ICP-OES - Inductively Coupled Plasma Optical Emission Spectrometry

=
Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES)

Atomic spectrometry
Atomic Absorption

Light of specific characteristic wavelength is

absorbed by promoting an electron to a higher
energy level (excitation)
Light absorption is proportional to
elemental concentration

Light of specific wavelength

from Hollow Cathode Lamp (HCL)
-

Atomic Emission
Light and heat energy from high
intensity source (flame or
plasma)

Mass Spectrometry

High energy (light and heat) promotes an

electron to a higher energy level (excitation).
Electron falls back and emits light at
characteristic wavelength
Light emission is proportional to
elemental concentration

Light and heat energy from high

intensity source (plasma)
-

High energy (light and heat) ejects electron

from shell (ionization). Result is free electron
and atom with positive charge (Ion)
Ions are extracted and measured directly in
mass spectrometer

Characteristics of instruments

Detection
Merit

ICP-MS

ICP-AES

mass

emission

absorbance

multielement

high sensitivity

damage from
high salinity

relatively low
sensitivity

monoelement

< ppt
100 ppb

0.1 ppb
10 ppm

high sensitivity

GF-AAS

multielement
Demerit

Ranges

1 ppb
100 ppb

Introduction to ICP-AES

Atomization Emission Sources

Flame still used for metal atoms

Electric Spark and Arc
Direct current Plasmas
Microwave Induced Plasma
Inductively Coupled Plasma the most important
technique

Advantages of plasma
Simultaneous multi-element Analysis saves
sample amount
Some non-metal determination (Cl, Br, I, and S)
Concentration range of several decades (wide
range)
Enable high resolution

Disadvantages of plasma
very complex Spectra - hundreds to thousands of
lines
Expensive optical components
Expensive instruments, highly trained personnel
required

Atomization
i.

Need to break sample into atoms to observe atomic spectra

ii.

Basic steps:
a) nebulization solution sample, get into fine droplets by spraying through thin nozzle
b) desolvation - heat droplets to evaporate off solvent just leaving analyte and other
matrix compounds
c) volatilization convert solid analyte/matrix particles into gas phase
d) dissociation break-up molecules in gas phase into atoms.
e) excitation and ionization with light, heat, etc. for spectra measurement.->cause the
atoms to become charged
Excitation and ionization/

Evaporation/

Vapouration /

Dissociation

Inductively Coupled Plasma

Inductively Coupled Plasma (ICP)
Plasma generated in a device called a Ar
cools outer tube, defines plasma shape
Rapid tangential flow of argon cools outer
quartz and centers plasma
Rate of Argon Consumption 5 - 20 L/Min
Radio frequency (RF) generator 27 or 41
MHz up to 2 kW
Telsa coil produces initiation spark

Torch

Magnetic field

Ions forced to flow in closed

path, Resistance to flow
causes heating

Ar charges
by Tesla coil
(high voltages at high frequency)

Temperature Regions
in Plasma Torch

Plasma characteristics
Hotter than flame (10,000 K) more complete atomization/
excitation
Atomized in "inert" atmosphere
Ionization interference due to high
density of e- is very small
Sample atoms reside in plasma for
~2 msec
Plasma chemically inert, little oxide
formation
Temperature profile quite stable
and uniform.

Instrumentation of ICP-AES
1.
2.
3.
4.
5.

Radio Frequency (RF) Generator

Sample Introduction System
Torch
Spectrometer (Polychromators)
Detector

Tail flame
Fireball

Spectrometer

Induction cell

Radiofrequency
generator

PMT

Coolant gas

Torch

Auxiliary gas

Sample capillary

Coating gas
Nebulizer

Computer
Computer

Peristaltic
purge

Spray chamber
Injector
gas
Sample
solution

To drain

Schematic diagram of ICP-AES instrument

A. RF Generator
Radio-Frequency (RF) Generator is a device that is used to
provide the power required for the generation and sustaining of
the plasma discharge.

The power required for ICP-AES measurements ranges

between 600 and 2500 W

B. Sample Introduction System

(1) Peristaltic Pump

Peristaltic Pump

(2) Spray Chamber

Scott chamber
- traditional equipment
- large volume

Cyclonic chamber
more aerosol
smaller volume
better wash out

Why we need Spray Chambers?

