Inductively Coupled Plasma Mass

Spectrometry
(ICP-MS)

Debjani Banerjee
Department of Chemical Engineering
IIT Kanpur
 Introduction
What is ICP-MS ?
Inductively Coupled Plasma Mass Spectrometry

Mass spectrometry (MS) is an analytical technique that ionizes chemical species and
sorts the ions based on their mass-to-charge ratio.

Inductively coupled plasma mass spectrometry (ICP-MS) is a type of mass

spectrometry which is capable of detecting metals and several non-metals at
concentrations as low as parts per billion on non-interfered low-background
isotopes.
Elemental Analysis with

Wide Elemental Coverage Extremely Low Detection Limits

(ppt/ppm) or (ng/L to mg/L)
Fast Analysis times (all
elements at once) Simple Spectra

High Throughput & Productivity Isotopic Information

Approximate detection capability of ICP-MS
Principle of Atomic Spectroscopy

Atomic Absorption Spectroscopy

(FAAS)
ICP-Mass Spectroscopy
Graphite Furnace AAS

(GFAAS)
Inductively Coupled Plasma -

Optical Emission Spectroscopy

Nucleus

Electron
 Atomic spectrometry

Atomic Absorption -
Light of specific characteristic wavelength is
absorbed thereby promoting an electron to a
Light of specific higher energy level.
wavelength from Hollow Light absorption is proportional to elemental
Cathode Lamp (HCL) - concentration

Atomic Emission High energy (light and heat) promotes an

-
electron to a higher energy level
Light and heat energy (excitation). Electron falls back and emits
from high intensity source light at characteristic wavelength
(flame or plasma) - - Light emission is proportional to
elemental concentration

Mass Spectrometry - High energy (light and heat) ejects electron

Light and heat energy from shell (ionization). Result is free
from high intensity electron and atom with positive charge (Ion)
source (plasma) Ions are extracted and measured directly in
mass spectrometer
-

An atom can only absorb the radiations that it is able to emit

 Types of Atomic Spectroscopy

Air/acetylene flame or an electrically heated Graphite tube is used to evaporate the solvent
and dissociate the sample into its component atoms. When light from a hollow cathode lamp
passes through the cloud of atoms, the atoms of interest absorb the light from the lamp. This is
measured by a detector, and used to calculate the concentration of that element in the original
sample

ICP-AES is a multi-element analysis technique that uses an inductively coupled plasma source
to dissociate the sample into its constituent atoms or ions, exciting them to a level where they
emit light of a characteristic wavelength. A detector measures the intensity of the emitted
light, and calculates the concentration of that particular element in the sample
 Crucial steps in atomic spectroscopies and
other methods
ICP-MS and AAS and AES, X-ray
other MS methods
methods

FAAS, AES GFAAS

 Basic Instrumental Components of ICP-MS

Interface: Links the atmospheric pressure ICP ion source to the high vacuum MS

Vacuum System: Provides high vacuum for Ion Optics, Quadrupole and Detector

Data Handling & System Controller: Controls all aspects of instrument control and
data handling to obtain final concentration results
ICP-MS Sample Introduction Area
Generation of Positively Charged Ions in Plasma
Peristaltic Pump:
Ensures constant flow of liquid
irrespective of differences in
viscosity between samples,
standards and blanks. Sample
pumped at 1ml/min
Micromist Nebulizer:
Liquid is converted into a fine
aerosol by pneumatic action of a
flow of argon gas (~1L/min)
smashing the liquid into tiny
droplets
Double Pass Spray
Chamber:
Spray Chamber only allows small
droplets (<10µm) to enter the
plasma. Larger droplets having
higher momentum collide with
wall of spray chamber, get
condensed & eventually fall out
by gravity through the drain
 ICP Plasma Ionization Source

Inductively coupled plasmas are formed by coupling energy produced by a RF generator to the
plasma support gas with an electromagnetic field. The field is produced by applying an RF
power (typically 700-1500 W) to a load coil.

