Elemental Spectroscopy

ICP-OES



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Content: ICP-OES
Fundamentals of ICP-OES


Instrument Components



Theory of Inductively Coupled Plasma
Optical Emission Spectroscopy



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ICP is shorthand for ICP-AES or ICP-OES.


What is ICP-AES? It is:
Inductively Coupled Plasma Atomic Emission Spectrometer.



ICP Basics
What is ICP-OES? It is:
Inductively Coupled Plasma Optical Emission Spectrometer.
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Atomic Emission Theory
Atomic emission spectroscopy (AES or OES) uses quantitative measurement of the
optical emission from excited atoms to determine analyte concentration

Analyte atoms in solution are aspirated into the excitation region where they are
desolvated, vaporized, and atomised by a plasma

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Atomic Emission Theory
Plasma Polychromator Detector

Inductively Coupled Plasma Atomic Emission Spectrometer
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Excitation
Excited State
Ground State
E
Relaxation
Excitation
Electrons can be in their ground state (unexcited) or
enter one of the upper level orbitals when energy is
applied to them. This is the excited state
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Atomic Emission
Photon
Excited State
Ground State
+ hv
A photon of light is emitted when an electron falls from
its excited state to its ground state
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Element Wavelengths
Each element has a unique set of wavelengths that it
can emit

180nm 800nm 400nm <-- visible --> <-- uv -->

1 2 3 4 5
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Atomic Emission explained
Atomic Emission the wavelength regions
Spectral Region
Vacuum UV Ultra-Violet Visible Near IR
Wavelength = nm
160 190 360 760 900
Lower wavelengths are shorter and have more energy,
higher wavelengths e.g. in the Visible region, are longer
and have less energy
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Effect of Temperature on Emission
Wavelength increasing ->
2000 k
3000 k
5000 k
Ca Na Li
K
Ca
Na Li
K
K Li Na
Ca Ba
Ba
Cu Mg
Mg Cu As Pb Mn
200 300 400 600 800
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Emission sources

Flames

Arcs / Sparks

Direct Current Plasmas (DCP)

Inductively Coupled Plasmas (ICP)
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Inductively Coupled Plasma (ICP)
source, plasma formation, plasma zones


Quartz torch surrounded by induction coil

Magnetic coupling to ionized gas

High temperature equivalent to 10,000k
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Plasma Advantages
High Temperature allows for full dissociation of sample
components
Argon is Inert non reactive with sample
Linearity analysis of samples from ppb to ppm range in the same
method
Matrix tolerance robust and flexible design with Duo and Radial
options
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Plasma Torch
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Plasma Zones
Plasma Zones
sample
6000 k
6500 k
7000 k
8000 k
10000 k
0
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20
25
observation
region (mm)
TEMPERATURE ~ 2X
NITROUS OXIDE
ACETYLENE FLAME
RESIDENCE TIME ~ 2MS
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Instrument Components
There are six basic
components to an ICP
1. Sample Introduction

2. Energy Source

3. Spectrometer

4. Detector

5. Electronics

6. Computer and Software
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Instrument Components
6. Computer and
Software
1. Sample
Introduction
2. Energy
Source
3. Spectrometer
4. Detector
5. Electronics
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1. Sample
Introduction The sample solution
cannot be put into the
energy source
directly. The solution
must first be
converted to an
aerosol.
The function of the
sample introduction
system is to produce
a steady aerosol of
very fine droplets.
Instrument Components
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1. Sample
Introduction
There are three basic
parts to the sample
introduction system.
i. the Peristaltic pump
draws up sample
solution and delivers it to
ii.the Nebulizer
which converts the solution
to an aerosol that is sent to
iii. the Spray chamber
which filters out the large,
uneven droplets from the
aerosol.
Instrument Components
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1. Sample
Introduction
i. the Peristaltic
pump



ii. the Nebulizer





iii. the Spray
chamber

Instrument Components
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Concentric Nebuliser
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2. Energy
Source The sample aerosol
is directed into the
center of the plasma.
The energy of the
plasma is transferred
to the aerosol.
The main function of
the energy source is
to get atoms
sufficiently energized
such that they emit
light.
Instrument Components
= plasma
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2. Energy
Source
There are three basic parts to the
energy source.
i. the Radio frequency generator
which generates an oscillating electo-
magnetic field at a frequency of 27.12
million cycles per second. This radiation
is directed to
ii.the Load coil
which delivers the radiation to
iii. the Torch
which has argon flowing through it which
will form a plasma in the RF field.
Instrument Components
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2. Energy
Source
i. the Radio
Frequency
generator



ii. the Load coil




iii. the Torch


Instrument Components
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Plasma Configuration
Axial

