Cook Book

COOKBOOK Book One
AI 1200
Atomic Absorption Spectrometer
Updated: Jan 2002
AI 1200 Cookbook
Table of Contents
AI 1200 COOKBOOK
Table of Contents
BOOK ONE- FAAS
Chapter 1: Theory of AAS
Introduction
Flame Atomic Absorption Spectrometry (FAAS)
Graphite Furnace Atomic Absorption Spectrometry (GFAAS)
Vapor Hydride Generation Atomic Absorption Spectrometry (VG AAS)
Chapter 2: AAS Instrumentation
Fundamentals
Light Source
Atomizer
Optics
Detector
Optics
Lenses
Mirrors
Monochromator
Diffraction Grating
Slit Width
Atomizer
Flame
Graphite Furnace
Detector
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5
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Chapter 3: Background Correction

Fundamentals
The Frequency of Measurement
The Interval between Measurements
The Function used to Calculate Net Absorption
Spectral and Structured Backgrounds
The Effect on the Linear Working Range
Deuterium (D2) Background Correction
Smith-Hieftje (S-H) Background Correction
Zeeman Background Correction
Comparison of Background Correction Methods
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Table of Contents
Chapter 4: Comparison of Analytical Techniques

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Things to Consider
Applications
Expected Concentration Ranges
Elements
Atomization Efficiency
Interferences
Spectral
Background
Matrix
Detection Limits
Sensitivity
Precision
Linear Working Range
Minimum Sample Volume
Sample Throughput
Sample Usage
Total Dissolved Solids
Method Development
Ease of Use
Automation/Unattended Operation
Costs
Initial Investment
Running Costs
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Chapter 5: Standard and Sample Preparation

Apparatus
Water
Standard and Blank Solutions
Sample Solutions
Storage of Solutions
Calibrations
Matrix Effects
Chemical Interferences
Incomplete dissociation of analyte compounds
Ionization
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AI 1200 Cookbook
Table of Contents
Chapter 6: FAAS Analytical Data Sheets

Introduction
THE ELEMENTS
Aluminum, Al
Antimony, Sb
Arsenic, As
Barium, Ba
Beryllium, Be
Bismuth, Bi
Boron, B
Cadmium, Cd
Calcium, Ca (air/acetylene)
Calcium, Ca (nitrous oxide/acetylene)
Cesium, Cs
Chromium, Cr (air/acetylene)
Chromium, Cr (nitrous oxide/acetylene)
Cobalt, Co
Copper, Cu
Dysprosium, Dy
Erbium, Er
Europium, Eu
Gadolinium, Gd
Gallium, Ga
Germanium, Ge
Gold, Au
Hafnium, Hf
Holmium, Ho
Indium, In
Iridium, Ir
Iron, Fe
Lanthanum, La
Lead, Pb
Lithium, Li
Lutetium, Lu
Magnesium, Mg
Manganese, Mn
Mercury, Hg
Molybdenum, Mo
Neodymium, Nd
Nickel, Ni
Niobium, Nb
Osmium, Os
Palladium, Pd
Phosphorous, P
Platinum, Pt
Potassium, K
Praseodymium, Pr
Rhenium, Re
Rhodium, Rh
Rubidium, Rb
Ruthenium, Ru
Samarium, Sm
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Table of Contents
Scandium, Sc
Selenium, Se
Silicon, Si
Silver, Ag
Sodium, Na
Strontium, Sr
Tantalum, Ta
Tellurium, Te
Thallium, Tl
Tin, Sn
Titanium, Ti
Tungsten, W
Uranium, U
Vanadium, V
Ytterbium, Yb
Yttrium, Y
Zinc, Zn
Zirconium, Zr
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Chapter 7: Practical Applications - FAAS

Marine
Water
Biological
Food
Agricultural
Petroleum
Miscellaneous
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References
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AI 1200 Cookbook - Book One
1 - Theory of AAS
Chapter 1:
Theory of AAS
Introduction
Flame Atomic Absorption
Spectrometry (FAAS)
Graphite Furnace Atomic Absorption
Spectrometry (GFAAS)
Vapor Hydride Generation Atomic
Absorption Spectrometry (VG AAS)
1 - Theory of AAS
Introduction
The essential elements of the theory behind the analytical technique of atomic
absorption spectroscopy (AAS) are compacted into the following paragraphs.
Atomic absorption spectroscopy (AAS) relies on the fact that the light
absorption of free atoms [1-7]. All atoms can absorb light, but only at discrete
wavelengths corresponding to the energy requirements of the particular atom. In
other words, each element absorbs light at some specific and unique wavelength and
does not absorb light at all on other wavelengths. For example, in a sample with
multiple elements (say, copper, lead, iron, and nickel), only copper will absorb light
that is at the characteristic wavelength for copper. Furthermore, the amount of light
absorbed depends on the number of absorbing atoms that are present in the light
path. All these factors enable AAS to be used as a tool for quantitative analysis.
In practice, measuring the amount of light absorbed by several known
standards allows a calibration curve to be constructed. Then, the unknown
concentration of a sample can easily be determined based on the amount of light it
absorbs.
The amount of light energy absorbed at this wavelength depends on the
concentration of the atoms in the medium (as dictated by Lamberts law and Beers
law). Lamberts law states that the portion of light absorbed by a transparent
medium is independent of the intensity of the incident light and each successive unit
layer of the medium absorbs an equal fraction of the light passing through it. Beers
law states that the light absorbed is proportional to the number of absorbing atoms
in the medium. Mathematically, when light of intensity Io passes through a medium
of length x with atom concentration of C, the intensity I of the light beam emerging
from the medium is given by:
I = Io e-kCx
where k is a proportionality constant (the absorption coefficient). The
absorption of the medium, A, is defined to be:
A = lg (Io/I) = kCx
This equation states that the absorbance, A, of the medium is linearly
proportional to the concentration of the absorbing atoms. The absorption coefficient
(or absorptivity), k, can be determined by constructing a calibration curve (i.e.
plotting the observed absorbance versus the known sample concentration). The
slope of the calibration curve is kx, and x is easily measurable or already known.
Unknown sample concentrations may be determined from the calibration curve based
on their measured absorbances.
Any way that you look at, every AAS experiment can be broken down to the
following procedure:
A sample has an unknown amount of a known element (e.g. the sample is

known to contain lead, but not how much lead). The sample must be made
into a homogeneous, liquid solution (if it is not already).
1 - Theory of AAS
A blank solution must be prepared. This blank must contain none of the
element of interest.
A series of standard solutions must be prepared. These standards have
known (but varied) concentrations of the element of interest. These
standards are used to prepare a calibration curve.
Analyze the blank solution to determine the "blank" absorbance value. This is
the absorbance value for a sample with a zero concentration of the element of
interest.
Individually analyze all of the standard solutions.
Construct a calibration graph. For the blank and each standard solution, plot
its absorbance value against its concentration.
Analyze the unknown sample. The concentration of the unknown sample,
based on its measured absorbance value, can be determined from the
calibration curve.
There are three main techniques of atomic absorption spectrometry: Flame

atomic absorption spectrometry (FAAS), graphite furnace atomic absorption
spectrometry (GFAAS), and vapor hydride generation atomic absorption
spectrometry (VG AAS). Each has its own distinct advantages and disadvantages.
Each has specific applications for which they are the superior AAS technique. For
example, FAAS is suitable for analyses where the sample is above trace quantities,
and where high sample throughput, ease of use, and low initial investment are
required. GFAAS is ideal for samples that are in the parts per billion (ppb) range and
where the sample volume is limited. VG AAS is useful for determining elements that
form volatile hydrides at sub-trace levels. A brief outline of each technique is
provided below.
Flame Atomic Absorption Spectrometry (FAAS)

The atomization process by which the atom population is generated is of
primary importance in AAS because analysis depends entirely on the fact that free,
uncombined atoms will absorb light of a particular wavelength. The key to successful
operation of an atomic absorption spectrometer lies in generating a supply of free,
uncombined atoms in the ground state and exposing this atom population to light at
the characteristic absorption wavelength. The source of energy for free atom
production is heat, most commonly in the form of an air-acetylene or nitrous oxideacetylene flame (Flame AAS). With this type of atomizer, the sample solution is
introduced in the form of a spray of fine droplets. This is accomplished by a
pneumatic nebulizer in most case. The spray of droplets is carried by a gas (usually
the oxidant for the flame) through the spray chamber and burner head into the
flame. The heat of the flame is sufficient to dry (desolvate) each of the sample
droplets and (usually) to decompose chemical components from the resulting dried
particles into their constituent atoms. Thus a population of ground state atoms is
created in the flame and atomic absorption measurements can be made.
Flame systems for AAS give excellent results, and they are simple,
inexpensive, convenient and extremely useful.
They permit rapid analytical
measurements through a very simple sample introduction technique. The major
limitation of flame AAS is that the burner-nebulizer system is a relatively inefficient
sampling device. Only a small fraction of the sample that is taken up reaches the
flame. Additionally, once atomized, the sample passes quickly through the light
path. An improved sampling device would atomize the entire sample and retain it in
the light path for an extended period of time to enhance the sensitivity of the

technique.
features.
1 - Theory of AAS
Electrothermal atomization using a graphite furnace provides these
Graphite Furnace Atomic Absorption Spectrometry (GFAAS)

Graphite Furnace Atomic Absorption Spectrometry (GFAAS) has gained a
reputation in the field of analytical chemistry as a routine technique for the
determination of very low levels of trace metals in a variety of sample matrices.
With GFAAS, the flame has been replaced by an electrothermally heated graphite
tube. The sample is injected directly into the tube as a small liquid volume (5 to 100
L), which is then heated in a programmed series of steps to remove the solvent and
major matrix components. Free analyte atoms in the gaseous state are eventually
produced inside the graphite furnace by rapidly heating with a strong electric current
to temperatures between 1500 and 3000C. All of the analyte is atomized, and the
atoms are retained within the tube (and the light path, which passes through the
tube) for an extended period (typically 0.2 to 0.5 second). The performance of this
technique relied on the stability of the temperature. The recently developed
transversely heated integrated contact graphite furnace ensures the temperature
over the entire length of the tube is very uniform. As a result, sensitivity and
detection limits are significantly improved while matrix interferences and memory
effects are reduced. After the measurement, the analyte vapor is then purged from
the graphite furnace by helium or argon gas. The magnitude of the absorbance is
recorded as a function of time by the readout system.
The mechanism of atomization in a graphite furnace depends significantly on
the chemical nature of the analyte element, the availability of active sites, the
gaseous species within the graphite furnace, the atomization temperature, and the
graphite furnace itself. After drying and pyrolysis the analyte atoms may be present
in reduced, oxidized or complex form. Upon heating the graphite tube to the
atomization temperature, free analyte atoms are generated by:
(1) vaporization of the reduced form from the surface,
(2) by dissociation of the oxide form into gaseous free analyte atoms as the
graphite tube heats up, and
(3) vaporization as oxides (or any other molecular species) and dissociation
into free analyte atoms in the gaseous phase.
Examples of these mechanisms are given below - where M is an analyte, C is
carbon and O is oxygen and subscripts g and s refer to gaseous and solid phases:
M (s)
MO (s) + C(s)
MO (s)
MO (g)
CO (g) + O (g)
M (g)
M (g) + CO (g)
MO (g)
M (g) + O (g)
CO2 (g).
Analysis times for GFAAS are longer than those for FAAS, and fewer elements
can be determined with this technique. Nonetheless, GFAASs enhanced sensitivity,
ability to analyze very small sample sizes, and ability to directly analyze certain
types of solid samples significantly expand the capability of atomic absorption
spectrometry.
1 - Theory of AAS
Vapor Hydride Generation

Atomic Absorption Spectrometry (VG AAS)
For the determination of As, Bi, Ge, Pb, Sb, Se, Sn, Te and Hg with AAS,
vapor/hydride generation (VG) techniques have been proven to provide very high
sensitivities and reduced interferences. With VG AAS, analytes are first reduced to
their corresponding volatile hydrides (or metallic form for Hg) by sodium borohydride
in an acidic medium. The vapors are then transported by a carrier gas into the
atomizer for atomization and AA measurement.
Aurora Instruments AI 1200 uses an open ended, temperature controlled
electrothermally heated quart tube for continuous flow vapor/hydride generation
determinations. The heating unit can be installed and removed easily.
1 - Theory of AAS
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1 - Theory of AAS
2 - Instrumentation
Chapter 2:
AAS Instrumentation
Fundamentals
Light Source
Atomizer
Optics
Detector
Optics
Lenses
Mirrors
Monochromator
Diffraction Grating
Slit Width
Atomizer
Flame
Graphite Furnace
Detector
2 - Instrumentation
Fundamentals
There are four components that are essential to every AAS instrument: a
light source, an atomizer, an optics system, and a detector.
Light Source
Usually a hollow cathode lamp (HCL) is used as the light source in AAS. A
less common light source is the electrodeless discharge lamp (EDL). An HCL
produces an intense, narrow line emission of light at a wavelength that is specific
to the element that the HCL cathode is coated with. Most elements emit at
multiple wavelengths, but all emissions are intense, sharp lines (called resonance
lines). For example, a copper HCL emits at 324.75 nm, 327.40 nm, 222.6 nm,
249.2 nm, and 244.2 nm. Generally, one line is more intense than the others
and is therefore the most sensitive and useful line for AAS analysis.
HCLs are coated with the element of interest to produce light of the
resonance wavelength(s) that is/are specific to element. When this light is
passed through a medium that contains atoms of the same element, the light will
be partially absorbed.
Atomizer
The purpose of an atomizer is to create a population of free atoms that is
suitable for absorption of light. The atomizer must have an energy source in
order to do this. Usually the energy comes from heat, and the most common
source of the heat is a flame (either an air/acetylene or a nitrous oxide/acetylene
flame). An AAS instrument with a flame atomizer is called a flame atomic
absorption spectrometer (FAAS). With a flame atomizer, the sample is
introduced into the flame as an aerosol (a mist of tiny droplets). The flame
burner head [8] is designed to be long, thin, and aligned with the light path.
Such a design causes the aerosol atoms to be atomized in the flame while they
are in the light path so that they can absorb the light.
A very important part of the atomizer system is the nebulizer. The
nebulizer is responsible for nebulizing a liquid sample into an aerosol. The
sensitivity of a FAAS instrument depends heavily on how efficiently the nebulizer
can convert a sample to an aerosol.
Optics
The optics system of an AAS instrument is responsible for getting the light
from the light source to the detector. Along the way, the light must be passed
through the atomized sample and through a monochromator. A monochromator
is used to isolate specific wavelengths from the bulk light that it receives. For
example, it may be necessary to isolate the analytical wavelength of interest
from light that was emitted from the fill gas of the HCL, or from stray room light
that entered the spectrometer.
Detector
The detector part of an AAS instrument measures how much light is
transmitted through the spectrometer. Most commonly a photomultiplier tube
(PMT) is employed for this purpose.
While the above four components are the essential ones of an AAS
instrument, there are still others that play important roles.
2 - Instrumentation
There inevitably are electronic devices that convert the signals from the
detector into something that is useful for the human researcher. Older
instruments used to employ signal meters and plotters that would chart the
strength of the absorbance signal on a moving strip of paper. Instruments of
today have replaced the meter and chart recorder with computer software that
has many more capabilities. Modern software provides real-time plots of
absorbance versus time, constructs calibration curves, and calculates statistics
such as RSD values.
On the starting end of the sample analysis spectrum, computer software
can keep track of samples that are running, that you will run, and that you did
run. It can also be used to setup and run the instrument without operator
intervention at all.
Optics
The ideal optics system will have the following characteristics:
Have 100% efficient light throughput. In other words, if there is no

atomized sample in the light path, then 100% of the light from the source
will reach the detector.
Allow zero stray light.
Provide a high signal to noise ratio (S/N).
Provide absolute selectivity and resolution for the wavelength being
measured.
Provide constant dispersion, regardless of wavelength.
Have no optical aberrations.
Provide unique performance over a wide wavelength range.
Unfortunately, there is no such thing as an ideal optics system. The best that
you can hope for is to have a system that is optimized for your needs.
There are two ways to control the path of light within an optics system: with
mirrors or with lenses. Most optics systems make use of both.
Lenses
Good quality lenses are made from silica glass and have good light
transmission over a broad wavelength range (~190 - 900 nm). Transmission
losses occur at both interfaces of the lenses (i.e. at the lens surface where the
light enters and at the lens surface where the light exits). The losses are
typically between 10-14% for each lens in the optical path.
A feature of lenses that must be kept in mind is that the refractive index
of the lens is dependent on the wavelength of the light being refracted. This
means that the focal length of the lens will be different for every wavelength.
Rather than moving a lens to keep the focal point in the same position for
different wavelengths, optics systems will keep their lenses fixed and tolerate the
relatively minor losses associated with the changing focal lengths.
Most lenses used are designed for wavelengths in the UV region. This is
because most analytical wavelengths are in this range and the median refractive
index is about 250 nm.
For an air/acetylene flame, where the path length is around 10 cm, the
losses due to focal length differences are negligible. For a nitrous
oxide/acetylene flame, however, the path length is only 5 cm and the losses can
start to become noticeable. In GF AAS, where the sample atomization occurs
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2 - Instrumentation
only at a small point in the center of the graphite tube, the focal length from the
light source is absolutely critical. As the light source wavelength is increased, the
focal point will move away from its original position at the center of the graphite
tube. Because of this, optics systems for GF AAS systems usually employ only
mirrors, and not lenses.
Mirrors
Mirrors perform much better than lenses, both in terms of reflecting
efficiency and focal length change. A mirror has a very thin (e.g. 2 m) top
coating of aluminum that reflects more than 90% of the light that strikes it (for
the range 190 - 900 nm). Also, when light reflects off a mirror there is no
change in the focal length. That is, the focal length of a mirror depends only on
its shape and is independent of wavelength.
Plane mirrors are used to fold light and curved mirrors (also called
collimating mirrors) are used to focus light. For example, a plane mirror is
needed to fold light around a 90 corner, and a curved mirror is needed to focus
that light onto an entrance slit. While the use of mirrors does solve the problem
of focal length differences, it raises the challenge of designing and manufacturing
focusing mirrors that are free from other optical aberrations, such as
astigmatism.
Because of the thinness of the mirror coating, mirrors are
extremely fragile and must be handled with care. Finger prints, and even soft
tissues, can irreversibly damage a mirrors coating. Reactive liquids and gases
can even cause harm. To increase their longevity, most optics mirrors are
further coated with a transparent silica or magnesium fluoride film for protection.
Even still, one should avoid any kind of direct contact with mirror surfaces.
Monochromator
There are several different designs of monochromators available. No
matter which design is used in an AAS instrument, however, some fundamental
principles remain the same. Light enters the monochromator through an
entrance slit. The light is folded and focused in the monochromator by use of
mirrors. The light is dispersed into its component wavelengths by some sort of
diffracting element. The diffracted light then leaves the monochromator through
an exit slit.
The most common monochromator design is the Czerny-Turner design,
which is used in the AI 1200. A schematic of this type of monochromator is
shown in Figure 2.1.
The Czerny-Turner monochromator uses two separate mirrors to collimate
and focus light. Mirror #1 receives the light that was focused through the
entrance slit. The light that reflects off this mirror is collimated into parallel
beams and then strikes the diffraction grating, which diffracts the light into a
spectrum of wavelengths. This spectrum is dispersed at a variety of angles,
depending on the wavelength of each component of the spectrum. The light then
strikes Mirror #2, which focuses the light through the exit slit and into the
detector. Some monochromators make use of only one mirror, but there is a
definite advantage to using two mirrors. The two mirrors will each be smaller
than a single mirror, so they are easier to manufacture. This means that there is
less chance for surface aberrations and therefore allows optimum light
throughput and resolution.
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2 - Instrumentation
Figure 2-1 Schematic diagram of a Czerny-Turner monochromator

