An Introduction to Inductively

Coupled Plasma - Mass

Spectrometry (ICP-MS)

ICPMS PEER GROUP

1st August 2003

ICPMS THE TECHNOLOGY DRIVING ALS

 What Is ICP-MS?

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 What is ICP-MS?
ICP-MS is a technique which
allows the analyst to identify
and quantify the
atomic/elemental make up of a
material.
It provides a high speed, multi-
element analysis.
It offers lower detection limits
than ICP-OES for most
elements.

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 How does an ICP-MS Work?
Basic Components of an ICP-MS System

S a m p l e I n t r o d u c t io n S y s t e m
( N e b u li z a t i o n )

I o n iz a t io n S o u r c e
( I n d u c t i v e l y C o u p l e d P la s m a )

D e t e c t io n S y s t e m
(M a s s S p e c tro m e te r)

A n a ly t ic a l R e a d O u t

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 Sample Introduction System

Purpose

To take solution samples and transport

them as a homogenous aerosol to the
plasma.

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 Sample Introduction System
Sample Introduction
System Main
Components
Peristaltic Pump
Nebulizer
Spray Chamber
Plasma Torch and
Injector

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 Sample Introduction System

Peristaltic Pump

 Ensures constant
flow rate of sample.
 Allows regulation of
uptake rate.

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 Sample Introduction System
Nebulizer
 Mixes Argon gas with Meinhard Nebulizer
sample solution to
produce a mist or aerosol.
 Many different nebulizers
are available, each with
their own advantages and
disadvantages depending
upon the application.

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 Sample Introduction System
Spray Chamber
 Separates out droplets by size.
 Large droplets removed by
collision with spray chamber
walls.
 Only droplets of the correct size
and velocity will make it
through the spray chamber to
the torch.
 Only around 2-3% of the
originally aspirated solution
reaches the torch.

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 Sample Introduction System
Plasma Torch and
Injector.
 Plasma gas flow ~15
l/min, reacts with RF
field to form the
plasma.
 Auxiliary gas flow
controls position of
plasma relative to the
torch.
 Nebulizer gas flow
provides gas flow to
the nebulizer and
carries the sample
aerosol into the
plasma.

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 How does an ICP-MS Work?
Basic Components of an ICP-MS System

S a m p l e I n t r o d u c t io n S y s t e m
( N e b u li z a t i o n )

I o n iz a t io n S o u r c e
( I n d u c t i v e l y C o u p l e d P la s m a )

D e t e c t io n S y s t e m
(M a s s S p e c tro m e te r)

A n a ly t ic a l R e a d O u t

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 Ionization Source

Purpose

The heat energy of the plasma firstly

dries the sample aerosol, and then
strips electrons from the elements to
create ions.

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 Ionization Source
What is a plasma?

A plasma is a stream of
highly ionized gas.
A plasma is electrically
conductive.
A plasma is affected by
magnetic fields.
Operate at ~ 6-10000 K.
Fourth state of matter.
Most common state of
matter in the universe.

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 Ionization Source

How do we make Plasmas?

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 Ionization Source
How Do We Make Plasmas?

A - Argon gas flows through three concentric tubes.

B - A copper coil, called the load coil, surrounds the
top end of the torch and is connected to a radio
frequency generator. When Rf power (typically 700-
1500 Watts) is applied to the load coil, A/C oscillates
at a rate corresponding to the frequency of the
generator (27 or 40 megahertz) which causes Rf
electric and magnetic fields to be set up.
C - With Argon flowing through the torch, a Tesla
spark is applied causing some electrons to be
stripped from the Argon atoms.
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 Ionization Source
How Do We Make Plasmas? - Continued

D - Stripped electrons are then caught in the

magnetic field and accelerated. The high energy
electrons collide with Argon atoms stripping off still
more electrons and propagating the chain reaction.
(adding energy to the electrons by the use of a coil is
called inductively coupling)
The Inductively Coupled Plasma (ICP) discharge is
sustained as long as the Rf energy is transferred
through the inductive coupling process.
E – The sample aerosol-carrying nebulizer flow
distorts the plasma.

