GBC 01-1005-00 SavantAA Software Operation Manual

SYSTEM 2000/3000
GRAPHITE FURNACE
GBC SCIENTIFIC EQUIPMENT

PTY LTD
AUTHORS:
Graeme Chapple
Nick Athanasopoulos
Edition: 1.1
Manual No. 01-0202-00

Designed and published by GBC Scientific Equipment Pty Ltd
GBC reserves the right to change specifications without notice.
Publication number 01-0202-00
Edition 1.1
July, 1991
2 GBC Graphite Furnace Methods Manual

Table of Contents
Page
1. Introduction 5
1.1 Atomic Absorption Spectroscopy 5

1.2 Choice of method, flame or furnace 6
1.2.1 Flame 6
1.2.2 Furnace 6
2. Furnace Atomic Absorption 7
2.1 Graphite tubes 7

2.2 Temperature program development 7
2.2.1 Dry 8
2.2.2 Ash 8
2.2.3 Atomize 9
2.2.4 Measurement mode 9
2.2.5 Gas flow selection 9
2.2.6 Reduced gas flow during atomization 9
2.3 Interferences 11
2.3.1 Physical 11
2.3.2 Chemical 11
2.3.3 Chemical Modification 11
2.3.4 Background correction 13
2.3.5 Incandescence 14
3. Platforms 15
3.1 Platform theory 15

3.2 Platform temperature program 15
3.2.1 Dry 15
3.2.2 Ash 16
3.2.3 Atomize 16
3.2.4 Cool down step 17
3.2.5 Sample volume optimization 17
4. Sample Preparation 18
4.1 Ashing technique 18

4.1.1 Wet Digestion Methods 18
4.1.2 Dry ashing 18
4.2 Chemical separations and concentration 20
GBC Graphite Furnace Methods Manual 3

Table of Contents (cont’d.)
4.2.1 Ammonium pyrolidine dithiocarbamate

extractions (APDC) 20
4.2.2 8-Hydroxyquinoline (oxine) extractions 22
4.2.3 Sodium diethyl-dithiocarbamate
extractions (NaDDC) 22
4.2.4 Ion exchange 23
4.3 Contamination 24
4.3.1. Storage Materials 24
4.3.2. Washing Procedures 24
4.3.3. Purity of Solutions 25
5. Developing a Method 26
5.1 Sample preparation 26

5.2 Instrument set up 26
5.3 Furnace optimization 26
5.4 Ash-Atomize plots 27
5.5 Furnace program testing 28
5.6 Background correction 28
5.7 Interferences 29
6. Analytical Methodology 31
6.1 Agricultural 31
6.2 Air particulates 32
6.3 Biological 33
6.4 Food products 35
6.5 Geochemical 36
6.6 Metallurgical 37
6.7 Petrochemical 38
6.8 Waters 39
6.9 Sensitivity 41
7. Analytical Data for the GF 2000/3000 43
8. References 53

1. Introduction
1.1 Atomic Absorption Spectroscopy
The technique of atomic absorption developed by Sir Alan Walsh of CSIRO in

the mid 1950’s has become the preferred method of elemental analysis. Walsh
discovered that the majority of free atoms in the commonly used flames are in
the ground state, and that the flames do not have enough energy to excite these
atoms (except for group 1 elements). A light source emitting a narrow spectral
line of characteristic energy is used to excite the free atoms formed in the flame.
The decrease in energy (absorption) is then measured.
The absorption is proportional to the concentration of free atoms in the flame,

given by the Beer-Lambert law.
Absorbance = 1og10 (I0/It ) = K.C.L.
Where I0 = intensity of incident radiation emitted by the light source.
It = intensity of transmitted radiation (amount not absorbed).
C = concentration of sample (free atoms).
K = Constant (can be determined experimentally).
L = Path length.
In practical atomic absorption analysis the Beer-Lambert law can be reduced to :
Absorbance = Log10 (I0/It) ∫C
The instrument is calibrated against standards of known concentrations and the

sample concentrations interpolated. The method is not absolute but comparative
and the constant KL does not have to be determined. As well as atomic
absorption occurring, there is also emission from the analyte element, other
species in the sample and the flame or graphite tube. To isolate the atomic
absorption from all other effects, the energy from the light source is “coded” by
modulation (turning ON and OFF at regular intervals) and the electronics are
synchronized to “see” only signals from this source. By this method, emission,
which is basically steady-state, is not seen by the electronics. Only atomic
absorption is observed.

1. Introduction
1.2 Choice Of Method—Flame Or Furnace
1.2.1 Flame
Flame atomic absorption is the more commonly used method of analysis,
providing excellent precision and ease of use. However, the nebulizer is at best
only 10% efficient, requiring moderately large sample volumes.
The nebulizer is also sensitive to physical properties of the sample such as

viscosity and the presence of dissolved solids. Viscosity changes affect the rate
of sample uptake, and hence the absorbance, requiring the samples and
standards to be closely matched. Nebulizers cannot accept high salt
concentrations or slurries.
1.2.2 Furnace
In a graphite furnace a discrete volume of sample (between 1 and 100 µL) is
atomized in a small cell. The cross sectional area of the cell (or, more commonly
called, tube) is small enough to create a dense population of atoms at
atomization, increasing sensitivity over flame by a factor of 20 - 1000. The
advantages of the furnace method include:
• High sensitivity
• Small sample volumes required
• Highly efficient sample usage (no waste)
• Low detection limits achievable
• Most samples can be analysed with little or no pretreatment

2. Furnace Atomic Absorption
2.1 Graphite Tubes
Many different materials have been investigated for use in electrothermal

atomizers, but none have been as successful as the pyrolytically coated graphite
tube. The furnace material must exhibit certain properties to ensure good
sensitivity and reproducibility of results. The following are typical of these
requirements:
• low porosity
• chemical inertness
• low levels of metal impurities
• good thermal and electrical conductivity
• high rigidity
• high melting point
• reasonable cost
• good machinability
• low thermal expansion
Graphite as a furnace material responds well to these criteria, but problems do

exist with porosity and chemical inertness.
By pyrolytically coating the tube, the sample is prevented from leaching through
the tube surface, thus reducing memory effects. This also reduces the risk of
carbide formation, a problem often associated with refractory elements.
The coating itself, typically 30 µm thick, is applied by thermally decomposing a
low molecular weight hydrocarbon such as methane (in its vapour state).
Oxidation of carbon is probably the most recognised obstacle in any carbon
furnace design. Once heated to high temperature, oxides of carbon are readily
formed, often creating tube-life problems. Two inert gases, argon and nitrogen,
are commonly used to create a shielding effect around the carbon components.
The latter is more commonly used because of its relatively low cost, but nitride
compounds can be formed with some elements (e.g. B, Ba, V). Argon should be
used with these elements.
Tube life also depends on the nature of the matrix, and the atomization
temperature used. The higher the temperature, the more susceptible the tube is to
oxidation. Similarly, highly acidic solutions (e.g. perchloric acid, hydrofluoric
acid) or oxidizing agents within the sample, will cause the surface to deteriorate.
2.2 Temperature Program Development
Temperature program development for graphite furnace analysis can be

categorized into three main stages, i.e., drying, ashing and atomizing the
sample.

2.2.1 Dry
Two methods can be used for this stage. For aqueous samples, the injection can
be made at an elevated temperature (120 ⊃C). Here the capillary is programmed
to contact the bottom of the tube and the sample is dried as it contacts the
surface, (flash volatilization). This method can also be applied to organic
solutions or high acid solutions where the sample tends to creep out of the tube
due to low surface tension.
The second method involves an injection at ambient temperature and a slow

ramp through the evaporation temperature. For complex matrix samples this
method is recommended. In a sodium chloride matrix, water can be entrained in
the crystal. A hot injection will cause rapid expansion of the water inside the
crystal, subsequently exploding the crystal and losing sample. This sample must
be dried and ashed through a series of stages, ensuring a uniform breakdown and
evaporation of solvent. If spitting or frothing occurs, particles can be ejected and
sensitivity will suffer.
Hot Injection Cold Injection
Fig. 1. Hot and cold sample injection
2.2.2 Ash
Depending on the complexity of the matrix, the ashing stage can be the hardest
area to refine. In the simplest case, an understanding of the individual matrix
components can assist in predicting their behaviour. Reference material quoting
melt and evaporation temperatures is readily available.
Successive measurements should be made using increasing ash temperatures
while monitoring the analyte absorbance (measured during the atomize stage).
The optimum ash temperature is usually the highest that can be used without
reducing the analyte absorbance. The ramp rate during the ash stage should be
chosen so as to avoid violent reactions or excessive release of smoke.
For more difficult unknown matrices, ashing can be quite complex, involving
trial and error method development. When volatilization of the matrix occurs at
the same temperature as atomization of the analyte, matrix modification can be
used to either decrease or increase either the ash or atomize temperature.
Volatile elements such as Cd, Zn and Pb, existing as chlorides, can be easily lost
during low temperature ashing but in the hydroxide or oxide form they are stable
at much higher temperatures. For example PbCl2 is volatile around 500 ⊃C,
whereas Pb(NO3)2 is stable at 800 ⊃C. If it is not possible to completely remove
the matrix during the ash stage, background correction can be used, provided
that the level of background does not exceed 2 absorbance units.

For aqueous solutions, extensive ashing is not required but an intermediate stage
is recommended to provide a starting point for ramping to atomize. (Maximum
ramp rate is 2000 ⊃C/sec). The intermediate stage should not exceed the
maximum ash temperature for the element.
2.2.3 Atomize
The atomization temperature will vary depending on the element being analysed
and the recommended temperatures in Table 5 should normally be followed. The
optimum ramp rate also varies with element. Most elements show maximum
sensitivity at 2000 ⊃C/sec but some (e.g. Pb) will exhibit better results at half
this rate. A compromise between atomize temperature and tube life must also be
examined. Ideally the lowest temperature showing good sensitivity is selected,
because at high temperature, oxidation of the carbon surface will be accelerated.
The atomize hold time should also be considered. Unnecessarily long hold times
at high temperature will also shorten the life of the tube.
2.2.4 Measurement Mode

The type of measuring mode will also be element and matrix dependent. The
peak height and peak area choice is usually decided by the mode giving the best
precision and accuracy for that particular application. Peak area will quite often
show better calibration linearity. The peak area mode often shows less chemical
interference and is usually used with the pyrolytic graphite platform.
2.2.5 Gas Flow Selection

Inert gas, typically nitrogen or argon is used to shield the graphite from a highly
oxidizing atmosphere, and to remove various sample components during the
program. Inert gas should always be selected during dry and ash stages. A gas
stop is usually used at the atomization stage to ensure sufficient residence time
of the atoms in the light path. The time of the gas stop should be minimized to
prevent air entering the tube.
Quite often argon can yield better sensitivity for particular elements. This is due
to the different chemical processes initiated by the two gases.
2.2.6 Reduced Gas Flow during Atomization

Where sensitivity is too high, selection of gas flow during atomization will
reduce the sensitivity by sweeping the atoms from the tube more quickly. This
reduced flow can be selected by programming AUXILIARY gas for 1-2 seconds
before and during the atomize steps, thus you can use the normal gas flow rate
during the DRY and ASH stages.
The figure overleaf shows the variation in Peak absorbance with gas flow for
three elements: Pb (a volatile element), Cu (an element with intermediate
atomization temperature), and V (a refractory element).
Maximum sensitivity is obtained with gas stop during the atomize stage.

Fig. 2. Variation in peak absorbance with gas flow

2.3 Interferences
2.3.1 Physical
The main problems associated with physical interferences include surface
tension, viscosity and background absorption.
If the sample solution matrix consists of organic solutions, high acid
concentrations or detergents, sample spreading may cause reduced sensitivity
and poor reproducibility. This is due to the variations in atomic distribution at
the atomization stage. These effects can be overcome by:
• reducing the sample volume

• lengthening the drying program
• flash volatilizing the sample (hot injection)
(The latter is discussed in detail under drying conditions).