The detector is dumb it doesnt know whether the light it receives is an
analytical signal or not. The detector merely counts the number of photons that
it receives (the intensity of the light) and sends a signal to an amplifier then
sends back to computer. So, it is the job of the monochromator to isolate a
specific, narrow resonance line from the rest of the spectrum before the light is
allowed to reach the detector. The monochromator ensures that only the
analytical wavelength of light reaches the detector. This wavelength selectivity is
achieved by rotation of the diffraction grating with respect to the incident light.
Turning the grating moves the spectrum across the exit slit, and therefore
changes the wavelength of light that passes through the slit. Another means of
controlling the light that passes through the exit slit is by changing the width of
the slit. A narrower slit allows two closely spaced wavelengths to be resolved,
but it also decreases the light throughput of the optics system as a whole. If
there are no interfering wavelengths close to the analytical wavelength, then a
wider slit can be used to increase the light throughput, say, improve the signal
noise ratio.
Other, less common used monochromator designs are the Ebert-Fastie
and the Littrow designs.
The Ebert-Fastie monochromator design makes use of a single, large
mirror to focus light. See Figure 2.2 for a schematic. One area of the mirror
collimates incoming light onto the diffraction grating and then another area of the
mirror focuses the light dispersed from the grating onto the exit slit. This single
mirror does both of the jobs of the double mirrors in the Czerny-Turner design. A
disadvantage of the Ebert-Fastie design is that the single mirror must be large.
This increases the probability of surface imperfections during the manufacture of
the mirror, which in turn impairs the light throughput and resolution of the
monochromator. An Ebert-Fastie monochromator is, however, less expensive
than a Czerny-Turner.
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2 - Instrumentation
Figure 2-2 Schematic diagram of an Ebert-Fastie monochromator

The Littrow monochromator design is similar to the Ebert-Fastie design in
that it also employs only one mirror. See Figure 2.3 for a schematic. The
difference lies in that the Littrow monochromator uses the same area of the
single mirror for collimating the light onto the grating as for focusing the
dispersed light onto the exit slit. This fact increases the chances of optical
aberrations (even more so than the Ebert-Fastie design).
Figure 2-3 Schematic diagram of a Littrow monochromator

Diffraction Grating
There are two types of diffraction gratings that are commonly used today
in AAS instruments: ruled gratings and holographic gratings. Ruled gratings
have been around longer than holographic gratings, which were only introduced
in the late 1960s. A grating, in general, is a closely spaced series of grooves in a
flat, reflecting surface. The grooves must be perfectly parallel and uniformly
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2 - Instrumentation
spaced from each other. The closer the grooves are spaced, the better the
resolving capability of the grating. Gratings are produced with groove densities
from 500 to 6000 grooves/mm.
The blaze wavelength of a diffraction grating is the wavelength of light
that will be most efficiently diffracted by the grating. Generally, gratings can be
used to diffract light that is 2/3 to 3/2 of the blaze wavelength. For example,
consider a grating blazed at 400 nm. The grating can be used for wavelengths
from 270 nm to 600 nm, but will diffract most efficiently wavelengths of 400 nm.
Ruled grating are physically etched, groove-by-groove, by a machine.
Basically, a mirror is mounted on a grooving machine, a diamond bit etches a
straight groove, the mirror is moved a short distance and then the bit etches
another straight groove parallel to the previous one.
Holographic gratings, on the other hand, are manufactured with light, not
a physical machine. A piece of glass is coated with a light-sensitive material,
which is then exposed to two parallel beams of coherent light that produce an
interference pattern on the coated glass. The bright areas of the interference
pattern (where the light beams add constructively) form the grooves in the
developed photoresist. A thin layer of aluminum is then applied onto the
etched glass piece to form a mirrored, grooved surface a diffraction grating.
The advantage of the holographic technique over the machine etching technique
is that the holographic technique produces no systematic errors, since the
grooves are the result of a perfect optical phenomenon. The machined
technique, on the other hand, is only as good as the quality of the etching
machine itself (which, for many purposes, is excellent, but will never be truly
perfect).
Gratings that are used in monochromators are always copies of master
gratings. A master grating is the original grating that was manufactured (either
holographically or physically). Subsequent gratings can be made from the
master by a process that essentially makes a molded copy of the master.
There are advantages and disadvantages to both types of gratings. The
appropriate one to use in a monochromator depends on several factors. Ruled
gratings produce significant more stray light than holographic gratings, and this
is especially true when groove density increases. For this reason, the maximum
groove density of rules gratings is around 3600 grooves/mm. Holographic
gratings can have up to 6000 grooves/mm. So, based on this factor, a
holographic grating is better to use if a higher groove density is required to
achieve a higher resolution and maintain a high signal to noise ratio.
Ruled gratings do exhibit significantly better efficiency than holographic
gratings. So, based on this factor, a ruled grating is more appropriate to use if
light throughput is critical (for example, if the light source is very weak). If the
light source is intense (as is the case in AAS instruments), then using a
holographic grating is more advantageous than using a ruled grating.
Slit Width
The slit width affects how much light enters and exits the monochromator,
and so is very important for light throughput. A wide slit width will allow more
light to reach the detector and will improve the signal strength. But, if nonanalytical lines also reach the detector, then this will increase the noise and
decrease the signal to noise ratio. Conversely, a narrow slit width will block out
all non-analytical wavelengths, but may reduce the light throughput so much to
make the signal to noise ratio unsatisfactory. So, the best slit width is the one
that allows the most light to reach the detector and blocks out most of the noise.
14
2 - Instrumentation
In other words, finding the optimum slit width is a compromise between

maintaining high light throughput and maintaining a high signal to noise ratio.
The maximum allowable slit width is generally determined by how closely
spaced the analytical line of interest and its nearest neighbor in the spectrum
are. The slit width must be narrow enough to block out any non-analytical lines,
since they would increase the noise that the detector would see. Every spectrum
is different, so the optimum slit width must be determined for each analysis. For
elements whose analytical wavelengths are high (for example, rubidium at 780
nm), the spectra are usually not as dense as for elements with shorter analytical
wavelengths (for example, zinc at 214 nm). Therefore, a larger slit width is
usually permissible for elements like rubidium, whereas elements like zinc usually
necessitate narrower slit widths.
Atomizer
The atomizer is arguably the most important part of an AAS instrument,
since this is where the sample is converted into atoms that can absorb light.
Having an efficient atomizer is essential. The absorbance signal is completely
dependent on how many atoms there are to absorb the source light. So, a good
atomizer will display good sensitivity to the sample being analyzed, and a poor
atomizer will display poor sensitivity.
The ideal atomizer has the following characteristics:
Atomizes 100% of the sample delivered to it.

No ionization occurs.
No sample is left in the molecular, complexed form.
Of course, no real atomizer is ideal, and the degree to which any sample
is atomized depends to a large extent on the element being analyzed.
Atomization is achieved by heating the sample to an extent where free
ground state atoms are formed. In FAAS, atomization is done with a flame. In
GFAAS, atomization is done with an electrically heated graphite tube furnace. In
VG-AAS, atomization is done with an electrothermally heated furnace or a flame.
Flame
The atomizer in a FAAS instrument uses a nebulizer to convert a liquid
sample into an aerosol. The sample is introduced into the nebulizer by aspiration
though capillary tubing. The aspiration occurs pneumatically from the flow of fuel
and oxidant gases through the nebulizer chamber. After the sample has traveled
through the capillary tubing, it strikes a glass impact bead. This impact bead is
designed so that when a stream of liquid strikes it, the liquid breaks apart into a
mist of drops (an aerosol). This aerosol invariably contains drops of many sizes.
The larger drops fall out, but the smaller drops remain suspended and are
thoroughly mixed with the fuel and oxidant gases as the mixture is carried into
the spray chamber. As the sample mist gets mixed with the gases, it moves
along through the spray chamber and up towards the burner head. The sample
entering the burner head is a uniform mixture of fuel gas, oxidant gas, and tiny
sample droplets. Once the mixture enters the flame, the process of atomization
by heat begins. The heat from the flame is usually sufficient to desolvate the
sample droplets. Then, the solid particles that were formed (e.g. salts) are
broken down, melted, or volatilized into gases. Finally, the molecules are
thermally dissociated into atoms that are capable of absorbing their characteristic
wavelength of light. Of course, the heat from the flame may be excessive and
15
2 - Instrumentation
may ionize some atoms (remove an outer electron from the atom), thus
decreasing the absorption signal. As well, the heat from the flame may be
insufficient and not atomize enough of the sample molecules. This also
decreases the absorption signal. The process of thermally atomizing the sample
in the flame is a complex equilibrium, and the actual chemistry inside the flame
at any stage (especially the atomization stage) is not clear. There are often
numerous side reactions that occur simultaneously.
The degree to which a sample may be ionized in a flame depends on the
element, since each element has different energy requirements for ionization. To
reduce ionization of atoms, easily ionizable elements (EIEs), such as the Group I
elements (Li, Na, K, Cs) can be added to the original sample solution. If the EIEs
are much more easily ionized than the sample atoms, then they will create a
large population of electrons in the flame and shift the atomization/ionization
equilibrium of the sample atoms towards the atomization side.
There are two types of flames that are commonly used for FAAS:
air/acetylene and nitrous oxide/acetylene. The air/acetylene flame (air being the
oxidant, acetylene being the reductant, or fuel) burns at around 2300 C. The
nitrous oxide/acetylene flame burns much hotter at around 3000 C. So, the
flame temperature is a factor when determining which type of flame is best
suited for atomization of a given element. Because of its cooler burning
temperature, the air/acetylene flame works well for elements that are relatively
easily atomized, such as copper, iron, nickel, and gold. The nitrous
oxide/acetylene flame, with its higher burning temperature, is needed to atomize
elements that require more energy to atomize, such as aluminum, silicon,
titanium, and tungsten.
Another important factor in optimizing the atomization of an element in a
flame is the stoichiometry of the oxidant and reductant gases. A lean flame is
fuel poor, and is therefore an oxidizing flame. A rich flame has excess fuel, and
is therefore a reducing flame. For each type of flame, certain elements are
atomized best in reducing flames, and certain elements are atomized best in
oxidizing flames. There is extensive data on the absorbance characteristics of all
the elements in flames. For example, in a reducing flame there are excess
carbon and hydrogen atoms present in the flame (from the acetylene molecules).
These excess atoms help break down the strong oxide bonds that form with some
elements, such as chromium. Other elements that are best atomized in a
reducing flame are tin and molybdenum. On the other end of the spectrum,
elements like silver, cadmium, gold, and nickel are best atomized in an oxidizing
flame. Some elements, like iron and gallium, are best atomized in a
stoichiometric flame (i.e. neither rich nor lean). Furthermore, some elements are
satisfactorily atomized over a wide range of flame gas mixtures. Copper, for
example, is atomized in both rich and lean flames. For this reason, copper is
often used to test or validate the sensitivity of an AAS instrument.
The major disadvantage of the flame atomization technique is that it is
very inefficient at converting the original sample to atoms. Overall, the atomizer
system of a FAAS instrument can convert less than 0.1% of the original sample
to absorbing atoms. The nebulizer component usually transports only less than
10% of the aspirated sample into the aerosol, and the other 90% is lost as waste
in the spray chamber and nebulizer chamber. Furthermore, the sample that does
make it into the flame (in aerosol form) is already greatly diluted from its mixing
with the flame gases. And once the sample gets atomized in the flame, the
atoms residence times in the light path are extremely short. Atoms travel
through the light path at great speeds (at least 1 cm/10 ms) as they exit the slit
in the burner head and travel up the flame.
16
2 - Instrumentation
Graphite Furnace
The graphite furnace (GF) atomizer solves the two major problems of the
flame atomizer: poor atomization efficiency and short residence times. A
graphite furnace is a tube that is connected to two low voltage electrodes. When
a current is forced through the tube, the tube heats up. The amount of heating
caused by the current flow can be accurately controlled, and the atomization of
samples in a graphite furnace is usually performed over several heating steps.
The graphite furnace is mounted in the electrodes so that one open end of the
tube faces the light source and the other open end faces the entrance to the
optics. This allows the light to pass freely through the graphite furnace along the
axis of the tube. The tube is aligned so that the light path travels down the
graphite tube axis and right through the center of the tube.
With a GF atomizer, a very small amount of liquid sample (between 5 and
100 L) is placed inside the center of the graphite tube. A heating program to
atomize the sample consists of at least three principal steps:
1. Drying Step
The graphite tube is quickly heated to a temperature just below the
boiling point of the solvent. Then the temperature is slowly ramped past
the boiling point. This step gently evaporates the solvent (without
causing splattering or sample ejection) and leaves the dried sample
inside the tube.
2. Ashing Step (or Charring)
This step removes any dry or semi-dry matrix that is left over from
the drying step. Matrix modifiers can be added to the sample before the
heating program to stabilize the sample during the ashing step. Modifier
gases, such as oxygen or hydrogen, can be added to the graphite
furnace workhead during the ashing step to help remove the matrix.
Ashing temperatures depend on the element being analyzed in its
matrix. For example, cadmium ashes at 300 C, arsenic at 1400 C, iron
at 600 C, and lead at 480 C.
3. Atomization Step
At this stage, the sample is a dry solid at the bottom of the graphite
tube. The sample is atomized by rapidly increasing the temperature of
the tube. The AI 1200 can heat at a rate upto 3800 K/s. The required
atomization temperature depends on the element being analyzed. For
example, cadmium atomizes at 1250 C, arsenic at 2250 C, nickel at
2250 C, and lead at 1400 C.
There are distinct advantages to the graphite furnace atomizer when its
performance is compared to the flame atomizer. The graphite furnace atomizes
100% of the sample (compared to less than 0.1% for the flame). Also, the
residence time of the atomized sample in the light path is much longer in the
graphite furnace than in the flame. The residence time in the graphite tube can
range from 0.2 to 0.5 second, whereas in the flame it is only milliseconds. Both
of these factors increase the sensitivity of the graphite furnace atomizer, and
detection limits with GFAAS are typically one to two orders of magnitude better
than with FAAS.
17
2 - Instrumentation
Detector
The detector is the part of the AAS instrument that receives the light
output from the monochromator. The detector quantifies how much light it
receives and creates an electrical current. That current is then amplified and
converted into a digital signal that is recorded by a data acquisition system. By
far the most common detector used in AAS instruments is the photomultiplier
tube (PMT).
Essentially, a PMT is a photon counter. Light from the monochromator
enters the PMT through a quartz window. Photons (the quantum packets that
make up light) strike the photocathode of the PMT. This converts the photon to a
photoelectron via the photoelectric effect. However, the production of a single
electron from a single photon wont generate a very strong signal, so an
amplification 5 or 6 orders of magnitude is required. This amplification is
achieved through the use of a series of 8 to 12 dynode plates. A voltage is
applied between the photocathode and first dynode (on the order of 100 V). This
voltage difference causes the photoelectron to accelerate from the photocathode
to the dynode. When it strikes the dynode, several more electrons are produced.
These electrons are in turn accelerated towards the second dynode, since there is
also a voltage difference across the first and second dynodes. Each of the
electrons striking the second dynode creates several more electrons. For
example, if the electron collision into the first dynode created 5 electrons, then
the collision of those 5 electrons into the second dynode will create 25 electrons.
This chain reaction of electron production continues along the series of dynodes.
If there are 12 dynodes in the chain, then the original single photon will produce
244,140,625 electrons from the final twelfth dynode. These final electrons are
then collected by the PMT anode. The current that can result from the collection
due to a single photon by the PMT can be as high as 100 mA! Clearly, PMTs are
extremely sensitive detectors. Furthermore, the large amplification of the signal
that is achieved by the PMT is achieved with very little increase in noise.
18
2 - Instrumentation
19
2 - Instrumentation
20
3 - Background Correction Methods
Chapter 3:
Background Correction
Methods
Fundamentals
The Interval between
Measurements
The Function used to Calculate
Net Absorption
Spectral and Structure
Backgrounds
The Effect on Linear Working
Range
Deuterium (D2) Background
Correction
Smith-Hieftje (S-H) Background
Correction
Comparison of Background
Correction Methods
21
Fundamentals
Background correction is a necessary part of any good AAS instrument. Basically,
there are two types of backgrounds that need to be corrected for: non-specific radiation
and non-specific absorption.
Non-specific radiation was dealt with in Chapter 2. Non-specific radiation is the
extra light (non-analytical wavelengths) that can pass through the optics of an AAS
instrument, enter the monochromator, and have the chance of reaching the detector. If
this non-specific radiation reaches the detector, it will result in a falsely signal. Nonspecific radiation can come from many sources, including the HCL fill gas, sunlight, room
light, and the light emitted by the flame itself. As was discussed in Chapter 2
(Monochromator section), it is the job of the monochromator to effectively filter all entering
light and allow only a specific, variable wavelength to exit and reach the detector. So, the
monochromator ensures that the only light that reaches the detector is the wavelength of
light that is being absorbed by the sample being analyzed.
The other type of background that must be corrected for is non-specific absorption
(and will be discussed in this chapter). This correction cannot be accomplished by the
monochromator, since it involves the same analytical wavelength that is selected by the
monochromator. Non-specific absorption (also called background absorption) has a
broadband effect and occurs when the source light is prevented from reaching the detector
by means other than absorption by analyte atoms, such as scattering and blocking of light
by other species in the light path. Molecular species and solid particles present in the flame
are the major causes of non-specific absorption. When the heat of the flame is not
sufficient to fully break down all molecular species (for example, matrix compounds), there
can be sufficient remaining molecules to absorb, block, or scatter the source light. These
molecules can be thought of as causing the same interference as putting ones hand in the
light path: the light gets blocked, less light reaches the detector, and a falsely high
absorbance signal results (because the signal analysis software thinks that less light is
reaching the detector because more light is being absorbed by the analyte atoms).
In FAAS, the background absorption is relatively minor (usually less than 0.05
absorbance units). In GFAAS, on the other hand, background absorption is severe and can
reach levels of 2.0 absorbance units. Therefore, effective background correction methods
become essential for accurate GF analyses.
There are three background correction methods currently being used by AAS
instrument manufacturers: Deuterium (D2), Smith-Hieftje (S-H), and Zeeman. For all
three methods, there are several common factors that determine the effectiveness of the
method:
The
The
The
The
The
frequency at which the peaks are measured;

interval between total absorbance and background absorbance measurements;
mathematical function used to calculate net atomic absorption;
ability to correct for spectral or structured background;
effect of the method on the linear working range.