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 Ionization Source
Plasma Processes
• Desolvation
• Remove solvent from
sample.
• Vapourization
• Decompose individual
particles into a gas of
individual molecules.
• Atomization
• Dissociate molecules into
atoms.
• Ionization
• Removal of electron

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 Ionization Source
Why use Plasmas in Analytical
Instruments?
Higher plasma temperatures
improve
excitation/ionization.
Flames and Furnaces have
upper ranges of 3000C,
plasmas easily attain 6000C
or higher.
The higher ICP
temperatures reduce many
chemical interferences.

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 Ionization Source
Condition of the sample in the plasma
• Most elements are 90% ionized in the 6000oC environment of the
plasma. Exceptions to this are:
 As - 52%
 Se - 33%
 S - 14%
 F - 0.0009%

• Singly charged positive ions predominate.

• There are some small doubly charged populations that exist, the
worst case is Ba++.

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 Ionization Source
Why use Plasmas in
Analytical Instruments?
Low background.
Low detection
limits.
Multielement
technique.
Extended
calibration range.

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 How does an ICP-MS Work?

Basic Components of an ICP-MS System

S a m p l e I n t r o d u c t io n S y s t e m
( N e b u li z a t i o n )

I o n iz a t io n S o u r c e
( I n d u c t i v e l y C o u p l e d P la s m a )

D e t e c t io n S y s t e m
(M a s s S p e c tro m e te r)

A n a ly t ic a l R e a d O u t

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 Detection System
Purpose
The mass spectrometer receives an ion stream
from the plasma. It then focuses the stream
and filters it so that only ions with a certain
mass-to-charge (m/z) ratio are allowed to
reach the detector.
The ion stream hits the detector, which
generates an electrical signal which is used
to determine how many hits/counts it has
received.

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 Detection System

The Mass Spectrometer consists of

several important sub-components:
 Ion extraction system (Interface)
 Ion Focusing System (Ion Optics)
 Vacuum System
 Mass Filter
 Detector

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 Detection System
The Interface

The interface is the region

between the plasma and
the central chamber of
the Mass Spectrometer

• The main function of the

interface region is to
extract ions from the
central channel of the
plasma and direct them to
where the mass
separation will take place.

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 Detection System
Main
Chamber

ICP
Skimmer
cone Sampler
cone
The Interface and Vacuum System
Ion extraction is achieved through use of vacuum
pumps.
A mechanical pump evacuates the region between
the sampler and skimmer cone. This serves to pull
ions from the plasma through the sampler orifice.
The main chamber is evacuated using powerful
turbo pumps which draw the ion stream from the
interface region through the skimmer orifice.

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 Detection System

The Vacuum System - Turbo Pumps

The turbo pump has two important purposes:

The first is to assist in ion extraction.

The second is to remove neutral species
from the main chamber so as to provide a
collision free path for the ion stream.

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 Detection System
Ion Optics
The function of the ion optics is
to focus the ions extracted by
Differential
Aperture Photon the interface and direct them
Stop
Sampler
into the mass filter.
Rf Only Skimmer

Mass Filter
Filter
Cylinder
Lens (E1) Using the electric field from
specially shaped metal pieces
(ion lenses), the ions are
pushed into the mass filter.
These electric fields are created
by applying an electric current
or voltage to the lens.
Mass Filter Ion Optics Interface

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 Detection System
Ion Optics
The Perkin Elmer ELAN series of instruments that ALS
Chemex uses has an adjustable voltage lens called an
AUTOLENS.
The Autolens is cylindrical in shape.
As the ion stream passes through the Autolens, the applied
voltage focuses the analyte of interest.
The voltage applied to the Autolens is computer controlled
and adjusts to an optimal voltage for each particular analyte.

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 Detection System
Mass Filter
After the ion stream is focused by the autolens, it then enters
the quadrupole mass filter.
A quadrupole is a set of four gold plated ceramic rods which
are set in a rigid mount.
The rods are charged, with opposing rods having the same
charge as shown below.

