Vasiliy V. Rosen, M.Sc.

, ZBM Analytical Laboratory

www.rosen.r8.org
2011
 ATOMIC SPECTROSCOPY

Absorption Spectroscopy: Emission Spectroscopy:

AAS FES, ICP-AES(OES)

Mass Spectrometry
ATOMIC SPECTROSCOPY

Ion Emission

Atom Emission

E – energy difference between two levels;

h – Plank’s constant, 6.626068 × 10-34 m2kg/s;
c – speed of light, 299 792 458 m/s;
λ – wavelenght, nm

After Boss. C.B. and Freden K.J. Concepts, Instrumentation and Techniques in
Inductively Coupled Plasma Optical Emission Spectrometry. 1997
 ATOMIC SPECTROSCOPY
Nebulizer converts the
solution into a spray

Flame (or Plasma) causes the solvent to evaporate,

leaving dry aerosol particles, then volatilizes the particles,
producing atomic, molecular and ionic species

After Skoog D. Fundamentals of Analytical Chemistry, 2004, p. 844

FLAME EMISSION SPECTROSCOPY (FES)

 Propane-butane flame ( 2000 – 3000 º C);

 Optical filter is used to monitor for the selected emission wavelength
produced by the analyte;
 Suitable for elements with low excitation energy (Na, K, Li, Rb and Ca).
FLAME EMISSION SPECTROSCOPY (FES)
Optic Filter
Flame

Data Display

Nebulizer

Flame Photometer M-410

(Sherwood Scientific, UK)
ATOMIC ABSORPTION SPECTROSCOPY (AAS)

 Gases mixture flame (1800 – 4500 º C): air-propane, air-acetylene etc. ;

 Atomic absorption spectrometry quantifies the absorption of ground state atoms in the
gaseous state ;
 The atoms absorb ultraviolet or visible light and make transitions to higher electronic
energy levels . The analyte concentration is determined from the amount of absorption.
ATOMIC ABSORPTION SPECTROSCOPY (AAS)
Elements detectable by AA are highlighted in pink
ATOMIC ABSORPTION SPECTROSCOPY (AAS)
Operation principle of AAS

Light source – hollow cathode lamp. Each element has its own unique lamp.
Atomic cell – flame (gas mixture) or graphite furnance (accepts solutions, slurries, or even
solids).
Detector – photomultiplier.

After G.Ma and G.W. Gonzales, http://www.cee.vt.edu

ATOMIC ABSORPTION SPECTROSCOPY (AAS)
 ATOMIC EMISSION SPECTROSCOPY

ICP-AES
Inductively Coupled Plasma -

Atomic Emission Spectrometry

 ICP-AES
Basics
Atomic emission spectroscopy measures the intensity of
light emitted by atoms or ions of the elements of interest at
specific wavelengths;
Inductively Coupled Plasma spectrometers use emission
spectroscopy to detect and quantify elements in a sample;
 ICP-AES uses the argon plasma (6000-10000º C) for
atomization and excitation of the sample atoms;
 ICP-AES determines approximately all of the elements
except gases and some non-metals (C, N, F, O, H).
ICP-AES SPECTROMETER ARCOS
Schematic diagram of the processes in the ICP

After Spectro Gmbh, Germany

 ICP SPECTROMETER

Main Systems

Sample Introduction System: to deliver the sample solution to the plasma.

Consists of pump, nebulizer and spray chamber.

 Plasma: to generate the signal. Plasma is forming in the torch from gas argon.

 Optics: to measure the signal.

Computer with appropriate software: for controlling the instrument and

measuring process.
ICP-AES: SAMPLE INTRODUCTION SYSTEM

Torch with Plasma

Nebulizer (cross-flow)
Spray Chamber

To Waste

Sample
Solution
Entrance
Argon Supply
 ICP-AES: PLASMA
Inductively Coupled Plasma Source
A plasma is a hot, partially ionized
gas. It contains relatively high
concentrations of ions and electrons.

Argon ions, once formed in a plasma, are

capable of absorbing sufficient power from
an external source to maintain the
temperature at a level at which further
ionization sustains the plasma indefinitely.
The plasma temperature is about 10 000 K.

After Manning T.J. and Grow W.P.,

1997
ICP-AES: PLASMA
Inductively Coupled Plasma Source
 ICP-AES: RADIAL (SOP) AND AXIAL (EOP)

SOP: Side-on-Plasma EOP: End-on-Plasma

 more suitable for hard matrices (concentrated samples);  more suitable for light matrices;
 alkali metals (Na, K, Li) calibration is more linear;  alkali metals (Na, K, Li) calibration is less linear;
 less spectral interferences;  more spectral interferences;
lower sensitivity (Limit-of-Detection is higher); higher sensitivity (Limit-of-Detection is lower);
ICP-AES: RADIAL (SOP) AND AXIAL (EOP)

After Spectro Gmbh, Germany

ICP-AES: OPTICS

After Spectro Gmbh, Germany

 ICP-AES: SAMPLE PREPARATION

Microwave-assisted Digestion

Hot Plate Digestion Block

Most samples have to be prepared for analysis by ICP. Solid samples are solubilized.
Organic matter is "mineralized" i.e. converted to inorganic compounds.
ICP-AES: CALIBRATION CURVE
ICP-AES: SPECTRAL INTERFERENCES

Au (gold) peak on 242.795 nm

 ICP-AES: SPECTRAL INTERFERENCES

Au (gold) peak on 242.795 nm is Au (gold) peak on 267.595 nm is free

interfered by Mn 242.794 nm of Mn interference!
 ICP-AES, FES AND AAS: APPLICATION

 Clinical Analysis: metals in biological fluids (blood, urine);

 Environmental Analysis: trace metals and other elements in waters, soils, plants,

composts and sludges;

 Pharmaceuticals: traces of catalysts used; traces of poison metals (Cd, Pb etc);

 Industry: trace metal analysis in raw materials; noble metals determination.

 Forensic science: gunshot powder residue analysis, toxicological examination

( e.g., thallium (Tl) determination)

 REFERENCES

Boss, C.B. and Freden, K.J. Concepts, Instrumentation and Techniques in Inductively

Coupled Plasma Optical Emission Spectrometry. 1997

Skoog, D. Fundamentals of Analytical Chemistry, 2004

Ma, G. and Gonzales, G.B. Flame Atomic Absorption Spectrometry.

http://www.cee.vt.edu

Manning T.J. and Grow W.P. Inductively Coupled Plasma Atomic Emission

Spectrometry. The Chemical Educator, v.1. N 2. 1997.

 Lecture by Dr. Mordechay Shoenfeld, “ICP-AES”, Course 71106, Faculty of

Agriculture, HUJI. 2010.