FUNDAMENTOS DE ICP– OES

Y SUS APLICACIONES EN
LAS DIVERSAS INDUSTRIAS
Lic. FELIPE NOLASCO CONTRERAS

Enero 2011
Atomic Theory
Plasma
Optics
Sample Introduction
Applications
Principle of optical emission
spectroscopy

Atoms
excited

Detector
Wavelength selector
Lens

Excitation
source
 Periodic table of elements

1 2
H He
2 3 Atomic number 26 5 6 7 8 9 10
Li Be Fe Chemical symbol B C N O F Ne Alkali metals
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar Alkaline earth metals
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Transition metals
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Lathanide series
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86

Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn Actinide series
87 88 104 105 106 107 108 109

Fr Ra Rf Ha Other metals

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 Nonmetals
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Noble gases
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
 Part I

Atomic Theory
What is an atom?
Atom particles

Protons contain
positive electrical
charges, electrons
contain negative
ones, and neutons Neutrons
have no charge. Protons
Nucleus

Electrons
Inside the atom

Atom Neutrons
shell
Protons
Nucleus
Electron
Quantum Leap
Emission of quanta
Electrons gain extra energy and jump to higher energy levels. When they
fall back to their original levels, they emit quanta.

Lower energy levels

Electrons leap
to higher
energy levels

Nucleus Nucleus

Electrons give out energy

Atomic Spectra

E = hv = hc/

E = energy between two states

h = 6.6256 x 10-27 erg sec
v = frequency
c = light speed
 = wavelength
Wavelengths

 Units
1 nm = 10-9 m
1 Å = 10-10 m

 Ranges
Infrared > 750 nm
Visible 400 - 750 nm
Ultraviolet < 400 nm
 Electromagnetic spectrum

Gamma X-Rays Ultra Visible Spectrum Infrared Radio Waves

Rays Violet (Microwave, TV, Radio)
0.01 nm 1 nm 100 nm 400-700 nm 1 mm 1 meter 1 km
 Spectral lines of atomic hydrogen

Balmer series
H

H

H

Lyman series
(ultraviolet)

H(violet) H(blue-green) H(red)

3.500 4.000 4.500 5.000 5.500 6.000 6.500

Paschen series
(infrared) Angstroms
 Bohr Model of Hydrogen

-
+

 Ground State Electron

 Quantized Orbitals
 Origins of Atomic Spectra
Decay with Excited
Emission of States
Light
+

E = h = hc/
 Many transitions are possible
 Emitted light depends on energy difference of
two states
h = Planck’s constant,  = frequency,
c = velocity of light,  = wavelength
 Lines library
U 251.573 1.5 1 *
Rh 251.575 5.0 1 I
Zn 251.581 1.5 1 I
+ Si 251.611 850.0 1 I 0.320
Ta 251.630 5.0 1 *
U 251.630 7.0 1 II
Th 251.643 4.0 1 II
Mn 251.673 5.0 1 II
Hf 251.668 500.0 1 II 0.460
Cr 251.692 3.0 1 I
Re 251.700 4.0 1 *
Fe 251.712 7.0 1 I
V 251.714 2.0 1 I
Ru 251.732 24.0 1 II
Ti 251.743 18.0 1 II
Mo 251.746 2.0 1 I
Nb 251.749 2.0 1 II
Rh 251.752 305.0 1 II
Fe 251.766 7.5 1 II
Mo 251.783 1 I
Co 251.787 12.0 1 I
Os 251.792 3.0 1 I
U 251.800 1.5 1 *
Fe 251.810 52.0 1 I
Atomic and Ionic Lines

 Atomic line
 Excitation of an electron of the atom

 Ionic line
 The atom is ionized
 A remaining electron is excited

Atomic lines require less energy

Choice of an internal standard

Element EI EA EI + EA
Ca II 315.8 6.11 7.05 13.16
II 317.9 7.05 13.16
II 396.8 3.12 9.23
Si I 212.4 6.62
Be II 313.0 9.32 3.96 13.28
Sc II 361.3 6.54 3.45 9.99
Y II 371.0 6.51 3.52 10.03
Be I 332.1 6.45
EI = ionization potential in eV
EA = atomization potential in eV
Internal standard Y-Cr
Relative to 1st measurement (grid=5%)

