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Fundamental Research in
ICP-OES and ICPMS
Fundamental
E
xciting research progress is be-
ing made to quantitatively link
i fundamental processes and prac-
research in ICP-OEStical ICP analysis (1-6). The results of
such fundamental research are used to
A single drop of sample aerosol under-
goes several processes as it travels through
the plasma. As the drop is heated, solvent
evaporates and leaves behind a particle of
analyte. After the particle is sufficiently
and ICPMS can improve practical analysis. Investigation heated, it begins to vaporize (or perhaps
and modeling of space charge effects have explode). Molecules or atoms are pro-
result in improved led to the development of ICPMS instru- duced; these are then atomized or ionized
ments that are less susceptible to matrix and diffuse rapidly. A small fraction of the
performance, effects. Plasma modeling has resulted in atoms and ions become excited and emit
improvements in practical analysis of light for ICP-OES. A minuscule fraction of
reliability, accuracy, semiconductor gases and development of the analyte ions (often less than one in a
helium plasmas for ICPMS. Some manu- million) reach the detector of the mass
and ease of use facturers claim that their instrument is spectrometer. Each of these processes is
better than others on the basis of funda- critically dependent on plasma characteris-
mental plasma properties such as electron tics, including gas temperature, electron
number density. concentration, electron temperature, and
Further improvements are unlikely to energy transport rates.
be gained from purely empirical approaches. Why is it so difficult to gain an accu-
One of the biggest dangers in ICP analy- rate understanding of the fundamental
sis today is the possibility of obtaining processes? The answer to this question
inaccurate results without any indication has several components. The processes
of a problem (3). Results from funda- overlap in time and space. Also, more than
mental research are needed to improve 106 polydisperse aerosol drops of sample
analysis accuracy, develop practical diag- typically enter the plasma each second.
nostics and intelligent instruments, and Drops of various sizes complete desolva-
reduce operator skill requirements. tion at different locations in the plasma.
Shorter sample washout times, reduced Atoms and ions produced from small
nebulizer-related noise, more efficient, drops, together with vaporizing particles
robust ion transport in ICPMS, and bet- and desolvating drops, can all be in the
ter precision are also likely to be observation volume. Even for a single
achieved. drop, particle vaporization, atomization,
and ionization occur concurrently, al-
though at different rates.
Converting samples into
signals The plasma is also spatially heteroge-
Four sets of processes control ICP signals: neous, and simple equilibrium-based mod-
plasma dynamics, aerosol generation and els are often inadequate to quantitatively
transport, production of ions (and atoms), describe the ICP. Energy is coupled mainly
and excitation or ion transport from the ICP into a donut-shaped region near the load
to the detector. Inaccuracy in practical anal- coil. Heat and chemical species are trans-
ysis can occur when the composition of the ported from this "energy addition region"
sample solvent (acid identity, concentra- to the center of the plasma, leading to large
John W. Olesik tion, organic solvent) and the sample itself temperature and concentration gradients. If
Ohio State University (the matrix) affects these processes. equilibrium could be assumed in the ICP, a
simple set of equations would describe ex- are up to 2000 K hotter than gas tempera- tions in solvent composition (including
citation and ionization. Instead, more com- tures (7), and the electron concentration acid identity and concentration) appear to
plex kinetic models are needed. calculated by using the measured electron originate primarily in the aerosol genera-
Finally, the effect of the sample on temperature is 3 to 10timeslower than die tion and transport processes.
plasma characteristics must be considered. measured electron concentration. For the commonly used pneumatic
Although less than 50 W of power is typi- Because energy is coupled mainly into nebulizers, the key design parameters
cally needed to convert the sample into free electrons in the ICP (the much more mas- have been empirically related to aerosol
atoms and ions, the sample can significantly sive ions respond too slowly to die oscillat- drop size (9). The primary aerosol pro-
affect die properties of the plasma. Emis- ing magnetic fields), energy must be trans- duced by the nebulizer is modified as it
sion intensity is a function of the number of ferred to Ar atoms via collisions. Models passes through the spray chamber be-
analyte ions in the observation zone and the are now being developed to account for the cause of evaporation, impact and drop
fraction excited, and ICPMS signals are a imperfect transfer of energy and dissimilar shattering, inertial deposition, and gravita-
function of the number of analyte ions in electron and gas temperatures. tional settling.