+
+ ++

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 Detection System
Mass Filter
When the charge on the rods
alternates at a certain
frequency, only ions with a
particular mass-to-charge ratio
spiral perfectly through the
quadrupole and reach the
detector.
All other masses are either lost
from the quadrupole or collide
with the negative rods.
By changing the frequency of
the alternating charge, ions of
different masses can be
analyzed.

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 Detection System
Quadrupole from a Perkin Elmer ELAN 6000

Detector

Quadrupole
Rodset

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 Detection System
The Detector
After the analyte ions have passed through the mass filter they
reach the detector.
The detectors used in the Perkin Elmer ELAN series are
impact sensitive electron multipliers. (shown below)

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 Detection System
The Detector
Ions exiting the quadrupole are
directed (via an electric field) on to an
impact sensitive film.
When the ions hit the film they
dislodge electrons on the outer layer
of the film.
The dislodged electrons then make
their way down a series of dynodes,
with electron multiplication occurring
at each successive dynode.
This is process is called electron
cascading.

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 How does an ICP-MS Work?

Basic Components of an ICP-OES System

S a m p l e I n t r o d u c t io n S y s t e m
( N e b u li z a t i o n )

E x c it a t i o n S o u r c e
( I n d u c t i v e l y C o u p l e d P la s m a )

D e t e c t io n S y s t e m
(S p e c tro m e te r)

A n a ly t ic a l R e a d O u t

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 Analytical Read Out

The amplified current

from the electron
multiplier is recorded.
The system software
then converts the
recorded signal to an
easily understandable
form, such as number
of counts or
concentration.

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 Analytical Read Out

Pb
208

52.4% Abundant

22.1% Abundant
Pb
206 207
Pb
24.1% Abundant

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 Analytical Read Out
From the analysis, we are
able to calculate the
intensity of the signal at a
particular mass. Sb 121 - Calibration Chart
By running standards of 2500000
known concentrations, we
then create a calibration 2000000

curve.
1500000

Intensity
Signal
Given an unknown sample,
we are able to determine 1000000

the intensity of the signal, 500000

and then interpolate the
concentration of a 0
0 5 10 15
particular element. Concentration (ppb)

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 Analytical Readout

INTERERENCES

When analysing the data, one needs to be

aware of interferences. Three types of
interference occur:
 Isobaric interferences
 Polyatomic interferences
 Doubly charged ion interferences

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 Analytical Readout
ISOBARIC INTERFERENCES

• Isobaric interferences arise when the analyte

mass coincides with an isotope of a different
element, for example, the major isotope of zinc
at mass 64 has an interference from a minor
nickel isotope.
• In cases like this, it is best to read one of the
other zinc isotopes that is free from interference.

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 Analytical Readout
POLYATOM IC INTERFERENCES

• Conditions in the plasma sometimes allow for the

formation of polyatomic ions. This occurs most
often with elements that are in high abundance
such as argon, oxygen and chlorine. Examples
of polyatomic interferences are :
• Ar-Cl on mass 75 (As) and 77 (Se)
• Cl-O on mass 51 (V)

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 Analytical Readout
DOUBLY CHARGED ION INTERFERENCES
• Conditions in the plasma can also permit the
formation of doubly charged ions. This is a problem
in that the quadrupole filters according to the mass-
to-charge ratio, not mass alone. So, this means
that Ba++ (m/z=138/2) will pass through the
quadrupole at the same time as Ga+ (m/z=69/1).
* Interferences from polyatomic and doubly charged
ions can be minimised by optimising the gas flow
and lens voltage.

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 ICPMS in Summary
IN SHORT, an ICPMS works in the
following way:
The ICP (Plasma) atomizes, and
then ionizes the introduced sample.
The sample stream is then focused
by an ion lens and passes through a
mass filter.
The ion stream then hits the
detector.
The number of hits or counts is then
converted to a concentration of
analyte by the system computer.

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