Cr Y Cr/Y

(1 = 100 ms)
Internal standard Y-Ni
Relative to 1st measurement (grid=5%)

Ni Y Ni/Y

(1 = 100 ms)
Internal standard Be-Ca
Relative to 1st measurement (grid=5%)

Ca Be Ca/Be

(1 = 100 ms)
Line intensity

hc 1 n(X)
I= gA exp(-E/kT)
4¶  Z

Low concentration of Ar compared to sample:

I = K × n(x)
 Part 2

Plasma
Inductively Coupled Plasma - ICP
Plasma

 Gas partly ionized

 Ionization degree
a = N/(N+N0)
N = density of the ionized atoms
N0 = density of the neutral atoms

 If a = 10-4 T = 7000 K
Generator

 27.12 MHz SPECTRO designed source delivers

stable excitation
 Free-running generator allows difficult samples
 Extremely stable plasma gives optimal
performance with minimum warming-up time
Electrical and magnetic fields

North

Magnetic
field lines

Current

South
Electrical and magnetic fields

 RF induces electrical and

magnetic fields

 First elastic collisions

– Ar + e- Ar+ + e-

 Cause ionization
– Ar+ + e- Ar + 2e-
Generator

 Durable ceramic amplifier tube

 Variable power: 700 W - 2500 W

 Robust excitation for a stable plasma

Generator

The generator is entirely computer controlled

 Allows different conditions for each element
concerning
 Power
 Gas
 Additional flow
 Mixed gas (oxygen)
 Conditions are stored in analytical methods
Three tubes torch

Emission 
region Torch symmetry
 Ar consumption
 Ease of ignition
 High salt capability

Argon

Sample flow
Function of the gas flows

 Coolant: 7-20 l/min

 Auxiliary: 0-3 l/min
 Aerosol: 0.5-1 l/min
 Plasma torch

Emission
 Fixed model
region  3 concentric tubes in
Plasma
Induction quartz
coils
 Demountable model
Magnetic  Possibility to change the
field
injector tube: quartz or
alumina

Quartz
tubes
Argon
tangential flow

Sample flow
Temperature Regions of the ICP
 Dual View Explained

To optical system
 The DV is an axial plasma

Mirror M can be rotated and

allows for axial or radial viewing

 Short viewing height

 Some DV-ICPs position not adjustable
 The DV is an axial plasma
 Prism - Splitting light

A prism is a specially shaped piece of glass that can split

white light into ist component colors.

White light

Prism

Colors of the spectrum

Echelles optics Sistems

Focusing mirror

Exit slit

Collimator mirror
Diffraction
grating
Entrance slit
 Optical System
Schematics: Paschen Runge
Brilliantly
constructed and
analytically superior: 7

The
design of the 1

patented optical
system 6
1 - Entrance slit
2 - Grating 3600 g/mm
3 - Grating 1800 g/mm
2 4 - Grating 3600 g/mm
5 - Virtual Entrance slit
6 - CCD Arrays 130-175 nm
7 - CCD Arrays 175-340 nm
8a
3 8 - CCD Arrays 340-770 nm

8b

4
8c
8d
Optical fiber

Cross-section Lengthwise section

Light

Core n1
Cladding n2 Reflected light
Light pulses hit the cable walls at an
angle and are reflected along the cable’s
length.

