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AA or ICP ? W h i c h Te c h n i q u e I s t h e
Best for Yo u r L a b o r a t o r y ?
The information here is very simplistic and is meant as an overview of AA and ICP. More
detailed documents related to AA and ICP are available.
AA vs. ICP
AA and ICP are both techniques for determining what elements and at what concentrations are
in a solution. Atomic Absorption (AA) is one process, while ICP (Inductively Coupled Plasma)
uses the process of atomic or ionic emission. Thus, AA uses absorption of light and ICP uses
emission of light. A simple example of emission can be seen when a pot of water boils over on
to a flame while cooking. The flame will change color and emit a yellowish-orange color from
sodium (Na) or salt in the tap water. Another example of the emission processes are fireworks.
Each different, bright color in the sky is the result of emission from different elements in the
periodic table. Every element can have this absorption/emission process depending on the
energy. The color or wavelength can help determine what element is present. The intensity or
brightness helps determine the concentration.
AA
Figure 1 is the basic configuration of an AA unit. The unit consists of a light source called a
hollow cathode lamp (HCL). Generally, every element to be analyzed requires its own HCL.
Multi-element HCLs exist, but with these it is best for the elements to have characteristics that
are similar like sodium (Na) and potassium (K), which are Group 1 alkali metals, or magnesium
(Mg) and calcium (Ca), which are Group 2 alkaline-earth metals.
Flame is typically used for measuring in the part per million range (ppm or mg/L), while
graphite furnace is for measuring in the part per billion range (ppb or ug/L). The
monochromator is used to separate the colors or wavelengths of light so the detector can
measure the intensity. The monochromator uses a grating to isolate a particular wavelength, for
example, copper at 324.8 nm. AA is typically a single-element technique, meaning one
element is measured at a time. Thus, in a multi-element analysis, all samples are measured for
copper, and then all samples are measured for iron, etc. The signal processor and the display
are your computer and monitor, respectively.
Flame AA generally uses two different types of flames as can be seen in Figure 2. An
air/acetylene flame has a temperature of about 2300 oC, while the nitrous oxide/acetylene flame
has a temperature of about 3000 oC. As can be seen in the periodic table below, elements with
a dark green triangle in the bottom right-hand corner use an air/acetylene flame, while
elements with a dark blue triangle in the bottom right-hand corner use a nitrous
oxide/acetylene flame. The burner head for the air/acetylene flame is standard, while the
burner head for the nitrous oxide/acetylene flame is optional.
There are two other techniques used for specific elements. The techniques utilize either a
hydride vapor generator (HVG) or a mercury vapor unit (MVU), which are optional accessories.
The HVG elements have a light green triangle in the bottom right-hand corner. Those elements
include arsenic (As), selenium (Se), and antimony (Sb), as well as mercury (Hg). The MVU can
also analyze mercury as shown in light blue. The difference between the HVG and MVU is that
the HVG can be used with an autosampler, but the MVU is strictly manual.
ICP
Figure 3 is the basic configuration of an ICP. The sample is introduced to the plasma (10,000
o
K) by a nebulizer. The standard nebulizer is a pneumatic nebulizer which uses gas (in this
case argon) to turn the liquid into an aerosol. Flame AA uses a similar pneumatic nebulizer.
There is also an optional ultrasonic nebulizer for increasing sensitivity (see Detection Limits
below).
Sample Throughput
Flame analysis takes about 5-10 seconds without an autosampler. Adding an autosampler
increases analysis time because there is more tubing the sample and the rinse must travel
thru. Consequently, time could double or triple. Adding a hydride vapor generator in between
the AA and autosampler adds more tubing, causing analysis time to be between 30 and 60
seconds. Graphite furnace AA is typically about 2-3 minutes because of various heating stages
called 1) drying, 2) ashing, 3) atomization, and 4) cleaning depending on the samples. ICP
measurement time is typically 30-60 seconds. Again, will the sampling be manual or
automated? Adding an autosampler will increase analysis time 30 to 60 seconds.
As a general rule, if analyzing 6 elements or less, then AA is the best method. For analyzing 7
elements or more, move to ICP. Also, the scientist must determine how many samples per day
will need to be analyzed. As the sample volume grows and the number of elements increases
then ICP may be the more appropriate technique.
Interferences
There are many types of interferences in AA and ICP but most can be corrected. Chemical
interferences are more common in AA, but many can be eliminated with chemical or matrix
modifiers. Because ICP has a very high temperature at 10,000 oK all the chemical bonds are
broken and there are no chemical interferences.
Ionization interferences can be a problem in Group II elements when using a nitrous
oxide/acetylene flame for AA. By adding Group I elements such as Cs or K, which are easily
ionized and thus a source of electrons, to the samples, the Group II element will shift the
equilibrium from the ionic form to the atomic form. Thus, the technique is called atomic
absorption, not ionic absorption. ICP already contains a very large number of electrons,
meaning ionization interferences are essentially eliminated.
Spectral interferences in AA are limited because of the large line spacing of the absorption
profile. In AA the “slit width” or bandwidth is set in the nanometer (nm) range. With ICP, as
mentioned above, there is a database of a least 110,000 lines, which may overlap wavelengths
or contain a line very close to the target element. The ICPE-9000 has a resolution of 5
picometers (pm), which is about 1000 times smaller than that used with AA. The advantage of
the ICPE-9000 database is “Method Diagnosis Assistant” software, which can analyze
overlapping emission lines from different elements and use another wavelength for the target
element(s) in the sample. The “Method Diagnostic Assistant” is for post-run analysis. There is
also a “Method Development Assistant” used prior to analysis to avoid these issues and to
select the correct wavelengths upfront.
Physical interferences are related to the solvent and matrix which ultimately affect droplet size.
AA has fewer physical interferences because the droplet sizes are larger and the nebulizer
efficiency is higher at about 5%. ICPs require smaller droplets and less sample (water vapor)
or the plasma will be extinguished. A typical pneumatic nebulizer is only about 1% efficient.
ICPs have many different types of nebulizers available depending on the solvent and matrix.
Torch orientation also plays a role in the physical interferences with respect to ICP as shown in
Figure 6. For samples containing high solids or salt matrices, plasma gas flow can be
disrupted, resulting in poor reproducibility. A radial orientation means the solids coming out of
the injector tip (red circle) will travel in the direction of gravity and lay on the bottom of the
quartz torch, and plasma gas flow will be altered. The ICPE-9000 utilizes a vertical orientation,
minimizing interference of the flow dynamics of the plasma.
Background Correction
The AA-7000 utilizes two types of background correction: deuterium (D2) and Self-Reversal
(SR), which cover 190-430 nm and 190-900 nm, respectively, or the entire analytical range.
The AA-7000 can perform a 1 point shifted wavelength correction. The ICPE-9000 can utilize a
1 or 2 point shifted wavelength correction. Shifting the background to the left, right, or both
from the target wavelength corrects for the background.
Cost
Initial purchase price has flame AA the least expensive, followed by graphite furnace AA,
followed by axial viewing ICP, and then dual-view ICP.