In the GBC System 2000/3000, sample spreading is minimized by the ridges in
the graphite tube which confine the sample to the central part of the tube.
At the other end of the scale, if a sample is highly viscous, the auto sampler can
retain small quantities on the outside of the capillary. This amount can vary
from one injection to another, subsequently giving poor reproducibility. This
can be overcome by diluting the sample with a low viscosity solvent or
detergent.
Background absorption is often encountered and is the most documented of all
physical interferences. Carbon particles can be released from the tube at the
atomization stage, momentarily attenuating the light beam. Organic matter still
present after ashing can be pyrolysed, causing attenuation by smoke. Most salts
will also cause significant background effects, if present during atomization.
2.3.2 Chemical
Stable compound formation can occur if the analyte element reacts with carbon
or nitrogen, yet the temperature is not high enough to dissociate these
compounds during atomization. This can be avoided by using pyrolytically
coated tubes and argon as an inert gas.
Volatile compound formation should be avoided to prevent premature loss of the
element during the ashing stages. Most metal chlorides will exhibit this trend.
Matrix modification should be used to convert the metal into another compound
which remains stable at higher temperatures. e.g. maximum ash for BaCl2 is 900
⊃C, minimum ash for BaO is 1500 ⊃C.
Acid selection can also play a major role in method development. Some acids
will cause severe depression, some will enhance the response, depending on the
element being analysed. Hydrochloric acid should be avoided as it can cause the
volatile compound formation previously described. (For further reading, see
references 101, 102, 106).
2.3.3 Chemical Modification

Quite often problems can exist where sample is lost due to volatile compound
formation. By reacting the sample with a desirable compound, the interference
can be avoided. For example:
REF. 1. Adding nickel in excess to arsenic solutions forms a stable nickel
arsenide which can withstand high ashing temperatures, but will readily
dissociate at a reasonable atomize temperature. Without nickel, arsenic is lost
before 300 ⊃C in the form of As2O3 or AsCl3.

REF. 2. Lead in a sodium chloride matrix is another difficult application. Lead

can be atomized at 1100 ⊃C and NaCl will vaporize at this temperature.
Addition of NH4NO3will increase the lead atomization temperature by forming
lead nitrate and form two new compounds of low ashing temperature.
PbCl2 + NaCl + 3NH4NO3 ® Pb(NO3)2 + 3NH4Cl + NaNO3

atomize vaporize atomize vaporize vaporize
1100 ⊃C 1100⊃C 1400⊃C 300⊃C 300⊃C
REF. 3. For trace analysis of drinking water, magnesium nitrate can increase
ashing temperatures quite considerably for Al, Be and Mn, and show slight
improvement for Cr, Co and Ni.
These three examples of modifier represent the three main categories of sample
modification:
• stabilizing volatile elements
• reduction of non atomic absorption at the atomize stage
• increasing analyte element sensitivity
The following table shows some more examples of the use of chemical
modifiers.
Table 1. List of common modifiers
Analyte Modifier Effect Reference
Cd, Al H3PO4 Converts to less volatile 6, 7

(1000 µg/mL) phosphate. Atomizes at higher
temperature.
Pb EDTA, citrate Atomize lead at lower 8, 9

(0.5-1% V/V) temperature than matrix
e.g., chloride.
P La(NO3)3 0.2% Permits higher ashing. 10
Pb, Cd Mg(NO3)2 Stabilizes Pb and Cd for 11

NH4H2PO4 higher ashing.
Hg (NH4)2S Allows higher ashing. 12
Pb NH4NO3 Products can be ashed at 13

low temperature.
As, Se Ni Forms arsenide or selenide 14

which atomizes at higher
temperature.
Si Ca(NO3)2 Enhances sensitivity 15

1000 µg/mL

2.3.4 Background Correction

Non specific attenuation of the hollow cathode lamp output by molecular
species or by scatter from particles is a major interference in graphite furnace
AA.
Typically a deuterium arc continuum source, having a broad-band output, is
used for background correction.
The hollow cathode lamp measurement (total absorbance) is taken, then the
deuterium lamp reading (background only) is subtracted from this value giving a
value for the analyte element being examined. These measurements are taken
very rapidly, (200 times per second), and the corrected atomic absorbance
computed electronically.
Fig. 3. Background absorbance profile

2.3.5 Incandescence
If the emission from the furnace is strong enough to “flood” the photomultiplier
tube with DC emission, a spurious absorption can be obtained. This is because
the amplification circuit cannot separate the modulated signal from the emission.
This incandescence is only a problem for elements that require high
temperatures and have wavelengths between 400-600 nm. Elements such as Ca,
Ba, Dy, Er, Sr, and Tb may show incandescence problems.
To minimise this interference:
• Properly align the furnace

• Increase the lamp current to reduce the photomultiplier gain
• Use reduced slit heights (G.F. slit mask)
• Reduce the atomization temperature
Fig. 4. Incandescent emission at atomization temperatures

3. Platforms
3.1 Platform Theory
Atomization from the wall of a furnace provides excellent sensitivity and

reproducibility for most applications. Occasionally, matrix effects cause
interferences that are unsolvable by program modification or by chemical
addition. These interferences stem from the atoms leaving the heated furnace
surface and re-combining in the cooler inert gas atmosphere inside the tube. This
re-combination usually occurrs with volatile elements (such as Pb, Cd etc.), in a
complex matrix (e.g., saline solutions, oil). Many of these samples, once
classified as too hard to analyse, can now be studied using a pyrolytic graphite
platform. (L’vov Platform. Ref. No. 17).
Fig. 5. Pyrolytic graphite platform
As can be seen from the diagram, the platform rests between the two small
partitions in the tube. It can be easily inserted in the tube using a pair of
tweezers and aligned properly when the tube is installed in the workhead.
L’vov has shown that vapour phase interferences can be reduced by atomising
from a furnace that has already achieved a steady state temperature.
This is achieved by placing the sample onto a platform made of solid pyrolytic
carbon that sits on the furnace wall.
The platform is in very weak thermal contact with the furnace wall, and as a
consequence, is heated by radiation from the tube walls. This ensures that it lags
behind the furnace wall temperature. Using this technique, the analyte
compounds are not vaporized until the furnace has reached a steady state
temperature.
3.2 Platform Temperature Program
3.2.1 Dry
Since the platform is in weak thermal contact to the furnace wall, the use of a
slow ramp during the dry stage is not required. A typical program is to ramp to
an elevated temperature (approx. 140-150 ⊃C), in one second and hold this
temperature for a long time, (typically 40-60 seconds). This will ensure the
platform slowly ramps to this temperature. The dry should be watched using a
dental mirror and the temperature and/or time adjusted. The temperature is too
high if the sample spits or bubbles during the dry stage.

3. Platforms
In some cases a second dry step may be required where the temperature is
increased to approx. 200-250 ⊃C to dry the sample more evenly in preference to
very long holds.
3.2.2 Ash
The ash stage is programmed in a similar manner to the dry stage. A higher than
normal wall ash temperature (approx. 200-400 ⊃C higher) is selected with a
ramp time of 1-5 seconds, and a hold of 10-40 seconds. The aim is to vaporize
into a hotter region and not to recombine. Since the platform heats up through
radiation, it will heat up slowly and duplicate a normal ramp used in wall
atomization. The aim in the ash stage is to select as high an ash temperature as
possible in order to eliminate as much matrix as possible without losing any
analyte.
3.2.3 Atomize
The atomization temperature for platforms is normally set similar to, or slightly
lower than, the typical wall atomization temperature. A platform is used to
atomize the sample into a constant temperature environment. This is
accomplished if the ramp rate is rapid and the final temperature is close to the
ash temperature (usually a temperature difference of 600-1500 ⊃C is used from
ash to atomize). In almost all cases use the maximum ramp rate for this step of
2000 ⊃C/sec. A CLEAN stage will always be required in platform atomization.
Fig. 6. Temperature vs. time curve for a graphite tube
The figure above shows the typical temperature versus time curve of a graphite
tube. It shows that the tube takes a finite time to stabilize the temperature, and
the analyte atomized from the wall will be atomized into this gas phase,
changing in temperature. When atomization is performed from the platform, it is
delayed for a short time, (typically 1-2 seconds) until the platform reaches the

3. Platforms
wall temperature. This ensures that the furnace walls and the gas phase have
reached equilibrium. The choice of maximum ramp rate and low atomization
temperature, accompanied by a higher ash temperature, ensures that the furnace
will reach the steady state more quickly.
If the final temperature is too high or the heating rate is too slow, the risk is that
the analyte will be vaporized into the gaseous phase while the temperature of the
gas is still changing, thus producing an interference. Since the actual heating rate
for the platform is slower than for wall atomization, most elements in a simple
matrix will show a loss in peak height measurement. The slower heating rate
however, produces a broadened peak and the use of integrated measurements
(peak area) will show no loss of sensitivity.
3.2.4 Cool Down Step

Where the platform is used at high temperatures (above 2400 ⊃C) a cool down
step may be required to be performed in order to allow the platform to cool
down to the same temperature as the tube wall. A typical cool down step is to
program 30 ⊃C at a ramp rate of 10 seconds and a hold of 10-15 seconds.
3.2.5 Sample Volume Optimization

The maximum volume that may be pipetted onto a platform will depend largely
on the type of sample. For samples with high surface tensions a volume of 40-50
µL can be injected, however with samples containing a large concentration of
nitric acid or surfactants, the maximum volume must be reduced due to
spreading of the sample. If too large a volume is used, the sample may spill over
the platform onto the furnace wall during the dry stage, yielding erroneous
results and shortening the tube life. For most applications the use of 10-20 µL
sample size has shown to be optimum. If greater volumes are required the
sample should be deposited, dried, and a further sample deposited (this can be
performed using multiple injections).

4. Sample Preparation
4.1 Ashing Techniques
4.1.1 Wet Digestion Methods

Wet digestion methods will often vary, depending on the complexity of the
matrix present. The correct combination of acids must be chosen to ensure no
loss of analyte element during digestion, and also the complete breakdown of
the matrix present.
The following description outlines a method for the analysis of heavy metals in
fish tissue.
REF. 5. A 1-5 g sample of tissue is accurately weighed, placed in a 50 mL

kjeldahl flask, and stoppered to prevent evaporation. The flask and tissue are
then incubated in a 95  0.5 ⊃C water bath enclosed in a perchloric acid fume
hood. 5 mL concentrated HNO3 is added to the flask. When the mixture turns
deep brown, a 5 mL solution of 3 parts concentrated sulphuric acid and 2 parts
concentrated perchloric acid is added. This mixture maximizes the oxidation of
the sample. The sulphuric acid and relatively low temperature prevents the
solution from either concentrating or going to dryness.
+
Note: Perchloric acid concentrations greater than 80 % and perchlorates formed
upon drying are highly unstable and very dangerous. For 1 g of sample the
digestion is accomplished in 45 minutes. Slightly longer times are required for
larger samples. Complete digestion of fatty acids is not accomplished. These are
separated via MIBK extraction.
4.1.2 Dry Ashing

A typical procedure for dry ashing involves a sample of known weight being
placed in a crucible, then into a muffle furnace which has been preheated to a
constant known temperature. The crucible is preferably made of platinum, but
materials such as porcelain, fused silica, vycor, iron or nickel are available.
When applying this technique, care must be taken, as three possible sources of
element loss are common:
1. Mechanical losses can occur during sample drying, e.g., if the sample
is dried too fast, particles may be ejected from the crucible. A slow,
even drying is required to prevent this from occurring.
2. Volatilization during the muffle furnace stage is often the cause of
sample loss. Low vapour pressure elements such as Sb, Cr, Mo, Fe,
Mg, Al, etc., are recovered quite easily from an ash at 550 ⊃C.
However, elements such as Cu, Cd, Se, Hg, etc., will be lost.
3. Retention of the sample on the walls of the crucible can occur with
most materials, but platinum can be an exception. The worst cases
can occur if the sample contains a metal halide or any phosphate
compound.
Losses from these processes can be quantified by comparison with a reference
standard of similar composition to that of the samples. This standard, (if
available), should be carried through the same procedure as sample and
calibration standards. If losses prove to be significant, another digestion
technique should be examined.

If the sample exists as a slurry, it must first be dried, preferably on a steam bath.
This is followed by charring with a bunsen burner. The crucible lid should
partially cover the crucible. This stage is complete when the distillation appears
to be finished. (i.e., no smoke is being expelled). The crucible is then transferred
to the muffle furnace (preheated to 220 ⊃C) and the temperature is slowly raised
to 550 ⊃C (element dependent). The crucible lid should also be placed in the
muffle furnace. Using 1:1 nitric acid, transfer the ash to a volumetric flask and
rinse the crucible and lid with acid into the volumetric flask.
Some examples of ashing techniques for individual elements are:
Lead:
Dry ash: 500 ⊃C. If present as a chloride severe losses occur.
Wet ash: Nitric acid/perchloric acid digestion. If organics are present in the
matrix, perchloric acid is not recommended as this is a potentially hazardous
combination. Problems can also occur if large amounts of calcium are present.
Selenium:
Dry ash: not applicable.
Wet ash: Perchloric/nitric acid or perchloric/nitric/sulphuric acid mixtures are
recommended. Excess nitric acid must always be present to prevent
preconcentration of the perchloric acid. Slow ramping to elevated temperature is
recommended.
Arsenic:
Wet ash: Nitric/perchloric/sulphuric acid. Nitric/perchloric acid. Nitric/sulphuric
acid.
Mercury:
Wet ash: 3:2:1 mixture of nitric/perchloric/sulphuric acid in digestion block is
commonly used, or a reflux system.
Chromium:
Dry ash: not recommended.
Wet ash: Nitric/sulphuric acid combinations are recommended as perchloric can
cause slight losses.