 Flexible and stable

 Total reflexion (n2<n1)
 Multiple spectrometers
 New monochromator design
The use of optical fibers

Fibers can be Fibers centered on

adjusted to proper ICP optical axis
observing height

Top view of the fibers

Side view of the fibers

Cross-section diagramm
of a diffracting grating
face angle or blaze angle


angle of incidence angle of diffraction

 
blaze wavelength
L L = land

ce
ve fa
groo

d
grating spacing
Grating equation

n = d(sin i + sin r)
b c

a = grating normal
b = incident angle i
c = refracted angle r
d d = grating space d

a
Al scan at 308.2 nm
for blank Al and 1ppm Al

OH 308.21 Al 308.22
Spectrometer evaluation criteria

 Quality of the grating

 Bandwith
 Light throughput
 Resolution
 Stray light
Light throughput

The light throughput is depending on

 entrance slit width
 exit slit width
 efficiency of the optical components:

Typical efficiency reached at 200 nm by

 Echelle grating : 20 %
 Prism : 60 %
 Mirror : 90 %
Resolution - definition

Resolution = Dispersion x Exit slit width

Example:
Spectrometer with
 1 m focal length
 Dispersion: 0.46 nm/mm
 Entrance slit width: 20 µm
 Exit slit width: 50 µm

Resolution = 0.023 nm + aberration term

 Resolution

Depends on
Intensity  ruling density of the
grating
Full width  focal length
Half maximum
 optical aberrations

Wavelength
Measured at half maximum
 Resolution - On-peak measurement of
Calcium traces in arsenic matrix
Intensity [cps]
400

360
Cd 100 ppb

320
As 2 ppm

280 As 2.5 ppm

240

200

160

120

4000 5000 6000 7000 8000 9000 Steps

Cd 228.802 nm and As 228.812 nm with a resolution of 11 pm

Advantages of multiple optical systems

 Optimal performance of each optic regarding

 resolution
 sensibility
 detection limits
 Wide wavelength coverage from Cl 134.7 nm to Cd
852.7 nm
 No mechanical compromises
 optical lines can be used several times
 no limit of dnymaic range
Multitasking

Data processing Instrument control

User interface Device control
Statistics Data evaluation

Generator
Host
Slave
Computer
(EPC 3)
(PC) Plasma

Spectrometers
RS 232

Accessories and devices

 Schematic summary of how analytical
results are obtained from a sample

sample emitted
introduction radiation Data Analytical
Sample Excitation Dispersion Detection
processing results

Solid  nebulizer  Flame  Prism  photoplate  manually  qualitative

Liquid  electrode  Arc  Diffraction  photomultiplier  computer  quantitative
Gas  hydride  Spark grating tube
generation  GDL  photo-diode
 MIP array
 DCP
 ICP
 Laser
 Part 4

Introduction system
Schematic diagram of sample
introduction and excitation process
excitation source
particle molecule atom ion

+
vaporization excitation excitation
dissociation ionization
desolvation

aerosol
Photon emission Photon emission
introduction of (atomic lines) (ionic lines)
solid sample

nebulization

liquid sample solid sample

 Schematic diagram of the
sample introduction system
Torch
 fixed
 demountable
 HF resistant

Spray chamber
Nebulizer
 concentric
 cross-flow
 slurry

Interchangeable boards for various applications:

aqueous, organic, HF, slurries, ...
Concentric nebulizer
nozzle
capillary shell

liquid
(sample)
input
gas input
(side-arm)

ca. 25 mm ca. 40 mm
Cross-flow nebulizer

Ar

Sample
 Babington nebulizer

Solution
(2 ml/min) Inner diameter 0.8 mm

V-groove

Argon
(1 l/min)

Aersosol
Spray chamber - double pass

aerosol
Double pass spray mist to
torch
chamber (Scott)

aerosol
from
nebulizer

to drain
Special Nebulizers with Cyclonic Spray chamber

Burgener Nebulizer
Aerosol transported to
Sample
the plasma
Ar
Sample
Ar

Modified Lichte Nebulizer

Capillary
Nebulizer

Sample Nozzle
Drain
Ar
Ultrasonic nebulizer

 Sample pumped onto the transducer

 Nebulization by crystal vibration

 Dessolvation
 Heating: evaporation of the solvent
 Cooling: solvent removed by condensation

 Improvement: 10 times in clean matrix

Working principle of an
ultrasonic nebulizer
heating tape

insulation injector gas

Plasma transducer plate

torch

cooling
water

sample
drain trap inlet drain trap
Hydride generation
Advantages and disadvantages
 Advantages
 50 - 100 times better LODs
 matrix separation

