ICP-MS, ICP-MS

What is ICP-MS?
Everything around us is made of different combinations of elements. When analysts need to identify
which elements something is made of, they will often use a technique called inductively coupled
plasma mass spectrometry (ICP-MS, or ICP Mass Spec). ICP-MS is an elemental analysis technique,
meaning it is used to measure elements, rather than the molecules and compounds that are measured
by LC/MS and GC/MS.

ICP-MS uses an argon (Ar) plasma – the ICP – to convert the sample into ions that are then measured
using a mass spectrometer – the MS. ICP-MS is similar to inductively coupled plasma optical emission
spectroscopy (ICP-OES), but ICP-OES uses an optical spectrometer to measure the light emitted from
elements as they pass through the plasma, whereas ICP-MS measures the elements (ions) directly.
Both techniques provide fast analysis of multiple elements in a sample, but ICP-MS provides much
lower detection limits than ICP-OES, so it’s a better choice for trace element analysis.

An ICP-MS instrument consists of the ion source (the ICP), a mass spectrometer (MS) – usually a
scanning quadrupole mass filter, and a detector. The ICP is at atmospheric pressure, while the MS and
detector operate in a vacuum chamber, so an ICP-MS also requires a vacuum pump, a vacuum
interface, and some electrostatic ion “lenses” to focus the ions through the system. Modern ICP-MS
systems also typically contain some device or mechanism to resolve spectral interferences.

How does an ICP-MS work?

An ICP-MS instrument uses a plasma (ICP) to ionize the elements in a sample and then measures the
ions using a mass spectrometer (MS).
The main components of a single quadrupole ICP-MS instrument are:

1. Sample introduction system to form a fine aerosol mist from the liquid sample
2. Plasma (ICP) to convert the elements in the sample aerosol to ions
3. Interface to extract the ions into the vacuum system
4. Ion lens to focus the ions and separate them from background signals
5. Collision/reaction cell (CRC) to resolve the analyte ions from interfering ions
6. Mass spectrometer (MS) to filter the analyte ions by mass
7. The electron multiplier detector
8. Data processing
Main components of a single quadrupole ICP-MS instrument.

A triple quadrupole ICP-MS (ICP-QQQ, sometimes also referred to as a “TQ”) includes all these
components but with the addition of another quadrupole mass filter between the ion lens (4) and the
CRC (5). The additional mass filter (Q1) of a QQQ filters the ion beam before the ions reach the CRC,
so only a single mass enters the cell at any given time. This tandem ICP-MS configuration (ICP-
MS/MS) means that reactive cell gases can be reliably used to resolve interferences, leading to lower
detection limits and better accuracy for some difficult analytes.

Main components of a triple quadrupole ICP-MS (ICP-QQQ) instrument.

Let’s look in a little more detail at the most important components of an ICP-MS instrument.

1. The sample introduction

ICP-MS is usually used to measure liquid samples. The sample solution is pumped into a nebulizer,
where the liquid is converted into a fine spray or aerosol mist using a jet of argon gas. The aerosol mist
passes through a spray chamber, where the larger droplets are removed. The fine droplets are carried
by the argon gas flow to the ICP plasma torch.

A nebulizer turns the liquid sample into an aerosol.

The aerosol passes through a spray chamber where the larger droplets are removed.

The sample introduction components are selected and optimized to work in combination with the ICP.
This means that the nebulizer and spray chamber are designed to produce an aerosol that can be
effectively processed by the plasma. The overall solution load, the aerosol density (number of
droplets), and the droplet size are key factor that affect the ability of the plasma to dry and decompose
the sample material carried in the droplets. The plasma is most effective at producing ions if the aerosol
contains small droplets of uniform size, dispersed across the central channel of the plasma.

2.The ICP (plasma) ion source

The term “plasma”, which refers to a substantially ionized gas, can apply to things as diverse as a
fluorescent light bulb and the sun. In the plasma used in ICP-MS, the ionized gas is argon, which flows
through a quartz tube. The energy is provided by a radio frequency (RF) generator operating at about
1.5 KW – around half the power of a typical domestic kettle. The RF energy is transferred to the argon
gas flow by inductive coupling from a load coil wrapped around the outside of the quartz tube. The
RF field causes free electrons in the argon gas flow to oscillate; causing them to collide with argon
atoms with enough energy to remove an electron, ionizing the argon atoms. The new argon ions and
electrons also oscillate in the RF field, leading to further collisions and further ionization in a process
that distributes energy through the gas stream to form the plasma. The energy density in the ionized
argon gas is very high, so the ICP reaches a temperature of 10,000 degrees Celsius – hotter than the
surface of the sun!