How rapid and transient the absorption peaks are dictates how fast absorption
measurements must be made [9, 10].
In GF analyses, signal durations are typically 0.2 to 0.5 seconds. The temporally
uniform, isothermal atomization of the AI 1200 provides peak durations that are in the low
end of this range. The non-specific absorbance normally exhibits similar peak durations.
Furthermore, the change in the absorbance values of these peaks can often be as high as
10 absorbance units per second. Therefore, a very high sampling frequency is required to
accurately measure the very rapid and narrow peaks and to determine peak shapes.
22
For a GFAAS system, a 10 Hz sampling frequency can produce significant errors in

the measurement of peak height and/or peak area. While the performance can be
improved if a 30 Hz frequency is used, the errors still remain significant. An increase to a
60 Hz sampling frequency will provide acceptable results in a GFAAS system. The AI 1200
utilizes a sampling frequency as high as 1000Hz in single beam mode and 120 Hz in double
mode, giving excellent peak definition and negligible errors in peak area and peak height
measurements.
The Interval between Measurements
The Net Absorbance Signal (NAS) is the analytical signal of interest. NAS is the
absorption of the light that is attributed only to the analyte atoms. It is obtained by
subtracting the Background Absorbance Signal (BAS) from the Total Absorbance Signal
(TAS).
Ideally, if BAS and TAS were measured simultaneously, then there would be no
error in the NAS calculation. In reality, however, only one measurement can be made at a
time. The best thing to do, then, is to make the time interval between successive
measurements as short as possible, to approach simultaneous measurements. The shorter
the time interval between a BAS measurement and a TAS measurement, the less error
there will be in the calculation of NAS. This factor is especially important for GFAAS, where
the background signal can change quite rapidly compared to the analyte signal.
The AI1200, which uses the D2 background correction method, uses a D2/HCL
modulation frequency of 1 KHz, resulting in a time interval between successive
measurements of less than 0.5 ms. With this system, the HCL and D2 lamps are alternately
pulsed so that only one light source is passing through the sample at a time. When the
HCL is pulsed, the D2 lamp is turned off and only the HCL light passes through the sample.
The signal measured is the TAS. When the D2 lamp is pulsed, the HCL is turned off and
only the D2 light passes through the sample. The signal measured is the BAS.
The Function used to Calculate Net Absorption
If a sufficiently fast switching frequency between the BAS and TAS measurements is
employed (such as in the AI 1200), then a simple subtraction of the BAS from the TAS can
be performed to obtain the NAS.
If relatively long time periods are elapsed between the BAS and TAS measurements,
then interpolation techniques will be needed to approximate the NAS values. Furthermore,
there are increased chances of significant changes in the background signals occurring over
the elapsed time periods. Therefore, these interpolation techniques are much more
susceptible to errors and inaccurate NAS values.
Spectral and Structured Background
Less than 1% of the samples encountered in the real world exhibit spectral or
structured background interferences that cannot be overcome by optimizing the atomizer
(for GFAAS, in particular, by optimizing the furnace heating program) and/or using an
appropriate chemical modifier.
The Effect on the Linear Working Range
Due to complex splitting patterns, the TAS response of an instrument equipped with
Zeeman background correction can be non-linear. As a result, when the BAS is subtracted
from the TAS, a roll over point on a calibration curve can occur. That is, two different
concentration values could correspond to a single NAS value. In such a case, the linear
dynamic range has been reduced by the effects of the background correction method.
In comparison, the D2 background correction method does not produce a roll over
point in calibration curves and so has no negative effects on the linear dynamic range.
23
Deuterium (D2) Background Correction

The light source used in the Deuterium (D2) background correction method is the
D2 lamp. The D2 lamp is a continuum source, rather than a sharp line emitter. That is, it
emits a spectrum of radiation covering 180 nm to 425 nm. Even though this means that
the use of the D2 method is limited to the UV range, it is not much of a detriment since the
most significant background absorptions occur at low wavelengths anyway.
See figure 3.1 for a graphical explanation of how D2 background correction works.
The key thing about D2 background correction is the assumption that the absorption of
radiation by the analyte atoms alone has a negligible effect on the D2 spectrum. The
monochromator exit slit is relatively wide (at least 0.2 nm), so a spectrum of D2 light of
that width is allowed through. Compare this to the tiny width of spectrum that the analyte
absorption occurs in (approximately 0.002 nm), and its easy to see how absorption
occurring in such small region of a wide spectrum will have a negligible effect on that
spectrums overall intensity. In other words, only a small fraction of the D2 spectrum is
attenuated by the analyte absorption, and the rest is completely unaffected. Conversely,
the atomic absorption due the analyte atoms has a significant effect on the intensity of the
HCL radiation, since the HCL line is very sharp and narrow to begin with.
But the absorption that occurs in real-life experiments is not due to analyte atoms
alone. It is always a combination of analyte absorption and background absorption.
Background absorption is broadband and so has an equal effect on the intensity of both the
HCL line and the D2 band. So, when the individual effects of the analyte absorption and
the background absorption are added together, the result is that the HCL line is attenuated
cumulatively by both and the D2 band is only attenuated by the broadband background
absorption. This fact forms the foundation of the D2 background correction method. When
the D2 lamp is pulsed, the absorption of the D2 band is measured (the BAS). When the
HCL lamp is pulsed, the absorption of the HCL line is measured (the TAS). The difference
between the two (TAS - BAS) is the absorption due to the analyte atoms alone (the NAS),
and this is the figure of analytical significance.
24
Figure 3-1 How D2 background correction works

(continued on next page)
25
Figure 3-1 (continued) How D2 background correction works

In an AAS instrument with D2 background correction, the optics will have to be
constructed to accommodate the additional D2 lamp, and they must also be designed to
ensure that the D2 light and the HCL light follow exactly the same path through the optics
system. In order to achieve accurate and reliable background correction, it is imperative
that the two light sources follow exactly the same path. If they did not, then the
background signal measured with the D2 lamp will have no relevance to the total
absorption signal measured by the HCL lamp. Imagine if the D2 light path went through
the top of a flame or graphite tube, and the HCL light path went through the bottom of
flame or graphite tube. In such a case, it cannot be assumed that the background in one
area is the same as the background in another. Unless both the background and total
absorption signals are measured along exactly the same path, then no net analyte
absorption signal can be determined. Today, instrument optics are easily manufactured
with enough precision and with adequate means of optimization to virtually eliminate all
problems due to poor optical path alignment.
26
Smith-Hieftje (S-H) Background Correction

The Smith-Hieftje background correction method is based on the phenomenon of
self absorption (or self reversal) that occurs when HCLs are operated at very high currents
[11]. When an HCL is operated at a very high current, the atoms that are sputtered inside
the HCL can sometimes absorb the radiation that is emitted by other atoms inside the HCL.
This causes the emission line to be broadened and the intensity of the emission line at the
resonance wavelength to be decreased. The resulting emission profile looks like a broad,
two-headed peak. The two heads sit on either side of the resonance wavelength, and the
valley between the peaks is right at the resonance wavelength (the atomic absorption
wavelength). Figure 3.2 shows emission profiles for an HCL line at different currents. At
low current, the line is sharp and narrow. As the current is increased, the line gets more
intense but it also broadens. At very high currents, self absorption occurs within the HCL,
and the two-headed peak straddling the resonance wavelength is observed.
Figure 3-2 The principle behind the Smith-Hieftje background correction technique
When the S-H method is used, the HCL is alternately pulsed between normal
operating currents (where no significant self absorption occurs) and high intensity currents.
The duration of the HI pulses is very short compared to the normal current pulses. During
the period of the normal pulses, the analyte absorbance signal is measured. During the
period of the HI pulse, the background absorbance signal is measured.
With the S-H method, the profile of the emission from a HCL is semi-broadband (in
that the emission has been broadened to an extent) and the intensity of the analytical
wavelength (the valley between the shoulders) has been reduced. So, during the HI pulse,
the wavelengths above and below the analytical wavelength (the shoulder wavelengths)
are used to measure the background absorbance. The attenuation of the alreadydiminished analytical wavelength by analyte atoms is negligible compared to the
attenuation of the shoulder wavelengths by the non-specific absorbing species. So, the
signal measured during the HI pulse is the background signal (BAS)
Of course, during the normal pulses, the HCL emits the same sharp line as for the
D2 background correction method. So, during the normal pulse of the HCL, the total
absorption signal (TAS) is measured.
A key advantage of S-H background correction method, in terms of accuracy, is that
only one lamp is needed. Since a single lamp acts as both the continuum source and the
sharp line emitter, there will never be any problems with the two optical paths not being
exactly the same.
27
However, there is also a disadvantage of the method related to accuracy. Since the
shoulder wavelengths of the HI pulse are used to measure the background (and not the
analytical wavelength itself), there is some degree of approximation going on when that
background measurement is subtracted from the total absorbance signal (for which the
analytical wavelength is used). The assumption is that the background doesnt change
much in the short spectral width between the two shoulder wavelengths. In practice, this
assumption is adequate.
There are several other disadvantages to the S-H background correction method.
While the requirement of a special HCL (designed for S-H background correction) cant
really be called a disadvantage in itself (since all background correction methods require
some kind of additional equipment), the fact that special HCLs are not available for all
elements limits the methods usefulness. Also, it is required that the high and low currents
of the HCL be stabilized before any measurements can be made. This results in a typical
sensitivity loss of 50%. Calibration curves can sometimes exhibit roll over points at higher
sample concentrations, so this decreases the linear dynamic range of analysis. Also, the SH method cannot correct for any structured or spectral interferences. Finally, the method
is limited to relatively low modulation frequencies (normal 10 Hz), so is incompatible with
the rapid transient signals common to GFAAS experiments.

This background correction method is based on the splitting of spectral lines that
occurs in magnetic fields [12]. In the presence of a magnetic field, an emission line from
an HCL will be split into pi () and sigma () lines. The original resonance line becomes
the pi line and remains at the resonance wavelength. There are two sigma lines and they
are shifted from the pi line (one above and one below) by thousandths of a nanometer.
The exact amount of the sigma lines shift depends on the strength of the magnetic field.
An important part of this background correction method is that the sigma lines are
perpendicular to the applied magnetic field, and the pi line is parallel. So, when a polarizer
is used to filter the light beam, the pi line can be excluded.
This method is effective because the species that are in most cases to blame for
non-specific absorption (molecules and solid particles) are not affected by the magnetic
field. So, when the magnetic field is applied, an accurate background absorption signal
(BAS) can be measured since the non-specific absorbing species remain unaffected and the
analytical resonance wavelength can be blocked by polarization. Of course, when the
magnetic field is not applied, the measurement made will simply be of the total absorption
signal (TAS). Again, the net absorption signal (the NAS, the absorption due to the analyte
atoms alone) is determined by the difference between the TAS and the BAS.
A key advantage to the Zeeman background correction method is that both the TAS
and BAS are measured along the exact same optical path, so the technique is very accurate
in that sense. As well, Zeeman-equipped instruments generally operate at a high
frequency of measurement (usually 120 Hz), so they are able to deal with the rapid
transient peaks that occur in GFAAS analyses. The Zeeman method is applicable to any
wavelength of light, so it works for all elements. This is in contrast to both the D2 and S-H
methods. The D2 method is limited to those elements with analytical wavelengths that fall
in the range 180 - 425 nm, and the S-H is limited by the availability of a HCL for the
element of interest. Furthermore, the Zeeman method is the only one that can correct for
spectral and structured background interferences.
While that last advantage listed may seem impressive, it is in reality of no
consequence. Less than 1% of samples that are run in labs today have problems with
spectral or structured background interferences that cannot be overcome with optimization
of the atomizer or by the addition of suitable chemical modifiers.
There are other drawbacks of the Zeeman background correction method that
should be mentioned. There is typically a sensitivity loss of 20% associated with the
Zeeman method (the exact value is determined by the magnetic susceptibility ratio of the
28
element being determined). Also, it frequently results in roll over of calibration curves at
higher concentrations, so the linear dynamic range is significantly reduced. Another
important point relates to the cost of the Zeeman instrumentation, which requires a
relatively large initial investment. This is a result of all the additional equipment that is
required on an AAS instrument equipped with Zeeman background correction (a stable
electromagnet, a power supply, and a polarizer).
Comparison of Background Correction Methods

An important part of the decision to purchase an AAS instrument is the decision of
which background correction method to include. In general, this decision is governed by
the applications that the instrument is expected to be used for. Of course, there are
specific applications that each background correction method is the best suited for. But it
is quite rare that an instrument will be dedicated for a single, specific type of analysis
throughout its entire lifetime. With that in mind, perhaps it is wisest to choose a
background correction method that is versatile and can meet the background correction
needs of the majority of samples encountered.
Table 3.1 below is a summary of the comparisons between the three background
correction methods discussed here.
Table 3.1: Summary Comparison of Background Correction Methods
D2
S-H
Sensitivity
Good
Poor, 50% loss
Type of Instrument
All
FAAS
Wavelength Range
180-425 nm
180-900 nm
Number of Elements
Limited to elements in
Limited to lamp
wavelength range
availability
Longevity of Lamp
Normal
Decreased
Calibration Linearity
Not affected
Roll over occurs
Linear Dynamic Range
Not affected
Decreased
Accuracy
Two optical paths
Good (single
must be optimized
optical path)
Correct for Spectral or
No
No
Structured Interferences?
Frequency of Measurement
120 Hz
10 Hz
Interval between
0.5 ms
2-4 ms
Measurements
29
Zeeman
Moderate, 20% loss
GFAAS
180-900 nm
All
Normal
Roll over occurs
Decreased
Good (single optical
path)
Yes
60-120 Hz
4.5 ms
D2 seems to be the overall best background correction method of all the three,
since it offers the broadest range of advantages and does not suffer in the really key areas
of sensitivity and calibration linearity.
There seems to be an impression in the analytical chemistry community that
Zeeman background correction is the superior method available. However, once the
factors have all been weighed, it should become apparent that this impression is flawed.
As was mentioned before, the fact that Zeeman method is the only one that can correct for
spectral and structured background interferences is of no consequence in over 99% of the
samples that will be encountered in a laboratory. Even if it is determined that this feature
is necessary and Zeeman background correction is required, there will be other important
factors that will suffer. Initially, the cost of the Zeeman instrumentation is very high
compared to D2 and S-H. Also, Zeeman has significantly poorer sensitivity, calibration
linearity, and linear dynamic range than the D2 method offers. Another misconception is
that D2 background correction is inadequate for samples with rapidly changing background
signals. The frequency of measurement and interval between measurements
characteristics show that D2 is on par or better than Zeeman is in these areas.
Based on all these considerations, the decision between the D2 and Zeeman
background correction methods can be boiled down to the following:
Choose D2
if you need:
Choose Zeeman
if:
maximum sensitivity
calibration linearity
maximum linear dynamic range
rapid measurement capability
low cost
30
you expect spectral and

structured background
interferences, and this overrides
all other factors
cost of equipment is no concern
31
32
4 - Comparison of AAS Techniques
Chapter 4:
Comparison of AAS
Techniques
Things to Consider
Applications
Elements
Interferences
Spectral
Background
Matrix
Detection Limits
Sensitivity
Precision
Sample Throughput
Sample Usage
Method Development
Ease of Use
Automation/Unattended Operation
Costs
Initial Investment
Running Costs
33
Things to Consider
When deciding whether to purchase a flame AAS or a graphite furnace AAS, one should
first make an assessment of ones analytical needs:
Which elements will I be analyzing?

What are the sample matrices?
What are the solvents?
How much sample volume will I have?
Do I need high throughput?
Will the concentrations be high or at trace levels?
What detection limits do I need?
How important are precision and sensitivity?
How skilled are the intended operators?
Can operators afford to spend time on method development and optimization?
How much money am I willing to spend?
Applications
The applications that you will be running (e.g. environmental, marine, petroleum,
mining) will play a part in determining the AAS technique that is right for you. However,
many of the techniques overlap when they are compared on the basis of applications.
Therefore, your particular application will be a relatively minor factor in the decision. That
aside, there are some applications that one technique is much better suited for than the
other (this is usually based on the element(s) being analyzed).
Its also important when deciding on a AAS instrument to think of the future. Will
your anticipated long-term needs be satisfied by the instrument that is appropriate to
purchase for your needs today?

Do you expect most of the samples that you will analyze to have high or low
concentrations? Since GFAAS is much more sensitive than FAAS (typically, GFAAS has
detection limits 100 to 1000 times better), it makes more sense to run the concentrated
samples on a FAAS, and use a GFAAS to run the trace analyses. Diluting samples down to
concentration levels that a GFAAS can handle is not only time consuming and labor
intensive, it also introduces the possibilities of errors and contamination.
Elements
The FAAS technique can analyze a total of 61 elements with its air/acetylene and
nitrous oxide/acetylene flames. The GFAAS technique can analyze a total of 41 elements.
Also, any element that GFAAS can analyze can also be analyzed with FAAS.
The atomization efficiency is arguably the most important performance
characteristic of any AAS technique. The air/acetylene flame burns at around 2300 C, and
the nitrous oxide/acetylene flame burns significantly hotter at around 3000 C. For some
elements, the cooler air flame is not hot enough to atomize the sample, and the nitrous
oxide flame is required instead. However, the excess energy of the hotter nitrous oxide
flame can ionize other elements. So, its often a trade-off with air flame atomizers. Some
elements have low atomization energies, and so are better suited to the cooler flame
34
(copper, iron, nickel, and gold). Others have high atomization energies, and so a nitrous
oxide flame is needed (aluminum, silicon, titanium, and tungsten).
And for some elements, no flame is hot enough to efficiently atomize the sample.
In these cases, the GFAAS technique is needed, because the furnace can reach
temperatures up to 3000 C.
Another consideration is the nebulization efficiency of the FAAS nebulizer. Only less
10% of original sample introduced into the spray chamber gets converted in an aerosol and
makes it into the flame for atomization. In this sense, the FAAS technique is very
wasteful. The GFAAS technique, on the other hand, is very efficient. All of the sample
deposited in the graphite furnace remains inside the furnace and therefore has a good
chance of being atomized. As well, atomized sample have relatively long residence times
inside the furnace tube (0.2 0.5 s)
Interferences
Spectral
Spectral interferences do occur, but are rare, in both FAAS and GFAAS techniques.
Background
Background interferences are much more common, and both techniques are
vulnerable. Background correction techniques are usually employed to compensate for the
interference.
In GFAAS, background interference typically arises from vaporized and atomized
matrix components.
Matrix
Matrix interferences can be serious for both FAAS and GFAAS analyses. For GFAAS,
the effects can be countered by adding modifiers to the samples. For FAAS, the ionization
buffers are usually employed to control matrix effects related to ionization.
Detection Limits
The detection limits of the GFAAS technique (ppb range) are generally 100-1000
times better than the FAAS technique (ppm range).
Sensitivity
This factor is closely linked to detection limits. GFAAS is much more sensitive than
FAAS, since the graphite furnace atomizer has much longer residence times and much
higher atomization efficiency than the flame atomizer.
Precision
The flame atomizer has better short term precision (0.5%) than the graphite
furnace atomizer (2-5%). Long term precision is usually better with the flame atomizer
too, since the graphite furnace invariably degrades and gets worn out as it is used.

The linear working range of the AAS technique is extremely important. It is the
concentration range over which standard samples can be measured and used to generate a
linear calibration curve. Having a narrow working range means that the calibration curves
usefulness is limited because not as many unknown samples will fall within the linear
calibration range.
35
In general, on an element-by-element basis, the linear working ranges of the FAAS

technique are better than those of the GFAAS technique. In this respect, FAAS is more
versatile and useful than GFAAS.

The minimum sample volume required to measure an absorption signal of a solution
can be very important sometimes, such as when there is almost no sample solution to
begin with.
The minimum volume required by the GFAAS technique is much smaller than for the
FAAS technique. GFAAS requires as low as 20 L of sample for a good measurement,
whereas FAAS requires at least 0.5 mL of solution.
Sample Throughput
The sample throughput is the rate at which individual samples can be analyzed. It
is often expressed in the format minutes per sample. FAAS has a higher sample
throughput rate than GFAAS. The reason for this is that the graphite furnace atomization
sequence has multiple steps, each with hold times, and a cool-down time is required at the
end of each analysis.
Typical sample throughput values are 10 seconds per sample for FAAS analyses and
4 minutes per sample for GFAAS analyses.
Sample Usage
Sample usage refers to how much sample is consumed by the instrument while it
performs an analysis. FAAS uses a lot of sample solution for each analysis, and much of it
is wasted and never even makes it into the atomizer for an absorption measurement.
GFAAS, on the other hand, uses very little sample and wastes none. The entire volume of
sample deposited in a graphite furnace remains in the graphite furnace during the
atomization steps.