Separation of small droplets from large ones

- small droplets to the plasma

- large droplets to the drain
Compensate pulsation of the pump

(3) Nebulizer

Transform a liquid sample into an aerosol

- direct introduction of a liquid would extinguish plasma
- two types of nebulizers are commonly used
(a) pneumatic nebulizers
(b) ultrasonic nebulizers
- mostly use of a peristaltic pump to transport

(a) sample to the nebulizers

(b) aerosol to the plasma

Torch

Plasma Torches
The plasma torch consists of three concentric quartz tubes
through which the gas (normally argon) flows:
- The outer tube contains the coolant gas flow, which
spirally flows tangentially through the torch at a high
velocity. This assists in cooling the torch and hence
prevents damage.
- The middle tube contains the auxiliary gas flow to
keep the plasma discharge away from the auxiliary
and nebulizer tubes
- The innermost tube has the nebulizer gas flow which
carries the sample aerosol to the plasma.

Viewing position of plasma

The plasma generated in an ICP can be viewed by the spectrometer,
side-on or end-on. These viewing positions are called radial and axial
viewing, respectively

Radial: light emitted from analyte has

to pass only a short distance in plasma

Axial: better collection

efficiency of emitted light

i.e. less chance of self absorption

i.e. improved sensitivity

4. Spectrometer (Polychromator)
The role of a spectrometer is to isolate the analytical wavelengths of interest
from the light emitted by the plasma source.
The advantage of polychromators is:
- capable of determining several analytes simultaneously.
- high sample throughput
- lower running cost

Echelle Polychromator

5. Detectors
Commonly used detectors:
Photomultiplier tubes (PMT)
Solid-state detectors:
Charge-coupled devices (CCD)arrays detector
Silicon photodiodes with thousands of individual
elements
Very sensitive, very well-suited to echelle grating
polychromators, very fast

Photomultiplier tubes (PMT)

Schematic diagram of
an end-on PMT

PMT consists of a photo-sensitive cathode and a series of dynodes, which are set at successively
more positive potentials until an anode is reached. Light comes from the plasma, passes through
the transparent casing of the multiplier and strikes cathode. This then emits electrons, which are
accelerated down the dynode chain. Each time an electron impacts with a dynode, a number of

secondary electrons are emitted.

CCD
Examples of the wavelength ranges covered
by individual CCD chips:

Chip 1
Chip 2
Chip 3
Chip 4
Chip 5
Chip 6
Chip 7

127,000 - 142,125 nm
141,285 - 160,681 nm
160,040 - 179,618 nm
178,704 - 198,477 nm
197,023 - 216,947 nm
215,903 - 235,897 nm
234,792 - 254,788 nm

Second Grating
2400 l/mm

K 766nm
First Grating
2924 l/mm

Virtual Entrance Slit

Li 670nm

Na 589nm
125nm

Entrance Slit
460nm

Multi CCD

Detection Limits of ICP-OES

Typical detection
limits (Varian Vista
MPX):
Considerations
include the number
of emission lines,
spectral overlap

Linearity can span

several orders of
magnitude.

Detection Limit
Element Wavelength (nm)
axial (ug/L)
Ag
328.068
0.5
Al
396.152
0.9
As
188.98
3
As
193.696
4
Ba
233.527
0.1
Ba
455.403
0.03
Ba
455.403
0.03
Be
313.107
0.05
Ca
396.847
0.01
Ca
317.933
0.8
Cd
214.439
0.2
Co
238.892
0.4
Cr
267.716
0.5
Cu
327.395
0.9
Fe
238.204
0.3
K
766.491
0.3
Li
670.783
0.06
Mg
279.55
0.05
Mg
279.8
1.5
Mn
257.61
0.1
Mo
202.03
0.5
Na
589.59
0.2
Ni
231.6
0.7
P
177.43
4
Pb
220.35
1.5
Rb
780.03
1
S
181.972
4
Sb
206.83
3
Se
196.03
4
Sr
407.77
0.02
Sn
189.93
2
Ti
336.12
0.5
Tl
190.79
2
V
292.4
0.7
Zn
213.86
0.2

Detection limit
radial (ug/L)
1
4
12
11
0.7
0.15
0.15
0.15
0.3
6.5
0.5
1.2
1
1.5
0.9
4
1
0.1
10
0.133
2
1.5
2.1
25
8
5
13
16
16
0.1
8
1
13
2
0.8

Sampling and sample preparation

Are the samples representative of what you are trying to

measure?
Will any elements volatilize during sample preparation?
How much contamination can the sample tolerate during
preparation?

Sample preparation
For many applications, the sample analyzed by ICP-AES will not be in
suitable form . In order to transform solid samples into suitable form
, sample pre-treatment is required.
The pre-treatment method used will be depend on the nature
of the sample and the element which are to be determined.
Those methods commonly used are:
- Dry-ash,
- Acid digestion,
- Fusion,
- Solubilization
- Microwave digestion.