 Disadvantages
 complex sample preparation
 chemical interferences (Cu on Se)
 matrix dependant
Continous on-line formation of
hydrides for ICP-AES
argon carrier gas (2.1 l/min)

sample solution (9.5 l/min)

1% NaBH4 in 0.1 M NaOH (4.7 l/min)

10% KI in 20% HCl

gases to ICP

phase separator

drain
 Blank and sample measurement control for
analysis with hydride generator

iodide or
peroxide solution
NaBH4 solution Ar carrier gas

gases to ICP
blank solution (acid)
1 2
pneumatic
waste valve
4 3

sample solution
drain

valve 1 and 2, 3 and 4 connected: blank measurement

valve 1 and 4, 2 and 3 connected: sample measurement
Hydride generation

 Chemical process:
reduction of elements to a volatile gas

 Mixture of NaBH4 and HCl

 Suitable for the following elements:

 As, Sb, Sn, Te, Ge, Bi and Hg
 Pb with special conditions
Sample presentation system for
slurry analysis with ICP-OES

straight inject tube

Babington nebulizer
conical spray chamber

argon
peristaltic drain
pump 10 cm
stirrer
 Typical sample presentation procedure for
slurry analysis
1. Grind to -325 (< 45µm) or -400 (<38µm) mesh in mill
(approx. 10 min.)

2. Weigh into disposal 50 ml beaker

3. Add 25 ml water

4. Add 1 drop of surfactant (Triton X-100)

5. Stir for 1 min.

Slurry analysis - conclusions

 Slurry nebulization with solids calibration

applicable to a range of difficult materials
 Control of particle size is critical

 Appropriate application of background correction

and internal standardisation improves accuracy
Calibration curve for V 292.402 nm
in Alumina by slurry analysis with
ICP-OES
Intensity Ratio (AU) CEK
60
x

50

40
x
30

x
20 x

10

0
0 0.005 0.01 0.015 0.02
% oxide
Al 266.917 nm Internal Standrad
Pre-concentration

 Sample pumped through a cellulose collector

 Matrix separation (Ca, Na, ...)

 Enrichment

 pH must be correctly adjusted to avoid matrix

effects
 Part 5

Applications
Analysis of waters
Overview of water types
 Drinking waters
 Ground waters
 Surface waters

 Waste waters
 Sludges
Analysis of waters
Normed standard procedures
 U.S. Environmental Protection Agency
 EPA 200.7 and EPA 200.15
 procedures for determination of 30 elements
 check of laboratory performance
 procedures included in SPECTRO Smart Analyzer

 German standard methods

 DIN 38406 and DIN 38414
 determination of 33 elements
Analysis of drinking waters
LODs for analysis with EOP

Element Wavelength LOD

[nm] [ppb]
As 188.98 0.20
Cd 228.80 0.02
Ni 231.60 0.06
Pb 220.35 0.18
Analysis of Organics

 Wear metals in engine oils

 Additives (Ca, Mg, Zn, P)
 Pb in gasoline
 Na and K in residuel fuel oil
 Oxygen addition
Analysis of organics
Oxygen addition
Analysis of
 Na
 K
in residuel fuel oils
Oxygen addition
Analysis of metals

 Trace elements in Fe, Cu, Al

 Elements in alloys
 Additives (Fe-Mn, Fe-Cr)
 Precious metals

 Sensitivity
 Accuracy for alloy elements
 Appropriate line selection
Analysis of metals
Precision and accuracy

 Internal standard
 Dynamic background correction
 Bracketing
Salt industry

 Impurities in NaCl, KCl, FeCl3, ...