The graphite furnace atomizer can handle relatively large amounts of dissolved
solids (> 20%), whereas the flame atomizer can only tolerate about 3% maximum (this is
the case for liquid introduction atomizers in general).
Method Development
The FAAS is easier to develop methods for than the GFAAS instrument. This is
mostly because of the strict constraints set on the optical alignment of the furnace atomizer
and the requirement of accurate and consistent sample injections. As well, the operation of
the FAAS doesnt require as much experience as the operation of the GFAAS. Nonetheless,
for both instruments, a skilled operator is required to develop a good method for a specific
application. Fortunately, most instruments come equipped with extensive libraries of premade, common methods that are ready to use.
Ease of use
The FAAS instrument is very easy to use, and an expert operator is not required for
routine analyses. The GFAAS instrument is also relatively simple and straight-forward to
use, but a skilled operator is still required because accurate and consistent sample
injections are essential for good results, even for the most routine analyses.
36
Automation/Unattended operation
GFAAS lends itself well to automation. The use of inert gases does not pose any
dangers, so unattended operation is also feasible. Overnight, automated operation of
GFAAS is commonly employed to achieve a higher sample throughputs. FAAS is equally
suited to automation, but unattended operation is unadvisable due to the use of
combustible gases. An operator should always be present to ensure the safe operation of
the instrument and to be able to deal with gas leaks or other emergencies as they arise.
Costs
Initial Investment
There is no way to specifically say how much an instrument will cost, since there are
many factors involved. The cost depends on the configuration, accessories, options,
background correction method, and, of course, the vendor. Roughly speaking, FAAS
instruments can cost from $20,000 to $35,000. GFAAS instruments are more expensive,
and usually cost about 2 times as much ($40,000 to $70,000).
Running Costs
Both techniques are comparable in terms of the costs of running the instruments on
a day to day basis, although FAAS is generally a cheaper instrument to run. There is a
constant expense for the fuel and oxidant gases in FAAS (although, air is free), and the
inert gas used in GFAAS (usually argon) isnt cheap. In addition, a periodic expense of the
GFAAS technique is the replacement cost of the graphite furnace atomization tube, which
has a limited life and needs to be replaced from time to time to ensure efficient
atomization.
Another consideration is whether your specific applications with GFAAS will require
clean room conditions. Maintaining clean room conditions is no small task and adds
considerably to the operating costs of the instrument.
The following table is a summary of the comparisons between FAAS and GFAAS.
Table 4.1: A Summary Comparison of Flame AAS and Graphite Furnace AAS
FAAS
GFAAS
Detection Limit
sub ppm
sub ppb
103
102
Precision
0.5%
2 - 5%
Sensitivity
good
excellent
Spectral Interferences
virtually none
occasionally
Chemical/Matrix Interferences
many
many
Ionization
occasionally
minimal
0.5 mL
20 L
Sample Throughput
~10 s/sample
~4 min/sample
Sample Usage
high
low
Number of Elements
61
41
Maximum Dissolved Solids
~ 3%
> 20%
Ease of routine use
easy
requires expertise
Method Development/Optimization
easy
difficult
Easily Automated?
moderately
yes
Combustible Gases?
yes
no
Initial Investment
low
high
Running Costs
low
moderate
37
38
39
5 - Standards and Sample Preparation
Chapter 5:
Standards and Sample
Preparation
Apparatus
Water
Standard and Blank
Solutions
Sample Solutions
Calibrations
Matrix Effects
Incomplete Dissociation
of Analyte Compounds
Ionization
40
Apparatus
All apparatus to be used during the process of an analysis, from the sample and
standard preparation to the introduction into the instrument, must be scrupulously clean.
Even glassware that had been cleaned previously and stored should be cleaned again
immediately before use.
As well, the instrument itself should be periodically cleaned to ensure that no
contamination errors or memory effects are introduced. In FAAS instruments, the sample
aspiration tubing is easily and inexpensively replaced. The nebulizer chamber should also
be cleaned and washed regularly. Residue buildup can be a problem, especially when flow
spoilers or baffles are employed. Corrosion resistant nebulizer should be used when
corrosive acids or organics are being analyzed (e.g. use a Teflon constructed spray
chamber and glass impact bead).
Volumetric flasks should be Class A (accurate to 0.01%), since Class B glassware
will introduce systematic measurement errors into your analysis.
Analytical balances should be high-accuracy and high-precision. Less than 1% error
is needed when weighing out samples to ensure minimal error in prepared solutions.
Pipettes and micropipettes should always be calibrated to ensure accuracy of
delivery volumes.
Water
All water used for AAS analyses should be deionized. Distilled water alone is likely
to have significant amounts of dissolved metals and gases, and can introduce significant
error into analyses. Using distilled water that has also been deionized is acceptable.
For some GF applications, particularly when trace levels are being determined,
simple deionized water is not good enough. In these cases, an ultra-pure water treatment
is needed (eg. the Millipore system).
In general, one can expect most acids to contain trace amounts of metallic
impurities. While the levels are trace, they can still introduce error in some applications
(particularly in trace-analyses and GF analyses). Fortunately, specially purified acids are
commercially available to alleviate this source of error.
Standard and Blank Solutions

Bulk standard solutions are available from many chemical suppliers, usually in 1000
mg/L (1000 ppm) concentrations. They have a shelf life of about one year. These bulk
standards come with certificates of analysis, and are traceable to NIST (National Institute
of Standards and Technology) standards. These bulk standards should be of the highest
purity available. Atomic Absorption grade is acceptable for many applications, but Ultrapure is preferred (and essential for very sensitive, trace-level determinations).
Bulk standard solutions can also be prepared by the operator, in the laboratory.
This method is useful to prepare standards from pure metals, metallic salts, and metal
oxides. When weighing out the raw materials, the materials must be treated to ensure that
they are in a pure, standard form. Metals should be washed with acetone or ether to
remove any oil layers. Oxide coatings can be removed by scrubbing them off the metals
surface (with an emery cloth, for example). Metal oxides, salts, and other compounds
should be dried for several hours at an elevated temperature to drive off excess water (110
C or higher will suffice). The material should be dried to a constant mass.
In the interest of minimizing errors, it is best to perform serial dilutions when
performing large dilutions of the bulk standards. For example, imagine that you needed to
prepare a 0.1 ppm standard from the 1000 ppm bulk. This is a dilution factor 10,000.
Rather than performing such a dilution in one step, it is advisable to break it into two
steps: perform a 100 times dilution, and then another 100 times dilution. The end result
41
is the same, but the chance for error is much less, since a small volume measurement
error has a relatively greater effect on a small volume than on a larger volume. However,
the error in volume measurements that do occur in the two step method are doubled, since
the dilution is performed twice. However, the relative effect of the volume measurement
error is of far greater concern. In this example, the two step dilution uses volumes of the
bulk standard that are 100 times greater than volumes used with the single dilution
method. Therefore, the two step dilution method, in theory, has 50 times less error.
Ideal standard solutions are solutions that are identical in chemical and physical
composition to the sample solutions, except that they have known concentrations of the
analytical component. Ideal blank solutions are solutions that are identical in chemical and
physical composition to the sample solution, except that they dont have any of the
component that is of analytical interest. Proper standards and blanks should be prepared
by the same procedure that the sample is prepared by. For example, if the sample is
microwave digested by nitric acid, then the standards and blanks should also be microwave
digested by nitric acid (expect that the standards will have a known amount of the
analytical component added, and the blanks will have none added).
Matching the physical properties of sample with standards and blanks is important
because the amount of solution that is aspirated by the nebulizer and into the flame
depends, to an extent, on the physical properties of the solution. The viscosity, density,
surface tension, and solvent vapor pressure will all affect the aspiration rate.
Sample Solutions
There are many different kinds of sample solutions. Sometimes the sample is
obtained from a third party, and is already in ready-to-analyze form. Often, however,
digestion and dissolution steps are required. In either case, it is important that sample
solutions be homogenous and free of solids. This is especially important for the GFAAS
analyses, since the sample volumes analyzed are much smaller than for FAAS. If 50 L of
a heterogeneous sample is deposited in the graphite furnace and analyzed, it is very likely
that its signal will be different from the next 50 L sample analyzed, producing inconsistent
results. In other words, it is very difficult to get a representative sample aliquot from a
heterogeneous sample solution.
It is recommended that all working standard solutions to be used in an analysis be
prepared (from the bulk standards) fresh on the same day as the analysis. All solutions
should be labeled and dated to keep track of them. This is to prevent any errors due to the
standard solution ions absorbing into the container walls, and also molecules leaching from
the container walls into the sample solution. The same applies to sample solutions. Bulk
solutions stored on the shelf for long periods should have high concentrations (at least
1000 ppm). There is significant degradation solutions with low concentrations (less than
10 ppm), mostly from adsorption onto the container walls, so it is imperative that they be
prepared fresh and utilized promptly.
Additionally, when storing solutions, it is good practice to use polyethylene
containers instead of glass vessels. This is because some metal ions have an affinity for
glass walls and will become adsorbed onto glass surfaces.
A common and convenient way to prolong the shelf life of working samples and
standards is to acidify the solutions with mineral acids to a pH of about 2. Nitric acid
(HNO3) is most frequently used.
42
Calibrations
The method of calibration used in an analysis depends almost entirely on the
chemical and physical properties of the unknown sample. For example, if the sample
solution has a very simple aqueous matrix, and its properties and behavior in the atomizer
are well known, then a normal calibration will be sufficient. On the opposite end of the
spectrum, if the sample solution has a complex matrix and the chemical and physical
properties are not all known, then a standard addition calibration method will be required.
The former case can be divided into two sub categories: samples with simple,
known matrices, and samples with complex, known matrices. In both cases, the matrices
are reproducible in the standards and samples, and so a normal calibration is sufficient. An
example of a simple, known matrix is a sample that has an unknown amount of copper
dissolved in nitric acid and water. An example of a complex, known matrix is a sample that
has an unknown amount of copper from a steel sample. This sample has a complex matrix
because there are other elements present (eg. iron, nickel, aluminum, and chromium).
The matrix is known because the amount of other elements present is roughly known.
The latter case can also be divided into two sub categories: complex, unknown
matrices, and organic matrices. In both cases, the matrix is not reproducible in the
standards and blanks, so the differences between the signals of the sample and standards
would be due to more factors than just the analytical component. An example of a
complex, unknown sample matrix is a sample with copper that was derived from raw oyster
meat by mechanical grinding, two-stage acid dissolution, and then furnace heating and
drying. While all the digestion steps could be reproduced in the standards and blanks, the
added matrix components from the oyster meat could not.
To accurately analyze samples with unknown matrices, a standard addition
calibration method is required. This usually means preparing a series of standards that
are prepared from samples of the unknown that have different-sized aliquots of the analyte
element added to them. The standards prepared in this way all have a matrix that is
approximately the same as the unknown sample, since all the standards were prepared
from the unknown sample.
The calibration curve is generated by first plotting absorbance versus amount of
standard added to unknown. The amount can be expressed as volume, mass, moles, or
whatever unit is appropriate. So, when the unknown is analyzed without any standard
added, the absorbance value is plotted at x = 0 mL. When the unknown is analyzed with,
for example, 0.5 mL of standard added, the absorbance is plotted at x = 0.5 mL. A
calibration curve is generated by continuing on in this manner. Extrapolation of the curve
to intersect the x-axis gives the concentration of analyte element in the original unknown
sample.
Matrix Effects
The precipitation of the element of interest from working solutions is a common
cause of inaccurate analyses. This is common, for example, with tin and silicon solutions.
The technique of AAS is based on the formation of ground state atoms being formed
in the atomizer, thereby making them capable of absorbing light. The usefulness of AAS
can be severely compromised when the formation of ground state atoms is inhibited in any
way. Chemical interference is one cause of such inhibition. Chemical interference is a
result of either of two phenomena:
(a) incomplete dissociation of analyte compounds
(b) ionization of analyte atoms
43
Incomplete Dissociation of Analyte Compounds

In general, this kind of chemical interference arises when refractory compounds of
the element of interest are introduced into the flame (or are formed in the flame).
Refractory compounds are not easily broken down by the energy of flame atomizers, and
therefore the atomizer is inefficient in producing neutral ground state atoms of the element
of interest.
A common way to prevent this type of chemical interference is to add an excess of
some other kind of element to the solutions. The refractory compounds must have a
greater affinity to form with the added element than with the element of interest. Thus,
the element of interest is freed up and the atomizer will be more efficient in producing
ground state atoms.
Ionization
Ionization of analyte atoms occurs when the energy of the atomizer is too high and
some of the ground state neutral atoms formed by the atomizer are actually ionized by the
high energy environment. Some elements are more prone to this than others. The alkali
and alkali earth elements, for example, are known as easily ionizable elements.
A common remedy for analyte ionization is to add an excess of another element
whose ionization potential is lower than the element of interest. When an excess of the
easily ionizable element is added, it creates an excess of electrons in the atomizer, and
thus shifts the ionization equilibrium to effectively eliminate ionization of the element of
interest.
44
45
46
6 - FAAS Analytical Data Sheets
Chapter 6:
FAAS Analytical Data Sheets
Introduction:
How to Use These Analytical Data Sheets
The following Analytical Data section is the heart of this cookbook. It has guideline
methods for each individual element. It is important to realize that the parameters listed
are only meant as guidelines. The parameter values listed will not necessarily lead to the
best performance on every instrument. Rather, they are to serve as a starting point for
developing optimized methods on an instrument-by-instrument basis.
For example, on page 56 is the analytical data for analyzing cadmium by FAAS. The
parameter PMT voltage is listed as 375 V. This does not mean that 375 V will be the right
voltage for every instrument. In fact, its very unlikely that it ever will be. Rather, the 375
V value is meant as a ballpark figure; it indicates that the PMT voltage of an optimized
method for measuring cadmium with FAAS should be around 375 V. This information is
valuable to the operators creating the method because they have a general idea before
hand of what the PMT voltage should be. When the operator creates a method for
cadmium, they can start at 375 V and make adjustments from there. This is much easier
and quicker than guessing at a starting point. The operator could guess to start at 100 V,
which would definitely be too low. Or the operator could guess to start at 600 V, which
would definitely be too high. In summary, the parameter values listed in the Analytical
Data sheets are meant as guidelines, or starting points, for creating optimized methods.
They are not meant as exact values that could be cut-and-paste into blank methods to
produce perfect, optimized methods every time.
There are a few things that the operator should know when looking at the Guideline
Parameters table of the data sheets. An oxidizing flame is fuel lean (relatively low ratio of
fuel to air) and is blue in color. A reducing flame is fuel rich (relatively high ratio of fuel to
air) and is orange or red in color. A stoichiometric (or neutral) flame has a fuel to air ratio
of one.
The characteristic concentration of an element is the concentration of analyzed
sample that would produce an absorption signal of 0.0044 Abs, or 1% absorption.
The working range is the concentration range within which a reasonably linear
calibration curve can be constructed. Excessive curvature of the calibration curve occurs
outside of this range.
Some graphs are included on the element data sheets if the absorption sensitivity of
the element is sensitive to the parameter in the graph. For example, a graph of
absorbance vs. lamp current is included on the data sheet for silver because the absorption
signal depends heavily on the lamp current. The graph gives the operator a general idea of
what kind of absorption changes to expect when the parameter is varied.
Information is provided on how to prepare standard solutions for each element.
Alternatively, certified standards can be purchased from chemical suppliers.
47
Information about common interferences is also provided for operator reference. It

would be wise to become familiar with these sections before analyzing an element. With
prior knowledge of interferences, major inconveniences and errors can be avoided.
The data sheets for the elements are arranged alphabetically by element name (not
by element symbol). For reference, the atomic number of each element is displayed in a
box along with the element symbol.
48
13
Al
Analytical lines:
Aluminum
309.3 nm
396.2 nm
Guideline Parameters - FAAS

Parameter
nitrous oxide/acetylene
reducing
5.0 mA
375 V
0.2 nm
1.0 mg/L
0.3 - 100 mg/L
Standard Solutions
Absorption Sensitivity
1
0.8
Absorbance
Flame:
Flame Stoichiometry:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.6
0.4
0.2
0
0
Dissolve 1.000 g of Al metal wire in 20 mL of

hydrochloric acid. Add a drop of mercury salt
catalyst. Dilute to 1 L with 1% (v/v) HCl to give a
1000 ppm Al solution. Retrieve the mercury by
filtering the solution.
Interferences
Aluminum is prone to ionization in the nitrous oxide
flame. Add an easily ionizable element (K or La,
0.1%) to alleviate this interference.
Absorption is depressed by silicon, calcium, and
phosphate.
Absorption is increased by iron, titanium, nickel, and
manganese.
49
25
50
75
Concentration (mg/L)
100
51
Sb
Analytical lines:
Antimony
217.6 nm
231.2 nm

Parameter
air/acetylene
oxidizing
10 mA
460 V
0.2 nm
(217.6nm upper; 231.2nm lower line)
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.15 mg/L
0.1-30 mg/L
Standard Solutions
0.6
0.4
0.2
Dissolve 1.000 g of antimony metal granules in

100 mL of HCl with 2 mL of HNO3. Dilute to 1 L to
give a 1000 ppm Sb solution (oxidation state
Sb(V)).
0
0
10
20
30
C oncentration (mg/L)
40
All solutions made from this stock solution should

be diluted with 10% HCl.
WARNING: This element is very toxic and

should be handled with extreme caution.
Personal protective equipment is essential.
Absorption Sensitivity vs. Fuel flow Rate

0.5
Absorbance
OR
Dissolve 2.743 g of K(SbO)C4H4O6 H2O
(potassium antimonyl tartrate) in H2O. Dilute to 1
L to give a 1000 ppm Sb solution.
0.4
0.3
0.2
0.1
0
0.5
Interferences
High levels of acids cause a depression of the
signal. Usually, matrix matching of solutions can
compensate for this interference.
Cu and Ni decrease the signal. This interference is
more pronounced in reducing flames than in
oxidizing ones.
50
1.5
2
2.5
Fuel Flow Rate (L/min)
3.5
33
As
Analytical lines:
Arsenic
193.7 nm
197.2 nm

Parameter
air/acetylene
reducing
20 mA
700 V
0.6 nm
A bsorption S ensitivity
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.6 mg/L
2 - 100 mg/L
0.6
0.4
0.2
0
0
40
80
C oncentration (m g/L)
Standard Solutions
120
Dissolve 1.3203 g of arsenious oxide (As2O3) in a

minimum volume of 20% (w/v) KOH. Neutralize with
HNO3 to a phenolpthalein endpoint. Dilute to 1 L with
1% (v/v) HNO3 to give a 1000 ppm arsenic solution.
WARNING: Arsenic is toxic and should be
handled with extreme care. Personal protective
equipment is essential.
Absorbance
0.4
Interferences
The flame itself absorbs or scatters more than half
of the source light at 193.7nm, so background
correction is highly advised.
The 189nm line is generally not used because of
heavy atmospheric absorption.
Total salt content greater than 1% can also cause
non-specific absorption.
51
0.3
0.2
0.1
0
1
1.5
2
2.5
56
Ba
Analytical lines:
Barium
553.6 nm
350.1 nm

Parameter
0.8
Absorbance
Flame:
reducing
HCL Current:
10 mA
PMT Voltage:
381 V
Slit Width:
0.2 nm
Characteristic
Concentration:
0.9 mg/L
Working Range:
0.4-150mg/L
Data collected with potassium chloride added
(final concentration of 2g/L) to suppress
ionization.
0.6
0.4
0.2
0
0
50
100
Standard Solutions
Dissolve 1.7785 g of BaCl2 2H2O (barium chloride)
in H2O. Dilute to 1 L to give a 1000 ppm Ba
solution.
OR
Dissolve 1.437 g of BaCO3 (barium carbonate) in a
minimum volume of 1:1 HCl. Dilute to 1 L with
1% HCl to give a 1000 ppm Ba solution.
Interferences
A b s o rb a n c e
0 .3
0 .2
0 .1
Barium is partially ionized in the nitrous oxide

flame. Addition of an alkali salt (eg. KCl, 0.1%)
can suppress the effects.
In samples with Ca, spectral interference arises
from the 553.6nm CaOH line.
52
be fore
a fte r
A d d itio n o f 2 g / L K C L
150
Be
Analytical lines:
Beryllium
234.9 nm

Parameter
reducing
10 mA
370 V
0.2 nm
0.012 mg/L
0.005-2 mg/L
1.2
1
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.8
0.6
0.4
0.2
Standard Solutions
0
0
1
2
3
Dissolve 1.000 g of beryllium metal wire in 1:1

HCl. Dilute to 1 L with 1% v/v HCl to give a 1000
ppm Be solution.
WARNING: This element is toxic and
should be handled with extreme care.
Personal protection equipment is essential.
Al, Mg, Na, and Si, when present at high levels,

can decrease the Be signal. The interference due
to Al can be reduced by the addition of 1% HF.
The interference due to Mg and Si can be reduced
by adding oxine.
53

0.5
Absorbance
Interferences
0.4
0.3
0.2
0.1
3.5
4.5
5.5
6.5
83
Bi
Analytical lines:
Bismuth
222.8
306.8
206.2
227.7
nm
nm
nm
nm

Parameter
1
0.8
Absorbance
Flame:
air/acetylene
oxidizing
HCL Current:
10 mA
PMT Voltage:
409 V
Slit Width:
0.2 nm
Characteristic
Concentration:
0.19 mg/L
Working Range:
0.4-35 mg/L
A higher HCL current provides a more

stable absorption signal.
Standard Solutions
0.6
0.4
0.2
0
0
Dissolve 1.000 g of Bi metal wire in a minimum

volume of 1:1 HNO3. Dilute to 1 L with 2% HNO3
to give a 1000 ppm Bi solution.
Interferences
10
20
30
40
Absorption Sensitivity vs. Slit Width

0.3
Absorbance
No major interferences to note.
0.2
0.1
0
0
54
0.2
0.4
0.6
Slit Width (nm)
0.8
B
Analytical lines:
Boron
249.7 nm
208.9 nm

