an energy
be placed downstream of the ion lens that will block both filter is placed at this point, it is possible to allow the analyte
photons and neutrals from passing any further into the ions to pass through the filter while the interferent ions will
spectrometer. be pushed back by the filter. This filter is commonly referred
to as a Kinetic Energy Discriminator. The collision cell will
Again, focusing ions in a mass spectrometer is like focusing
reduce the background but often the analyte signal is
light in an optical spectrometer. However, the optical spec-
attenuated with this technique.
trometer uses an optical lens to bend the light beam, while
the mass spectrometer uses an electrical field to focus the Reaction cells operate under a different principal than collision
ion beam. cells. Reaction cells use chemistry and take advantage
of exothermic (fast) and endothermic (slow) reactions.
The collision and/or reaction cell Interferent ions tend to react with an active gas like ammonia
Interferences in ICP-MS do not occur nearly as frequently exothermally while analyte ions react endothermally. If we
as in ICP-OES, however, when they are present, they can pass interferent ions and analyte ions through a cloud of
have a serious impact on the performance of the system. a reactive gas, we will find that the interferent ions will be
Interferences in ICP-MS are caused by ions generated from converted chemically to a new species. In our example of
the plasma, the sample, or a combination of the two. ArO, the ion is converted to a neutral atom. Since the neutral
Interfering ions carry a mass to charge ratio that is identical atom no longer carries a charge, it is not stable in the quadru-
to that of the analyte ion. Below is an example of a com- pole of the reaction cell and it is rapidly evacuated from
mon interference and the ion impacted. This example the cell. The analyte ion retains its ionic nature and passes
demonstrates how collision and reaction cells function. through the reaction cell and into the filtering quadrupole.
Reaction cells remove interfering ions very effectively as they
Argon from our plasma and oxygen from the sample matrix preserve the analyte ions.
combine to form a polyatomic that carries a mass of 56 amu.
Iron has several isotopes but the isotope with the greatest The mass filtering quadrupole – separating ions
abundance occurs at mass 56 amu also. While we may elect
The mass spectrometer separates the singly charged ions
to use an alternative mass for iron, such as the isotope at
from each other by mass, serving as a mass filter. Three
mass 54, we will not be achieving the best detection limits
main types of mass spectrometers are used in commercial
possible with that isotope. If we attempt a measurement at
ICP-MS systems: quadrupole, time-of-flight, and magnetic
mass 56 without removing the ArO interferent, we also will
sector. The quadrupole is the type most commonly used in
not be obtaining the best possible detection limit since we
routine analytical instrumentation. A quadrupole consists of
will have an exceptionally high background. This is where
4 rods approximately 20 cm in length and 1 cm in diameter
the collision and reaction cells come into play. Both the
arranged as shown in Figure 5.
collision cell and the reaction cell are placed ahead of the
filtering quadrupole. For reasons that a physicist can explain, The quadrupole mass spectrometer works by allowing only
collision cells use hexapoles and octapoles while reaction one mass to pass through to the detector at any given time.
cells use quadrupoles. The quadrupole actually sorts on the mass-to-charge (often

The collision cell works on a straightforward principal that

the interfering ion – ArO in this case – is significantly larger
than the analyte ion – Fe. If both ions are allowed to pass
through a cloud of inert atoms, the interferent ion will collide

Figure 4. The ICP-MS interface.