4.2 Chemical Separations and Concentrations
Sample preparation prior to analysis can often be complex, depending on the

matrix present and the concentration of the element in solution. If the element is
below the detection limit, or is affected by an interferent, some sample
pretreatment is required.
For example:
1. Deproteinization of biochemical samples can be achieved by the
addition of 1:1 10% trichloroacetic acid with the sample (e.g., serum,
blood). This is then shaken and centrifuged. The metal-protein bonds
are broken and the metal is taken into the supernatant. This method is
usually applied to flame techniques, as furnaces can break down
protein bonds in situ.
2. Preconcentration by evaporating the solvent is often used to bring low

concentration samples into the range of the furnace’s capability. e.g.,
100 mL evaporated to 10 mL will concentrate the element to 10 times
the previous concentration.
3. Wet and dry ashing procedures are used to remove an interfering

matrix. These methods are explained in a later section.
4. Co-precipitation involves an exchange of the matrix from a difficult

one to a matrix that will not interfere. e.g., La(OH)3 can be used for
As, Se, Sn, and Te. (REF. 16).
Solvent extraction of trace metals is the most common separation technique used
by analysts today. The popularity of the technique is due to the fact that it
presents few problems with interferences and can be highly specific in
extracting individual elements. Particular elements can be separated individually
by adjusting the pH of the solution.
4.2.1 APDC
Ammonium pyrolidine dithiocarbamate (APDC) is often used because the
complexes formed are readily soluble in a number of ketones:
• Methyl-iso-butyl-ketone (MIBK) allows a concentration of 10 times.
• N-amyl methyl ketone allows a concentration of up to 50 times.
• Chloroform allows a concentration of more than 50 times.

Table 2. pH factors for the solvent extraction of trace elements.
APDC - MIBK, pH EXTRACTION RANGE

Element pH Element pH
As 1-6 Rh 1-12
Bi 1-6 Ni 2-4
Cd 1-6 Pb 2.5-3
Co 2-4 Pd 4-6
Cu 1-8 Pt 3
Fe 2-5 Sb 4
Ga 4 Se 3-6
In 2-10 Te 4
Mn 2-4 Tl 3-10
Mo 3-4 V 4
Ru 1-10 Zn 2-6
Procedure for extraction with MIBK (from Watson, REF. 18).

Dissolve 1 g of APDC in water, dilute to 100 mL and filter before use. To
50 mL of sample, add 5 mL of APDC solution and adjust to the required pH
with ACETIC ACID or CAUSTIC SODA solution. The pH should be 5 except
for arsenic, molybdenum, thallium and tungsten (pH3). For manganese, raise to
pH12, mix, stand for 2 min then adjust to pH5. With chromium and
molybdenum, heat to 80 ⊃C for 5 min before proceeding. Transfer the solution
to a 100 mL separating funnel and extract the complex (which may have
precipitated) into 4 mL of methyl-isobutyl ketone by vigorously shaking for 30
seconds, then stand for 2 minutes. Transfer the aqueous phase to another
separating funnel and repeat the extraction with 1 mL of
methyl-iso-butyl-ketone. Discard the aqueous phase (which should now be
colourless), combine the extracts in the first funnel, mix and filter through a
cotton wool plug into a small beaker. This solution is injected into the furnace.
If a particular metal will not react with APDC, other extraction systems can be
used.

4.2.2 Oxine
Oxine can be used for Sr, Mg, Al, Ca, La and Zr using xylene as the solvent.
Table 3. pH factors for trace metal extraction with oxine-xylene
OXINE - XYLENE pH Extraction Range
Element pH range Element pH range
Ag 8 - 9.5 Mn 7 - 10
Al 5 - 11 Mo 1-5
Bi 3 - 11 Ni 4 - 10
Ca 11 Pb 6 - 10
Cd 6 - 10 Pd 6 - 10
Co 5 - 10 Th 4 - 10
Cu 4 - 12 Ti 3-9
Fe 5 - 10 U 5-9
Ga 4 - 10 V 3-6
Hf 5 - 11 Y 7 - 10
Ho 5-7 Yb 9 - 11
In 4 - 10 Zn 4-5
La 7 - 10 Zr 2-4
Transfer 10-100 mL of sample to a 250 mL beaker and adjust the volume to 100
mL with distilled water. Prepare a blank solution and sufficient standards in the
same manner. Adjust the pH of the samples and standards to the pH range listed
above, with either 2.5% HCl or 10% NaOH and a pH meter. Extract the
complex with xylene using the procedure outlined in the APDC section above.
4.2.3 NaDDC (Sodium dimethyldithiocarbamate)

NaDDC can be used for Ag, Hg and Ti using MIBK as the solvent.
Table 4. pH factors for trace metal extraction using NaDDC-MIBK
Element pH Element pH
Ag 4 - 11 Ni 5 - 11
As 5-6 Pb 4 - 11
Bi 4 - 11 Pd 4 - 11
Cd 4 - 11 Sb 4-9
Co 4 - 11 Se 4-6
Cu 4 - 11 Sn 5-6
Fe 4 - 11 Te 4-8
Hg 4 - 11 Tl 5 - 13
In 4 - 10 Ti 4 - 11
Mn 6-9 Zn 4 - 11
Transfer a volume of sample (100 mL max.) into a 250 mL beaker and adjust the
volume to 100 mL with distilled water. Prepare a blank and sufficient standards
in the same manner and adjust the volume of each to 100 mL with distilled
water. Adjust the pH of the samples and standards to the pH range listed above
with 0.3N HC1 solution or 2.5N NaOH solution, using a pH meter. Transfer

each sample and standard to a 200 mL volumetric flask and add 2 mL of fresh
NaDDC solution and mix. Add 10 mL of MIBK and shake for two minutes.
4.2.4 Ion Exchange

An alternative method to solvent extraction involves the use of an ion exchange
column, and an appropriate adsorbing resin. The element is separated from the
matrix by selective adsorption onto the resin at a particular acid concentration.
Careful selection of acid, resin, and acid concentration will enable the analyst to
separate most metals from their corresponding matrix.
Investigations by Strelow (Ref. 105, 107-110), have provided a comprehensive
overview of conditions for particular elements and their relative affinities for
various resins.
The affinity is determined by the distribution co-efficient (Kd) of the element in
question.
amount of element in resin grams of dry resin

Kd = x
amount of element in solution mLs of solution
The higher the “Kd” value, the greater the affinity for the resin. A low
concentration acid will typically have a high “Kd” value and will be used to
remove the analyte element from the solution. The element can then be isolated
by eluting with a higher concentration of the acid.
Typical resins used for anion and cation exchange include Dowex resins, Biorad
series and Chelex 100. (For further information see Ref. 105, 107-110).

4.3 Contamination
Glassware used in furnace analysis should be meticulously cleaned to prevent

contamination from the surface of the glass. Washing with detergent followed
by several rinses with distilled water is necessary. Volumetric flasks and
pipettes should also be soaked for 24 hours in 10-20% HNO3. Volumetric flasks
can be stored containing this solution, then rinsed with distilled water before
use. Elements such as sodium, magnesium and zinc are commonly found at high
levels on glassware surfaces.
Pre-cleaned glassware open to the environment can collect airborne particulates
which can cause contamination problems. Airborne dust can contain high levels
of iron, copper, potassium and calcium. One dust particle falling onto a furnace
tube during a run can dramatically change results. This is often the cause of
erroneous results in a poorly designed laboratory.
Ideally, for studying ultra-trace levels, a clean room with filtered air and an
adequate extraction system should be used. Benches and surfaces should be
cleaned regularly to prevent build-up of particulates.
4.3.1. Storage Materials

Materials used for sample storage vary considerably in their properties.
Borosilicate glass is often used, but is not highly recommended. Potassium,
sodium, boron, silicon and aluminium can be leached from the surface of the
glass on contact with hydrofluoric acid and various alkaline solutions. In these
cases, plastic containers can be used. These include polypropylene (PP),
polyvinyl chloride (PVC), teflon (PTFE), and polyethylene.
The order of preference of materials for storage vessels is:
1. Polyethylene
2. Teflon (expensive)
3. Polypropylene (high levels of Cd and Zn; can adsorb Ag readily)
4. Borosilicate glass (some elements)
4.3.2. Washing Procedures

After purchasing plastic containers, careful washing procedures should be
applied to remove all contaminants retained during manufacture. These can
come from air particles or often when the plastic comes in contact with
chemicals or machinery involved in the manufacturing process. The most
common problems associated with plastics involve permeability to solvents.
However, this will only occur over long storage times, and will be humidity
dependent. Typically, the loss of solvent might be 1% per year.
A recommended washing procedure for new plastics and glassware is as
follows:
1. Fill with 30 % V/V HC1 and leave to soak for 2 days.
2. Rinse with distilled water, fill with 30% V/V HNO3 and leave to soak for
two days.
3. Rinse with distilled water (container can be left filled with this solution).
4. Air dry/oven dry (low temp for plastics approx. 60 ⊃C).

4.3.3. Purity of Solutions

Flame atomic absorption, typically aimed at the part per million range, requires
high levels of contamination before any significant change can be noticed in the
sample readings. However, graphite furnace work is aimed at the part per billion
range and is highly susceptible to contamination from a wide range of sources.
Water should be prepared via one or more purification methods, depending on
the purity required. Equipment and methods available include distillation units,
deionizing units, reverse osmosis, ion exchange columns, filtering and
electrodialysis. For trace work, water should have a minimum resistivity of 18
megohms/cm at 25 ⊃C, be filtered through a 0.2 µm membrane filter and passed
through an ion exchange column. Standards are commonly prepared from high
purity reagents such as BDH “Aristar range” acids and 1000 ppm stock
solutions. Standards may be prepared by a series of dilutions using glass pipettes
or by a single step using micro pipettes, although these are not recommended for
highly accurate dilutions.
+
Note:
1. All standards, blanks and samples should be acidified, typically 1.0 %
HNO3 is sufficient.
2. Blanks should be prepared using the same method as applied to
sample and standards. i.e., any contamination will be in blanks as
well as standards.
3. Before running samples, check that good sensitivity can be achieved
with standard solutions. Compare results with the quoted
characteristic mass, thus checking the efficiency of the method.
For further reading, Ref. 104.

5. Developing A Method
Method development for Graphite Furnace AAS can be fraught with problems if
a systematic approach is not used. The increasing use of graphite furnace
analysis, primarily due to its enhanced sensitivity, has produced a lot of
literature describing incurable interferences and non-reproducible results,
branding graphite furnace a difficult technique.
Contamination can be introduced in several places during the analysis. The
acids, solvents, or other reagents used during sample preparation, the containers,
glassware, and even the laboratory environment can be a source of
contamination. The key to minimizing contamination is to simplify the method
as much as possible. Minimize the number of sampling steps and additives that
may be deemed essential by the latest paper.
5.1 Sample Preparation
The sample should be in liquid form with a low viscosity to enable easy and
reproducible pipetting into the graphite furnace. If the sample is in a solid form,
establish whether the sample has to be totally decomposed to obtain the analyte,
or whether an acid extraction process will be adequate. Does the sample require
filtration? Remember that any particles that may be injected will almost
certainly degrade the precision of the analysis.
The acid of choice is an OXY-ACID such as nitric or sulphuric acid.
Hydrochloric acid should be avoided because of volatile chloride formation.
Check the instrumental parameters required such as wavelength, slit, lamp
+
current and whether background correction is required.
Note:
For all wavelengths below 425 nm, background correction can be performed but
will not be essential for all analyses and elements.
Check the sensitivity (concentration of element to produce an absorbance of 0.3
for a 20 mL injection) from the sensitivity section of this manual and calculate
whether the sample will require dilution or concentration.
5.2 Instrument Set-up
The instrument should be turned on and optimized approximately 10 minutes

prior to commencement of analysis. (The deuterium lamp should also be turned
on).
The workhead should be aligned in the optical beam, the G.F. slit mask selected
to reduce the slit height and reduce the emission from the furnace walls entering
the photomultiplier tube.
5.3 Furnace Optimization
Check the analytical data in this manual for the element of interest. Either make
a standard, or preferably dilute a sample that will produce approx. 0.3
absorbance, when using the maximum ash and typical atomize temperature
given. Construct an ash/atomize plot for the element.