Analysis using ICP Sample preparation

Dry Ashing
Dry at 105 -100
Muffle
furnace

Ash at 200-800

crucible

sample

Dissolve the ashed sample in

acids, usually HCl, H2SO4,
HNO3 and HCl/ HNO3

Preparation is simple and widely applicable but sample losses

through volatilization and retention

Acid Digestion
Use of strongly oxidizing mineral acid, such
as HNO3, HF, H2SO4 and HClO4 to oxidize
the resistant components, with gentle heat.
It can be carried out in closed or open
reaction systems. Closed systems minimize
the losses in volatilization.

Advantages:

Disadvantages:

Analysis using ICP Sample preparation

Salt Fusion
Sample is mixed in a platinum crucible with a flux
which attacks all the major rock-forming silicates.
Fused in a furnace.
Cooled to room temperature.

Muffle
furnace

Dissolved in HNO3.
Fusion methods are commonly used with geological samples. crucible Sample + Flux

Advantages:

Disadvantages:

Analysis using ICP Sample preparation

Microwave digestion
Microwave sample preparation
uses microwave power to heat
several samples at once, which
can speed up a digestion
processes.

Advantages: improved detection

limits, low acid concentration
and a reduced need for dry
ashing or fusion.

Reaction pressure, temperature

and time are computer controlled

Preparation of Solid Sample

Acid digestion apparatus: microwave system

Plug
Safety Disk
Seal
Screw Cap
Supporting Vessel
Pressure vessel (TFM)
Liner
Bomb Jacket
Vessel Base Plate

Microwave sample preparation system

MULTIWAVE (Anton Paar GmbH)

Analysis using ICP Sample preparation

Microwave digestion
USEPA method 3051: MICROWAVE ASSISTED ACID DIGESTION OF SEDIMENTS,
SLUDGES, SOILS, AND OILS

Digestion vessels carefully acid washed and rinsed with water before use.

Sample up to 0.5 g and 10 ml of concentrated HNO3 are placed in microwave vessel.

(For soils, sediments, and sludge use no more than 0.50 g. For oils use no more than 0.25 g.)

Sample vessel equipped with a single-port cap and a pressure relief valve.
The vessels are capped and heated by a suitable laboratory microwave unit.
The vessel contents are filtered, centrifuged, or allowed to settle and then
diluted to volume and analyzed.

Advantages:

Disadvantages:

ICP/AES INTERFERENCES

Spectral Interferences
Physical Interferences

Chemical Interferences
Memory Effect

 Spectral interferences:
caused by background emission from continuous or recombination phenomena,
stray light from the line emission of high concentration elements,
overlap of a spectral line from another element,
or unresolved overlap of molecular band spectra.

Corrections
Background emission and stray light compensated for by subtracting
background emission determined by measurements adjacent to the analyte
wavelength peak.
Correction factors can be applied if interference is well characterized
Inter-element corrections will vary for the same emission line among
instruments because of differences in resolution, as determined by the
grating, the entrance and exit slit widths, and by the order of dispersion.

The Example for Choosing Wavelength in ICP-AES

Element wavelength Element wavelength
(nm)
(nm)

Physical interferences
Cause
effects associated with the sample nebulization and transport
processes.
Changes in viscosity and surface tension can cause significant
inaccuracies,
especially in samples containing high dissolved solids
or high acid concentrations.

Salt build up at the tip of the nebulizer, affecting aerosol flow rate
and nebulization.

Reduction

by diluting the sample

or by using a peristaltic pump,
by using an internal standard
or by using a high solids nebulizer.

Physical interferences

Wavelength calibration

 Chemical interferences:
include molecular compound formation
Normally, this effect is not significant with the
ICP technique.
Chemical interferences are highly dependent
on matrix type and the specific analyte
element.

Combined Effects

Compensation : (a) matrix of standards should be closely matched with that

of the samples (matrix-matched calibration)
(b) Matrix removal

Memory interferences:
When analytes in a previous sample contribute to the
signals measured in a new sample.
Memory effects can result
from sample deposition on the uptake tubing to the nebulizer
from the build up of sample material in the plasma torch and
spray chamber.

The site where these effects occur is dependent on the

element and can be minimized
by flushing the system with a rinse blank between samples.

High salt concentrations can cause analyte signal

suppressions and confuse interference tests.

Calibration curves of ICP-AES