die ICP and the fraction of ions that reach Barnes and co-workers (8) have devel- For a particular pneumatic nebulizer
the detector. Therefore, single measure- oped fluid dynamics-based models to de- and spray chamber, the gas flow rate and
ments of analyte emission or MS signal scribe the spatial structure of the ICP sample uptake rate are the key variables
alone are insufficient to investigate any one starting from input power, torch and load that control drop size and transport effi-
of the fundamental processes involved in coil geometry, and gas flow rates. These ciency into the ICP. Smaller primary aero-
ICPMS. Laser-induced fluorescence mea- models, although not entirely accurate, sol drops are produced as the gas flow rate
surements can provide information on the are now being used to design practical is increased, whereas changes in uptake
number of analyte ions in a given volume of ICPs and are being modified to include rate have a smaller effect on average drop
the ICP; a combination of emission and nonequilibrium effects. size. The spray chamber removes most
fluorescence can be used to determine Aerosol generation and trans- large drops before the aerosol enters the
numbers and excitation of ions. port. Liquid samples must be converted ICP; however, the transport efficiency of
Plasma dynamics. The plasma con- into aerosol drops that are small enough even small drops is less than 10% at sample
verts the sample into free ions (for ICP- to be vaporized in the ICP. The total vol- uptake rates of 1 mL/min. As a result, typi-
MS) or free, excited atoms or ions (for ume of liquid entering the plasma must cally less than 2% of the sample aerosol
ICP-OES). Starting from Ar and electrical also be limited (typically 30 uL/min or reaches the plasma.
power (the input ingredients to the plas- less). Drift, noise, inefficient use of sam- It has been suggested that drop colli-
ma), the chemistry of the Ar ICP would ple, and matrix effects caused by varia- sions and coalescence to form larger drop-
seem to be simple, described primarily by lets reduce the aerosol transport effi-
the formation of argon ions and electrons ciency as the sample uptake rate is in-
from elemental Ar. Most analyte atoms creased (10). The amount of sample that
and ions are excited by collisions of elec- enters the plasma barely changes as the
trons, and the probability of producing an liquid uptake rate is increased from 0.4 to
excited atom or ion is dependent on the 2.0 mL/min. Although the average drop
electron concentration and velocity (tem- size grows slightly as the liquid flow rate
perature). The gas temperature (which is increased (Figure la), the loss of aero-
describes the kinetic energy of the Ar at- sol of all sizes in the spray chamber rather
oms) likely controls the desolvation and than production of fewer small primary
vaporization of the sample. The research drops causes the decrease in transport
challenges are to develop fundamental efficiency (Figure lb). Changes in the
models that relate chemical composition nebulizer gas flow rate predominately af-
and temperature of the plasma to each fect the primary aerosol and have less
other, to develop models that predict the effect on losses in the spray chamber.
spatial structure of the ICP, and to make Analysis of small volumes requires high
reliable experimental measurements to aerosol transport efficiencies. Fortunately,
assess and improve the models. as rhe liquid flow rate delivered to the nebu-
If the ICP were in local thermodynamic lizer decreases, transport efficiency into the
equilibrium (LTE), a simple expression plasma increases, probably because fewer
would relate electron concentration, tem- droplet collisions (and coagulation) occur
perature, and pressure, and the electron Figure 1 . Effects of sample uptake in the spray chamber. Transport efficien-
temperature and the gas temperature rate on sample aerosol. cies of up to 87% have been obtained using
would be the same. Does mis simple LTE (a) Primary drop size distribution of sample pneumatic nebulizers at liquid flow rates of
approach to relate temperature and chemi- uptake rates of 0.4, 1.0, and 2.0 mL/min. 1 uL/min or less with tertiary to primary
cal composition of the Ar plasma work? Not (b) Ratio of tertiary to primary aerosols aerosol volume ratios > 1 for some drop
showing more extensive aerosol losses as the
exactly. Measured electron temperatures uptake rate is increased. diameters. The direct injection nebulizer