Parameter
reducing
10 mA
481 V
0.2 nm
14 mg/L
8-3000 mg/L
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.6
0.4
0.2
Standard Solutions
0
0
Dissolve 44.095 g of Na2B4O7 10H2O (sodium

borate) in H2O. Dilute to 1 L to give a 5000 ppm
B solution.
OR
Dissolve 28.60 g of H3BO3 (boric acid), in H2O.
Dilute to 1 L to give a 5000 ppm B solution.
0.4
55
Absorbance
Boron is the one of the least sensitive elements in

AAS due to the formation of stable oxides, nitrides
and carbides.
The sensitivity can be improved by converting it to
volatile boric acid methyl ester or to volatile
fluoride by reaction with copper hydroxyfluoride.
High levels of sodium can cause interference,
which can be alleviated by using a stoichiometric
flame. However, sensitivity is sacrificed.
3000
Absorption Sensitivity vs. Slit Width
Store solutions in polyethylene bottles.
Interferences
1000
2000
0.3
0.2
0.1
0
0
0.2
0.4
0.6
Slit Width (nm)
0.8
48
Cd
Analytical lines:
Cadmium
228.8 nm
326.1 nm

Parameter
Absorbance vs. Concentration
air/acetylene
oxidizing
5.0 mA
375 V
0.2 nm
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.8
0.6
0.4
0.2
0
0.01 mg/L
0.02 - 2.5 mg/L
1
2
Concentration (ppm)
Standard Solutions
WARNING: Cadmium is a toxic element

and should be handled with extreme care.
Interferences
56
0.44
Absorbance
Dissolve 1.000 g of Cd metal strip in a minimum

volume of 1:1 HNO3. Dilute to 1 L with 1% HNO3
to give a 1000 ppm Cd solution.
Absorbance vs. Fuel flow rate
0.43
0.42
0.41
0.4
0.4
0.6
0.8
1
1.2
1.4
1.6
20
Ca
Analytical lines:
Calcium
422.7 nm
239.9 nm

Parameter
A b s o r p tio n S e n s itiv ity
1
0 .8
Abso rban ce
Flame:
air/acetylene
reducing
HCL Current:
10 mA
PMT Voltage:
254 V
Slit Width:
0.2 nm
Characteristic
Concentration:
0.066 mg/L
Working Range:
0.005 - 4 mg/L
The absorption sensitivity is very

dependent on the fuel flow rate and
burner head position.
The best precision is achieved with an

oxidizing flame, and best sensitivity with a
reducing flame.
A wide slit width can be used for

determinations in the air flame, but is not
recommended for the nitrous oxide flame.
0 .6
0 .4
0 .2
0
0
6
9
12
C o n c e n tr a tio n (m g / L)
15

0.15
Add 2.497 g of dried CaCO3 (calcium carbonate) to 50

mL of H2O. Dissolve with a minimum volume of 1:4
HNO3, adding the acid dropwise. Dilute to 1 L to give
a 1000 mg/L Ca solution.
Absorbance
Standard Solutions
0.1
0.05
0
0.5
Interferences
In the air/acetylene flame, interferences such as
refractory oxide depress the calcium absorbance.
Addition of a releasing agent such as strontium or
lanthanum is used to release calcium atoms for
determination.
57
1
1.5
2
2.5
20
Ca
Analytical lines:
Calcium
422.7 nm
239.9 nm

Parameter
Standard Solutions
Add 2.497 g of dried CaCO3 (calcium carbonate) to 50
mL of H2O. Dissolve with a minimum volume of 1:4
HNO3, adding the acid dropwise. Dilute to 1 L to give
a 1000 mg/L Ca solution.

1
A bso rban ce
0.8
0.6
0.4
0.2
0
0
0 .5
1
1.5
C o n c e n tr a tio n ( m g / L)
0.2
0.1
0
3
4.5
6
7.5
Interferences
A b s o r p tio n S e n s itiv ity v s . s l it W id th

0 .4
0.35
A b s o rb a n c e
In the nitrous oxide flame, ionization can be a

problem, but is easily solved by adding 1% of an
easily ionized alkali salt.
Sensitivity is depressed when elements forming
oxy salts are present, including beryllium,
aluminum, phosphorous, titanium, and silicon.
The addition of 1% lanthanum or strontium can
improve sensitivity.
There are no notable chemical interferences.
0.3
Absorbance
Flame:
reducing
HCL Current:
15 mA
PMT Voltage:
240 V
Slit Width:
0.2 nm
Characteristic
Concentration:
0.0096 mg/L
Working Range:
0.005 - 2 mg/L
The absorption sensitivity is very

dependent on the fuel flow rate and
burner head position.
The best precision is achieved with an

oxidizing flame, and best sensitivity with a
reducing flame.
A wide slit width can be used for

determinations in the air flame, but is not
recommended for the nitrous oxide flame.
0 .3
0.25
0 .2
0
0 .2
0.4
S lit W i th ( n m )
58
0.6
0 .8
55
Cs
Analytical lines:
Cesium
852.1 nm
894.5 nm

Parameter
air/acetylene
oxidizing (lean, blue)
10 mA
455 V
0.2 nm
0.07 mg/L
0.03 - 15 mg/L
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.6
0.4
0.2
0
Standard Solutions
10
15
20
Dissolve 1.267 g of cesium chloride (CsCl) in

deionized water. Dilute to 1 L to give a 1000 ppm
cesium solution.
Interferences
0.4
0.35
Absorbance
Ionization interference can be reduced by adding

0.1% of an alkali salt.
Strong mineral acids can decrease the sensitivity,
and so matrix matching is advised.
0.3
0.25
0.2
0.5
59
1
1.5
24
Cr
Analytical lines:
Chromium
357.9 nm
425.4 nm

Parameter
air/acetylene
reducing
10 mA
348 V
0.2 nm
(3 5 7 . 8 7 n m , u p p e r ; 4 2 5 .4 4 n m lo w e r lin e )
1
0.8
Abso rban ce
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.04 mg/L
0.04 - 10 mg/L
Standard Solutions
0.6
0.4
0.2
0
0
Dissolve 1.000 g of chromium metal wire, or

potassium dichromate (K2Cr2O7), in 1:1 HCl. Heat
to speed up dissolution. Dilute to 1 L to give a
1000 ppm Cr solution.
Interferences
4
6
8
10
A b s o r p tio n S e n s iti v ity v s . Fu e l flo w R a te
60
A b s o rb a n c e
The reducing air-acetylene flame provides the

most sensitivity to Cr absorbance. However, the
stability of aqueous Cr solutions is subject to the
solution acidity. Different ionized states of Cr
exhibit different sensitivities in the reducing airacetylene flame. The addition of 20g/L ammonium
chloride, 4g/L potassium thiocyanate, 20g/L
potassium persulfate or 10g/L ammonium
hydrogen fluoride, either alone or together with 2
g/L sodium sulfate may eliminate this effect.
The presence of Co, Fe and Ni (particularly in
perchloric acid) causes depression of Cr
absorbance. Cu, Ba, Al, Mg and Ca are also
reported to interfere with the Cr absorbance. The
extent of the interference is strongly dependent
on the flame stoichiometry.
This interference can be eliminated by using
oxidizing air-acetylene flame or nitrous oxideacetylene flame with the compromise of sensitivity
loss.
0 .3
0 .2
0 .1
0
1.5
2
2.5
F u e l F lo w R a te ( L/ m in )
24
Cr
Analytical lines:
Chromium
357.9 nm
425.4 nm

Parameter
reducing
10 mA
321 V
0.2 nm
0.068 mg/L
0.1 - 15 mg/L
(3 5 7 . 8 7 n m , u p p e r ; 4 2 5 .4 4 n m lo w e r lin e )
1.2
Abso rban ce
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.8
0.4
Standard Solutions
10
15
20
Dissolve 1.000 g of chromium metal wire, or

potassium dichromate (K2Cr2O7), in 1:1 HCl. Heat
to speed up dissolution. Dilute to 1 L to give a
1000 ppm Cr solution.
Interferences
Ab so r pt io n Sen s itivity vs . F ue l flo w Rat e
61
0 .4
A b so rb a nc e
The reducing air-acetylene flame provides the

most sensitivity to Cr absorbance. However, the
stability of aqueous Cr solutions is subject to the
solution acidity. Different ionized states of Cr
exhibit different sensitivities in the reducing airacetylene flame. The addition of 20g/L ammonium
chloride, 4g/L potassium thiocyanate, 20g/L
potassium persulfate or 10g/L ammonium
hydrogen fluoride, either alone or together with 2
g/L sodium sulfate may eliminate this effect.
The presence of Co, Fe and Ni (particularly in
perchloric acid) causes depression of Cr
absorbance. Cu, Ba, Al, Mg and Ca are also
reported to interfere with the Cr absorbance. The
extent of the interference is strongly dependent
on the flame stoichiometry.
This interference can be eliminated by using
oxidizing air-acetylene flame or nitrous oxideacetylene flame with the compromise of sensitivity
loss.
0 .3
0 .2
0 .1
0
2
Fu e l F lo w Ra te (L /m in )
27
Co
Analytical lines:
Cobalt
240.7 nm
346.6 nm

Parameter
A b s o r p tio n S e n s iti v ity
air/acetylene
oxidizing
7 mA
425 V
0.2 nm
( 2 4 0 .7 3 n m u p p e r ; 3 4 6 .5 8 n m l o w e r lin e )
1
0.8
A b s o rb a n c e
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.04 mg/L
0.03 - 8 mg/L
Standard Solutions
0.6
0.4
0.2
0
0
Dissolve 1.000 g of Co metal wire in a minimum

volume of 1:1 HNO3. Dilute to 1 L to give a 1000
ppm Co solution.
2
4
6
A b s o r p tio n S e n s i tiv i ty v s . Fu e l flo w R a te

0.5

However, Co is found naturally with Ni, and high
Ni levels (> 1.5 ppm) can depress the Co signal.
A b s o rb a n c e
Interferences
0.4
0.3
0.2
0.5
1.5
Fu e l Flo w R a te ( L/ m in )
A b s o r p tio n S e n s i tiv i ty v s . La m p C u r r e n t
A b s o rb a n c e
0.5
0.4
0.3
0.2
0
62
10
15
La m p C u r r e n t ( m A )
20
29
Cu
Analytical lines:
Copper
324.7 nm
327.4 nm

Parameter
air/acetylene
oxidizing
6 mA
290 V
0.2 nm
Absorbance Sensitivity
1
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.03 mg/L
0.02 - 6 mg/L
0.8
0.6
0.4
0.2
0
0
2
4
Standard Solutions
Interferences
No major interferences.
However, when Zn is present at high
concentrations, the Cu signal can be decreased.
This interference can be alleviated by using a lean
air/acetylene flame or a nitrous oxide/acetylene
flame.
63
Absorbance vs. HCL current
0.6
Absorption
Dissolve 1.000 g of copper metal wire in a

minimum volume of 1:1 HNO3. Dilute to 1 L to
give a 1000 ppm Cu solution.
0.4
0.2
0
4
8
10
HCL current (mA)
12
66
Dy
Analytical lines:
Dysprosium
421.2 nm
404.6 nm
416.8 nm

Parameter
reducing
15 mA
400 V
0.2 nm
0.58 mg/L
0.3-150 mg/L
Standard Solutions
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic conc.:
Working Range:
0.6
0.4
0.2
Dissolve 1.148 g of dysprosium oxide (Dy2O3) in a

minimum volume of HCl. Dilute to 1 L with 1%
v/v HCl to give a 1000 ppm Dy solution.
Interferences
Ionization in the nitrous oxide flame can be
reduced by the addition of an ionization
suppressant (eg. 0.1% of an alkali salt).
In the presence of H2SO4 and H3PO4, the Dy signal
is enhanced.
In the presence of Al, Si, HF, Dy signal is
decreased (especially when Na is also present), so
matrix matching is advised for such matrices.
Dy is one of the lanthanide elements, which are
known to display complex mutual interference
patterns.
64
0
0
50
100
150
68
Er
Analytical lines:
Erbium
400.8 nm
389.3 nm

Parameter
reducing
10 mA
350 V
0.2 nm
0.58 mg/L
0.5-150 mg/L
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
0.6
0.4
0.2
Standard Solutions
Dissolve 1.143 g of erbium oxide (Er2O3) in a
v/v HCl to give a 1000 ppm Er solution.
Interferences
The presence of Al, Si, and HF can all decrease
the Er signal when Na is present, so matrix
matching is advised for such matrices.
Er is one of the lanthanide elements, which are
patterns.
65
0
0
50
100
150
200
63
Eu
Analytical lines:
Europium
459.4 nm
333.4 nm
321.3 nm

Parameter
reducing
10 mA
350 V
0.2 nm
0.4 mg/L
5-80 mg/L
Standard Solutions
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
0.6
0.4
0.2
Dissolve 1.1579 g of europium oxide (Eu2O3) in a

v/v HCl to give a 1000 ppm Eu solution.
Interferences
the Eu signal when Na is present, so matrix
Eu is one of the lanthanide elements, which are
patterns.
66
0
0
25
50
75
100
64
Gd
Analytical lines:
Gadolinium
368.4 nm
405.8 nm

Parameter
reducing
10 mA
350 V
0.2 nm
29.3 mg/L
20-6000 mg/L
Standard Solutions
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
0.6
0.4
0.2
Dissolve 1.1526 g of gadolinium oxide (Gd2O3) in

a minimum volume of HCl. Dilute to 1 L with 1%
v/v HCl to give a 1000 ppm Gd solution.
Interferences
The presence of Al, Fe, Si, fluorides, and
phosphates can all significantly decrease the Gd
signal (even at moderate levels), so matrix
Gd is one of the lanthanide elements, which are
patterns.
67
0
0
2000
4000
6000
31
Ga
Analytical lines:
Gallium
294.4 nm
287.4 nm
403.3 nm

Parameter
air/acetylene
oxidizing
5 mA
502 V
0.2 nm
1.0 mg/L
1-100 mg/L
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
(294.4nm upper; 287.4nm middle,
403.3 nm lower line)
Standard Solutions
0.6
0.4
0.2
0
Dissolve 1.000 g of gallium metal in a minimum

volume of aqua regia (1:3 HNO3:HCl). Heat to aid
dissolution. Cool and dilute to 1 L with 1% v/v
HCl to give a 1000 ppm Ga solution.
50
100
150
200
Interferences
Absorbance
Ionization interference can occur in the nitrous

oxide acetylene flame, but it is eliminated by the
addition of an ionization suppressant (an alkali
salt).
The sensitivity in an air/acetylene flame is roughly
half that of the nitrous oxide/acetylene flame at
the 287.4 nm line.
0.3
0.2
0.1
0
0.5
68
1.5
2
2.5
32
Ge
Analytical lines:
Germanium
265.2 nm
259.3 nm
303.9 nm

Parameter
1
0.8
Absorbance
Flame:
reducing
HCL Current:
5 mA
PMT Voltage:
350 V
Slit Width:
0.6 nm
Characteristic
Concentration:
1.26 mg/L
Working Range:
2-300 mg/L
the 265.2 nm line is a doublet

(265.1/265.2 nm)
0.6
0.4
0.2
0
Standard Solutions
Dissolve 1.000 g in 5 mL of conc. HF in a Teflon

vessel. Slowly add conc. HNO3 dropwise until the
dissolution is complete. Dilute to 1 L with H2O to
give a 1000 ppm Ge solution.
Store the solutions in polyethylene bottles, not
glass.
WARNING: HF (hydrofluoric acid) is a very
toxic acid and should be handled with
extreme care. Personal protective
Interferences
No interferences to report.
69
100
200
300
79
Au
Analytical lines:
Gold
242.8 nm
267.6 nm

Parameter
1
0.8
Absorbance
Flame:
air/acetylene
oxidizing
HCL Current:
10 mA
PMT Voltage:
323 V
Slit Width:
0.2 nm
Characteristic
Concentration:
0.085 mg/L
Working Range:
0.1 - 16 mg/L
The 242.9nm line is more sensitive, but the

267.6nm line can be more precise because it
is more intense.
0.6
0.4
0.2
0
0
Standard Solutions
10
15
20
Store standard solutions in amber bottles. Make

working solutions with 10% HCl.
Absorbance
Dissolve 1.000 g of Au metal foil in a minimum

volume of aqua regia. Dilute to 1 L to give a 1000
ppm Au solution.
0.25
0.2
0.15
0.1
Interferences
0.5
0.3
0.2
0.1
0
0
70
2.5
Absorption Sensitivity vs. Lamp Current
Absorbance
Large quantities of mineral acids and elements such

as iron, copper, calcium, cobalt, tin and other noble
metals can depress signal. Adding 1% uranium, as a
releasing agent, or dilute Cu-Cd buffers, can alleviate
these effects.
Nitrous oxide-acetylene flame can reduce the
interferences but the sensitivity is also reduced.
1
1.5
2
10
15
20
Lamp Current (mA)
25
72
Hf
Analytical lines:
Hafnium
286.6 nm
307.3 nm
377.8 nm

Parameter
reducing
10 mA
400 V
0.2 nm
11 mg/L
20-2500 mg/L
Standard Solutions
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
0.6
0.4
0.2
Dissolve 1.000 g of hafnium metal in a Teflon

vessel by slowly adding 5 mL of HF dropwise.
Slowly add 10 mL of HNO3 dropwise, allowing the
reaction to diminish between additions. Cool and
dilute to 1 L to give a 1000 ppm Hf solution.
Store the solutions in polyethylene bottles.
extreme care. Personal protection
Interferences
At higher hafnium concentrations, oxides can
form. This can create calibration curve rollover.
To eliminate this effect, add 0.2% Al and 1% HF
to all solutions.
In general, the Hf signal is decreased by alkali and
alkaline earth metals, and H2SO4. Many transition
metals also cause interferences. The use of an
oxidizing nitrous oxide/acetylene flame can often
reduce these interferences.
71
0
0
500
1000
1500
2000
2500
67
Ho
Analytical lines:
Holmium
410.4 nm
412.7 nm
425.4 nm

Parameter
reducing
15 mA
400 V
0.2 nm
0.88 mg/L
0.4-200 mg/L
Standard Solutions
Dissolve 1.146 g of holmium oxide (Ho2O3) in a
v/v HCl to give a 1000 ppm Ho solution.
Interferences
the Ho signal, so matrix matching is advised for
such matrices.
72
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
0.6
0.4
0.2
0
0
50
100
150
200
49
In
Analytical lines:
Indium
303.94 nm
325.61 nm

Parameter
air/acetylene
8 mA
393 V
0.2 nm
0.2 mg/L
0.2 - 30 mg/L

1
0.8
A b s o rb a n c e
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.6
0.4
0.2
0
Standard Solutions
10
20
30
40
Dissolve 1.000 g of indium metal wire in a minimum

volume of 1:1 HCl. Gentle heating and adding ~1mL
of HNO3 will aid dissolution. Dilute to 1 L with 1%
(v/v) HCl to give a 1000 ppm indium solution.
0.5
When large excesses of Cu, Zn, Sn, Al, Fe, Mg, Si

or phosphate are present, the sensitivity is
decreased. Matrix matching of samples and
standards is advised.
Ionization occurs in the nitrous oxide/acetylene
flame.
Absorbance
Interferences
0.4
0.3
0.2
0.5
73
1
1.5
77
Ir
Analytical lines:
Iridium
208.9 nm
264.0 nm

Parameter
air/acetylene
reducing
10 mA
400 V
0.2 nm
1
0.8
0.8 mg/L
4-150 mg/L
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
Standard Solutions
Dissolve 2.294 g of (NH4)2IrCl6 (ammonium
hexachloroiridate) in a minimum volume of 1%
v/v HCl. Dilute to 1 L with 1% HCl to give a 1000
ppm Ir solution.
Interferences
There are many interferences to note. Some
metals (Al, Cu, K, La, Na, Pb, and Pt) increase the
signal, and other metals (Fe, Ni, Pd, Sn, and Ti)
decrease the signal.
The degree of interference depends largely on the
concentration ratio of Ir to interfering species.
Therefore, matrix matching of all solutions is
important.
Many interferences are eliminated in the nitrous
oxide/acetylene flame, but sensitivity is generally
decreased by 50%.
74
0.6
0.4
0.2
0
0
50
100
150
200
26
Fe
Analytical lines:
Iron
248.3 nm
372.0 nm