5.4 Ash/Atomize Plots
Ash/Atomize plots are performed to establish the maximum ash temperature that
can be used for the particular matrix, and the minimum atomize temperature that
can be used. A minimum atomize temperature prolongs the life of the graphite
tube and using a higher ash temperature will yield a minimum of matrix residue
prior to atomization, hence minimizing any interference.
To produce an ash/atomize plot, select the recommended atomize temperature
and vary the ashing temperature in 100 ⊃C steps. Commence from
approximately 50% of the maximum ash recommended until an ash temperature
is reached where the atomization signal (PEAK HEIGHT or PEAK AREA)
starts to decrease, indicating a loss of analyte in the ash stage.
+ Note: Ensure that a constant atomization ramp rate is maintained when the ash
temperatures are changed.
Once the ash temperature has been optimized, the atomize temperature is varied
from a low temperature (usually 600-1000 ⊃C above the ash temperature) until
the measured signal reaches a well defined plateau, or the maximum temperature
of 3000 ⊃C is attained. The atomize temperature selected will be on the plateau
for the majority of cases, except where the presence of very high background
signals or interference effects may require the ash or atomize temperatures to be
de-optimized to reduce the sensitivity of both signals.
Fig. 7. Ash/atomize plot

5.5 Furnace Program Testing
Once a furnace program has been selected, a more detailed investigation is

required.
1. A blank should be run and checked for contamination. Blank levels should
be as close as possible to zero. However, this is not always possible. The
levels should be kept below 0.1 abs. Higher levels should be examined
further and the contamination corrected.
2. A standard should be run several times (between 5-10 times), and the
reproducibility checked. With auto-samplers, most elements should produce
an RSD of better than 5%. Areas to check if RSD’s are high include:
• The dry stage should produce an even drying without spitting or

bubbling.
• The injection capillary is clear, and the sample is deposited in the tube
and does not “Run-Up” the outside of the capillary. (If this occurs, wipe
the capillary with a tissue soaked in acetone).
• There are no air bubbles in the injected volume and it is reproducible.
• The rinse bottle is full, and there is a stream of rinse solution through the
capillary during the second rinse time at the beginning of a run.
+ Note: on first powering up the system, the rinse will be initiated for 60
seconds.
3. Run the calibration standards to confirm the top standard is in the optimum
working range (normally less than 0.8 abs., however, for most elements this
can be extended to 1.0 abs. or more).
4. Using a sample, check:

• That the concentration is within the range of the calibration standards
prepared.
• That the background absorbance is not excessive.
+ Note: Background absorbance plus atomic absorbance should be less

than 2 absorbance units for a System 2000, and less than 2.5 absorbance
units for a System 3000.
5.6 Background Correction

To check the amount of background in your samples, use the following modes:
Instrument mode
To measure absorbance of: System 2000 System 3000
Background ABS + B/ONLY Abs. Background Only

Analyte ABS + B/CORR Abs. B.C. On
Total Absorbance ABS Abs. B.C. Off
If the background is found to be excessive, there are several alternatives

available:

• Sample dilution is the simplest method to reduce background, however,

this will only be possible where there is adequate sensitivity.
• Use an alternative higher wavelength where background is not as severe.
An example is the analysis of LEAD, where the 217.0 nm line is most
sensitive, but the 283.3 nm line has less background absorption, and is
the preferred line.
+
Note: there will be a sensitivity loss in doing so.
• Adjust the atomize ramp rate to a slower rate, thus separating the analyte
and background peaks. This will enable a reading to be made of the
analyte peak only.
• Use a chemical modifier to either remove the species causing the
interference, or shift the analyte peak away from the background.
• Use chemical modification in conjunction with a L’vov platform.
5.7 Interferences
To check for the presence of interferences in your analysis, it is necessary to run

your standards using the temperature program developed above, and construct a
calibration curve. A standard additions run should be performed using a sample
with a low absorbance (in PEAK HEIGHT and PEAK AREA modes).
The slopes of the calibration and standard addition curves should be compared
and if the slopes differ by less than 10 %, the analysis is deemed interference
free and the calibration standards prepared can be used. If the slopes differ by
more than 10%, an interference is confirmed and a further investigation is
necessary to try and eliminate or minimize the interference.
Methods that can be looked at are:

1. Dilution
2. Chemical modification
3. Chemical modification and platform atomization
4. Separation of the interferent from the analyte by chemical means
If chemical modification and/or platforms are used, the ash/atomize
temperatures have to be re-optimized. After all of the attempts at reducing the
interference have been unsuccessful, a standard additions method should be used
for each sample, or a set of closely matched matrix standards prepared.

Perform furnace optimization and run

a calibration curve and standard additions
experiments on the furnace/sampler program Dilute
finalised using peak height and peak area
to determine if interference is a problem.
YES
The determination is
deemed interference Do the slopes of
free and a calibration NO calibration curve YES Is the sensitivity
curve with simple and standard sufficient to allow
standards using a additions differ dilution?
platform and chemical by more than 10%?
modifier can be used.
YES NO
Use a recommended chemical modifier to

either remove the interfering matrix or
enable higher ash temperatures to be
used. Recheck the ash/optimize curves
and optimize the furnace program.
Repeat the calibration curve/standard
addition runs.
The determination is Do the slopes of

deemed interference NO calibration curve
free and a calibration and standard
curve with simple additions differ
standards and modifier by more than 10%?
can be used.
YES
Use a platform and/or chemical modifier.

The furnace program will have to be
modified. Compare a calibration curve
using modifier and a standard additions
run with a sample using peak heights
and peak area.
The determination is
deemed interference Do the slopes of
free and a calibration NO calibration curve
curve with simple and standard
standards using a additions differ
platform and chemical by more than 10%?
modifier can be used.
YES
Can you use a chemical or other

separation technique to remove
the analyte or interferent?
YES NO
Use a standard additions

Start again method for all samples
at the or produce a set of
beginning. closely matrix-matched
standards.
Fig.8. Checking for the presence of interference

6. Analytical Methodology
6.1 Agricultural
The success of an agricultural system is highly dependent on the owner’s

understanding of the nutrient requirements of his product, and the naturally
occuring nutrient cycle within his immediate environment. If further input is
required to maximize the yield of his produce, some type of soil and plant
analysis is necessary to establish the exact proportions. Graphite Furnace can be
applied to this type of analysis quite easily. Plant material will usually require
some form of digestion prior to analysis, and soils will require a separation
technique because of the complexity and variability of the matrix.
A typical acid mixture for plant analysis might be:
1 mL sulphuric Acid, 1 mL perchloric Acid (60%), 5 mL nitric acid mixed with
0.1 g of plant material. This should cause complete dissolution of the organic
matrix. For soils, an aqua regia digest followed by an MIBK-chloroform
extraction is common.
Table 5. Reference materials for soil and plant analysis
ELEMENT MATRIX KEY WORDS REF
Various Soil extracts Dithiazone extracts 95
Various Pepperbush powder Reference material 96
Pb Environmental HC104, HN03, HF 97

samples
Mo Plant tissue HC104/HN03 98
Ni Plant material MIBK 99
Mo Plant samples HN03/H202 100

6.2 Air Particulates
Atmospheric pollution has become a major topic of concern in recent years.

Graphite furnace has been successfully applied to trace metal analysis in this
area, mainly because of its excellent sensitivity. The preferred sampling method
involves using some type of air filtration unit, followed by analysis of the filter
itself. Various methods include total dissolution of the filter paper by wet or dry
ashing, acid leaching the filter paper or addition of a known amount of the paper
directly into the furnace. Filtering allows the volume of air sampled to be
regulated to fit the analytical range of the technique, or to simulate the human
uptake rate. Chronic poisoning in an industrial environment can be caused by
long term accumulation of some elements. This situation can be duplicated by
sedimentation, where collecting vessels are placed at various locations around
the factory and sampled over certain time intervals. This provides only an
approximation because of the many variables present. Acute poisoning can be
tested by taking samples over a short time interval.
For quantitative results, it is important that a known volume of air is sampled.
Table 6. Reference materials for air particulate analysis.
Pb Airborne particulates Phosphoric acid 76

Pb Urban air Cellulose filter 77
Sb Air Scrubber system 78
Various Aerosols Sample prep only 79
Various Particulate matter in air Sampling filter 80
Ni, V Airborne particulates Nitric acid 81
Various Atmosphere Review 82
Pb Airborne to water NaDDC/EDTA 83

6.3 Biological
Graphite furnace AA has fast become the preferred technique for trace element
analysis in human tissue and fluids. Small sample volumes and good sensitivity
are two reasons for its success.
The two main categories investigated are essential trace elements and toxic trace
elements. Levels of essential elements must be maintained above a certain limit,
because a deficiency in one can quite often relate to a certain disease. On the
other hand an excess of a toxic element can be just as detrimental to a person’s
health.
Arsenic, barium, cadmium, lead, mercury and tin are typical toxic elements.
The following is a table of normal levels of essential elements found in serum

and urine: (REF. 19 and REF. 4).
Table 7. Normal levels of essential elements found in serum and urine.
ELEMENT SERUM mg/100 ml URINE mg/100 ml
Iron 120 180

Copper 120 60
Zinc 100 900
Selenium 1 30
Manganese 0.2 300
Chromium 0.4 10
Cobalt 0.02 100
Vanadium 1 16
Nickel 0.5 85
Contamination associated with biological analysis has become a major area of

research in recent years. Early work using inadequate instrumentation provided
many misconceptions concerning levels of trace elements in biological fluids.
Verification of results by comparison with other instrumentation, reference
material or alternative sample preparation should be standard procedure until the
method is established.
Possible analytical errors include improper sampling, absorption loss or
contamination from container walls and procedural errors. Stainless steel
syringes used for sampling can quite often lead to serious errors because of
elements such as manganese, nickel and chromium in the steel. In these cases
plastic sampling devices should be used. Often the analyst himself is a major
source of error, carrying particles on his clothing, hands and hair. Wearing
plastic gloves can also cause problems with static charge, which attracts airborne
particulates from the laboratory environment onto the gloves.

Table 8. Reference material for analysis of biological samples
Se Urine Wet oxidation 20

Pb Fish tissue Matrix modification, L’vov 21
platform
Pb Blood Triton X 22
Pb Blood Platform, 02 ash 23
Various Biological samples Review 24
Cd Blood (NH4)2 HP04 25
Cr Urine Background correction 26
Cd Urine Matrix modifier 27
Au, Co, Li Blood plasma Bovine plasma 28
Al Neuronal tissue Triton X 29
Al Blood, serum, dialysis fluid and Acid washing 30
waters
Various Blood serum (SIMAAC) 31
Cd Urine Comparison samples 32
Bi Serum and urine EDTA 33
Ga Biological material EDTA 34
Various Biological fluids Method evaluation 35
Cd, Co, Zn Parotid saliva Gel filtration 36

6.4 Food products

Analysis of foodstuffs and beverages for trace elements is becoming a necessary
part of the food industry as emphasis is placed on dietary intake. Essential
element levels in cereals and fruit juices are of major interest, as are toxic
elements in canned food and fish tissue. Sample preparation varies greatly,
depending on the matrix present. Wet ashing is common, and extraction
methods are often used.
The following is a simple method for the analysis of celery, spinach, lettuce and
tomato crops:
2 g of the dried (80 ⊃C) vegetable powder is placed in a 75 mL digestion tube
and 20 mL of Aristar nitric acid and 15 mL of Aristar sulphuric acid is added.
This solution has to stand for 2 hours to prevent excessive foaming. The tube is
then gently heated in a dry block heater, with the temperature being raised to
400 ⊃C over 3 hours. The solution will normally char, but then begin to clarify.
The heating is stopped and when the tube has reached approximately 150 ⊃C,
Aristar hydrogen peroxide is added, dropwise into the tube until the solution in
the tube is completely clear. The solution should be free from precipitates and
other solids. The clear solution is made up to 75 mL with 1% w/v phosphoric
acid. This addition forms a stable Pb (IV) phosphate complex which prevents
normal lead precipitation. The metals Fe, Cu and Zn can be directly analysed by
aspiration into an air/acetylene flame.
Standardization is done by calibration curves using known standards, or the
standard additions technique is used to assess metal recovery. Low levels of Ni,
Cr, Cd and Pb are detected using the graphite furnace. A 20 mL volume of the
digested sample solution is injected into the graphite tube for analysis.
Table 9. Reference materials for analysis of food products
Cd Dried foods Slurry technique 89

Pb, Cd Foods Dry ash 90
Various Fruit juice HN03 91
Pb Beer (sample prep only) DDDC complex 92
Various Oil and fats 02 stream 93
Various Fresh water Solid sample 94

