1. Vasiliy V. Rosen, M.Sc., ZBM Analytical Laboratory
www.rosen.r8.org
2012

2. The role of chemical elements in plants
(adopted from Munson R., 1997, and Macnicol R., 1984)
Essential
Major Micronutrients Toxic
Carbon (C) Boron (B), Silver (Ag)
Oxygen (O) Chlorine (Cl) Aluminium (Al)
ICP
Hydrogen (H) Copper (Cu) Arsenic (As)
Iron (Fe) Barium (Ba)
Nitrogen (N) Manganese (Mn) Berillium (Be)
Phosphorus (P) Molybdenum (Mo) Cadmium (Cd)
Potassium (K) Zinc (Zn) Mercury (Hg)
Nickel (Ni) Lead (Pb)
Sodium (Na) Cobalt (Co) Lithium (Li)
EA Silica (Si) Chromium (Cr)
Calcium (Ca) Selenium (Se) And all
Magnesium (Mg) Vanadium (V) micronutrients at
Sulfur (S) critical
concentration

3. EA – ELEMENTAL ANALYSIS OF C, H, N, S AND O
Sample state: dried, ground with a mill, 0.5-0.5 mm; or liquid
Sample weight: 2 – 3 mg
Supply: gases (He and O2 extra-pure)

4. EA – ELEMENTAL ANALYSIS OF C, H, N, S AND O
He
Sample combustion at 1020º – 1800º C
Oxidation by pure O2 to CO2, H2O, SO2, NOx
Catalyst - CuO
Reduction: Copper wires remove O2 and reduces NOx
to N2, SO3 to SO2
Catalyst - Cu
Chromatographic separation of N2, CO2, H2O and SO2

5. 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

6. ATOMIC EMISSION SPECTROSCOPY
ICP-AES
Inductively Coupled Plasma
Atomic Emission Spectrometry

7. 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 (6000º-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).

8. Schematic diagram of the processes in the ICP
Flame (or Plasma) causes the
solvent to evaporate, leaving dry
aerosol particles, then volatilizes the
particles, producing atomic,
molecular and ionic species
After Spectro Gmbh, Germany

9. ICP-AES SPECTROMETER ARCOS

10. ICP SPECTROMETER
Main Systems

11. ICP-AES: SAMPLE INTRODUCTION SYSTEM
Torch with Plasma
Nebulizer (cross-flow)
Spray Chamber
To Waste
Sample
Solution
Entrance
Argon Supply

12. 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

13. ICP-AES: PLASMA
Inductively Coupled Plasma Source

14. ICP-AES: RADIAL (SOP) AND AXIAL (EOP)
After Spectro Gmbh, Germany

15. 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);

16. ICP-AES: OPTICS
After Spectro Gmbh, Germany; Boss. C.B. and Freden K.J. Concepts,
Instrumentation and Techniques in ICP-OES. 1997

17. ICP-AES: CALIBRATION CURVE

18. ICP-AES: SPECTRAL INTERFERENCES
Sulfur in plant sample Boron in plant sample
Boron in plant sample
Boron in standard
Sulfur in standard
(1 mg/L)
(10 mg/L)
Sulfur spectral interference on Boron line 182.6 nm

19. 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.

20. ICP-AES AND EA: APPLICATION
 Environmental Analysis: trace metals and other elements in waters, soils, plants,
composts and sludges;
Clinical Analysis: metals in biological fluids (blood, urine);
 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)