The plasma is formed from argon gas flowing in a quartz tube.

The argon gas is ionized by a radio frequency generator. The sample aerosol is carried through the
center of the plasma.
The argon gas passing through the outer quartz tube flows at a rate of around 15 liters per minute. This
“plasma gas” forms the plasma and cools the quartz tube to prevent it from melting. Two additional,
smaller quartz tubes are positioned concentrically inside the outer tube, together making up the plasma
“torch”. The middle quartz tube carries an auxiliary gas flow which pushes the base of the plasma
away from the inner quartz tubes to prevent them from melting. The smallest tube – known as the
“injector” – carries the aerosol droplets from the spray chamber to the plasma at a flow rate of around
1 liter per minute. The injector tube typically has an internal diameter (ID) of around 2 mm or more,
so the carrier gas travels at high speed, punching a hole through the plasma to form an elongated
“torus” or donut shape. The aerosol droplets are carried through the center of the plasma, where the
droplets are dried and the sample material is decomposed and dissociated into individual atoms, which
are then ionized.

Almost all ICP-MS instruments use an RF generator operating at a frequency of 27.12 MHz (27.12
million cycles per second). This is lower than the standard 40.68 MHz frequency traditionally used for
ICP-OES instruments. The lower frequency plasma is preferred for ICP-MS as it has a thicker “skin
depth”, which means the plasma energy extends closer to the central channel where the aerosol droplets
are processed. This is important for the performance of an ICP used for MS, where the higher central
channel temperature provides better ionization and so higher sensitivity.

The plasma of an ICP-MS plays a critical role in decomposing the sample matrix, dissociating potential
interferences, and ionizing the analyte atoms. Indeed, the overall performance of an ICP-MS is highly
dependent on the plasma torch design and operating conditions. For example, for a given carrier gas
flow rate (e.g. 1 liter per minute), the linear gas velocity through the torch injector is inversely is
proportional to the square of the injector ID. This means that changing the injector ID from 1.5 mm to
2.5 mm causes the carrier gas velocity to change from 9.43 m/s to 3.4 m/s, almost a 3-fold decrease.
A higher carrier gas velocity means the plasma only has a few milliseconds to process the aerosol
droplets to form ions, so a high plasma temperature is critical for optimizing these processes. A lower
carrier gas velocity means the aerosol droplets spend more time exposed to the hottest part of the
plasma, so matrix decomposition is better. A wider torch injector also contributes to lower levels of
spectral interferences and higher ionization of analyte ions, critical parameters in most ICP-MS
applications.

Processes to convert aerosol droplets to ions in the plasma.

Some ICP-MS applications use different torch designs. Options include a demountable torch with a
platinum or sapphire injector tube for use with samples prepared in highly corrosive acids like HF.
Torches with a narrow injector are also available and are typically used for analysis of volatile solvents
and other specialized applications.

The degree of ionization of each element in the plasma depends on the element’s ionization energy (or
ionization potential, IP) and the plasma temperature. The IP is the amount of energy input that causes
one electron to be removed from a neutral atom to create an ion. Argon is an ideal support gas for ICP-
MS because it has a first IP that is above the first IP of most other elements, but below their second IP
(the energy input required to remove two electrons). This property of argon means that most elements
that pass through the ICP-MS plasma are converted efficiently to singly charged positive ions (M+),
with only a small percentage of doubly charged ions (M2+) being formed. Under typical plasma
conditions, most naturally occurring elements are at least 75% ionized, which is one of the main
reasons for the very high sensitivity of ICP-MS. A few important elements are less well ionized,
however, notably As, Cd, and Hg. Good plasma optimization is important to achieve high sensitivity
and low detection limits for these elements.

Plot showing degree of ionization (% of atoms converted to ions) plotted against first ionization
potential for all elements.

