Principle of Graphite Furnace, Hydride

Generation and Cold Vapor Techniques for

Trace Metals Analysis

Dr. Mohammad Moniruzzaman

Principal Scientific Officer
Officer In-Charge (Chief Coordinator)
CARF, BCSIR, Dhaka
 Graphite Furnace Atomic Absorption Spectroscopy
(GF-AAS)
Also known as electrothermal Atomizers
Electrothermal atomization is usually performed with a graphite furnace
although vertical crucible furnace and open filaments have been employed.
Electrothermal (non flame) atomizers offer several attractive features that
complement flame AAS.
1. Only small amounts (10-8 to 10-11 absolute) of analyte are
required.
2. Solid can be analyzed directly, often without any
pretreatment.
3. Small amount of liquid samples, 5 to 50 L.
4. Background noise is very low.
5. Sensitivity is increased because the production of free
analyte atom is more efficient than with a flame.
 Graphite Furnace
 The graphite furnace tube is continually bathed in an
inert gas (i.e. Ar) to prevent the furnace from oxidation.
 Inert gas reduces the oxide formation and increases the
atomization efficiency.
 On the negative side, matrix effects are usually more
severe, and precision, typically 5% to 10% compares
unfavorably with that of flame AAS.

March 29, 2024 3

 Graphite Furnace

March 29, 2024 4

 Graphite Furnace Atomization

March 29, 2024 5

 GFA Atomization Steps

Drying or desolvation step

Ashing step
Atomization step
Cleaning step

March 29, 2024 6

 Drying Steps
 Like the desolvation step in flame AAS, the solvent is removed.
 In the drying cycle, the sample is heated for 20 to 30 seconds at
130 °C to evaporate any solvent or extremely volatile matrix
components.
 Generally the heating temperature is set at 60-150oC for water-
based samples and 50-100oC for organic-based samples.

-3000

-2500
-2000

-1500

-1000
-500

March 29, 2024 7

 Ashing Steps
 The ash or char step is performed at an intermediate temperature (often
500 °C) to volatilize higher boiling point matrix components and to
pyrolyze matrix materials that will crack and carbonize.
 During this stage, organic matter in the sample is ashed or converted into
water, CO2 and volatile inorganic compounds.
 Ideally, the temperature should be high enough to remove all volatile
components without loss of the analyte.
 Loss of analyte may occur if the ashing temperature is too high or is
maintained for too long
-3000

-2500

-2000

-1500

-1000
-500

March 29, 2024 8

 Atomization Steps
 In the atomization step, maximum power is applied to raise the
furnace temperature as quickly as possible to the selected
atomization temperature.
 The analyte is vaporized and atomized to produce atomic vapor
at around 2000- 3000oC.
 The analyte residue is volatilized and dissociated into free atoms
that will absorb light from the AAS source. The transient
absorption signal must be measured rapidly.
-3000

-2500

-2000

-1500

-1000
-500

March 29, 2024 9

 Cleaning Steps
 To evaporate remaining metal and salt which remains in the
graphite tube.
 Carried out at 3000oC but lower temperature desirable.
 Cleaning temperature is normally atomization temperature
plus 200oC.

-3000

-2500

-2000

-1500

-1000

-500

March 29, 2024 10

 GFA Heating Steps

March 29, 2024 11

 Instrumentation

Three components of GF:

1. Work head
2. Power unit
3. Controls for the inert gas supply

 A heated graphite atomizer consists of a hollow graphite cylinder 28 mm

long and 8 mm in diameter, the interior of which is coated with pyrolytic
graphite.
 Electrodes at each end of the cylinder are connected to a power supply.
 A metal housing surrounding the furnace is water-cooled to allow the
entire unit to be rapidly restored to ambient temperature after each run.
 Inert gas usually argon (99.997%), enters the cylinder at both ends and
exists through the samples introduction port at the center of the cylinder.
 Instrumentation
 Gas Flow:
1. The gas flow removes the matrix components vaporized
during the ashing step.
2. Prevent subsequent vaporization during the atomization
step and thereby large background absorption signal
3. Prevents oxidation of the graphite cylinder during the
heating cycles.
 Auto Sampler: Liquid samples are introduced with micro-syringe
through the small opening in the top of the cylinder and place on
a thin graphite plate or platform that is located within the cylinder.
 Solid samples can be introduced through the end of the cylinder
on a microdish made of tungsten. The sample is heated by
radiation from the walls of the cylinder, which equals the walls
and vapor to reach a steady-state temperature before the sample
is atomized.
 GFA Tubes

March 29, 2024 14

 GFA Tubes

Platform type graphite tubes

March 29, 2024 15

 Auto Sampler

1. Improves productivity for multiple samples.

2. Preparation of calibration standards.
3. Auto-dilution of samples.
4. Addition of matrix modifiers.
5. For flame micro sampling and GFA.