Parameter
A b s o rp tio n S e n s itiv ity
air/acetylene
oxidizing
5 mA
511 V
0.2 nm
( D o u b le t 2 4 8 .3 3 n m , u p p e r lin e ;
3 7 1 .9 9 n m , lo w e r lin e )
1
0 .8
A b s o rb a n c e
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.045 mg/L
0.03 - 8 mg/L
Standard Solutions
0 .6
0 .4
0 .2
0
0
Dissolve 1.000 g of iron metal strip in 20mL of 1:1

HCl. Dilute to 1 L to give a 1000 ppm Fe solution.
3
6
9
C o n c e n tra tio n ( m g / L)
12
Interferences
A b s o r p tio n S e n s itiv ity v s . Fu e l f lo w
R a te
0 .5
A b s o rb a n c e
Silicon, aluminum, manganese, and sulfates can

all depress the signal, but the effect gets weaker
at higher measurement heights in the flame.
Citric acid depresses the absorption signal, and
the effect can be reduced by adding phosphoric
acid to the samples.
Two oxidation states of Fe can occur in a reducing
flame.
0 .4
0 .3
0 .2
0 .1
0.5
1
1.5
A b s o r p tio n S e n s itiv ity v s . La m p C u r r e n t
A b s o rb a n c e
0.5
0.4
0.3
0.2
0
75
10
15
20
La m p C u r re n t (m A )
25
57
La
Analytical lines:
Lanthanum
550.1 nm
418.7 nm
403.7 nm

Parameter
reducing
13 mA
400 V
0.2 nm
60 mg/L
20-10000 mg/L
Standard Solutions
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.6
0.4
0.2
0
Dissolve 11.730 g of La2O3 (lanthanum oxide) in a

give a 10,000 ppm La solution.
Interferences
Ionization interference occurs in the nitrous
oxide/acetylene flame. Add an ionization
suppressant (K, Cs, or another alkali) to reduce
this effect.
Al, Fe, Si, fluorides, and phosphates all depress
the La signal.
Matrix matching of all solutions is recommended.
76
5000
10000
15000
82
Pb
Analytical lines:
Lead
217.0 nm
283.3 nm
261.4 nm

Parameter
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
air/acetylene
oxidizing
5 mA
497 V
0.2 nm
0.08 mg/L
0.1-15 mg/L
Standard Solutions
(upper line 217 nm, lower line 283.30nm)
Dissolve 1.598 g of lead nitrate

(Pb(NO3)2) in 1% (v/v) HNO3. Dilute to
1 L to give a 1000 ppm lead solution.
Absorbance
0.8
OR
Dissolve 1.000 g of lead metal wire in
1:1 HNO3. Dilute to 1 L with deionized
water to give a 1000 ppm lead solution.
0.6
0.4
0.2
0
0
WARNING: This element is toxic and

Personal protective equipment is
essential.
5
10
15
There are no cationic interferences, but

several anionic ones. At high
concentrations (relative to lead),
phosphate, carbonate, iodide, fluoride,
and acetate anions can all depress the
lead signal. These interferences can be
alleviated by the addition of 0.1 M
EDTA.
For multielement lamps with copper, the
copper 216.5nm line may interfere with the
217nm lead line. The 283.3nm lead line
should be used instead.
77
0.15
0.1
0.05
0
1
1.5
2
2.5

0.2
Absorbane
Interferences
Absorbance

0.2
0.15
0.1
0.05
0
0
10
15
Lamp Current (mA)
20
Li
Analytical lines:
Lithium
670.8 nm
610.4 nm

Parameter
air/acetylene
oxidizing
5 mA
283 V
0.2 nm
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.01 mg/L
0.01 - 2.5 mg/L
0.6
0.4
0.2
0
Standard Solutions
Dissolve 5.324 g of lithium carbonate (Li2CO3) in a

minimum volume of 1:1 HCl. Dilute to 1 L to give
a 1000 ppm Li solution.
0.5
1
1.5
2
2.5

0.4
Ionization is a consideration, but can be

compensated for by adding K.
For geological samples, interferences are from the
presence of high concentrations of aluminum,
phosphate, fluoride and perchlorate.
Nitrous oxide/acetylene flame can remove the
above interferences.
Absorbance
Interferences
0.3
0.2
0.1
0.5
1
1.5
2
2.5
Absorbance
0.4
0.3
0.2
0.1
0
78
10
15
Lamp Current (mA)
20
71
Lu
Analytical lines:
Lutetium
336.0 nm
356.8 nm

Parameter
reducing
10 mA
400 V
0.2 nm
4.5 mg/L
3-1500 mg/L
Standard Solutions
Dissolve 1.137 g of lutetium oxide (Lu2O3) in a
minimum volume of 1:1 HNO3. Dilute to 100 mL
to give a 10,000 ppm Lu solution.
Interferences
The presence of Al, Fe, Si, fluorides, and
phosphates can all decrease the Lu signal, so
matrix matching is advised for such matrices.
Lu is one of the lanthanide elements, which are
patterns.
79
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
0.6
0.4
0.2
0
0
500
1000
1500
12
Mg
Analytical lines:
Magnesium
285.2 nm
202.6 nm

Parameter
air/acetylene
oxidizing
5 mA
331 V
0.2 nm
( 2 8 5 . 2 1 n m , u p p e r ; 2 0 2 .5 8 n m , lo w e r )
1
0.8
0.0024 mg/L
0.002 - 0.5 mg/L
A bso rban ce
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.6
0.4
0.2
0
Standard Solutions
Dissolve 1.000 g of magnesium metal strip slowly

in a minimum volume of 1:1 HCl. Dilute to 1 L to
give a 1000 ppm Mg solution.
0 .2
0.4
0 .6
0 .8
A b s o r p tio n S e n s itiv i ty v s . Fu e l f lo w R a te
0.3
Interferences from higher concentrations of Si, Al,

Ti, and P can be eliminated by adding lanthanum
chloride.
flame, so ionization suppressants must be added
to solutions.
80
A b s o rb a n c e
Interferences
0.2
0.1
0
0.5
1
1.5
2
F u e l F lo w R a te ( L/ m in )
2 .5
25
Mn
Analytical lines:
Manganese
279.5 nm
279.8 nm
280.1 nm

Flame:
air/acetylene
oxidizing
HCL Current:
10 mA
PMT Voltage:
339 V
Slit Width:
0.2 nm
Characteristic
Concentration:
0.021 mg/L
Working Range:
0.02 - 5 mg/L
the S/N ratio can be improved by using a

wide slit width and measuring absorption with
the triplet 279.5/279.8/280.1 nm. However,
the characteristic concentration is 0.1 mg/L
and calibration linearity is compromised.
(Doublet 279.8/280.1 nm, upper line;
279.48nm, lower line)
1.2
0.9
Absorbance
Parameter
0.6
0.3
0
0
4
6
Standard Solutions
Interferences

0.5
Absorbance
Dissolve 1.000 g of manganese metal wire in a

give a 1000 ppm Mn solution.
Signal suppression was observed in the presence

of silicon, phosphorus, borate, tungstate,
dichromate, silicate, cyanide, and rhenium.
The use of a nitrous oxide/acetylene flame can
reduce these interferences. However, sensitivity
is sacrificed.
Some complexing agents (eg. EDTA, NTA) can
increase the signal in an air/acetylene flame.
0.4
0.3
0.2
0.1
0.5
1.5
2
2.5
Absorbance
0.5
0.4
0.3
0.2
0
81
10
15
20
Lamp Current (mA)
25
80
Hg
Analytical lines:
Mercury
253.7 nm

Parameter
air/acetylene
4 mA
308 V
0.2 nm
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
3 mg/L
2 - 500 mg/L
0.6
0.4
0.2
0
0
Standard Solutions
WARNING: Mercury is very toxic and should be

Interferences
Mercury (I) is more sensitive than mercury (II).
Mercury (II) can be reduced to mercury (I) by
ascorbic acid, stannous chloride, and other
reductants, thus falsely increasing the signal.
High cobalt levels will interfere with the 253.7nm
mercury line.
It is advisable to check and correct for nonspecific absorption.
82
750

0.2
Absorbance
Dissolve 1.080 g of mercury (II) oxide (HgO) in a

minimum volume of 1:1 HCl. Dilute to 1 L with
deionized water to give a 1000 ppm mercury
solution.
OR
Dissolve 1.354 g of mercuric (II) chloride (HgCl2)
in 10mL of HNO3. Dilute to 1 L with deionized
water to give a 1000 ppm mercury solution.
150
300
450
600
0.15
0.1
0.05
0
0.5
1
1.5
42
Mo
Analytical lines:
Molybdenum
313.3 nm
320.9 nm

Parameter
reducing
10 mA
445 V
0.6 nm
0.64 mg/L
0.2 - 125 mg/L
1
0 .8
Abso rban ce
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0 .6
0 .4
0 .2
0
Standard Solutions
Dissolve 1.000 g of molybdenum metal strip into

hot conc. HNO3. Cool and dilute to 1 L to give a
1000 ppm Mo solution.
OR
Dissolve 1.840 g of (NH4)6Mo7O24 4H2O
(ammonium heptamolybdate tetrahydrate) in 1%
v/v NH4OH (ammonium hydroxide) and make up
to 1 L with the NH4OH to give a 1000 ppm Mo
solution.
Interferences
The signal can be depressed in the presence of
Ca, Fe, Sr, and sulfate. The effects can be
reduced by the addition of 1-3 g/L aluminum.
When Mo is determined in an air/acetylene flame,
the sensitivities are 3-10 times poorer than those
obtained with a nitrous oxide/acetylene flame. As
well, there are far fewer interferences in the
nitrous oxide flame.
83
25
50
75
1 00
125
60
Nd
Analytical lines:
Neodymium
492.5 nm
463.4 nm
486.7 nm

Parameter
reducing
15 mA
450 V
0.2 nm
12.2 mg/L
10-1500 mg/L
Standard Solutions
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
0.6
0.4
0.2
Dissolve 1.167 g of neodymium oxide (Nd2O3) in a

minimum volume of HNO3. Dilute to 100 mL with
1% v/v HNO3 to give a 10,000 ppm Nd solution.
Interferences
The presence of Al, Fe, Si, and HF can all decrease
the Nd signal, so matrix matching is advised for
such matrices.
Nd is one of the lanthanide elements, which are
patterns.
The presence of Pr (another lanthanide element)
can cause interference with the overlap of its
492.5 nm line.
Neodymium, Nd
84
0
0
1000
2000
3000
4000
28
Ni
Analytical lines:
Nickel
232.0 nm
341.5 nm

Parameter
air/acetylene
oxidizing
7 mA
449 V
0.2 nm
0 .8
A bso rban ce
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.042 mg/L
0.07 - 10 mg/L
0 .6
0 .4
0 .2
0
0
Standard Solutions
12
C o n c e n tra tio n ( m g / L)
Dissolve 1.000 g of nickel metal wire in 1:1 HNO3.

Dilute to 1 L in 1% v/v HNO3 to give a 1000 ppm
Ni solution.
Interferences
At the 232.0 nm absorption wavelength, it is
common for non-specific absorption to occur. This
is especially a problem when non-dissolved
species are present. To alleviate this interference,
a background correction method must be
employed. Non-specific absorption is not a
problem at the 341.5 nm wavelength.
Fe or Cr present at high levels can increase the Ni
signal.
The use of a nitrous oxide/acetylene flame will
remove most interferences, but signal sensitivity
will be sacrificed.
Absorbance
0.5
0.4
0.3
0.2
0.5
1
1.5
A b s o rp tio n S e n s itiv ity v s . La m p C u r r e n t
A b s o rb a n c e
0.5
0.4
0.3
0.2
0
85
10
15
La m p C u r re n t (m A )
20
41
Nb
Analytical lines:
Niobium
334.9 nm
408.0 nm
374.0 nm

Parameter
reducing
15 mA
400 V
0.2 nm
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
23 mg/L
20-6000 mg/L
Standard Solutions
0.6
0.4
0.2
Dissolve 5.000 g of niobium metal in a Teflon

vessel by slowly adding 5 mL of conc. HF
dropwise. Add 10 mL of conc. HNO3 dropwise to
complete the dissolution. Dilute to 1 L to give a
5,000 ppm Nb solution.
Store solutions in polyethylene bottles.
Interferences
At higher concentrations of niobium, oxide
formation can occur. This results in calibration
curve roll-over. This effect can be countered by
adding 0.2% Al and 1% HF.
Ionization interference is common, but can be
suppressant (an alkali salt such as K or Cs).
86
0
0
2000
4000
6000
76
Os
Analytical lines:
Osmium
290.9 nm
305.9 nm

Parameter
reducing
10 mA
400 V
0.2 nm
2.2 mg/L
1-300 mg/L
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
Standard Solutions
Obtain a certified stock standard solution of 1000
ppm osmium from a chemicals supplier.
OR
Dissolve 1.340 g of OsO4 (osmium tetroxide) in

100 mL of H2O. Add a NaOH (sodium hydroxide)
pellet to aid the dissolution. Dilute to 1 L to give a
1000 ppm Os solution.
Os solutions are unstable and fresh solutions
should be prepared frequently. Store solutions in
glass bottles.
All solutions made from this stock must be made
with 1% v/v H2SO4.
WARNING: OsO4 is very toxic and volatile.
Avoid inhaling the vapors. Handle this
substance with extreme care. Personal
protective equipment is essential.
Interferences
The nitrous oxide/acetylene flame is about 5 times
more sensitive than the air/acetylene flame.
87
0.6
0.4
0.2
0
0
100
200
300
46
Pd
Analytical lines:
Palladium
244.79 nm
247.64 nm

Parameter
air/acetylene
5 mA
625 V
0.2 nm
0.05 mg/L
0.6 - 10 mg/L
(244.79 upper; 247.64 lower line)
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.6
0.4
0.2
0
0
5
10
Standard Solutions

0.5
Absorbance
Dissolve 1.000 g of palladium metal wire in a

minimum volume of aqua regia. Evaporate to
dryness. Dissolve in 5mL of conc. HCl and 25mL
warm water. Dilute to 1 L to give a 1000 ppm
palladium solution.
OR
Dissolve 2.672 g of ammonium chloropalladite
((NH4)2PdCl4) in deionized water. Dilute to 1 L to
give a 1000 ppm palladium solution.
15
0.45
0.4
0.35
0.3
0.5
1
1.5
Interferences
A b s o r p tio n S e n s itiv ity v s . La m p C u r r e n t
A bso rb a nce
The signal is decreased by cobalt, nickel,

aluminum, and HF.
The interference can be improved by adding
lanthanum or 0.01 M EDTA, and also by
measuring higher in the flame.
The nitrous oxide/acetylene flame removes many
interferences, but sensitivity is greatly sacrificed.
0 .5
0 .4
0 .3
0 .2
0
88
5
10
15
20
15
P
Analytical lines:
Phosphorous
213.6 nm
214.9 nm

Parameter
Flame:
reducing
HCL Current:
10 mA
PMT Voltage:
507 V
Slit Width:
0.2 nm
Characteristic
Concentration:
92 mg/L
Working Range:
400-30000 mg/L
the analytical lines are a doublet:

213.6/214.9 nm.
Standard Solutions
Dissolve 37.138 g of dry NH4H2PO4 (ammonium
dihydrogen orthophosphate) in H2O. Dilute to 1 L
to give a 10,000 ppm P solution.
Interferences
There is little mention of interferences in the
literature.
However, matrix matching of solutions is advised
as a precaution.
89
Absorbance
1.2
0.8
0.4
0
0
10000
20000
30000
40000
78
Pt
Analytical lines:
Platinum
265.9 nm
299.8 nm

Parameter
air/acetylene
10 mA
384 V
0.2 nm
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.6 mg/L
0.4 - 120 mg/L
0.6
0.4
0.2
0
0
50
100
150
Standard Solutions
Dissolve 2.275 g of ammonium chloroplatinate
((NH4)2PtCl6) in deionized water. Dilute to 1 L with
more water to give a 1000 ppm platinum solution.
High levels of most noble metals and acids can

decrease the platinum signal. These can be
compensated for by adding 0.2% lanthanum in
1.0% HCl or by making solutions 2% in copper.
Most interferences are eliminated in the nitrous
oxide/acetylene flame, but the sensitivity is
sacrificed.
Absorbance
Interferences

0.4
0.35
0.3
0.25
0.2
0.5
It is advisable to matrix-match standards

with the samples.
1
1.5
Absorbance
0.4
0.35
0.3
5
90
10
15
20
Lamp Current (mA)
25
19
K
Analytical lines:
Potassium
766.5 nm
769.9 nm
404.4 nm

Parameter
( u p p e r lin e 7 6 6 . 4 9 n m , lo w e r lin e 7 69 .9 0
air/acetylene
oxidizing
5 mA
416 V
0.2 nm
nm )
1
0 .8
A b s o rb a n c e
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
A b s o r p ti o n S e n s iti v ity
0.0066 mg/L
0.02 - 1.5 mg/L
0 .6
0 .4
0 .2
0
0
Standard Solutions
Dissolve 1.907 g of dry potassium chloride (KCl)
in H2O. Dilute to 1 L to give a 1000 ppm K
solution.
0.5
1
1 .5

(0.5 mg/L)
0.4
K can be partially ionized in the flame. The

addition of another easily ionizable element, such
as La or Cs salts, can suppress this effect.
High levels of mineral acids can depress the
signal.
91
Absorbance
Interferences
0.3
0.2
0.1
0.9
1.2
1.5
1.8
59
Pr
Analytical lines:
Praseodymium
495.1 nm
513.3 nm
491.4 nm

Parameter
reducing
10 mA
450 V
0.2 nm
33 mg/L
100-5000 mg/L
Standard Solutions
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
1
0.6
0.4
0.2
0
0
Dissolve 1.170 g of praseodymium oxide (Pr2O3)

in a minimum volume of HCl. Dilute to 100 mL
with 1% v/v HCl to give a 10,000 ppm Pr solution.
Interferences
An excess of Si decreases the Pr signal.
Pr is one of the lanthanide elements, which are
patterns.
92
1000
2000
3000
4000
75
Re
Analytical lines:
Rhenium
346.0 nm
346.5 nm
345.2 nm

Parameter
reducing
13 mA
450 V
0.2 nm
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
14.7 mg/L
10-2000 mg/L
Standard Solutions
0.6
0.4
0.2
0
Dissolve 1.554 g of KReO4 (potassium perrhenate)

in H2O. Dilute to 1 L with 1% v/v H2SO4 to give a
1000 ppm Re solution.
Interferences
The signal is depressed by the presence of Al, Ba,
Ca, Fe, K, Mg, Mn, Mo, Pb, and most transition
group metals. The use of a more oxidizing flame
can often alleviate these interferences somewhat.
Matrix matching of all solutions is recommended.
93
500
1000 1500
2000
2500
45
Rh
Analytical lines:
Rhodium
343.49 nm
339.69 nm

(343.49nm, upper; 339.69 nm lower line)
Parameter
air/acetylene
8 mA
328 V
0.2 nm
0.11 mg/L
0.03 - 20 mg/L
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.6
0.4
0.2
0
0
Standard Solutions
Dissolve 4.120 g of ammonium hexachlororhodate
trihydrate ((NH4)3RhCl6 3H2O) in a minimum volume
of 10% (v/v) HCl. Dilute to 1 L with 10% (v/v) HCl to
give a 1000 ppm rhodium solution.
Interferences
10
15
20
25

0.5
Absorbance
Working standard solutions should also be made with

10% HCl.
0.45
0.4
0.5
Adding 1.0% Na2SO4 relieves some chemical

interferences, and also improves linearity and
sensitivity.
Most elements interfere unpredictably.
Phosphoric and sulfuric acids decrease the
sensitivity, while alkali metal sulfates increase
sensitivity.
The nitrous oxide/acetylene flame removes

many interferences, but sensitivity is
sacrificed.
94
1
1.5
37
Rb
Analytical lines:
Rubidium
780.0 nm
794.8 nm

Parameter
(780.0nm, upper line; 794.8 nm lower line)
air/acetylene
8 mA
467 V
0.6 nm
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.015 mg/L
0.05 - 5 mg/L
0.6
0.4
0.2
0
Standard Solutions
Dissolve 1.415 g of rubidium chloride (RbCl) in

deionized water. Dilute to 1 L to give a 1000 ppm
rubidium solution.
1
2
3
Interferences
Rubidium is relatively easily ionized, but this can
be controlled by adding 0.1% alkali salt.
Aluminum and mineral acids can depress the

signal in the lower flame region, and so
matrix matching of the standards to the
samples is advised.
95
Absorbance
0.65
0.6
0.55
0.5
0.5
1
1.5
44
Ru
Analytical lines:
Ruthenium
349.9 nm
392.6 nm