3. The vacuum interface

The plasma ion source and the quadrupole mass spectrometer are separated by a vacuum interface,
which transfers ions from the plasma (at atmospheric pressure) to the mass spectrometer (in a vacuum
chamber). The interface consists of a series of cooled metal plates or “cones” with small holes in them
to allow the ions to pass through. The typical arrangement uses a sampling cone to extract ions from
the plasma, followed by a skimmer cone to sample the central portion of the ion beam to pass to the
high vacuum region.
Layout of an ICP-MS system showing vacuum interface between the plasma and mass spectrometer.

Small cone apertures – around 0.5 to 1.0 mm – are preferred as they provide optimum vacuum
conditions for operation of the quadrupole mass filter and detector. Lower vacuum pressure (less
residual gas) leads to higher ion transmission, less peak broadening due to scattering, and lower
background. But small aperture cones are more difficult to manufacture precisely and lead to fewer
ions being extracted from the plasma and passed through the interface. Smaller cone apertures would
also be more susceptible to clogging if the sample matrix was not completely dissociated in the plasma.
These considerations mean that the performance benefits of using small cone apertures can only be
realized if the ICP-MS system has a very robust, high temperature plasma and a high transmission ion
lens system.

An ICP-MS interface includes a sampling cone (left) and skimmer cone (right).

4. Ion focusing and separation

After the ions pass through the interface cones, they are focused into a narrow beam using an ion
“lens”. The lens is composed of several metal plates with adjustable voltages applied to them. A plate
with a positive voltage repels the positively charged ions while a plate with a negative voltage attracts
the ions. A combination of lens plates with different voltages is used to steer and focus the ions.
As well as focusing the ions to maximize transmission and therefore sensitivity, the ion lens also
separates the ions from the neutral particles and photons extracted from the plasma. These uncharged
particles would cause a high background signal, so they must be prevented from passing through the
vacuum system and reaching the detector. This is usually achieved by deflecting the ions off axis,
while the photons and neutrals, being uncharged, continue in a straight line and so are removed from
the ion beam. Several different ion lens designs are used in ICP-MS, but all have the same goal of
providing high transmission for ions of all masses, while minimizing background signals due to
photons and neutral particles.

Cutaway showing position and operation of the ion lens.

5. Collision/reaction cell
Since the early 2000s, nearly all new ICP-MS systems have included a collision/reaction cell (CRC)
to resolve spectral overlaps caused by unwanted ions that appear at the same mass as the analyte ions
being measured. By far the most significant spectral overlaps in ICP-MS are caused by molecular (or
“polyatomic”) ions. A polyatomic ion overlap occurs when a combination of atoms forms an ion at the
same mass as an analyte of interest. For example, 40Ar can combine with 16O to create an
ArO+ polyatomic ion at mass 56, overlapping the major isotope of iron (56Fe). Similarly, 40Ar can
combine with 35Cl to form an ArCl+ polyatomic ion at mass 75, overlapping the only isotope of arsenic
(75As). Polyatomic ion overlaps have been a longstanding problem in ICP-MS, so the development of
CRCs to address these overlaps was a major factor in improving data accuracy and increasing adoption
of ICP-MS across many routine industries.
A CRC consists of an ion guide – usually an octopole or quadrupole – positioned in an enclosed
chamber (or “cell”), that can be pressurized with a gas. Small entrance and exit apertures maintain the
cell pressure while allowing the ions to enter and exit the cell. The process used to remove the
interferences depend on the gas (or gases) added to the cell and can be broadly divided into collision
and reaction modes.
Cutaway showing position of the collision/reaction cell between the ion lens and mass filter of a single
quadrupole ICP-MS. The cell can be pressurized with a collision or reaction gas to resolve interfering
ions.

Collision mode
In collision mode, the CRC is pressurized with a nonreactive gas – usually helium (He). Ions passing
through the CRC collide with the He atoms, losing a small amount of kinetic energy with each
collision. Polyatomic ions always have a larger ionic cross section than analyte ions of the same mass,
so polyatomic ions collide more often than the analyte ions do. The different collision rates mean the
polyatomic ions emerge from the cell exit with lower residual energy than the analyte ions. The low
energy ions are rejected from the ion beam by a positive bias voltage “step” using a process called
kinetic energy discrimination (KED).
Collision mode requires that all the ions enter the cell with a narrow ion energy spread. Also, the ion
guide must minimize scattering losses to provide high ion transmission at the high cell gas pressures
and high collision rates required for effective KED.
He KED can be considered as a universal CRC mode, as the same cell conditions can be used to resolve
multiple polyatomic ion overlaps on multiple analyte masses in multiple different sample types.