6.5 Geochemical
Geochemical analysis requires a homogeneous mixture of the sample, usually
obtained by fine grinding. The sample can then be leached by boiling dry in
aqua regia, followd by a dissolution of salts in dilute nitric acid. Alternatively, a
wide range of extraction techniques is available.
Geological samples typically require background correction because of the high
levels of alkali metals present. Standard additions is also recommended, as
matching of standards is difficult when each sample matrix is different.
Table 10. Reference materials for the analysis of geochemical samples
Various Organic extract Organic aminohalide

extracts 66
Various Geological materials 10 % aliquot 336 in MIBK 67

(sample prep only)
Au Geological materials DIBK, MIBK 68

(sample prep only)
Silicate rock Problems associated 69

with acid dissolution
Bi Rocks HF-HC104 70
Sn Ore samples HF/HN03 dissolution 71

(sample prep only)
Li Silicate rocks HF/HN03/HC104 72

(sample prep only) dissolution
Te Geological materials MIBK 73
Various Coal fly ash HF, H3B04 74
Au Gold plant barren solutions Automated flame 75

(sample prep only)

6.6 Metallurgical
Most cities today are characterised by tall buildings, bridges and many other
constructions, all relying on the strength of the building materials used. It is
common knowledge today that low levels of certain metals can adversely affect
the physical properties of these materials, especially alloys and steels.
Dissolution of the metal sample is typically carried out by acid addition and
gentle heating. Mixtures of (1:1) nitric acid/deionized water and (1:1:1) nitric
acid/hydrofluoric acid/deionized water are commonly used but special cases will
require other acids. Hydrochloric acid should be avoided due to problems
associated with volatile compound formation in the furnace.
In most cases, the analyte element is in the presence of high concentrations of
other elements. Occasionally these other elements can interfere with the
analysis, so it is always wise to run reference standards with the samples. These
standards are available for the more common combinations of alloys and steel.
Recoveries of these standards determine the efficiency of the methodology.
Table 11. Reference materials for the analysis of metallurgical samples
Al Low alloy and stainless steel HCl, HN03 59
Various Iron and Steel 40 % HN03 60
Various High purity nickel Nitric acid 61
As, Sb, Se, Te High purity copper Nitric acid 62
Pb, Bi, Se, Te, Sn Complex alloys Solid sample 63
In Metallic zinc and lead Ion exchange 64
Cr, Fe, Ni Lithium metal La(OH)3 65

Co-precipitation

6.7 Petrochemical
Levels of trace metals in petroleum products are of major importance in the

petrochemical industry. Several areas of application are:
1. Fe and Ni will poison catalysts if they reach certain levels in crude

oil.
2. Vanadium can form refractory compounds in furnaces and cause

corrosion of engines when present in fuel oils.
3. Engine failure can be prevented by monitoring the presence of wear

metals in lubricating oil. A sudden increase in Ag, Si, Cr, Sn, Fe or
Pb can indicate breakdown of a certain component in the engine.
4. Sources of oil spillage can be identified by determining the levels of

trace elements in the oil.
5. Trace elements are used as additives to oils and fuels to improve

performance.
Several methods of sample preparation are available. The method used depends
on the volatility of the element and the complexity of the matrix. Viscous
samples can be diluted with a range of organic solvents and injected directly into
the furnace (hot injection is recommended). Very light oils require no dilution.
The samples can also be dry ashed and dissolved in acid (non volatile elements
only), or an acid digest can be used.
Note: Evaporation can be a problem with organic solvents if the sample is left in
+
an open container for long periods. This increases the concentration of the
analyte. A maximum sample volume of 20 µL is recommended for organic
solutions unless the hot injection technique is used.
Table 12. Reference materials for the analysis of petrochemical samples
Fe, Ni Crude oils 84
P Oils MIBK extracts 85
Various Petroleum Modified furnace products 86
As Shale oil THF 87
P Gasoline La(NO3)3 88

6.8 Waters
Over the past several decades there has been extensive research into
understanding the immediate and long term effects of industrial waste disposal
on ecosystems. The distribution of this waste through the river systems, drinking
water supplies and eventually into the oceans, has been systematically studied
and recorded by bodies worldwide. Graphite furnace has become one of the
most recognized techniques in this field. Pure waters typically require little if
any modification before analysis other than filtering and acidification. They are
low in salinity and total dissolved solids, and neutral in pH.
Sea and estuarine water often require chemical modification to eliminate
chemical interferences caused by the chloride present. Ammonium nitrate can be
used to modify the sample in the furnace or some form of ion exchange can be
used to separate the element from the matrix prior to the furnace measurement.
These samples are high in salinity and high in total dissolved solids. Method
development for industrial waste samples can be quite complex if the analyte
element is tightly bound to its matrix. In a river, the waste from several
industries can combine to form a matrix which is difficult to digest, and signal
depression during the analysis is possible.
Table 13. Reference materials for the analysis of water samples
Various Sea water NH4NO3 37
Si Deionized process water Aqueous 38
Hg Sea water APDC-chloroform 39
Pb, Cd Waters La addition, platform 40
Se, Sb Sea water APDC, C18-bonded 41

silica gel
As, Sb, Se, Te Environmental water samples Acid enhancement 42
Various Sea water Electrode position 43
Various Effluent and natural water APDC, 2-4 dimethyl-4 44

-heptanone
Zn Sea water Organic matric modification 45
Various Sea water Back extraction Hg (II) 46
Bi Sea water NaHBO4 reduction 47
Pb Sea water Time expansion 48
Sb Natural waters G.F. with hydride 49
Al Natural waters Phosphoric acid 50
Ionic alkyl lead Water NaDDC/EDTA 51
Various Sea water CHELEX 100 52

Table 13. cont’d.

Various Sewage sludge Various pretreatment 53

methods only
Co, Cd, Zn, Ni Sea water Dithiocarbamate 54
Various Water Ascorbic acid 55
As Sea water Ion exchange 56
Various Natural waters Mg(NO3)2 modifier 57
Se Sediments, waters G.F. + hydride 58
Se, As Environmental samples Nickel modifier 111

6.9 Characteristic Concentration (sensitivity)
Sensitivity is denoted by the characteristic mass or characteristic concentration.

These are the mass or concentration of an element giving a peak absorbance of
0.0044 abs. (1% absorption). With furnace methods, the sample volume can
vary with viscosity, sample availability and tube loading capacity. Because of
this, characteristic mass is usually quoted rather than characteristic
concentration. Picogram (10-12 g) is the unit used for quantifying characteristic
mass.
Mass in pg = Volume in mL x Concentration in ng/mL
e.g., 20 mL of 100 ng/mL aluminium
20 mL of 100 ng/mL = 20 mL of 100 pg/µL

= 2000 pg Absolute
Characteristic mass = mass of sample x 0.0044

absorbance of sample
e.g., If 2000 pg gives a response of 0.8 absorbance units
X pg gives a response of 0.0044 absorbance units
X = 11 pg characteristic mass
The lower limit of the normal working range is typically 10 times the
characteristic mass.
The following units are all equivalent:
pg/µL = ng/mL = µg/L

pg/µg = ng/mg = µg/kg
In Table 14 below, characteristic concentration (in ng/mL) is quoted for each

element on a 20 µL sample size for ARGON and NITROGEN, as well as an
absolute pg value for ARGON gas.

Table 14. Characteristic concentrations using argon and nitogen gas for 20 µL injection.
Element Characteristic Concentration Characteristic Mass

(ng/mL) (pg)
Argon Nitrogen Argon
______________________________________________________________
Ag 0.04 0.04 0.9
Al 0.25 0.45 5.0
As * 0.3 0.3 6
Au 0.2 0.3 4
B 50 - 1000
Ba 0.6 2.0 12
Be 0.035 0.045 0.7
Bi 0.35 0.35 7.0
Ca 0.03 0.07 0.6
Cd 0.013 0.013 0.25
Co 0.2 0.2 4.0
Cr 0.08 0.09 1.5
Cs 0.3 0.4 6.0
Cu 0.13 0.14 2.5
Dy 1.8 1.8 35
Er 3.8 4.3 75
Eu 0.8 1.0 15
Fe 0.08 0.08 1.5
Ga 1.0 1.5 20
Hg 18 19 350
In 1.3 2.3 25
K 0.025 0.035 0.5
Li 0.13 0.18 2.5
Mg 0.01 0.013 0.2
Mn 0.035 0.05 0.7
Mo 0.4 0.8 8.0
Na 0.01 0.01 0.2
Ni 0.25 0.25 5
P* 100 - 2000
Pb 217 0.13 0.13 2.5
Pb 283.3 0.28 0.28 5.5
Pd 0.6 0.6 12
Pt 4.5 5.5 90
Rb 0.06 0.10 1
Ru 1.3 1.3 25
Sb 0.45 0.50 9
Se * 1 1.1 20
Si 1.3 1.4 25
Sn 1.1 1.2 22
Sr 0.15 0.3 3
Tb 0.18 - 3.5
Te 0.9 0.9 18
Ti 2.3 3 45
Tl 1.0 1.2 20
V 1.0 1.1 20
Zn 0.01 0.01 0.25
* Chemical modifier used

7. Analytical Data For GF2000/3000
Table 15, commencing on p 46, is a quick guide to the optimum ash and
atomization temperatures for each element.
The atomization temperatures will vary with the matrix and as such should be
taken as a guide only, although these temperatures will be fairly close.
Atomization stage ramp rates are not included as these vary widely with the
element and matrix. However, in general, the maximum ramp rate of
2000 ⊃C/sec will yield the highest absorbance. The ramp rates will naturally
require optimization to suit the individual analysis, especially where a large
background absorbance is found to be present. The ramp rate can be reduced to
enable resolution of the atomic and background signals.
The conditions shown in Table 15 were determined using aqueous standards
made up in 0.5% HNO3, using the same drying conditions, 20 µL injected
volume and gas stop conditions for atomization.
Characteristic Concentration:
This is the concentration of the element which will yield an absorbance of
0.0044 in peak height mode with a new pyrolytic coated furnace. The
characteristic concentration is determined on a 20 microlitre sample size for
argon and nitrogen. An absolute value (characteristic mass) is also given for
argon.
Typical Response:
The concentration of element that produces approximately 0.3 abs is given for a
20 microlitre sample using argon. This is obtained for simple standards and a
figure within 25% of this value can be expected. This figure is given so that the
optimum working range can be determined. (The optimum absorbance range is
0.1 to 0.8 abs).
Ash Stage:
The maximum ash temperature for a nitric acid medium is given. This will vary
with the matrix and should be determined for your particular samples by starting
at a level about 60% of the quoted maximum and performing a single sample
run. Record the absorbance and increase the ash temperature approximately 100
⊃C and re-run the sample. The point at which the absorbance is reducing is
where analyte is lost during the ash stage, so reduce the ash temperature to a
+
level where analyte is not lost.
Note: Maintain the same atomize ramp rate when varying the ash temperature.

Dry Stage and Injection Volume:

Injection volume used to generate the data was 20 µL. The dry stage was a two
step COLD injection program:
STEP FINAL RAMP HOLD INERT AUX READ

NUMBER TEMP TIME TIME GAS GAS ON
(⊃C) (sec) (sec)
1 90 10 5 YES NO NO
2 120 30 10 YES NO NO
For volumes of 20 µL or less this program will be satisfactory. For volumes up

to 60 microlitre the ramp stage of step 2 should be increased so that the sample
dries without splattering and bubbling prior to the end of the second stage.
For volumes greater than 60 µL a HOT injection was found to give the best
performance. The HOT injection again comprised a two stage program, with the
sample injected at the beginning of step 2:
STEP FINAL RAMP HOLD INERT AUX READ

NUMBER TEMP TIME TIME GAS GAS ON
(⊃C) (sec) (sec)
1 120 1 1 YES NO NO
2 140 10 1 YES NO NO
The second step is added to ensure the sample is dry. Otherwise a higher
temperature would have to be selected for Step 1. With this program, 100
microlitre volumes have been successfully dried. The Step 1 final temperature
will have to be determined for each sample matrix and furnace. This is typically
15 - 20 ⊃C above the point at which a sample dries when using the COLD
injection program shown above.
Inert/Auxiliary Gases:
The System 2000 and System 3000 have selection for two gases, INERT and
AUXILIARY. For most applications the INERT gas is nitrogen and the
AUXILIARY gas is argon. This enables the less costly nitrogen to be used
during the dry stage, and argon during the atomize stages for elements that
require argon for best sensitivity.
Where reduced sensitivity is required, inert gas flow during atomization can be
selected. To do this auxiliary gas can be set for the reduced flow and selected
during atomization. (Typically a flow of 4 - 6 flow units is used during Dry and
+
Ash stages).
Note: A gas should always be connected to the INERT input since this is used
for the RINSE of the SAMPLER. The GF2000/3000 will not function without
inert gas present.