Parameter
air/acetylene
oxidizing
10 mA
400 V
0.2 nm
1
0.8
0.57 mg/L
1-150 mg/L
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
Standard Solutions
0.6
0.4
0.2
Dissolve 2.052 g of ruthenium chloride

(RuCl3 3H2O) in 25% (v/v) HCl. Dilute to 1 L with
25% (v/v) HCl to give a 1000 ppm ruthenium
solution.
Interferences
Ruthenium sensitivity is decreased by
molybdenum, but increased by platinum, rhodium,
lanthanum, and HCl. In general, however, most
elements interfere unpredictably.
The nitrous oxide/acetylene flame removes most
interferences, and the addition of 0.5% lanthanum
improves sensitivity.
96
0
0
50
100
150
62
Sm
Analytical lines:
Samarium
429.7 nm
476.0 nm

Parameter
reducing
10 mA
450 V
0.2 nm
6.1 mg/L
10-1500 mg/L
Standard Solutions
Dissolve 1.159 g of samarium oxide (Sm2O3) in a
minimum volume of HCl. Dilute to 100 mL with
10% v/v HCl to give a 10,000 ppm Sm solution.
Interferences
Sm is one of the Lanthanide elements, which are
patterns.
97
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
0.6
0.4
0.2
0
0
500
1000
1500
2000
21
Sc
Analytical lines:
Scandium
391.2 nm
327.4 nm
326.9 nm

Parameter
reducing
10 mA
400 V
0.2 nm
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.40 mg/L
0.5-80 mg/L
0.6
0.4
0.2
Standard Solutions
Dissolve 1.534 g of Sc2O3 (scandium oxide) in a

minimum volume of 1:1 HCl. Dilute to 1 L to give
a 1000 ppm Sc solution.
Interferences
Ionization in the nitrous oxide/acetylene flame can
be controlled by the addition of an alkali salt to all
solutions.
Significant signal depression occurs when fluoride,
sulfide, or sulfate anions are present. Many
cations are known to increase or decrease the
signal when present at high levels. To
compensate for these interferences, matrix
matching of all solutions is advised.
98
20
40
60
80
100
34
Se
Analytical lines:
Selenium
196.0 nm
204.0 nm

Parameter
air/acetylene
oxidizing
10 mA
458 V
0.2 nm
0.8
A b s o rb a n c e
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.17 mg/L
0.8 - 40 mg/L
0.6
0.4
0.2
0
0
Standard Solutions
Dissolve 1.000 g of selenium metal pellets in a
minimum volume of 1:1 HNO3. Heat gently to
help the dissolution. Cool the solution and dilute
to 1 L to give a 1000 ppm Se solution.
Interferences
The analytical line of 196.03 nm is at the start of
UV range, where the flame gases can absorb and
scatter part of the radiation. Therefore, use of
background correction is recommended. The
absorption by the flame is reduced when a nitrous
oxide/acetylene flame is used, but sensitivity is
also reduced.
99
40

0.3
0.25
Absorbance
WARNING: Selenium is a toxic element and

10
20
30
0.2
0.15
0.1
1
1.2
1.4
1.6
1.8
14
Si
Analytical lines:
Silicon
251.6 nm
221.1 nm

Parameter
reducing
5 mA
497 V
0.2 nm
1.2 mg/L
3-400 mg/L
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
(upper line 251.6nm, lower line 221.1nm)
0.6
0.4
0.2
0
0
100
200
Standard Solutions
Fuse 2.139 g of silicon dioxide with 8 g of NaOH

(sodium hydroxide) in a zirconium crucible. Cool
the melt and dissolve it with 100 mL of 1:3 HCl.
Dilute to 1 L to give a 1000 ppm Si solution.
0.3
Absorbance
OR
Fuse 2.139 g of silicon dioxide with 20 g of Na2CO3
(sodium carbonate) in a platinum crucible. Cool the
melt and dissolve it with H2O. Dilute to 1 L to give a
1000 ppm Si solution.
300
0.2
0.1
0
5
Interferences
In acidic solutions, silicon can precipitate out and

cause lower signals. To keep Si in solution, add 1%
HF.
Large excess of alkali and aluminum causes signal
enhancement.
100
10
47
Ag
Analytical lines:
Silver
328.1 nm
338.3 nm

Parameter
air/acetylene
oxidizing
5 mA
270 V
0.2 nm
0.016 mg/L
0.02 - 4 mg/L
be poor due to the low
in solutions.
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
Ag sensitivity can
dissociation of Ag
0.8
0.6
0.4
0.2
0
0
Standard Solutions
Dissolve 1.000 g of Ag metal strip in 20 mL of 1:1
nitric acid. Dilute to 1 L to give a 1000 ppm Ag
solution.
Interferences

0.3
Absorbance
Silver is sensitive to light. Store stock solutions in

amber bottles and in closed cupboards.
2
3
0.2
0.1
0
0
Acetic acid increases absorption.

Mineral acids and aluminum decrease absorption.
Silver is precipitated by bromide, chloride,
chromate, iodide, iodate, permanganate, and
tungstate.
5
10
15
Lamp Current (mA)
20

0.2
Absorbance
0.15
0.1
0.05
0
0.5
101
1
1.5
2
2.5
11
Na
Analytical lines:
Sodium
589.0
589.6
330.2
330.3
nm
nm
nm
nm

Parameter
Dissolve 2.542 g of dry NaCl salt (sodium

chloride) in H2O. Dilute to 1 L to give a 1000 ppm
Na solution.
Interferences
Na is easily ionized in the flame, so an ionization
suppressant must be added to eliminate this
interference (Cs, K, or some other alkali salt).
High levels of mineral acids can decrease the
sensitivity.
A b s o rb a n c e
0.8
0.6
0.4
0.2
0
0
0 .2
0 .4
0.6
0.8
0.35
0.3
0.25
0.5
1
1.5
2
Absorption Sensitivity vs.

Addition of Ionization Suppressant
0.6
0.5
0.4
0.3
0.2
before
after
Addition of 1 g/L Cs
102
0.4
Absorbance
Standard Solutions
( 5 8 9 .0 0 n m u p p e r ; 5 8 9 . 5 9 n m lo w e r li n e )
1
Absorbance
Flame:
air/acetylene
oxidizing
HCL Current:
10 mA
PMT Voltage:
244 V
Slit Width:
0.2 nm
Characteristic
Concentration:
0.0032 mg/L
Working Range:
0.002 - 1 mg/L
the 589.0/589.6 nm doublet can be used to
increase the S/N ratio, but calibration
linearity is sacrificed.
the 589.0 nm line is more sensitive than the
589.6 nm line.
the 330.2/330.3 nm lines are also a
doublet.
2.5
38
Sr
Analytical lines:
Strontium
460.7 nm
407.8 nm

Parameter
1
0.8
Absorbance
Flame:
air/acetylene
oxidizing
HCL Current:
10 mA
PMT Voltage:
452 V
Slit Width:
0.2 nm
Characteristic
Concentration:
0.018 mg/L
Working Range:
0.007-3 mg/L
ionization.
0.6
0.4
0.2
0
Standard Solutions
Dissolve 2.415 g of Sr(NO3)2 (strontium nitrate) in

100 mL of H2O and 10 mL of conc. HCl. Dilute to
1 L to give a 1000 ppm Sr solution.
OR
Dissolve 1.685 g of SrCO3 (strontium carbonate)
in 10 mL of 1:1 HNO3. Dilute to 1 L to give a
1000 ppm Sr solution.
Interferences
The air/acetylene flame is not as sensitive as the
nitrous oxide/acetylene flame, and more chemical
interferences are known in the air flame.
In the air flame, Al, Si, Ti, Zr, phosphate, and
sulfate all decrease the signal. To alleviate these
effects, add 1% La or the complexing agent EDTA
to all solutions.
Strontium undergoes ionization in both the nitrous
oxide and air flames. To reduce this interference,
add an ionization suppressant (eg. K, Cs, or other
alkali salt) to all solutions.
103
1
2
3
73
Ta
Analytical lines:
Tantalum
271.5 nm
277.6 nm
275.8 nm

Parameter
reducing
10 mA
450 V
0.2 nm
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
12 mg/L
20-3000 mg/L
Standard Solutions
Dissolve 1.000 g of tantalum metal strip in a
Teflon vessel by carefully adding 5 mL of conc. HF
dropwise.
Dissolve the remaining metal by slowly adding
conc. HNO3 dropwise. Dilute to 200 mL to give a
5,000 ppm Ta solution.
Store all solutions in polyethylene bottles.
WARNING: HF (hydrofluoric acid) is a toxic acid
and should be handled with extreme care.
Interferences
Oxide formation in the flame is common and
results in calibration curve roll-over at higher
concentrations. To alleviate this problem and
improve calibration curve linearity, add 0.2% Al
and 1% HF to all solutions.
The signal is interfered with in varying ways when
alkali metals, sulfates, phosphates, and mineral
acids are present in various combinations. Matrix
matching of all solutions is recommended.
104
0.6
0.4
0.2
0
0
1000
2000
3000
52
Te
Analytical lines:
Tellurium
214.27 nm
225.9 nm

Parameter
air/acetylene
15 mA
470 V
0.2 nm
0.23 mg/L
0.3 - 60 mg/L
1
0.8
A b s o rb a n c e
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.6
0.4
0.2
0
0
Standard Solutions
Dissolve 1.000 g of tellurium metal granules in a
minimum volume of 1:1:1 HNO3:HCl:water. Heat to
aid dissolution, but do not boil. Dilute to 1 L with 1%
(v/v) HCl to give a 1000 ppm tellurium solution.
20
40
60

0.45
Interference occurs in the presence of high levels

of Ca, Cu, Si, Na, Zn, and Zr. Matrix matching of
standards is advised.
At low tellurium concentrations, acids and
dissolved carbon dioxide can cause non-specific
absorption, so the use of background correction is
prudent.
105
Absorbance
Interferences
0.4
0.35
0.3
0.5
1
1.5
81
Tl
Analytical lines:
Thallium
276.8 nm
258.0 nm

A b s o r p tio n S e n s i tiv ity
Parameter
( 2 7 6 . 8 n m u p p e r ; 3 7 7 . 6 n m lo w e r lin e )
air/acetylene
oxidizing
5 mA
484 V
0.2 nm
0.13 mg/L
0.1-20 mg/L
1
0 .8
A b s o rb a n c e
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
Standard Solutions
0 .6
0 .4
0 .2
0
0
Dissolve 1.303 g of thallous nitrate (TlNO3) in

20mL of 1% (v/v) HNO3. Dilute to 1 L with
deionized water to give a 1000 ppm thallium
solution.
Interferences
Many significant interferences exist.
Matrix matching of standards is advised for
samples with high levels of interfering elements.
flame.
106
10
15
20
25
30

0.4
0.35
Absorbance
WARNING: This element is toxic and should be

0.3
0.25
0.2
0.5
1.5
2
2.5
50
Sn
Analytical lines:
Tin
224.6 nm
286.3 nm

A b s o rp ti o n S e n s itiv ity
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
reducing
10 mA
536 V
0.2 nm
( 2 2 4 . 6 1 n m , u p p e r ; 2 8 6 .3 3 n m lo w e r lin e )
0.8
A bso rban ce
Parameter
1.5 mg/L
1 - 200 mg/L
0.6
0.4
0.2
0
0
Standard Solutions
Dissolve 1.000 g of tin metal granules in 100 mL
of conc. HCl. If necessary, heat gently to aid
dissolution. Cool and dilute to 1 L to give a 1000
ppm Sn solution.
Interferences
1 00
150
2 00
C o n c e n tr a ti o n ( m g / L)
250
A b s o r p tio n S e n s itiv i ty v s . Fu e l f lo w R a te
0.4
0.3
A b s o rb a n c e
Solutions made from this bulk standard should all

be made with 10 % v/v HCl.
50
0.2
0.1
0
While the nitrous oxide/acetylene flame is not

quite as sensitive as the air/acetylene flame, it is
preferred because it has significantly less
interferences, particularly when complex matrices
are involved.
A b s o r p tio n S e n s itiv ity v s . S l it W id th
A b s o rb a n c e
0.4
0.3
0.2
0.1
0
0
107
5
6
7
0 .2
0.4
0 .6
S lit W i d th ( n m )
0.8
22
Ti
Analytical lines:
Titanium
364.3 nm
365.4 nm
399.0 nm

Parameter
Standard Solutions
Dissolve 1.000 g of titanium metal in 10 mL of HF
and 10 mL H2O by slowly adding (dropwise) 20
mL of HNO3. After each addition, allow the
reaction to diminish before the next addition.
Dilute to 1 L to give a 1000 ppm Ti solution.
OR
Dissolve 1.000 g of titanium metal in 100 mL of
1:1 HCl. Cool and dilute to 1 L to give a 1000
ppm Ti solution.
Solutions made from this bulk standard should all
be made with 10% v/v HCl.
Interferences
Ionization interferences can be relieved by adding
an alkali salt as an ionization suppressant.
Most metals, as well as fluoride, chloride, and
ammonium, will increase the titanium signal.
108
1
0.8
Absorbance
Flame:
reducing
HCL Current:
10 mA
PMT Voltage:
400 V
Slit Width:
0.2 nm
1.7 mg/L
Working Range:
1-300 mg/L
ionization.
0.6
0.4
0.2
0
0
100
200
300
400
74
W
Analytical lines:
Tungsten
255.1 nm
268.1 nm
400.9 nm

Parameter
Standard Solutions
1
0.8
Absorbance
Flame:
reducing
HCL Current:
13 mA
PMT Voltage:
450 V
Slit Width:
0.2 nm
Characteristic
Concentration:
7.9 mg/L
Working Range:
10-1500 mg/L
the 400.9 nm line is not the most

sensitive line, but it affords a good S/N ratio.
0.6
0.4
0.2
0
Dissolve 1.000 g of tungsten metal in 20 mL HNO3

and 10 mL HF in a PTFE vessel. Dilute to 1 L to
give a 1000 ppm W solution.
OR
Dissolve 8.975 g of Na2WO4.2H2O (sodium

tungstate) in 20 mL H2O. Mix with 10 mL of 10%
w/v NaOH. Dilute to 1 L to give a 5,000 ppm W
solution.
Interferences
High levels of some mineral acids combined with
the presence of some elements (eg. Co, Cu, Fe,
and K) can cause interference. Matrix matching of
all solutions is recommended.
109
500
1000
1500
2000
92
U
Analytical lines:
Uranium
358.5 nm
351.5 nm
348.9 nm

Parameter
reducing
10 mA
450 V
0.2 nm
180 mg/L
400 - 30000 mg/L
Standard Solutions
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
0.6
0.4
0.2
Dissolve 21.10 g of uranyl nitrate hexahydrate

(UO2(NO3)2 6H2O) in water. Dilute to 1 L to give a
10,000 ppm U solution.
WARNING: U is a radioactive element,
and should be handled and stored with
appropriate care. Personal protective
equipment is also advised.
Interferences
Ionization interferences can be countered by
adding 0.1 % of an ionization suppressant (eg.
alkali salt).
In a complex matrix with excesses of other
elements (eg. Al, Co, Fe, Ni, Pb), the U signal can
be increased. Therefore, matrix matching is
required for such matrices.
110
0
0
5000
10000 15000 20000

25000
23
V
Analytical lines:
Vanadium
318.4 nm
306.6 nm
370.4 nm

Parameter
Standard Solutions
Dissolve 1.000 g of Vanadium metal granules in a
minimum volume of HNO3. Dilute to 1 L with 1%
v/v HNO3 to give a 1000 ppm V solution.
Interferences
Ionization interferences can be controlled by the
addition of an ionization suppressant (alkali salt)
to all solutions.
High levels of Al, Fe, Ti, ammonium and H2SO4 can
increase the signal. Some interference can be
reduced by adding an excess of Al. Matrix
matching of all solutions is advised.
111
(318.4 nm upper; 306.6 nm lower line)
1
0.8
Absorbance
Flame:
reducing
HCL Current:
10 mA
PMT Voltage:
308 V
Slit Width:
0.2 nm
Characteristic
Concentration:
0.44 mg/L
Working Range:
0.5-100 mg/L
ionization.
0.6
0.4
0.2
0
0
25
50
75
100
70
Yb
Analytical lines:
Ytterbium
398.8 nm
364.4 nm
246.5 nm

Parameter
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
reducing
(rich, red cone 1-2 cm)
5 mA
350 V
0.2 nm
0.07 mg/L
0.04-15 mg/L
1
0.8
Absorbance
Flame:
0.6
0.4
0.2
0
0
Standard Solutions
Interferences
The presence of Al, Fe, Si, and HF can all decrease
the Yb signal, so matrix matching is advised for
such matrices.
Yb is one of the Lanthanide elements, which are
patterns.
112
15
Absorbance vs. HCL current
0.6
Absorption
Dissolve 1.139 g of ytterbium oxide (Yb2O3) in a

v/v HCl to give a 1000 ppm Yb solution.
5
10
0.4
0.2
0
4
8
10
HCL current (mA)
12
39
Y
Analytical lines:
Yttrium
410.2 nm
407.7 nm
414.3 nm

Parameter
reducing
10 mA
400 V
0.2 nm
5.5 mg/L
2-500 mg/L
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.6
0.4
0.2
0
0
Standard Solutions
Dissolve 1.270 g of Y2O3 (yttrium oxide) in
v/v HCl to give a 1000 ppm Y solution.
Interferences
To reduce ionization interferences, add an
ionization suppressant (alkali salt) to all solutions.
The signal is depressed by the presence of Al, K
and some mineral acids. Matrix matching of all
solutions is recommended.
113
500
1000
1500
2000
30
Zn
Analytical lines:
Zinc
213.9 nm
307.6 nm

Parameter
A b s o r p tio n S e n s iti v ity
air/acetylene
oxidizing
5 mA
422 V
0.2 nm
1
0.8
A b s o rb a n c e
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Characteristic
Concentration:
Working Range:
0.008 mg/L
0.01 - 2 mg/L
0.6
0.4
0.2
0
Standard Solutions
Dissolve 1.000 g of zinc granules in a minimum

volume of 1:1 HCl. Dilute to 1 L with 1% v/v HCl
to give a 1000 ppm Zn solution.
At the 213.9 nm analytical line, non-atomic

absorption can cause interference. The use of a
background correction method is advised.
There are no significant chemical interferences to
note.
1 .6
A b s o r p tio n S e n s iti v ity v s . Fu e l flo w R a te

0.3
A b s o rb a n c e
Interferences
0.4
0 .8
1 .2
0.2
0.1
0
0.8
1
1 .2
1 .4
1 .6
A b s o r p tio n S e n s iti v ity v s . La m p C u r r e n t

0.4
A b s o rb a n c e
0.3
0.2
0.1
0
0
114
10
15
20
40
Zr
Analytical lines:
Zirconium
360.1 nm
303.3 nm
352.0 nm

Parameter
reducing
10 mA
450 V
0.2 nm
11 mg/L
10-2000 mg/L
1
0.8
Absorbance
Flame:
HCL Current:
PMT Voltage:
Slit Width:
Working Range:
0.6
0.4
0.2
Standard Solutions
Dissolve 1.000 g of zirconium metal in 10 mL of

HF and 10 mL of H2O in a Teflon vessel. Slowly
add 20 mL of HNO3 dropwise. Allow the reaction
to diminish between additions. Dilute to 1 L to
give a 1000 ppm Zr solution.
Interferences
Reduce ionization interferences by adding an
ionization suppressant (an alkali salt) to all
solutions.
Oxide formation in the flame is common and
results in calibration curve roll-over at higher
concentrations. To alleviate this problem and
improve calibration curve linearity, add 0.2% Al
and 1% HF to all solutions. As well, the
interferences can also be reduced by using a more
oxidizing flame. However, sensitivity will then be
compromised.
115
500
1000
1500
2000
116
117
118
7 - Practical Applications FAAS
Chapter 7:
Practical Applications - FAAS
Marine
Water
Biological
Food
Agricultural
Petrochemical
Miscellaneous
119
Application #AA-17
The Determination of Metal Cations in Sea Water by Flame AAS
Classification: Marine
Sample matrix: Sea water
Introduction
Elements of Ca, K, Li, Mg, Na,

interest: Rb, Sr
This application describes the procedure and methods for

determining common metal cations in sea water.
Reagents
Needed
Artificial seawater will be made from the following: calcium

carbonate, CaCO3; magnesium oxide, MgO; potassium carbonate,
K2CO3; sodium chloride, NaCl; (1:1) hydrochloric acid, HCl.
Standard
Solutions
Weigh out 0.999 g of CaCO3, 2.974 g of MgO, 1.414 g of K2CO3,

and 25.41 g of NaCl. Transfer to a 1 L volumetric flask, and
dissolve in a minimum volume of the HCl. Dilute to 1 L with
deionized water to give a solution of 10,000 ppm Na, 1250 ppm
Mg, 400 ppm Ca, and 400 ppm K.
Sample
Preparation
Filter all seawater samples through 0.45 micron Millipore filters.