Reaction mode
Reaction mode uses the same CRC hardware as collision mode, but the cell is pressurized with a
reaction gas such as H2, O2, NH3, CH4, N2O, or CH3F, rather than He. Reaction mode can be extremely
efficient, as a reaction between the ion and the cell gas molecule often occurs within the first few
collisions, whereas He KED requires multiple collisions and therefore higher cell gas pressure.
Reaction gas methods are also more specific than He KED, because the gas must be selected based on
its different reaction chemistry with the interfering ion and the analyte isotope. Analysts must therefore
know which interfering ions they are trying to resolve before they select the reaction gas.
Reactive cell gases differ from He KED in that they can be used to resolve interferences other than
polyatomic ions. These other spectral overlaps – such as isobaric overlaps, doubly charged ion
overlaps, and adjacent mass peak-tail overlaps – are less common than polyatomic interferences but
can still be significant.
The other major difference compared to He KED is that reactive cell gases can form new reaction
product ions that may overlap a required analyte. The potential for new product ion interferences has
meant that single quadrupole ICP-MS users tend to use reaction gas methods only when the sample
matrix is consistent and the interferences are predictable. This limitation does not apply to triple
quadrupole ICP-MS (ICP-QQQ) in MS/MS mode, however. The additional quadrupole mass filter
before the CRC of an ICP-QQQ instrument means the composition of the ion beam entering the CRC
is consistent even when the sample matrix varies. As a result, MS/MS controls the reaction chemistry
and removes the possibility of cell-formed product ion overlaps being formed.

Reaction mode operation with single quadrupole ICP-MS configuration

Reaction mode operation with triple quadrupole ICP-MS configuration.

Reactive cell gas methods combined with ICP-MS/MS have allowed analysts to perform completely
new applications that have been impossible to address with conventional single quadrupole ICP-MS.
New users may be overwhelmed by the range of reaction gas modes and analysis possibilities available
with ICP-QQQ. But the technique is well established, the reaction chemistry is well understood, and
there are software tools and published methods available to support users in setting up many typical
analyses.

6. The mass spectrometer (MS)

Most ICP-MS instruments use a quadrupole (or “quad”) mass spectrometer to filter ions by mass, or,
more accurately, by mass to charge ratio (m/z). Since most ions produced by the ICP are singly charged,
ICP-MS can usually be considered to produce a “mass spectrum”.
A quadrupole mass filter consists of two pairs of rods; opposite pairs of rods are connected to separate
electrical supplies. An out of phase RF voltage and a positive or negative DC voltage is applied to the
two pairs of rods (RF/+DC on the y-axis rods and RF/-DC on the x-axis rods). The electric field that
is set up in the space between the rods determines the “set mass” of ions that can travel stably along
the quadrupole axis and pass through the mass filter. The alternating electric fields destabilize the
trajectories of all ions above and below the set mass, so ions at any mass other than the set mass are
rejected from the ion beam.

Quadrupole mass filter used in most ICP-MS instruments. RF and DC voltages filter the ions by mass
to charge ratio (m/z), allowing only 1 m/z at a time to pass through to the detector.

The quadrupole set mass is controlled by the applied rod voltages, which can be changed very rapidly.
This means the quadrupole can scan very rapidly across the mass range, for example from Li (mass 7)
to U (mass 238) more than 10 times per second. With each quadrupole scan, the ions present at each
mass are passed to the detector and counted.
In normal quantitative “spectrum” and isotope ratio analysis, the mass spectrum is built up from
multiple scans across the selected masses. Other measurement modes include time resolved analysis
(TRA), where the ion counts collected in each quadrupole scan are saved on a time-based scale. Single
mass monitoring is also available and is typically used for measurements such as single nanoparticle
analysis.