March 29, 2024 16

 Matrix Modifier
 Palladium (II) nitrate is a useful chemical modifier that stabilizes
many elements to temperatures several hundred degrees higher
than possible otherwise.
 Palladium modifies the analyte element by converting it to a
more thermally stable species.
 Pd reduces analyte volatility and permits a higher temperature
for the ash step, which more efficiently removes bulk matrix
constituents without loss of analyte element.
 Thus palladium reduces signal dependency on the sample
composition and produces greater consistency in absorption
analyte signals.
 Nickel Nitrate may also be used as matrix modifier for some
elements as for example Lead (Pb) in water samples.
Matrix Modifier
 Duel Atomizer
 Easy switch over between GFA and flame atomizer.

 High Precision x and y-axis motorized movement.

March 29, 2024 19

 Background
Corrections
 Background absorption and scattering are
commonly encountered in ETA. The background
correction may be eliminated by three different
ways
 Using continuum source of light (D2 lamp)
 Using Zeeman effect
 source self-reversal
 Typical Detection Limit

March 29, 2024 21

 Flame Vs GFA

March 29, 2024 22

 ♦ Flame AAS
High stability
Quick analysis
Measurement at ppm level
♦ Graphite Furnace AAS
Measurement of sub-ppb level
Need specific timings - drying, ashing, atomization
processes
♦ Generally, high sensitivity measurement for Flame AAS is
preferred as it is fast and gives stable results.

March 29, 2024 23

 Selection of Method

 Flame AAS applicable at moderate levels in

complex-matrix system.
 Flame AAS, solvent extraction is used for lower
levels.
 GFA can increase sensitivity (use matrix
modifiers).
 HVG for As & Se; MVU for Hg.

March 29, 2024 24

 Hydride Vapor Generation
(HVG) Atomic Absorption
Spectroscopy

March 29, 2024 25

Hydride Vapor Generation (HVG)
Hydride Vapor Generation
 Some volatile elements like As, Hg, Se, Sn, B are best quantified by
analyzing their hydrides.
 Conversion of elements to metal hydrides by sodium borohydride
under acidic condition.
 The generation of Arsenic hydride known as arsine (gas) is based
on the reaction of acidified aqueous solution of the test element,
with a reducing agent such as sodium borohydride (NaBH4).
 Detection limit improved to ppb level.

March 29, 2024 26

 HVG Reaction

March 29, 2024 27

 HVG Flow Line
 Arsine hydride gas is transported with inert carrier gas to the quartz cell.
 The arsine gas in the quartz cell is atomized by heating the quartz cell
with an air-acetylene flame or electrothermal heating system.

March 29, 2024 28

 HVG Electric Heater

March 29, 2024 29

 Preparation of Reagents and Standards

Deionized water
All reagents and standards are prepared in reagent water with
electrical resistivity of > 16 .
Hydrochloric acid: Analytical reagent grade with arsenic
concentration less than 0.1 ppb
Nitric acid: Analytical reagent grade certified for AA use. For sample
digestion.
Inert gas: Inert, carrier gas (argon) with high purity (99.9997%).
 Preparation of the reductant

Prepare 500 mL 0.6% w/v NaBH4 in 0.5% w/v NaOH solution for
daily use, in acid cleaned polypropylene bottle and preserve it
at 40C to extend the life of the solution to about one week.
Use this solution after bringing it to room temperature.
 Note: Addition of 20% KI to the samples and the standards
keeping them under this condition for 1-3 hrs hrs at room
temperature, before analysis might give better recovery of As.
 All samples and standards should be run at room
temperature.
Mercury Cold Vapor Atomic
Absorption
Spectrophotometry
 Methodology of Hg Cold Vapor Technique
 An extremely sensitive determination of
mercury is accomplished by a non-flame
atomization at room temperature. Can
detect 0.1 ppb mercury
 In this technique, mercury (e.g., in air,
water, occupational samples, or food
sample) is collected in a KMnO4 solution.
 The permanganate oxidizes organic
mercury compounds, as well as elemental
mercury, to produce mercury ions, for
analysis.
 The excess permanganate is destroyed
with hydroxylamine, and a reducing agent
such as SnCl2 is added to reduce the
mercury ions to elemental mercury.
 Methodology of Cold Vapor Technique

 This elemental mercury has an appreciable vapor pressure at room

temperature; and by bubbling a gas such as nitrogen through the
solution in an Erlenmever flask, the mercury vapor can be swept into a
glass tube (with quartz and windows to pass the UV radiation), aligned
in the light path of the atomic absorption spectrophotometer.

 The mercury vapor absorbs the lines of mercury just as atomic

mercury in a flame does.

 Again, the atomization efficiency is greatly improved over flame

atomization methods, with typical detection limit of a few nanograms
or less.
 MVU Flow Line

March 29, 2024 35

Thank you……