Atomization Gas Selection:

For best sensitivity the inert (and auxiliary) gas should be OFF during
atomization.
When zero gas flow is used, a gas stop step of 1 second should be included prior
to atomization to ensure the gas flow is zero at the beginning of atomization.
If sample concentration is high and you do not wish to dilute, gas flow during
atomization will reduce the sensitivity (see section 2.2.6).
Atomization Read Selection:

A read command can be selected during any stage in the program, however, the
peak height (or peak area) function will only record the last 10 seconds of the
reading. Typically the READ is selected at the beginning of the atomization step
and turned OFF during the CLEAN stage of the program. Ensure that at the end
of the ASH stage the absorbance is stable and at a minimum.
Clean Stage:
For most analyses it will be advisable to have a CLEAN stage after the
atomization read stage, where the furnace is either held at the same temperature
or raised to a higher temperature with gas flow to remove the sample from the
furnace and reduce any memory effect. This is particularly important for
elements that require a high atomization temperature.

Table 15. Optimum ash and atomization temperatures
Element Max Ash Atomize Characteristic Characteristic Typical Response

In HNO3 Temp Concentration Mass (conc. for 20µL to
Ar N2 Ar give approx.
0.3 abs) Ar
⊃C ⊃C ng/mL ng/mL pg ng/mL
Aluminium 1400 2500 0.25 0.45 5 20

Al The 309.3 nm line is preferred where background correction is required. The
396.2 nm line is more linear and is preferred where background is not present.
Chemical modifiers normally used for Al are Ca(NO3)2, Mg(NO3)2, phosphoric
acid. Argon is the preferred gas for aluminium determinations.
WAVELENGTH: 309.3 nm SLIT: 0.5 nm LAMP CURRENT: 10 mA
Antimony 600 2000 0.45 0.5 9 35

Sb A super lamp will yield a better sensitivity and a better detection limit. Ni can be
used as a chemical modifier at a level of 10 mg (e.g., 10 mL of 1000 mg/mL
Ni).
WAVELENGTH: 217.6 nm SLIT: 0.2 nm LAMP CURRENT: 10mA
Arsenic 800* 2300 0.3 0.3 6 25

As 300 Use of Ni as a chemical modifier improves sensitivity and allows a higher ash
temperature to be used. Ni is added at a level up to 10 mg (e.g. 10 mL of 1000
mg/mL, Ni). Use of super lamp will improve sensitivity and detection limit. The
pure line source of a super lamp enables a wider slit width to be used in order to
improve the noise performance.
* using chemical modifier.

Barium 1400 2500 0.6 2.0 12 45

Ba Argon is preferred for this analysis since barium forms stable nitrides. Tube
cleans will be required to remove contamination. Ensure careful alignment of
furnace to eliminate incandescence. Use maximum lamp current and minimum
slit width to minimize this effect.
Beryllium 900 2300 0.035 0.045 0.7 2.5

Be
Bismuth 500 2000 0.35 0.35 7.0 25

Bi Ni has been used as a chemical modifier. A super lamp will yield a better
sensitivity and detection limit.


0.3 abs) Ar
Boron 800 2900 50 - 1000 3500

B Barium hydroxide is used as a chemical modifier at a level of 30 mg Ba. Other
chemical modifiers that can be used are Ca and La. Argon is the only gas that
can be used.
Cadmium 300 1800 0.013 0.013 0.25 1.0

Cd Several chemical modifiers have been used for Cd, some of the more common
are Phosphoric acid and ammonium phosphate salts. These allow an ash
temperature of up to 600 ⊃C. A super lamp can provide better sensitivity and
detection limit.
Caesium 400 2200 0.3 0.4 6.0 20

Cs WAVELENGTH: 852.1 nm SLIT: 1.0 nm LAMP CURRENT: 15 mA
Calcium 1000 2600 0.03 0.07 0.6 2.0

Ca Furnace optimization is important to minimize incandescence. Calcium is very
sensitive and very abundant. Contamination is a problem. Ensure calcium
contamination levels in the furnace and blanks are minimized.
Chromium 1100 2500 0.08 0.09 1.5 5.5

Cr Contamination is a problem with Cr determinations, especially where chromic
acid washing is used. A CLEAN step might be required to remove memory from
the furnace after each firing.
Cobalt 800 2300 0.2 0.2 4.0 15

Co WAVELENGTH: 240.7 nm SLIT: 0.2 nm LAMP CURRENT: 6 mA
Copper 800 2300 0.13 0.14 2.5 10.0

Cu WAVELENGTH: 324.7 nm SLIT: 0.5 nm LAMP CURRENT: 4 mA
Dysprosium 1100 2700 1.8 1.8 35 120

Dy Ensure careful alignment of the graphite tube atomizer to minimize
incandescence from the tube.


0.3 abs) Ar
Erbium 1000 2700 3.8 4.3 75 260

Er Ensure careful alignment of the graphite tube atomizer to minimize
Europium 1000 2500 0.8 1.0 15 55
Eu Ensure careful alignment of the graphite tube atomizer to minimize
Gallium 500 2200 1.0 1.5 20 70

Ga WAVELENGTH: 287.4 nm SLIT: 0.2 nm LAMP CURRENT: 5 mA
Gold 600 2400 0.2 0.3 4 14

Au WAVELENGTH: 242.8 nm SLIT: 0.5 nm LAMP CURRENT: 4 mA
Indium 700 2000 1.3 2.3 25 90

In WAVELENGTH: 303.9 nm SLIT: 0.2 nm LAMP CURRENT: 5 mA
Iron 800 2300 0.08 0.08 1.5 6.0

Fe WAVELENGTH: 248.3 nm SLIT: 0.2 nm LAMP CURRENT: 7 mA
(217.0 nm)
Lead 400 2000 0.13 0.13 2.5 9
Pb (283.3 nm)
0.28 0.28 5.5 20
The 283.3 nm line is the preferred line for routine analysis due to the lower
non-atomic absorption and the more linear calibration curve. Several chemical
modifiers are used for lead analysis. Some of these are: EDTA, phosphoric acid,
ammonium phosphate salts, ascorbic acid, tartaric acid and
sucrose. Use of a super lamp will produce better sensitivity and detection limit.
The 217.0 nm line is the line at which the super lamp performs best.
Lithium 800 2400 0.13 0.18 2.5 9.0

Li WAVELENGTH: 670.8 nm SLIT: 0.5 nm LAMP CURRENT: 5 mA
Magnesium 800 2200 0.01 0.013 0.2 0.7

Mg Magnesium is a common contaminant in the environment, and the furnace
technique is extremely sensitive. Clean the tube several times prior to analysis
and check the contamination level in tubes and reagents.


0.3 abs) Ar
Manganese 700 2400 0.035 0.05 0.7 2.5

Mn WAVELENGTH: 279.5 nm SLIT: 0.2 nm LAMP CURRENT: 5 mA
Mercury 100 1600 18 19 350 1250
Hg Several chemical modifiers have been reported for mercury with 1% (NH4)S2
and K2Cr2O7 being the most common. They allow ash temperatures of up to 300
⊃C to be attained. The use of gold solutions to form amalgums has also been
reported.
Molybdenum 1200 2700 0.4 0.8 8.0 30

Mo Argon is the preferred gas for molybdenum. A CLEAN stage will be required to
remove memory from the furnace.
Nickel 900 2400 0.25 0.25 5.0 20

Ni WAVELENGTH: 232.0 nm SLIT: 0.2 nm LAMP CURRENT: 4 mA
Palladium 1000 2500 0.6 0.6 12 45

Pd WAVELENGTH: 244.8 nm SLIT: 0.2 nm LAMP CURRENT: 5 mA
Phosphorus 700* 2700 100 - 2000 7000

P Argon is the recommended gas. Lanthanum nitrate is used as a chemical
modifier at a concentration of 0.1 %. Sensitivity and detection limit will
improve with the use of a super lamp.
* Using chemical modifier.
Platinum 1100 2800 4.5 5.5 90 320

Pt Argon is the preferred gas.
WAVELENGTH: 265.9 SLIT: 0.2 nm LAMP CURRENT: 10 mA
Potassium 700 2000 0.025 0.035 0.5 1.7

K Potassium is a common contaminant and the analysis of potassium is extremely
sensitive. Run several blanks and check the contamination level on tubes and
reagents.
Rubidium 600 2000 0.06 0.10 1.0 5.5

Rb WAVELENGTH: 780.0 nm SLIT: 0.2 nm LAMP CURRENT: 10 mA


0.3 abs) Ar
Ruthenium 600 2800 1.3 1.3 25 90

Ru WAVELENGTH: 349.9 nm SLIT: 0.2 nm LAMP CURRENT: 10 mA
Selenium 700 2400 1.0 1.1 20 70
Se Nickel nitrate is used as a chemical modifier at a concentration of 0.05 to 0.1%
Ni. Use of a super lamp will improve sensitivity and detection limits. Maximum
ash without chemical modifier is 300 ⊃C.
Silicon 1000 2700 1.3 1.4 25 100

Si Carbide formation is a problem with silicon determinations, and a CLEAN step
will be required.
Silver 400 2000 0.04 0.04 0.9 3.0

Ag WAVELENGTH: 328.1 nm SLIT: 0.5 nm LAMP CURRENT: 4 mA
Sodium 700 2000 0.01 0.01 0.2 0.7

Na Sodium is a common contaminant and the determination of sodium is extremely
sensitive by graphite furnace. Run several CLEAN programs and check
contamination levels of all reagents and tube.
Strontium 1000 2600 0.15 0.3 3 12

Sr Memory can be a problem with strontium analysis, and incorporating a tube
clean in the program is essential to remove it. Incandescence could also be a
problem at this wavelength if high atomization temperatures are used. Argon is
the preferred gas.
Tellurium 500 1800 0.9 0.9 18 70

Te WAVELENGTH: 214.3 nm SLIT: 0.5 nm LAMP CURRENT: 7 mA
Thallium 400 2200 1.0 1.2 20 70

Tl 1% H2SO4 has been used as a chemical modifier for the analysis of thallium.
Tin 800 2500 1.1 1.2 22 75

Sn Chemical modification with 1% diammonium hydrogen citrate has been
reported. Other chemical modifiers used are EDTA, NH4H2PO4, (NH4)2HPO4.


0.3 abs) Ar
Titanium 1200 2900 2.3 3 45 190

Ti Argon is the preferred gas. Tube CLEAN should be carried out as part of the
program to reduce memory effects. A lower atomization temperature of 2700
⊃C and longer hold time could yield better precision and will improve tube life.
Vanadium 1200 2700 1.0 1.1 20 70

V A tube CLEAN should be incorporated in the temperature program. An atomize
temperature of 2900 ⊃C could yield better sensitivity, but with reduced tube life.
Zinc 400 1800 0.01 0.01 0.25 0.8

Zn Zinc is a common contaminant and the determination of zinc is extremely
sensitive by graphite furnace. Run several CLEAN programs and check
contamination levels of all reagents and tube.


8. References
General
1. EDIGER R.D. :Atomic Absorption Newsletter, Vol. 14, p 127, 1975.
2. EDIGER R.D., PETERSON G.E., and KERBER J.D.: Atomic Absorption

Newsletter. Vol. 13, p 16, 1974.
3. MANNING D.C., SLAVIN W.: Applied Spectroscopy, Vol. 37, No. 1,

1983.
4. PRICE W.J.: Spectrochemical Analysis by Atomic Absorption,

Heydon Press, p 260, 1979.
5. CHEROFF B.: A Method For Wet Digestion Of Fish Tissue For Heavy
Metal Analysis. Dept. Biology and Institute of Marine Sciences,
Adelphi University. Garden City, New York.
6. BRODIE K.G., MATOUSEK J.P.: Determination of cadmium in air by non

flame atomic absorption spectrometry.
Anal. Chim. Acta., Vol. 69, p 200, 1974.
7. CRANEY C.L., SWARTOUT K., SMITH F.W., and WEST C.D.:

Improvement Of Trace Aluminium Determination By
Electrothermal Atomic Absorption Spectrophotometry Using
Phosphoric Acid. Anal. Chem., Vol. 58, pp 656-658, 1986.
8. DOLINSEK F., STUPAR J.: Analyst, Vol 98, p 841, 1973.
9. EBERT J., JUNGMANN H.Z.: Anal. Chem., Vol. 46, pp 270-287, 1974.
10. PREVOT A.P., JAUNIAUX M.G.: Rapid Determination of Phosphorus

In Oils by Flameless Atomic Absorption. Atomic Absorption
Newsletter, Vol. 17, No. 1 Jan-Feb, 1978.
11. MANNING D.C., SLAVIN W.: Applied Spectroscopy, Vol. 37,

p 1, 1983.
12. PRICE W.J.: Spectrochemical Analysis by Atomic Absorption.