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referred to as m/z) ratio of the ions. The quadrupole does most of the excess sample matrix ions and gasses. Routine
this by setting up the correct combination of voltages and maintenance on the vacuum system generally consists of
radio frequencies to guide the ions with the selected m/z changing the oil in the roughing pumps every 12 to 18 months.
between the four rods of the quadrupole. Ions that do not
have the selected m/z pass out through the spaces between The detector – counting ions
the rods and are ejected from the quadrupole. The mass The ions exiting the mass spectrometer strike the active
spectrometer can move to any m/z needed to measure the surface of the detector and generate a measurable electronic
elements of interest in the sample analyzed. For example, to signal. The active surface of the detector, known as a
measure sodium, which has a single isotope at mass 23, the dynode, releases an electron each time an ion strikes it.
mass spectrometer can be set to allow ions with m/z = 23/1 In Figure 6, the ion exiting the quadrupole strikes the first
to pass. For copper, which has an isotope at mass 63, the dynode which releases electrons and starts the amplification
mass spectrometer can be set to pass ions with m/z = 63/1. process. The electrons released from the first dynode, strike
If a doubly charged ion were formed, for example Ba+2, the a second dynode where more electrons are released. This
mass spectrometer would need to be set for a m/z of 69/1 cascading of electrons continues until a measurable pulse is
to allow this ion to go through. created. By counting the pulses generated by the detector, the
Even though the quadrupole mass spectrometer only allows system counts the ions that hit the first dynode. Compared
one m/z to pass through the rods at any given time, the with AA and ICP-OES, the detectors used in ICP-MS are not
voltage settings on the rods can be changed rapidly. The much different than the photomultiplier tubes used as the
quadrupole can scan from m/z = 1 to m/z = 240 in less than detectors in these optical instruments. Instead of detecting
0.1 seconds. This is called the scan speed of the quadrupole. the light emitted by an analyte, the actual analyte ion itself
is being detected.
This is the reason ICP-MS can determine so many different
elements quickly even though only one mass goes through Data handling and system controller
the quadrupole at a time. All ICP instruments require computers and sophisticated
Another way to think of this is to compare it to AA or ICP-OES. software to control the plasma and mass spectrometer as
Instead of using an optical grating in a monochrometer to well as perform calculations on the data collected.
separate out the wavelength of light for the element being Instrument status and control
determined, the mass spectrometer separates the ions on
the basis of their mass and charge. All the parts of the ICP-MS discussed above are under software
control. The software makes sure each part of the instrument
The vacuum system – provides correct operating is working properly and can provide the operator with useful
pressure information regarding the instrument status.

The distance from the interface to the detector of an ICP-MS Data handling and calculation
is typically one meter or less. If an ion is to travel that
The software also translates
distance, it cannot collide with any gas molecules. This
the ion counts measured
requires removal of nearly all of the gas molecules in the
by the detector into useful
space between the interface and the detector to create a
information. The ICP-MS
vacuum. This task is accomplished using a combination of
instrument can provide
turbomolecular pumps and mechanical roughing pumps
data in one of four ways –
called the vacuum system. The turbomolecular pumps work
semi-quantitative analysis,
like jet turbines and are capable of rapidly pumping a chamber
quantitative analysis, isotope
to a pressure of 1 x 10-5 Torr. The roughing pump connected
dilution analysis, and isotope
to the interface area (where the cones are located) removes
ratio analysis.

Signal
Out

Figure 6. ICP-MS detector.

Figure 5. Quadrupole mass filter.