Samples analyzed for Na, Mg, Ca, and K will need to be diluted to
be brought into the linear working range.
Samples analyzed for Rb, Sr, and Li can be analyzed directly,
without dilution.
Guideline
Instrument
Parameters
Refer to Chapter 6, FAAS Analytical Data Sheets, for guideline

parameters for analyzing each element.
120
Application #AA-18
The Determination of Common Metals in Natural Water
by Flame AAS
Classification: Water
Sample matrix: Natural water
Introduction
Elements of Ca, Cu, K, Li,

interest: Mg, Mn, Na, Sr,
Zn

determining common metals in natural water samples.
Reagents
Needed
2.497 g of dried CaCO3 (calcium carbonate)

1.000 g of copper metal wire
1.907 g of dry potassium chloride (KCl)
5.324 g of lithium carbonate (Li2CO3)
1.000 g Mg metal strip
1.000 g of manganese metal wire
2.542 g of dry NaCl salt (sodium chloride)
2.415 g of Sr(NO3)2 (strontium nitrate)
1.000 g of zinc granules
11.730 g of La2O3 (lanthanum oxide)
conc. hydrochloric acid (HCl) and nitric acid (HNO3)
Standard
Solutions
All solutions can be used directly as prepared (according to

instructions in Chapter 6, FAAS Analytical Data Sheets), expect for
Ca and Mg, which require further dilution.
To both Ca and Mg solutions, dilute with the 5% w/v La and conc.
HCl to give a solution with 0.25% w/v La and 5% v/v HCl.
Sample
Preparation
Filter all water samples through 0.45 micron Millipore filters, to

remove particulate matter and to avoid blockage of capillary
tubing.
Prepare a reagent blank for use in the Ca and Mg analyses.
Guideline
Instrument
Parameters
Refer to Chapter 6 for guideline parameters for analyzing each

element.
For the Ca and Mg analyses, it is required to also measure blank
solutions of the reagents used (La and HCl).
121
Application #AA-19
The Determination of Copper and Zinc in Blood Serum and Plasma
by Flame AAS
Classification: Biological
Sample matrix: Blood serum, blood plasma
Introduction
Reagents
Needed
Standard
Solutions
Sample
Preparation
Guideline
Instrument
Parameters
Elements of interest: Cu and Zn
This application describes the procedure and methods for determining

copper and zinc in blood serum and plasma samples.
Normal levels for Cu and Zn in blood serum are 0.7-1.4 ppm for Cu,
and 0.5-1.5 for Zn.
1.000 g of copper metal wire
1.000 g of zinc granules
1:1 nitric acid (HNO3), 1:1 hydrochloric acid (HCl)
Glycerol
Prepare the standards for Cu and Zn according to Chapter 6, FAAS
Analytical Data Sheets.
The standards are to be prepared in glycerol to create similar
viscosity properties in the standards that are present in the samples.
Dilute 1 mL of the original blood sample with 5 mL water. Centrifuge
the sample for 10 minutes to separate out the protein matter. The
supernatant fluid can be used directly for the analysis.
Refer to Chapter 6, FAAS Analytical Data Sheets.
122
Application #AA-20
The Determination of Iron and Nickel in Vegetable Oil
by Flame AAS
Classification: Food
Sample matrix: Vegetable oil
Introduction
Reagents
Needed
Standard
Solutions
Sample
Preparation
Guideline
Instrument
Parameters
Elements of interest: Fe and Ni
This application describes the procedure and methods for determining

iron and nickel in vegetable oil samples. The advantages of this
method are that the sample and standard preparations are simple
and quick. An alternative method is to char and ash the sample, but
it is a tedious and very long process. However, it is a more accurate
alternative.
Typical levels of Fe and Ni in vegetable oil are 3.8 ppm Fe, and 17
ppm Ni.
This method can also be applied to analyze for several other
elements, including Cu, Ca, K, Mg, Mn, Na, and Rh.
1.000 g of Fe metal strip
1.000 g of Ni metal wire
1:1 nitric acid (HNO3), 1:1 hydrochloric acid (HCl)
Glycerol
An organic solvent: MIBK, kerosene, acetone, ethanol, or isoamyl
acetate/methyl alcohol
The preparation of the standards is different from the procedure
described in Chapter 6, FAAS Analytical Data Sheets. Sample
viscosity is a major factor in these analyses. To compensate for this,
the standards should all be made with glycerol to simulate the
viscosity properties that are found in the oil samples.
200 ppm Fe standard solution:
Dissolve 0.2020 g of dried ferric cyclohexane butyrate/in 5 mL of the
organic solvent used to prepare the sample (eg. kerosene) and 2 mL
of 2-ethylhexanoic acid). Heat gently to aid dissolution. Make up to
100 mL with the organic solvent.
450 ppm Ni standard solution:
Repeat the above procedure, substituting 0.3080 g of dried nickel
cyclohexane butyrate for the iron compound.
When working solutions are made, be sure to dilute with an
appropriate volume of glycerol to simulate the viscosity of the oil
sample.
Dissolve 10 g of the vegetable oil sample in 100 mL of one of the
organic solvents listed above (eg. kerosene).

It is required to measure blanks prepared from the organic solvent
used (eg. kerosene) and glycerol.
123
Application #AA-16
The Determination of Potassium in Fertilizer by Flame AAS
Classification: Agricultural
Sample matrix: Fertilizer
Introduction
Elements of K
interest:

determining potassium in fertilizers. Due to the expected high
levels of K, the less sensitive analytical line at 404.4 nm will be
used. This avoids the need to dilute solutions excessively.
Reagents
Needed
Distilled water.
Standard
Solutions
Sample
Preparation
Refer to Chapter 6, FAAS Analytical Data Sheets, for information on

preparing K standard solutions.
Guideline
Instrument
Parameters
Weigh out 2.5 g of the dried fertilizer sample, and transfer it to the
250 mL volumetric flask. Add 200 mL of distilled water to the
flask, and bring to a boil. Boil for at least half an hour. Cool the
mixture, and then make up to the mark with deionized water.
Remove the particulate matter by allowing the mixture to stand
overnight or by filtration. Transfer a 25mL aliquot of the liquid to a
100 mL volumetric flask, and make up to the mark. For very
concentrated samples, greater dilutions may be necessary.
124
Application #AA-16A
The Determination of various Metals in Plant by Flame AAS
Classification: Agricultural
Sample matrix: Plant Material
Introduction
Elements of Al, Ca, Fe, K,

interest: Mg, Mn, Na, Zn
This application describes the procedure and method for

determining various metals in plant material digested in nitric and
perchloric acids.
Reagents
Needed
70% nitric
1.000 g Al
2.497 g of
1.000 g of
1.907 g of
1.000 g of
1.000 g of
2.542 g of
1.000 g of
acid (HNO3) and 70% perchloric acid (HClO4)

metal wire
dried CaCO3 (calcium carbonate)
Fe metal strip
dry potassium chloride (KCl)
magnesium metal strip
manganese metal wire
dry NaCl salt (sodium chloride)
zinc granules
Standard
Solutions
All solutions can be used directly as prepared (according to

instructions in Chapter 6, FAAS Analytical Data Sheets). Stock
standards of each element should be 1000 ppm.
Prepare all working standards (from 0.5-40 ppm), in 4% HClO4.
Sample
Preparation
Carry out the following acid digestion in a fume hood, and behind a
blast shield. Wear appropriate personal protective equipment,
including gloves and protective eyewear.
Accurately weigh about 0.25 g of the plant tissue in a 19 mm (27
mL) test tube. Put the tube in an aluminum test tube block on a
hot plate. Add 1 mL 70% HNO3 and 4mL of HClO4. Heat for 2
hours at 120 C. Ramp the temperature to 180 C over 3 hours to
drive off the nitric acid. The digestion is complete when white
fumes evolve (from the HClO4). It is very dangerous to boil the
HClO4 to dryness.
Quantitatively transfer the test tube contents to a 25 mL volumetric
flask and make up to the mark with water.
Guideline
Instrument
Parameters
Refer to Chapter 6 for guideline parameters for analyzing each

element.
125
Suggested concentrations of standards (ppm)

ELEMENT:
Al
Ca
Fe
K
Mg
Mn
Na
Zn
Calculations
Standard #1
5
10
2
5
5
1
1
0.5
Standard #2
10
20
5
10
10
3
2
1
Standard #3
20
40
10
20
20
5
5
2
A moisture factor is used in the final calculations to compensate for

the mass of water lost from the plant tissue upon heating. The
moisture factor is determined by accurately weighing about 2 g of
the sample, heating it in an oven at 80 C for 1 day, and then
reweighing the sample.
Moisture factor = (mass after heating)/(mass before heating)
126
Application AA-7
Preparation of Petrochemical Samples for Atomic Absorption
Spectrometric Analysis
Introduction:
Atomic absorption spectrometry (AAS) has been used in three major areas for the
elemental analysis of petroleum products: crude oil, fuels and lubricants, and wear metal
analysis [13]. Flame AAS is recommended for the determination of higher concentration
metals and graphite furnace techniques for trace metals.
Sample Preparation:
Three sample preparation methods are currently employed for the determination of metals
in petroleum products:
1. Dilution of the petrochemical sample in an organic solvent such as methyl isobutyl
ketone (MIBK) or a mixed solvent system such as toluene and glacial acetic acid.
2. Ashing of the sample and dissolution with an appropriate acid.
3. Acid digestion.
Dilution
Some petrochemical samples can be directly nebulized into a flame or injected into a
graphite furnace for analysis. However, when the sample is too volatile, too viscous or the
content of the element of interest is too high in the sample, dilution is required.
The dissolution of oil/fuel samples in organic solvents is fast and simple. The degree of
dilution and choice of solvent will depend on the nature of the sample, the expected level of
the element of interest and the background signal appearing during atomization. The
volatility of the solvent plays an important role in the selection of drying conditions and the
use of an autosampler. Where evaporation is a problem, the sample container should be
sealed and the sample dispensed manually and/or a less volatile solvent employed. Mixed
solvent and emulsion systems allow the use of inorganic salts for the preparation of
standards and calibration curves.
Table 7.1 lists a number of organic solvents commonly used in oil/fuel analysis together
with their boiling points which can be used as a guide for setting the drying conditions for
GFAAS. With regular furnace technique (i.e. not a fast drying furnace technique), most
solvents can be dried at a temperature below their boiling point. For a 20 to 40 l sample,
a drying step at temperature setting of 80 to 90% of the boiling point for 30 to 60 seconds
has been found to be adequate in most analyses. The dispensing characteristics of the
solvent should be studied prior to analysis in order to determine the maximum injection
volume. The dispensed volume varies depending on the surface tension of the solvent.
Generally injection volumes between 20 and 40 l are used.
127
Table 7.1. Solvents commonly used as diluents in AAS
Solvent
Boiling point
(C)
Kerosene
175 - 325
Tetralin
207
Shellsol T
186 - 214
DIBK
166
Cyclohexanol
161
3-heptanone
148
m-xylene
139
Iso-amylalcohol
132
MIBK
118
Toluene
112
2-methy, propan-1-ol
108
Isopropanol
83
Carbon tetrachloride*
77
Tetrahydrofuran*
65
Chloroform*
62
* Not suitable for flame AAS.
Specific
gravity
0.78
0.97
0.75
0.81
0.96
0.82
0.80
0.81
0.79
0.86
0.78
0.78
1.59
0.88
1.47
Ashing of the oil sample

The procedure for ashing oil is based on the method developed by Milner, Glass, Kirchner
and Yurick [14]. The procedure for the analysis of iron is described as follows.
The oil sample (2 g) was treated with concentrated sulphuric acid (2 g) and heated on a
hot plate until dry in a vycor crucible. The crucible was transferred to a muffle furnace and
ashed at 550C until all traces of carbon were removed. This was indicated by the absence
of a charcoal color and took about 30 minutes. After cooling the sample was treated with
concentrated hydrochloric acid (6 ml) and filtered through a Whatman filter paper. The
solution was then made up to 25 ml with pure water.
This ashing method will give total metal content which represents the sum of particulate
and soluble metal. However, volatile metals such as lead and selenium will be lost during
the ashing process.
Acid digestion
Acid digestion of oil samples permits the retention of volatile elements that may be lost
during ashing or masked by background interference. During the past years, microwave
oven assisted acid digestion has gained increased popularity. This technique makes acid
digestion much faster and simpler. References on oil sample digestion with acids can be
found in the literature.
128
Application Notice #AA-14

The Determination of Silicon by Flame AAS
Introduction:
Flame AAS with a nitrous oxide/acetylene flame is often a favorable method for the
determination of silicon because of its ease of use and high sensitivity. However, the
sensitivity and measurement precision vary quite drastically depending on the
spectrometer used as well as the flame and chemical conditions. This application notice
summarizes the parameters that are critical to the optimization of flame AAS for the
analysis of silicon.
Important Factors to be Considered:

1. The Flame and its Stoichiometry:
The sensitivity for silicon depends significantly upon the stoichiometry of the nitrous
oxide/acetylene flame. The best sensitivity is obtained with a fuel-rich flame. For
example, using nitrous oxide and acetylene flow rates of 11 and 5.0 L/min. respectively,
the absorbance of a 100 ppm silicon solution was about 0.5. However, if the acetylene flow
rate was reduced to 4.0 L/min. the absorbance of a 1000 ppm silicon solution might not be
detected. The operator must carefully optimize the fuel rates of his or her system to
ensure maximum performance. The data supplied by the manufacturer can be used as a
reference, however, because many commercially available instruments (other than the AI
1100) rely on a gas flow calibration the values displayed by the instrument may not be the
actual flow rates.
2. Bandwidth:
The most sensitive line for silicon is at 251.6 nm, however, the silicon spectrum around this
line is quite complicated. A narrow bandwidth is essential to resolve this line and thus
achieve the best possible sensitivity and most linear calibration curve. It has been proven
with experiments that the use of a bandwidth higher than 0.7 nm will significantly decrease
the sensitivity and degrade the linearity of the calibration curve. The optimum signal-tonoise ratio and an acceptable linearity can be obtained using a bandwidth of 0.2 nm.
Slightly further improvement in linearity is observed with a smaller bandwidth, however,
the increased PMT voltage which is required results in poorer signal-to-noise ratios.
3. The Acidity of the Sample:
The determination of silicon in a nitrous oxide/acetylene flame is virtually free of
interferences, however, the fact that silicon is rapidly precipitated from acid solutions can
cause difficulties. It is recommended that any silicon solutions be prepared in basic media.
In addition, the burner height and lamp current should also be optimized. It is easiest to
use a relatively highly concentrated solution at the beginning of the optimization to ensure
a signal can be seen.
129
Typical Instrument Conditions:

Below are some typical conditions for silicon determination with a nitrous oxide/acetylene
flame using Aurora Instruments AI 1100 Atomic Absorption Spectrometer:
Parameter
Bandwidth
Lamp Current
Wavelength
PMT voltage
Integration time
Acetylene flow rate
Nitrous oxide flow rate
Suggested Setting
0.2 nm
12 mA
251.6 nm
336 V
5 seconds
5.0 L/min.
preset
130
131
References
References
1.
Alkemade, C.Th.J. and Herrmann, R., Fundamentals of Analytical Flame

Spectroscopy, Adam Hilger, New York, 1979.
2.
Lvov, B.V., Atomic Absorption Spectrochemical Analysis, Adam Hilger, London, 1970.
3.
Mavrodineanu, R. and Boiteux, H., Flame Spectroscopy, John Wiley and Sons, New
York, 1965.
4.
Price, W.J., Spectrochemical Analysis by Atomic Absorption, Heydon & Son Ltd,
London, 1979.
5.
Rains, T.C., Atomic Absorption Spectrometry-Theory, Design and Application, S.J.

Haswell, ed., Elsevier, New York, 1991.
6.
Van Loon, J.C., Analytical Atomic Absorption Spectroscopy- Selected Methods,

Academic Press, New York, 1980.
7.
Welz, B. and Sperling, M., Atomic Absorption Spectrometry, 3rd. edition, Wiley-VCH,
New York, 1999.
8.
Cresser, M.S., J. Anal. At. Spectrom., 8, 270,1993.
9.
Holcombe, J.A. and Harnly, J.M., Anal. Chem., 57, 1983, 1985.
10. Williams, R.R., Anal. Chem. 63, 1638, 1991.

11. Smith, S.B. and Hieftje, G.M., Appl. Spectrosc., 37, 419, 1983.
12. Fernandez, F.J., Bohler, W., Beaty, M.M. and Barnett, W.B., Atom. Spectrosc., 2, 73,
1981.
13. Buell, B.E., Appl. At. Spectrosc., 2, 53, 1978.
14. Milner, O.I., Glass, J.R., Kirchner, J.P. and Yurick, A.N., Anal. Chem., 24, 1728, 1952.
132
References
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COOKBOOK Book One

Updated: Jan 2002

Chapter 3: Background Correction

Chapter 4: Comparison of Analytical Techniques

Chapter 5: Standard and Sample Preparation

Chapter 6: FAAS Analytical Data Sheets

Chapter 7: Practical Applications - FAAS

AI 1200 Cookbook - Book One

AI 1200 Cookbook - Book One

A sample has an unknown amount of a known element (e.g. the sample is

AI 1200 Cookbook - Book One

There are three main techniques of atomic absorption spectrometry: Flame

Flame Atomic Absorption Spectrometry (FAAS)

AI 1200 Cookbook - Book One

Electrothermal atomization using a graphite furnace provides these

Graphite Furnace Atomic Absorption Spectrometry (GFAAS)

AI 1200 Cookbook - Book One

Vapor Hydride Generation

AI 1200 Cookbook - Book One

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AI 1200 Cookbook - Book One

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AI 1200 Cookbook - Book One

AI 1200 Cookbook - Book One

AI 1200 Cookbook - Book One

Have 100% efficient light throughput. In other words, if there is no

AI 1200 Cookbook - Book One

AI 1200 Cookbook - Book One

Figure 2-1 Schematic diagram of a Czerny-Turner monochromator

AI 1200 Cookbook - Book One

Figure 2-2 Schematic diagram of an Ebert-Fastie monochromator

Figure 2-3 Schematic diagram of a Littrow monochromator

AI 1200 Cookbook - Book One

AI 1200 Cookbook - Book One

In other words, finding the optimum slit width is a compromise between

Atomizes 100% of the sample delivered to it.

AI 1200 Cookbook - Book One

AI 1200 Cookbook - Book One

AI 1200 Cookbook - Book One

AI 1200 Cookbook - Book One

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AI 1200 Cookbook - Book One

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AI 1200 Cookbook - Book One

3 - Background Correction Methods

AI 1200 Cookbook - Book One

3 - Background Correction Methods

frequency at which the peaks are measured;

The Frequency of Measurement

AI 1200 Cookbook - Book One

3 - Background Correction Methods

For a GFAAS system, a 10 Hz sampling frequency can produce significant errors in

AI 1200 Cookbook - Book One

3 - Background Correction Methods

Deuterium (D2) Background Correction

AI 1200 Cookbook - Book One

3 - Background Correction Methods

Figure 3-1 How D2 background correction works

AI 1200 Cookbook - Book One

3 - Background Correction Methods

Figure 3-1 (continued) How D2 background correction works

AI 1200 Cookbook - Book One

3 - Background Correction Methods

Smith-Hieftje (S-H) Background Correction