 Appropriate introduction system

 Part 6

Analysing samples
General aspects of ICP-OES
 Comparison method
 Standards and samples Intensity

identical

Concentration
Preparation of standards

 Multi-element method

 Prepare separately major and minor elements

to avoid contamination

 Acids contamination
BEC-value
 BEC: Background
Equivalent Concentration Intensity

 Detection limit = BEC/50

Concentration

BEC
Dissolution

 Is it possible with ICP?

 detection limit
 Acids
 contamination
 Quantity to dissolve
 best BEC
 Filtration of the samples
 SiO2 instability
Formulars for the calculation
of the detection limit
(Int (standard) - Int (spectr. background))
1 SBR =
Int (spectr. background)

c(standard)
2 BEC =
SBR

3 x RSD (spectr. background) x BEC

3 cDL =
100

4 cDL = 0.03 x RSD (spectr. background) x BEC

Units

1 % 10 g/l
1 g/l 1000 ppm
1 g/kg
1 ppm 1000 ppb
1 mg/l
1 mg/kg
1 µg/l 1 ppb
1 µg/kg
Scanning

 Blank contamination

 Background correction

 Interferences
Background correction

 Standards and samples matrix is not equivalent

 Improvement of the accuracy

at detection limit level
Background correction
Regression

 Dissolution method
 Regression model
 1st degree
 2nd degree
 Corrections
 additative
 multiplicative
 Standards selection for standardization
Regression
Intensity
320 K

280 K

240 K

200 K

160 K

120 K

80 K

40 K

0K
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Concentration
Routine analysis

 Parameters
 rinse time
 integration time
 number of measurements

 Contamination between different sample

 Line broadening
Intensity [cps]
7000

6000 Zn 2 ppm

Ni 1000 ppm
5000
Cu 1000 ppm
4000
Fe 1000 ppm
3000

2000

1000

3000 4000 5000 6000 7000 8000 9000 Steps

Impossibility of Zn 213.86 nm determination in Ni 213.86 matrix and the problem

of line broadening effect
Additive correction

 Two elements emit the same wavelength

 Measure of the disturber

 Substraction of the disturber intensity

Additive correction
Intensity
4800
4400
4000
3600
3200
2800
2400
2000
1600
1200
800
400
0
0 4 8 12 16 20 24 28 32 36 40 44 48 52
Concentration
Additive correction
Intensity

4800
4400
4000
3600
3200
2800
2400
2000
1600
1200
800
400
0
0 20 40 60 80 100 120 140 160 180 200 220
Concentration
Multiplicative correction

 One element changes the emission intensity of

another one
 Measure of the disturber element
 Correction calculated with the influence of the
disturber element
Internal standard

 Accuracy for major elements

 One or several elements are added accurately to
standards and samples
 Improve precision and accuracy
RSD 0.1 - 0.2 %
 Atomization energy
 Ionization energy
100% correction

 Sum of all analyzed elements

 Correction to adjust sum to 100 percent

 All elements must be analyzed

 Matrix effects must be minimized
 Sample preparation errors must be compensated
(Weight, volume, ...)
Dynamic correction

 Control sample measured every n samples

 Results calculated with the evolution of the
control sample

 Accuracy for major elements

 Standardization not necessary
 Part 7

Adjustment of the operating

conditions
Checklist for ICP adjustments

 Observation of Y (1000 ppm)

 Influence of the gas flows
 auxiliary flow - cooling flow - nebulizer flow
 Influence of the power
 control of the power (MgII/MgI)
 Adjustment of the optical axes with transient
 UV - fibres
Checklist for ICP adjustments

 Auxiliary flow
 no deposit of salt or carbon (organic) at the top of
the injector

 Nebulizer (carrier flow)

 carrier flow speed - injector tube - additional flow

 Control of leaks
 balljoints - nebulizer O-rings
Efficient spectrum control
Optical System Highlights

 Recording of the complete relevant

spectrum from 130 to 770 nm
 Never before seen resolution of 8.5
picometer in the important range of
130 to 340 nm and 15 picometer for
higher wavelengths
 Access to additional wavelengths for
the halogens
 Many new lines for ultra trace
determination
 Interference-free emission lines for
complex matrices
 Smart Background Correction (SBC)

 Novel background correction approach

Advantages
- No definition of background positions required
- Consideration of partial spectral overlap
- Consideration of different background signal levels
- Consideration of structured background
 Comparison of correction methods
No correction

Traditional interference correction

With SBC
GRACIAS POR SU ATENCION