Radial

Axial and Radial
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Radial or Axial Configuration
Radial design Robust, fewer interferences
Petrochemical
Metallurgy


Axial design best sensitivity,
lowest detection limits
Environmental
Chemical
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Axial Advantage
Much more light available. This gives you the opportunity to
achieve Lower Detection Limits than Radial Plasma

BUT- unfortunately, you also get...

More Matrix Interferences

Slightly Reduced Dynamic Range
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Duo viewing
Axial view plasma looks down the central channel of the plasma,
this provides the best sensitivity and detection limits
DUO this is an axially configured plasma that also allows for radial
view through a hole in the side of the axial torch
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Dual View Optics
Axial view
Radial view
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Instrument Components
3. Spectrometer
Once the atoms in a
sample have been
energized by the
plasma, they will emit
light at specific
wavelengths. No two
elements will emit
light at the same
wavelengths.
The function of the
spectrometer is to
diffract the white light
from the plasma into
wavelengths.
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Simultaneous Optics Echelle Spectrometer
ICP-Source
Detector
Prism
Grating
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Instrument Components
3. Spectrometer
There are several
types of
spectrometers
used for ICP.
Regardless of type,
all of them use a
diffraction grating.
For the iCAP, an
echelle
spectrometer is
used. The
components in this
spectrometer are
shown at left.
CID Detector
Focusing
Mirror
Prism
Collimating
Mirror
Shutter
Slit
(dual)
Echelle
grating
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iCAP Optics - Polychromator
High resolution
7pm @ 200nm
High image quality & low stray light
aberration compensation over whole CID
High energy throughput
double pass prism
All lines on chip
anamorphic magnification
Stable
thermal insulation & heater control to 0.1
0
C

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Instrument Components
4. Detector
Now that there are
individual wavelengths,
their intensities can be
measured using a
detector. The intensity
of a given wavelength
is proportional to the
concentration of the
element.
The function of the
detector is to measure
the intensity of the
wavelengths.
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Charge Injection Device Array Detector
>291,600 addressable silicon-based
photo detectors
Full Spectrum Imaging
Random Access Integration (RAI)
Inherently Anti-blooming
Non Destructive Readout (NDRO),
allows the S/N ratio to be improved by
repeatedly reading each pixel
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Instrument Components
4. Detector The detector is a
silicon chip that is
composed of many
individual photo-
active sections called
picture elements.
These picture
elements, or pixels,
will build up charge
as photons impinge
on them. Individual
pixels are of a size
such that they can be
used to measure
individual
wavelengths.

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Emission lines appear as points of light
177 nm
800 nm 740 nm
178 nm
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Readout Subarray - CID
Intensit
y
Wavelength
28 by 28 mm
detector element
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What you get
Full, continuous
wavelength coverage;
never miss an analyte
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Power and flexibility
Rapid qualitative analysis
Ability to analyze for elements in the
future without rerunning samples
Fingerprinting
Matrix or spectral subtraction

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Instrument Components
5. Electronics
The output from the
detector is processed
by a set of
electronics. The
electronics control the
detector as well as
collect the readings
from the pixels
The function of the
electronics is to
measure and process
the output of the
detector.
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Instrument Components
6. Computer and Software
The software, via a
computer, controls and
runs the instrument. Not
only are measurements
made but the other five
components of the
instrument are controlled
and monitored by the
computer and software,
The function of the
computer and software is
to operate, monitor, and
collect data from the
instrument.
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ICP Basics
ICP Performance
Typical analysis time for ICP is ~2-3 minutes. This includes
flush time, multiple repeats, printing, etc. (Analysis time is
independent of the number of elements being determined)

Typical precision, amongst repeats within an analysis, is
~0.5%

Typical drift is 2% per hour

Typical detection limits are ~ 1-10 parts per billion