Heyden Press, 1979.
13. EDIGER R.D., PETERSON G.E., and KERBER J.D.: Application of the
Graphite Furnace to Saline Water Analysis.
Atomic Absorption Newsletter, Vol. 13, No. 3, May-June, 1974.

8. References
14. EDIGER R.D.: Atomic Absorption Newsletter, Vol. 14, p 127, 1975.
15. THOMPSON K.C., GODELEN R.G., and THOMERSON D.R.: Anal.

Chim. Acta., Vol. 74, p 289, 1975.
16. BEDARD M., KERBYSON J.D.: Can J Spectrosc., Vol. 21, p 64,
1976.
17. L’VOV B.V.: Electrothermal Atomization - The Way Towards

Absolute Methods of Atomic Absorption Analysis. Spectrochim.
Acta., Vol. 338, p 153, 1978.
18. WATSON C.A.: Ammonium Pyrolidine Dithiocarbamate, Monograph

74. Hopkins & Williams. Chadwell Heath, England, October, 1971.
19. VERSIECK J., CORNELIUS R.: Normal levels of trace elements in

human blood, plasma or serum. Anal. Chim. Acta., Vol. 116,
p 217, 1980.
Biological
20. JANGHORBANI M., TING B.T.G., NAHAPETIAN-ARA and

YOUNG V.R.: Conversion of urinary selenium to selenium (iv)
by wet oxidation. Anal. Chem., Vol 54, pp 1188-1190, 1982.
21. THOMAS M.W., BRUMBAUGH W.G.: Matrix Modifier and L’vov

platform for elimination of matrix interferences in the analysis of
fish tissues for lead by graphite furnace atomic absorption
spectometry. Anal. Chem., Vol. 54, pp 1032-1037, 1982.
22. ATHANASOPOULOS N., CHAPPLE G.: The Determination of Lead in

Blood by Graphite Furnace AA.
GBC Application Note, No 2, 1986.
23. SCHUTTLER I.L., DELVES T.H.: Determination of lead in blood by

atomic absorption spectometry with electrothermal atomization.
Analyst, Vol. III., June, 1986.
24. VEILLON C.: Trace Element Analysis of Biological Samples (report).

Analytical Chemistry, Vol. 58, No. 8, July 1986. 85IA.
25. FALK H., HOFFMAN E., LUDKE C., OTTAWAY J.M., and
LITTLEJOHN D.: Studies on the Determination of Cd in Blood by
Furnace non thermal excitation spectrometry. Analyst, Vol. III,
March, 1986.
26. HALLS D.J., FELL G.S.: The Problem of Background Correction in the
Determination of Chromium in Urine by Atomic Absorption
Spectrometry with Electrothermal Atomization. Journal of
Analytical Atomic Spectrometry, Vol. 1, April 1986.

8. References
27. FIETSMA K.G., FRANKE J.P., and DE ZEEUW R.A.: Comparison of

some matrix modifiers for the determination of cadmium in urine
by atomic absorption spectrometry with electrothermal
atomization. Analyst, Vol 109, June, 1984.
28. MAESSEN F.J.M., POSMA F.D., and BALKE J.: Direct

Determination of Gold, Cobalt and lithium in Blood Plasma Using
the Mini Massmann Carbon Rod Atomizer. Analytical Chemistry,
Vol. 46, No. 11, September 1974. 1445.
29. PIERSON K.B., EVENSON M.A.: Measurement of Aluminium in

Neuronal Tissue using Electrothermal Atomization Atomic
Absorption Spectrophotometry. Anal. Chem., Vol. 58, No. 8,
July 1986. 1745.
30. BROWN A.A., WHITESIDE P.J., and PRICE W.J.: Determination of Al

in Blood, Serum, Dialysis Fluids and Waters by Graphite
Furnace. International Clinical Products Review, Jan/Feb 1984.
31. LEWIS S.A., O’HAVER T.C., and HARNLY J.M.: Determination of

metals at the microgram per litre level in blood serum by
simultaneous multielement atomic absorption spectrometry with
graphite furnace atomization. Anal. Chem., Vol. 57, pp 2-5, 1985.
32. DUNGS K., NEIDHART B.: Analysis of urine samples by

electrothermal atomization & atomic absorption spectrometry: a
comparison of natural and control material. Analyst, Vol. 109,
July, 1984.
33. BERTHOLF R.L., RENOE B.W.: The Determination of bismuth in

serum and urine by electrothermal atomic absorption spectrometry.
Anal. Chimica Acta., 139 (1982) 287.
34. NAKAMURA K., FUJIMORI M., TSUCHIYA H., and ORII H.:
Determination of gallium in biological materials by electrothermal
atomic absorption spectrometry. Anal. Chim. Acta., 138 (1982) 129.
35. AMOS M.D., BENNETT P.A., BRODIE K.G., LUNG P.W.Y., and
MATOUSEK J.P.: Carbon rod atomizer in atomic absorption and
fluorescence spectrometry and its clinical application.
Anal. Chem., Vol. 43, No. 2, Feb, 1971.
36. LANGMYHR F.J., EYDE B.: Determination of the total content and
distribution of cadmium, copper and zinc in human parotid saliva.
Anal. Chim. Acta., 107 (1979) 211.
Water
37. EDIGER R.D., PETERSON J.D., and KERBER J.D.: Application of the
graphite furnace to saline water analysis. Atomic Absorption
Newsletter, Vol. 13, No. 3 May-June 1974.

8. References
38. The determination of silicon in deionized process water by graphite

furnace AAS. Analytical note, Spectrochimica Acta, Vol. 39B,
No. 4, p 597, 1984.
39. FILIPELLI M.: Determination of trace amounts of mercury in sea water

by graphite furnace atomic absorption spectrophotometry.
Analyst, Vol. 109, April 1984.
40. HUNT D.T.E., WINNARD A.D.: Appraisal of selected techniques for the
determination of lead and cadmium in waters by graphite
furnace atomic absorption spectrometry.
Analyst, Vol. III, July, 1986.
41. STURGEON R.E., WILLIE S.N., and BERMAN S.S.: Preconcentration

of selenium and antimony from sea water for determination by
graphite furnace atomic absorption spectrometry.
Anal. Chem., Vol. 57, pp 6-9, 1985.
42. KONSELMAN G.C., HUFF E.A.: The determination of arsenic,

antimony, selenium & tellurium in environmental water samples
by flameless atomic absorption. Atomic Absorption
Newsletter, Vol. 15, No. 2, March-April, 1976.
43. BATELY G.E., MATOUSEK J.P.: Determination of heavy metals in

sea water by atomic absorption after electrode position on
pyrolytic graphite coated tubes. Anal. Chem., Vol. 49,
2031, 1977.
44. BONE K.M., HIBBERT W.D.: Solvent extraction with ammonium

pyrolidine dithiocarbamate and 2, 6 dimethyl-4-heptanone for
the determination of trace metals in effluents and natural
waters. Anal. Chim. Acta., Vol. 107, p 219, 1979.
45. GUEVREMONT R.: Organic matrix modifiers for direct

determination of zinc in sea water by graphite furnace atomic
absorption spectrometry. Anal. Chem., Vol. 53, pp 911-914,
1981.
46. LO J.M., YU J.C., HUTCHINSON F.I., and WAL C.M.: Solvent

extraction of dithiocarbamate complexes and back extraction with
mercury (II) for determination of trace metals in sea water by
atomic absorption spectrometry. Anal. Chem., Vol. 54,
pp 2536-2539, 1982.
47. LEE D.S.: Determination of bismuth in environmental samples by

flameless atomic absorption spectrometry with hydride generation.
Anal. Chem., Vol. 54, p 1682, 1982.

8. References
48. GREY R., ATHANASOPOULOS N.: Application of time expansion to

graphite furnace AAS in the analysis of water. National
symposium on absorption spectrometry abstracts, Feb 13-15
1984, Presented at Pittsburg, 1982.
49. ANDREAE M.O., ASMODE J., FOSTER P., and VAN’T DACK L.:
Determination of antimony (III), antimony (V) and
methylantimony species in natural waters by atomic absorption
spectrometry with hydride generation. Anal. Chem., Vol. 53,
pp 1766-1771, 1981.
50. CRANEY C.L., SWARTOUT K., SMITH III F.W., and WEST C.D.:
Improvement of trace aluminium determination by electrothermal
atomic absorption spectrophotometry using phosphoric acid.
Anal. Chem., Vol. 58, p 656, 1986.
51. CHAKROBORTI D., VAN CLEAVENBERGEN R.J.A., and ADAMS

F.C.: Determination of total ionic alkyllead in water by electro-
thermal atomization atomic absorption spectrometry. Journal of
Analytical Atomic Spectrometry, Vol. 1, p 293, Aug., 1986.
52. POULSON A.J.: Effects of flow rate and pretreatment on the extraction
of trace metals from Estuarme and coastal sea water by
chelex 100. Anal. Chem., Vol. 58, pp 183-187, 1986.
53. CARRONDO M.J.T., PERRY R., and LESTER J.N.: Comparison of

electrothermal atomic absorption spectrometry of the metal content
of sewage sludge with flame atomic absorption spectrometry in
conjunction with different pretreatment methods.
54. BRULAND K.W., FRANKS R.P., KNAUER G.A., and MARTIN J.H.:
Sampling and analytical methods for the determination of copper,
cadmium, zinc, nickel at the nanogram per litre level in sea water.
55. TOMINAGA M., UMEZAKI.: Comparison of ascorbic acid & related

compounds as interferences, suppressors in electrothermal atomic
absorption spectrometry.
56. PERSSON J., IRGUM K.: Determination of dimethyl arsenic acid in sea
water in sub ppb range by electrothermal atomic absorption
spectrometry after preconcentration on an ion exchange column.
Anal. Chim. Acta., Vol. 138, 111, 1982.
57. MANNING D.C., SLAVIN W.: The determination of trace elements in

natural waters using S.T.P.F. Applied Spectroscopy,
Vol. 37, No. 1, 1983.

8. References
58. WILLIE S.N., STURGEON R.E., and BERMAN S.S.: Hydride

generation atomic absorption determination of selenium in marine
sediments tissues and sea water with in situ concentration in a
graphite furnace. Anal. Chem., Vol. 58, 1140.
Metallurgical
59. PERSSON J., FRECH W., and CEDERGEN A.: Determination of Al in

low alloy and stainless steels by ETA. Anal. Chim. Acta.,
Vol. 89, p 119, 1977.
60. SHAW F., OTTAWAY J.M.: The determination of trace amounts of

aluminium and other elements in iron and steel by atomic
absorption spectrometry with carbon furnace atomization.
The Analyst, Vol. 100, No. 1189, p 217.
61. FORRESTER J.E., LEHECKA V., JOHNSTON J.R., and OTT W.L.:
Direct determination of trace quantities of antimony, arsenic,
bismuth, cadmium, lead, selenium, silver, tellurium and thallium in
high purity nickel by electrothermal atomic absorption
spectrometry. Atomic Absorption Newsletter,
Vol. 18, No. 4, July-August, 1979.
62. HAYNES B.W.: Arsenic, antimony, selenium and tellurium

determinations in high purity copper by electrothermal
atomization. Atomic Absorption Newsletter,
Vol. 18, No. 2, March-April, 1979.
63. MARKS J.Y., WELCHER G.G., SPELLMAN R.J.: Atomic absorption

determination of lead, bismuth, selenium, tellerium, thallium and
tin in complex alloys using direct atomization from metal chips in
the graphite furnace.
Applied Spectroscopy, Vol. 31, No. 1, p 9, 1977.
64. BRAJTER K., OLBRYCH E.: Application of electrothermal atomic

absorption spectrophotometry to the determination of trace
amounts of indium in metallic zinc and lead.
Sieszynska Analyst, Vol. III, September, 1986.
65. BENISCHEK-HUBER., BENISCHEK F.: Electrothermal atomic

absorption spectrometric determination of chromium, iron and
nickel in lithium metal. Anal. Chim. Acta., Vol. 140, p 205, 1982.
Geological
66. CLARK R.J.: Electrothermal atomization atomic absorption conditions
and matrix modifications for determining Sb, As, Bi, Cd, Ga, Au,
In, Pb, Mo, Pd, Se, Ag, Te, Th & Sn following back extraction of
organic aminohalide extracts. Journal of Analytical Atomic
Spectrometry, Vol. 1, August, 1986.