PHZ: Sample desolvation

IRZ: Atomization
NAZ: Ionization
Degree of Ionization, First & Second Ionization
potentials of selected elements

Argon first ionization potential ~ 15 eV

Most elements have first ionization potentials below 10 eV, hence >50% ionization
Very few elements have second ionization potential below 10 eV, less doubly
charged species
ICP Interface Region
A section that connects the
ionizing section at ambient
pressure to the mass
spectrometer at high
vacuum(~10-6 torr).

Function is to export the

ions produced in argon plasma
and transport them to the
mass spectrometer

Two metallic (Ni or Pt) cones

with small orifices(1mm)-
Sampler and Skimmer Cones
directs the expanded gas jet of
ions into the MS
 ICP Ion Focussing Region
One or more electrostatically
controlled lens component
made up of series of metallic
plates or cylinders having a
voltage placed on them

Ions are separated from

Photons & Neutrals
by positioning MS off-axis to
the ion beam or using a
Physical barrier
Out of a million ions generated in the plasma, only one actually reaches the
detector due to higher concentration of matrix elements than analyte.
Role of ion focussing is to transport maximum number of analyte ions from
the hostile environment of plasma to the MS via the interface.
Photons & Neutrals cause signal instability & contribute to background
noise.
Voltages on the ions lens components electrostatically steer the ions of
interest into the MS.
 Mass Analyzer- Quadrupole
• Quadrupole is a sequential mass filter, Made of stainless steel or molybdenum
which separates ions based on their with ceramic coating, 15-25 cm in length,
m/z. 1cm in diameter
• Measurement of the m/z of the ion
allows qualitative identification of the
isotope or molecule. Magnitude of the
ion current is used to provide
quantitation of the amount of the
analyte in the original sample.
• Two pairs of parallel cylindrical rods to
which a varying AC voltage plus a DC
voltage is applied.
• Any ion above or below the set mass of
the quadrupole enters an unstable
trajectory and gets lost from the ion
beam.
• Varying the AC and DC voltages,
different masses can be selectively
allowed to pass through.
 Ion Detectors
Detector in ICPMS ensures high sensitivity and low background noise.

Detector is an Electron Multiplier Device which can generate a measurable signal pulse from
the impact of a single ion.

A positive ion arrives at the mouth of the detector, it is deflected onto the first dynode, held
at a high negative voltage.

The impact of the ion releases several free electrons from the dynode surface, which are
repelled from the high negative voltage at the front and strike the next dynode.

 Each electron which strikes a dynode releases several electrons from that surface and hence
the device is called "electron multiplier". The multiplication factor builds up a pulse large
enough to be measured reliably as an ion "count".
 Spectral Interferences
Introduction:
Polyatomic or molecular Spectral Interferences severely compromise detection capability of
certain elements by ICP-MS using the Quadrupole mass analyzer technology. Generated by
combination of Plasma/nebulizer Gas, solvent and matrix derived ions.
EXAMPLES OF SPECTRAL INTERFERENCES

Plasma Gas Interference:

Most abundant isotope of Ar is at mass 40 which
dramatically interferes with the most abundant
isotope Of Ca at mass 40.
Combination of argon and oxygen in an aqueous
sample generates the 40Ar16O+ interference, which
has a significant impact on the major isotope of Fe
at mass 56.

Solvent Based Interferences: In a HCl acid medium, 40Ar+ combines with the most
abundant chlorine isotope at 35 amu to form 40Ar35Cl+, which interferes with the only
isotope of As at mass 75.
Isobaric Interferences: Direct overlap from a different element with an isotope at the
same nominal mass known as an isobaric interference, e.g. 114Sn overlap on 114Cd
**Doubly-charged species resulting from ions created by the loss of two electrons instead
of just one. Because the quadrupole separates ions based on m/z (mass over charge ratio),
a doubly-charged ion (M2+) will appear at mass M/2. An example of a doubly-charged
interference would be the 136Ba2+ overlap on 68Zn+
 Collision Reaction Cell (CRC)-Removal of
Spectral Interferences
The CRC devices in commercial ICP-MS instruments have been designed to remove polyatomic
species
Modes of Operation:
No-gas mode - no gas in the cell - the instrument performs like a standard ICP-MS. High
sensitivity is achieved for all elements. This mode is typically used for uninterfered elements
such as Be, Hg, Pb.