7. The electron multiplier detector

The detector used in most ICP-MS systems is a discrete dynode electron multiplier (DDEM). The EM
uses a high voltage electrode (or dynode) positioned so that ions that emerge from the quadrupole
strike the dynode. Each ion that strikes the first dynode releases one or more electrons from the dynode
surface. These electrons strike the second dynode, releasing further electrons to strike the third dynode
and so on down the detector. By the final dynode, the cascade of electrons has built up to a high enough
level that it can be recorded as a pulse or “count” by the EM electronics. At very high ion count rates
– above about 1 million counts per second (cps), the detector switches automatically to a low-gain (or
“analog”) mode. This allows intense signals from high concentration elements to be measured without
overloading the detector.
Electron multiplier (EM) detector showing build-up of electron cascade down the detector dynodes to
generate an ion pulse or count.

The EM detector can detect individual ions, so ultralow concentrations can be detected. But the EM
also has extremely wide dynamic range – around 10 or 11 orders of magnitude. In practical analytical
terms, this means ICP-MS can detect a trace element like uranium at a concentration below 0.1 ppt
(0.0000001 ppm) while also measuring a major element, such as sodium in seawater, at 1.18% (11,800
ppm). A total concentration range of more than 11 orders of magnitude, measured in the same
acquisition.

8. Data processing
For each mass measured, the counts registered by the detector are processed by the data analysis
software on the instrument control workstation computer. For conventional quantitative analysis, the
software calculates the concentration of each element in the unknown samples by comparing the
measured counts in the sample to the counts in a known-concentration reference solution. Usually
several reference solutions or “standards” are measured to create a calibration plot of counts vs known
concentration for each element.
A typical calibration plot for ICP-MS quantification of uranium using standards prepared at
concentrations between 0.1 and 1000 ng/L (ppt).

Other types of ICP-MS measurements include speciation analysis, which uses chromatographic data
analysis tools such as peak integration, and single particle and single cell applications, where
specialized data processing tools are used.

The main components of an ICP-MS instrument.

ICP-MS is typically used to analyze samples that are liquids (such as water) or that can be dissolved,
or acid digested, to give a liquid. But ICP-MS is very versatile and can easily measure organic solvents,
detect extremely small (nano)particles, or be connected to accessories that allow direct analysis of
solid materials or gases. ICP-MS can also be coupled to a chromatographic separation device, such as
an HPLC, IC, GC, CE, or Field Flow Fractionation (FFF), to provide information on the different
chemical forms or “species” of each element in a sample. And, as a mass spectrometric technique,
ICP-MS can also separate and measure the individual isotopes of an element, so it can be used for
applications where isotopic abundances or isotope ratios are of interest.

ICP-MS analysis is used in practically every industry from routine environmental monitoring,
consumer product testing, food and pharmaceutical safety applications, through life science and
clinical research, mining and metals analysis, geochemistry, nuclear, and petrochemicals, to measuring
trace metal contaminants in high purity chemicals and materials used in semiconductor manufacturing.

ICP-MS can measure virtually every naturally occurring element plus many non-natural “radiogenic”
isotopes such as technetium, neptunium, plutonium, and americium. The only elements that ICP-MS
can’t measure are H and He (which are below the mass range of the mass spectrometer), Ar, N, and O
(which are present at high level from the plasma and air), and F and Ne (which can’t be ionized in an
argon plasma). Of these “impossible” elements, even F can be analyzed indirectly using a triple
quadrupole ICP-MS.

One of the reasons ICP-MS is so widely used is that it provides extremely low detection limits for
nearly all the elements it can measure. ICP-MS can detect many elements at levels below 0.1 part per
trillion (ppt) – equivalent to one drop of water (50 uL) in 200 Olympic-sized swimming pools (500
million liters). But ICP-MS can also measure elements at concentrations up to 100s or even 1000s of
parts per million (ppm). One thousand ppm is 0.1%, and the concentration range from 0.1 ppt to 0.1%
 covers 10 orders of magnitude. No other technique has such broad elemental coverage, low detection
limits, and wide measurement range.
What is ICP-MS used for?
ICP-MS is a fast, multielement analysis technique that can measure almost every element in almost
any sample type. Labs that perform elemental analysis by ICP-MS are often in industries that analyze
a lot of samples and measure a lot of elements in each sample. Examples of these industries include
environmental monitoring (of river water, drinking water, estuarine and seawater, waste, soil and
sediment digests, biota, etc.), routine measurements for food safety, pharmaceutical materials analysis,
and consumer product testing (toys, textiles, etc.). Other industries where ICP-MS is widely used
include semiconductor and pure chemicals manufacturing, life science, clinical research,
geochemistry, mining, nuclear sciences, materials research, metrology, and academia.