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 Semi-quantitative analysis Isotope ratio
For some analyses, it is not necessary to calibrate the ICP-MS Since ICP-MS instruments measure specific isotopes of an
for each element. After the instrument has been calibrated element, the ratio of two or more isotopes can readily be
using a single solution containing as few as three elements, determined. Isotope ratio determinations are used in a
a high-quality semi-quantitative analysis for 82 elements variety of applications including geological dating of rocks,
can be performed in just a few minutes. Semi-quantitative nuclear applications, determining the source of a contaminant,
analysis provides a fingerprint of the elements present in and biological tracer studies.
a sample and the approximate concentrations of each
Isotope dilution
element. This information can help determine what stan-
dards are necessary for quantitative analysis. Additionally, Isotope dilution experiments can also be performed by
semi-quantitative analysis can provide valuable information ICP-MS. In isotope dilution, the sample is spiked with an
on what other elements are present in a sample that could enriched isotope of the element of interest. The enriched
cause interferences and potentially affect the results. In the isotope acts as both a calibration standard and an internal
example shown in Figure 7, the concentration of zinc has standard. Because the enriched isotope has the same chemical
been determined to be 76 ppb. The software does this by and physical properties as the analyte element, it is the best
comparing the measured spectrum of the unknown sample possible internal standard. For this reason, isotope dilution
(in blue) to the known isotopic fingerprints for each element. is recognized as being the most accurate type of all analyses
When a match is obtained (shown in red), the element is and is often used to certify standard reference materials.
identified and the concentration estimated by comparing the
Automated quality control checking
measured signal to a stored response file for that element.
The software can also monitor calibration, check standard
Quantitative analysis responses and take actions to correct any problems with the
The ICP-MS accurately determines how much of a specific analysis, using the automated quality control checking feature.
element is in the material analyzed. In a typical quantitative In addition, check standard and spike recoveries can be
analysis, the concentration of each element is determined by calculated and compared to acceptable limits. The user can
comparing the counts measured for a selected isotope to an specify what action to carry out for quality control samples
external calibration curve that was generated for that ele- that are outside established limits – from recalibration and
ment. Liquid calibration standards are prepared in the same re-running samples to flagging samples and continuing the
manner as used in AA and ICP-OES analysis. These standards analysis.
are analyzed to establish the calibration curve. The unknown
samples are then run and the signal intensities are compared
to the calibration curve to determine the concentration of
the unknown. Figure 8 shows an example calibration curve
for the determination of lead.

Figure 8. Quantitative calibration curve for lead at 10, 20, and 100 ppb.

Figure 7. Semi-quantitative analysis.

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Summary 35 elements in a sample in two to three minutes. Because
There are many similarities between ICP-MS and the other the spectrometer and all the accessories are under computer
analytical tools used in the laboratory, such as Atomic control, the system can literally operate 24 hours per day,
Absorption and ICP-Optical Emission Spectrometry. The 7 days per week, and analyze over 300 samples per 24-hour
ICP-MS is another way to determine the elemental con- day. In short, no other technology can provide the low
tent of samples. ICP-MS accomplishes this by counting the detection limits and the high productivity for elemental analysis
number of ions at a certain mass of the element instead of offered by ICP-MS. This guide is intended as a quick general
the light emitted by the element, as in optical techniques. overview of ICP-MS. For those interested in more details
Sample preparation for ICP-MS is very similar to that used in regarding the design and operation of ICP-MS instruments,
AA and ICP-OES, and in many cases is identical. Standards additional details can be found in the scientific literature (1-4).
are analyzed to generate a calibration curve and the signals
from unknown samples are compared against the calibration References
curve to determine the concentration of each metal in the 1. “Applications and Technology of a New ICP-MS
sample. Collision cells and reaction cells are used to reduce Spectrometer,” Atomic Spectroscopy, Special Issue,
interfering ions that can degrade detection limits. The Vol. 16, No. 1, Jan/Feb, 1995.
software reports data and results for quantitative, semi-
2. “Method Development Strategies for ICP-MS,” Ruth Wolf
quantitative, isotope ratio or isotope dilution analyses. ICP-MS
and Zoe Grosser, American Environmental Laboratory,
has many advantages over other technologies, such as AA
February 1997.
and ICP-OES, for determining the elemental composition
of samples. ICP-MS generally has fewer interferences than 3. “Mass Spectrometry of Inductively Coupled Plasmas,”
ICP-OES and is much faster than AA and Graphite Furnace R.S. Houk, Analytical Chemistry, Vol. 58, No, 1, 1986.
AA for the determination of multiple analytes per sample.
4. “An Improved Interface for ICP-MS,” D.J. Douglas and
ICP-MS detection limits are generally much lower than those
J.B. French, Spectrochimica Acta Part B, Vol. 41B, No. 3,
that can be achieved by ICP-OES and GFAA. Quadrupole
1986.
ICP-MS instruments are capable of measuring as many as

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