Helium (Collision) mode - used for all analytes that suffer matrix-based Interferences are
removed based on their physical size. Since all polyatomic interferences are larger than the
analytes they interfere with, they will collide with the He cell gas atoms more frequently than
will the smaller analyte ions. The polyatomic ions will therefore lose more energy and will be
prevented from entering the mass analyzer by a positive discrimination voltage. This is known
as Kinetic Energy Discrimination (KED).

Hydrogen (Reaction) mode - used only for the very few situations where He collision mode
is not efficient enough, which is only for intense plasma-based interferences.
Collision Mode:
Reaction Mode:
Reaction Mode:
 Standard Preparation
Standards can be prepared directly by dissolution of the metal or metal salt. Prepared
solutions are also commercially available.

If similar multi-elemental analyses are being performed on a routine basis, pre-prepared
multi-element solutions are commercially available from a number of suppliers.

Typical concentrations in the prepared stock solutions would be 1000 mg/L or 1000 ppm

Pipette 1 ml of Analyte from a stock solution of 1000 ppm to a volumetric flask (100 ml).
Make the solution up to volume with water. The concentration in this intermediate solution
is: 10 ppm for Analyte. Transfer 1 ml of the above solution to a volumetric flask (100 ml) and
make up to volume using dilute trace metal grade nitric acid. The resulting concentration of
Analyte will be 0.1 ppm or 100 ppb. Prepare 5 Standards in accordance with concentrations
that you expect in your sample but less than 500 ppb.

Each standard sample (10 ml) should be prepared in millipore water and 2% trace metal
grade HNO3.
 Total dissolved solids must not exceed 0.1 wt %.(e.g. 0.1 g per 100 ml of solution). There
must be no suspended solids ( if in doubt filter a portion with 0.2 micron cellulose nitrate
syringe filter).
Sulphuric acid is to be avoided because it forms polyatomic species and causes rapid
damage to the Ni interface cones. HF can harm plasma torch and spray chamber.
 Contamination issues
Various factors influence the ability to get the correct result with any
trace element technique. Potential Sources of contamination must be
addressed
 ICPMS is mainly for liquid samples. Laser Ablation and other methods for Solid Samples.

Total Dissolved Solids (TDS) must be kept below 0.2%

Common dissolution agents are nitric acid, perchloric acid, hydrofluoric acid, aqua regia,
hydrogen peroxide, or various mixtures of these—typically used for metals, soils or
sediments, minerals and biological samples. The acid concentration in the final solution
being presented to the instrument should ideally be 2–3% maximum. Appropriate corrosion-
resistant sample introduction components should be used for HF. Hydrochloric, sulfuric, and
phosphoric acids should be avoided due to matrix interferences. Nitric acid should be the
preferred choice
Ultrapure reagents & millipore water & Argon should be used for preparation and dilution.
Reagents should not contaminate or interfere with the analysis. Manufacturers of
laboratory chemicals now offer ultra-high purity grades of chemicals, acids specifically for
use with ICP-MS. Shelf life of all chemicals should be noted.
Liquid Samples should be stored in clean containers. Potential Contaminants can be your
glasswares. Contamination during preparation, dilution, storage & sample introduction
affect reagent blank levels and negatively impact instrument and method detection limits.
PTFE or PFA, although costly are considered the cleanest materials. Analyst must be careful
about some common trace element contaminants found in human body.
ICP-MS is a technique capable of quantifying up to 75 different elements. It is therefore
absolutely critical to use calibration standards that have been specifically made for a multi-
element technique such as ICP-MS. Calibration standards made from high purity metal salts
must be evaluated for potential interferents.
 Methods of Quantitation
Semi Quantitative Analysis:

If data quality objectives for accuracy and precision are less
stringent, ICP-MS offers a very rapid semiquantitative mode of
analysis. This technique enables you to automatically determine the
concentrations of up to 75 elements in an unknown sample, without
the need for calibration standards.