Liquid sample analysis

Liquid sample introduction is by far the most common route by which samples are introduced into an
ICP-MS instrument, partly because liquid calibration standards are widely available and can easily be
prepared with all the required analytes at the appropriate concentrations. Because liquid sample
analysis is so convenient, solid samples are often converted to liquids using acid digestion to dissolve
the sample matrix, or acid extraction to extract the analytes into a solution for analysis. Most routine
ICP-MS applications use a conventional pneumatic nebulizer to introduce the liquid samples. Total
concentrations of the elements of interest are measured against a calibration generated from the
analysis of standards of known concentration.
When very large numbers of samples must be measured, labs will often employ a “discrete sampling”
device. These devices work by loading the sample into a loop and then injecting the contents of the
loop into a carrier stream flowing to the ICP. Discrete sampling speeds up ICP-MS analysis by
enabling the next sample to be loaded into the loop while the previous sample is being measured. This
allows faster overall ICP-MS analysis, reducing analysis time from a typical value of around 3 minutes
per sample to less than 1 minute per sample for a triplicate multielement analysis.
ICP-MS applications include more unusual measurements where the relative abundances of the
different isotopes of an element are of interest, as in isotope ratio or isotope dilution analysis. ICP-MS
can also run a quick scan across the whole mass range, giving approximate or “semi-quantitative”
results for all elements without needing specific calibration standards. This type of screening analysis
is extremely useful for contaminant surveys of environmental or food samples, identifying the cause
of heavy metal poisoning, and for fault finding defects in products.
In some applications, a normal “total” elemental concentration measurement does not give sufficient
information. In these cases, separate analysis of the different chemical forms or “species” of an element
may be required.

Speciation analysis
ICP-MS speciation analysis involves coupling the ICP-MS to some form of chromatography device to
separate the different chemical forms of an element. The ICP-MS detects the elemental signal as
normal, but the different chemical forms are introduced sequentially to the ICP-MS for separate
detection and quantification. High performance liquid chromatography (HPLC, often just called “LC”)
is the most widely used separation technique, but ion chromatography (IC), gas chromatography (GC),
capillary electrophoresis (CE), field flow fractionation (FFF), and hydrodynamic chromatography
(HDC) are among the other separation techniques that have been coupled to ICP-MS. Examples of
applications where speciation analysis is required include separating the different forms of chromium
(Cr), where the trivalent form (Cr(III)) is harmless, but the hexavalent form (Cr(VI)) is toxic. Similarly,
inorganic arsenic (As) is much more harmful than the common organic forms (such as arsenobetaine)
found at high levels in some seafoods. And food safety checks may require specific determination of
the level of methyl mercury and organotin compounds in fish and shellfish, rather than just total
mercury and total tin.
Speciation analysis with ICP-MS extends far beyond separating toxic and non-toxic forms of an
element in environmental and food samples, though. Many industrial processes require assessment of
the chemical form of the element, either to ensure the product performs as intended, or to identify
contaminants that may affect the process or lead to unwanted emissions. Examples of these types of
industrial speciation measurements include monitoring mercury compounds in petrochemical refinery
feedstocks to avoid catalyst poisoning and corrosion in the cracking process equipment. In
semiconductor manufacturing, GC-ICP-MS is used to measure trace hydride gas contaminants in the
arsine gas used as a precursor in non-silicon semiconductor device fabrication.