8. References
67. VIETS J.G., O’LEARY R.M., and CLARK R.J.: Determination of As, Sb,
Bi, Cd, Cu, Pb, Mo, Ag, Zn in geological materials by atomic
absorption spectrometry, Analyst, Vol. 109, December, 1984.
68. BRANCH C.H., HUTCHINSON D.: Comparison between iso-butyl

metyl ketone and di-isobutyl ketone for the solvent extraction of
gold and its determination in geological materials using atomic
absorption spectrometry, Analyst, Vol. III, February, 1986.
69. MAQUEDA C., RODRIQUEZ J.L.P., and JUSTO A.: Problems

associated with dissolution of silicates by acid mixtures.
Analyst, Vol. III, September, 1986.
70. KANE J.S.: Determination of nanogram amount of Bi in rocks by AAS

with electrothermal atomization.
Anal. Chim. Acta 106, 1979, p 325.
71. SHARMA K.D., JAIN M.P.: A rapid method for determination of tin or
ores, concentrates and residues by AAS.
American Laboratory, April, 1986.
72. ZHANG L.X., HU-SHI-FU.: Determination of lithium in silicate rocks by

graphite furnace atomic emission spectrometry.
International Laboratory, May, 1986.
73. CHAO T.T., SANZOLONE R.F., and HUBERT A.E.: Flame &
Flameless atomic absorption determination of tellurium in
geological materials. Anal. Chim. Acta 96, 1978 p 251.
74. SILBERMAN D., FISHER G.L.: Room temperature dissolution of coal

fly ash for trace metal analysis by atomic absorption spectrometry.
Anal. Chim. Acta. 106, 1979, p299.
75. BRANDT P.J., VAN DALEN J.H., and WESSELS F.W.: The
automatic determination of trace amounts of gold in plant barren
solutions. Journal of the South African Institute of Mining and
Metallurgy, June, 1980, p 197.
Air Particulates
76. MATOUSEK J.P., BRODIE K.G.: Direct Determination of Lead
Airborne Particulates by Non Flame Atomic Absorption.
Anal. Chem., Vol. 45, No. 9, August 1973.
77. DE JONGHE W., ADAMS F.: The Determination of Organic and

Inorganic Lead Compounds in urban air by AAS with ETA.

8. References
78. CROSS J.B.: Determination of stibine in air with pyridine-silver

diethyldithio-carbamate scrubber and flameless AAS.
Anal. Chem., Vol. 51, p 2033, 1979.
79. GELADI P., ADAMS F.: Determination of Cd, Cu, Fe, Pb and Zn in
aerosols by AAS. Anal. Chim. Acta., Vol. 96, p 229, 1978.
80. THOMASSEN Y., SOLBERG R., and HANNSEN J.E.: AAS

Determination of Metals in Particulate Matter in Air by Direct
Atomization. Anal. Chim. Acta., Vol. 90, p 279, 1977.
81. ELAINE M.M., SUTTER V., and LEROY M.J.E., Nature of the
interference of nitric acid in the determination of nickel and
vanadium by atomic absorption spectrometry with electrothermal
atomization., Anal. Chim. Acta., Vol. 96, p 243, 1978.
82. SNEDDON J.: Direct and near real time determination of metallic
compounds in the atmosphere by AA. American Laboratory,
p 43, March, 1986.
83. CHAKROBORTI D., VAN CLEAVERBERGEN R.J.A., and ADAMS

F.C.: Determination of total ionic alkyl-lead in water by
electrothermal atomization atomic absorption spectrometry.
Journal of Analytical Atomic Spectrometry, Vol. 1, August, 1986.
Petroleum Products
84. MAY L.A., PRESLEY B.J.: Comparison of flameless AA with NAA
analysis for Fe & Ni in crude oil residues.
Anal. Chim. Acta., 83, 1976, p 385.
85. PREVOT A., JAUNIAUX M.G.: Rapid Determination of phosphorus in

oils by flameless atomic absorption. Atomic Absorption
Newsletter, Vol. 17, No. 1, Jan-Feb, 1978.
86. BRODIE K.G., MATOUSEK J.P.: Application of the carbon rod

analyser at absorption of petroleum products. Anal. Chem.
43, 1557, 1971.
87. FABEC J.L.: Direct determination of arsenic in shale oil and its
products by furnace atomic absorption spectrometry with a THF
solvent system. Anal. Chem., 1982, Vol. 54, pp 2170-2174.
88. DRISCOLLD J., CLAY D.A., ROGERS C.H., JUNGERS R.H., and
BUTLER F.E.: Direct determination of phosphorus in gasoline
by flameless atomic absorption spectrometry. Anal. Chem.,
Vol. 50, No. 6, May, 1978.

8. References
Foods
89. OLAYINKA K.O., HASWELL S.J., and GRZESKOWAIK R.:
Development of a slurry technique for the determination of
calcium in dried foods by electrothermal atomization atomic
absorption spectrometry.
Journal of Analytical Atomic Spectrometry, Vol. 1, August, 1986.
90. MUYS T.: Quantitative determination of lead and cadmium in foods by

programmed dry ashing and atomic absorption spectrophotometry
with electrothermal atomization.
Analyst, Vol. 109, February, 1984.
91. HARNLY J.M.: Aerosol deposition — carbon furnace atomization for

simultaneous multielement atomic absorption spectrometry.
Journal of Analytical Atomic Spectrometry, Vol. 1, August 1986.
92. LEE M., BROWN A. DR.: Looking for lead in beer.

Brewers Guardian, February, 1985.
93. RAPTIS S.E., KAISER G., and TOLG G.: The decomposition of oils and
fats in a stream of oxygen for the determination of trace
elements. Analytica Chim. Acta., 138, 1982, 93.
94. LORD D.A., MCLAREN J.W., and WHEELER R.C.: Determination of

trace metals in fresh water mussels by atomic absoption
spectrometry with direct solid sample injection.
Anal. Chem., Vol. 49, No. 2, 1977, p 257.
Agricultural
95. IU K.L., PULFORD I.D., and DUNCAN H.J.: Determination of Cd, Co,
Cu, Ni & Pb in soil extracts by dithizone extraction and AAS with
electrothermal atomization. Anal. Chim. Acta, 106, 1979, p 319.
96. OKAMOTO K., YAMAMOTO Y., and FUWA K.: Pepperbush

powder, a new standard reference material.
Anal. Chem., 50, 1978, 1950.
97. NI Z.M., HAN H.B., and LE X.C.: Determination of lead by graphite

furnace atomic absorption spectrometry with argon-hydrogen as the
purge gas using low temperature hydrogen.
Al. Atomic Spectrometry, Vol. 1, April, 1986.
98. STEINER J.W., RYAN K.M., Rapid atomic absorption spectroscopic

analysis of Molybdenum in plant tissue with a modified carbon rod
atomizer. Analyst, Vol. 109, May, 1984.
99. GREEN R.J., ASHER C.J.: Measurement of submicrogram amounts of

nickel in plant material by electrothermal atomic absorption
spectroscopy. Analyst, Vol. 109, April, 1984.

8. References
100. HOENIG M., ELSEN Y.V., and CAUTER R.V.: Factors influencing the
determination of molybdenum in plant samples by
electrothermal atomic absorption spectrometry.
Anal. Chem., 1986, 58, 777.
Miscellaneous
101. MATOUSEK J.P., POWELL H.K.J.: Halogen assisted volatilization in
electrothermal atomic absorption spectroscopy: control of memory
effects. Dept. of Analytical Chemistry, The University of New
South Wales, P.O. Box 1, Kensington, N.S.W., 2033, Australia.
102. MATOUSEK J.P. (address as above).: Interferences in electrothermal

atomic absorption spectrometry.
103. LIDDELL P., ATHANASOPOULOS N., GREY R., and ROUTH

M.W.: The effect of background correction speed on the accuracy
of atomic absorption measurement.
American Laboratory, November, 1986.
104. ADELOJU S.B., BOND A.M.: Influence of Laboratory environment on

the precision and accuracy of trace element analysis.
Anal. Chem., 1985, 57, 1728-1733.
105. VAN DER WALT T.N., and STRELOW F.W.E.: Determination of

magnesium in alumina ceramics by atomic absorption
spectrometry after separation by ion exchange chromatography
(sample prep only). Anal. Chem., 1985. 57, 2889.
106. CZOBIK E.J., MATOUSEK J.P.: Interference effects in furnace

atomic absorption spectrometry. Anal. Chem., Vol. 50, 1978.
107. STRELOW F.W.E., TOERIEN F.V.S.: Separation of Pb (2) from

Bi(2), Th (3), Cd (2), Hg (2), Au (3), Pt (4), Pd (2) and other
elements by an ion exchange chromatography.
Anal. Chem., Vol. 38, No. 4, 1966.
108. STRELOW F.W.E., WEINERT C.H.S.W., and ELOFF C.: Distribution

co-efficients and an ion exchange behaviour of
elements in Oxalic Acid - Hydrochloric Acid mixtures.
Anal. Chem., Vol. 44, 2352, 1972.
109. STRELOW F.W.E., and BOTHMA C.J.C.: An ion exchange and

selectivity scale for elements in Sulphuric Acid media with
strongly basic resins. Anal. Chem., Vol. 39, No. 6, May, 1967.
110. STRELOW F.W.E., VANZYL V.C.R., and ELOFF C.: Distribution

co-efficients and cation exchange behavior of elements in
Hydrochloric Acid - Acetone. Anal. Chem., Vol. 43, 870, 1971.
111. ATHANASOPOULOS N., CHAPPLE G.: The determination of

arsenic & selenium in environmental samples using the
System 2000 Graphite furnace. GBC Application Note No. 5.

8. References
Notes:

8. References
Notes:

GBC 01-1005-00 SavantAA Software Operation Manual

Hochgeladen von

Dokumentinformationen

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

GBC 01-1005-00 SavantAA Software Operation Manual

Hochgeladen von

Copyright:

Verfügbare Formate

SYSTEM 2000/3000

GBC SCIENTIFIC EQUIPMENT

Manual No. 01-0202-00

2 GBC Graphite Furnace Methods Manual

1.1 Atomic Absorption Spectroscopy 5

2. Furnace Atomic Absorption 7

2.1 Graphite tubes 7

3.1 Platform theory 15

4.1 Ashing technique 18

GBC Graphite Furnace Methods Manual 3

4.2.1 Ammonium pyrolidine dithiocarbamate

5.1 Sample preparation 26

7. Analytical Data for the GF 2000/3000 43

4 GBC Graphite Furnace Methods Manual

1.1 Atomic Absorption Spectroscopy

The technique of atomic absorption developed by Sir Alan Walsh of CSIRO in

The absorption is proportional to the concentration of free atoms in the flame,

Absorbance = 1og10 (I0/It ) = K.C.L.

Where I0 = intensity of incident radiation emitted by the light source.

It = intensity of transmitted radiation (amount not absorbed).

C = concentration of sample (free atoms).

K = Constant (can be determined experimentally).

In practical atomic absorption analysis the Beer-Lambert law can be reduced to :

Absorbance = Log10 (I0/It) ∫C

The instrument is calibrated against standards of known concentrations and the

GBC Graphite Furnace Methods Manual 5

1.2 Choice Of Method—Flame Or Furnace

The nebulizer is also sensitive to physical properties of the sample such as

6 GBC Graphite Furnace Methods Manual

2.1 Graphite Tubes

Many different materials have been investigated for use in electrothermal

Graphite as a furnace material responds well to these criteria, but problems do

2.2 Temperature Program Development

Temperature program development for graphite furnace analysis can be

GBC Graphite Furnace Methods Manual 7

The second method involves an injection at ambient temperature and a slow

Hot Injection Cold Injection

Fig. 1. Hot and cold sample injection

8 GBC Graphite Furnace Methods Manual

2.2.4 Measurement Mode

2.2.5 Gas Flow Selection

2.2.6 Reduced Gas Flow during Atomization

GBC Graphite Furnace Methods Manual 9

Fig. 2. Variation in peak absorbance with gas flow

10 GBC Graphite Furnace Methods Manual

• reducing the sample volume

(The latter is discussed in detail under drying conditions).

2.3.3 Chemical Modification

GBC Graphite Furnace Methods Manual 11

REF. 2. Lead in a sodium chloride matrix is another difficult application. Lead

PbCl2 + NaCl + 3NH4NO3 ® Pb(NO3)2 + 3NH4Cl + NaNO3

Table 1. List of common modifiers

Analyte Modifier Effect Reference

Cd, Al H3PO4 Converts to less volatile 6, 7

Pb EDTA, citrate Atomize lead at lower 8, 9

P La(NO3)3 0.2% Permits higher ashing. 10

Pb, Cd Mg(NO3)2 Stabilizes Pb and Cd for 11

Hg (NH4)2S Allows higher ashing. 12

Pb NH4NO3 Products can be ashed at 13

As, Se Ni Forms arsenide or selenide 14

Si Ca(NO3)2 Enhances sensitivity 15

12 GBC Graphite Furnace Methods Manual

2.3.4 Background Correction

Fig. 3. Background absorbance profile