General principle is to measure the entire mass spectrum, without

specifying individual elements or masses.

A positive or negative confirmation can be made for each element

present in the sample.

Semiquant, as it is often called, is an excellent approach to rapidly

characterize unknown samples.
 Methods of Quantitation
Quantitative Analysis:
Quantitative analysis in ICP-MS is the fundamental tool used to determine analyte
concentrations in unknown samples.
The instrument is calibrated by measuring the intensity for all elements of interest in a
number of known calibration standards that represent a range of concentrations likely to be
encountered in your unknown samples.
Software creates a calibration curve of the measured intensity versus concentration for each
element in the standard solutions
Once calibration data are acquired, the unknown samples are analyzed by plotting the
intensity of the elements of interest against the respective calibration curves. The software
then calculates the concentrations for the analytes in the unknown samples.
This type of calibration is often called external standardization and is usually used when
there is very little difference between the matrix components in the standards and the
samples
 Quantitative Analysis
A statistical least squares regression fit of the data is obtained. The "goodness of
fit" of the regression is used as a measure of the reliability of the calibration. The
correlation coeficient (R2) should be computed at 0.999 or better. Precision of
measurement is reported at % RSD.
The %RSD provides an estimate of the
consistency of the analyses of the same
standard, or in other words, the
reproducibility of the measurement

Name Conc (ppb) RSD

Blank 0N/A

100 99.756 4.5

200 194.194 4.6

300 297.13 7

400 395.577 4.3

500 507.632 4.6

Figures of Merit
The sample introduction system, Constant motion and pressure of the pump
comprising the peristaltic pump, rollers on the pump tubing, made from a
nebulizer, spray chamber, and drain polymer-based material, ensure a continuous
system, takes the initial abuse from flow of liquid to the nebulizer. Pump tubing
the sample matrix, and as a result, has the tendency to stretch , which changes
is an area of the ICPMS that the amount of sample being delivered to the
requires a great deal of attention nebulizer

Tip of the nebulizer

should not get blocked. Routine Drain of spray chamber
must function properly.
Microscopic particles can
build up on the tip of the
Maintenance Malfunctioning or leaking
drain can produce
nebulizer without the Staining and discoloration changes in the spray
operator noticing, which, of the outer tube of the chamber backpressure,
over time, can cause a quartz torch because of producing fluctuations in
loss of sensitivity, heat and the corrosiveness the analyte signal,
imprecision, and poor of the liquid sample can resulting in erratic and
long-term stability. cause electrical arcing imprecise data

The most common types of problems associated with the interface are blocking or
corrosion of the sampler cone & skimmer cone
 Important Criteria
Selecting a technique requires the consideration of a
variety of important criteria, including:

• Detection limits
• Analytical working range
• Sample throughput
• Data quality
• Cost
• Interferences
• Ease-of-use
• Availability of proven methodology
Comparison of ICP-MS & other techniques
ICP-MS Applications
 References
1) Robert Thomas, A Practical Guide to ICPMS, CRC Press
2) Howard E. Taylor, Inductively Coupled Plasma Mass Spectrometry,
Practices & Techniques, Academic Press
3) S. M. Nelms, ICP Mass Spectrometry Handbook, Blackwell
Publishing, CRC Press
4) Steve J Hill, Inductively Coupled Plasma Mass Spectrometry and its
Applications, Blackwell Publishing
5) Akbar Montaser, Inductively Coupled Plasma Mass Spectrometry,
Wiley
6) Edmond de Hoffman & Vincent Stroobant, Mass Spectrometry,
Principles & Applications, Wiley
7) Agilent ICPMS 7900 Manual and Videos
8) The 30 minute guide to ICP-MS by Perkin Elmer
9) Inductively Coupled Plasma– Mass Spectrometry (ICP-MS) for
Quantitative Analysis in Environmental and Life Sciences: A Review of
Challenges, Solutions, and Trends.
Thank you for your attention!!
Monochromator
Comparison of ICP-MS & other techniques