Nanoparticles and single cells

As well as measuring the amount of the elements dissolved in the sample solution, ICP-MS can also
be used to measure the composition of tiny particles suspended in the liquid. Large (micron size)
particles would be removed by the nebulizer and spray chamber of the ICP-MS, so cannot be measured.
But very small (nano-scale) particles remain suspended in the aerosol droplets and are carried to the
plasma. When these “nanoparticles” (NPs) are destroyed and atomized in the plasma, they give a
“plume” of ions, which can be detected as a signal pulse above the constant background signal from
the dissolved element. Nanoparticle analysis using single particle ICP-MS (spICP-MS) is of increasing
interest as researchers strive to understand more about the impact of NPs on environmental and
biological systems. NPs are also becoming more widely used in industrial processes, consumer
products, paints, and coatings, and for applications such as drug delivery and agrochemicals. A related
application uses a special, low flow sample introduction system to deliver intact single cells to the
plasma – single cell ICP-MS (scICP-MS). This approach allows the metal content of individual cells
to be measured to aid understanding of biological and biopharmaceutical processes.

Solid sample analysis

While liquid sampling dominates, solids can also be analyzed by ICP-MS using an appropriate
accessory. A laser ablation (LA) device can be connected to an ICP-MS to perform direct solids
analysis by LA-ICP-MS. LA-ICP-MS involves placing the sample into a chamber on a special mount,
then focusing a high energy beam from a pulsed laser onto the sample surface. Solid particles ablated
and vaporized from the sample surface are swept up with a gas stream (usually helium) and carried to
the ICP torch, where they are decomposed, dissociated, atomized, and ionized in the same way as for
normal aerosol droplets.
LA-ICP-MS is sometimes used for bulk (whole sample) analysis in applications such as quality control
of metals, alloys, glasses, and ceramics where digesting the material might be difficult. But the real
benefit of LA-ICP-MS is that the laser can be focused to a beam size of only a few microns, so analysis
of small samples or a very tiny part of a larger sample is possible. This capability enables nearly non-
destructive analysis of precious samples such as gemstones, archaeological artifacts, pottery, coins,
paint fragments, and so on. A similar approach can be used for LA-ICP-MS analysis of airborne
particulate analysis, where particles are collected on a sampling filter, providing composition
information of individual particles for environmental and workplace dust analysis. LA-ICP-MS is also
applied in criminalistics, the analysis of crime scene debris such as glass fragments from a road traffic
accident, pen ink from a ransom note, fibers from a garment, soil from the sole of a shoe, gunshot
residue, and many other such materials.
When combined with precise automated sample position control, LA-ICP-MS can be used for 2D or
3D mapping of the distribution of elements within a sample – often termed “imaging”. By continually
scanning the ICP-MS while slowly moving the laser ablation “spot” across the sample surface, a
chemical profile or map of the sample composition can be produced. LA-ICP-MS imaging is used in
geological studies (geoimaging) and the same technique can be applied to biological materials, such
as teeth, bones, and tissue sections (bioimaging).

Gas analysis
For direct analysis of elements in gases, a special gas handling device is used to introduce gases into
the ICP. ICP-MS gas analysis applications include measuring volatile organometallic compounds in
natural gas, headspace sampling for flavor and fragrance testing of ingredients and foodstuffs, and
measuring trace contaminants in raw materials in chemical and petrochemical manufacturing. Many
of these types of applications can be performed using GC-ICP-MS, where a gas chromatograph (GC)
is connected to an ICP-MS instrument using a heated transfer line. The GC processes the sample using
standard gas sampling accessories, and the ICP-MS detects and quantifies the compounds as they
emerge from the GC column. GC-ICP-MS applications often have parallels in organic GC mass
spectrometry (GC/MS) but, for compounds that contain a heteroelement that can be measured by ICP-
MS, the ICP-MS detector enables lower detection limits, better specificity, and the potential for
compound-independent calibration.
Direct analysis of gaseous samples is also becoming increasingly important in applications such as
ensuring workplace safety in semiconductor fabrication, where organometallic gases may be used in
manufacturing processes. Methods have been developed that employ an ICP-MS instrument fitted with
a gas-exchange device (GED) where compounds in the lab air are transferred by gas exchange into an
argon stream, which is then passed to the ICP

ICP-MS is a fast and sensitive elemental analysis technique that can measure almost all the naturally
occurring elements and many non-natural, radiogenic elements as well.

Find out more about the Agilent 7850 ICP-MS, 7900 ICP-MS and 8900 ICP-QQQ models, and see
how they could transform your laborato