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Report

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

0003-2700/96/0368-469A/$12.00/0 Analytical Chemistry News & Features, August 1, 1996 4 6 9 A


© 1996 American Chemical Society
Report

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

470 A Analytical Chemistry News & Features, August 1, 1996


(DIN) and the thermospray, ultrasonic, and
oscillating capillary-based nebulizers can
also deliver small volumes of sample into
the ICP efficiently. High-efficiency nebuliz-
ers that consume only 10-50 uL/min of
sample, but produce signals similar to neb-
ulizers using 1 mL/min of sample, have
recently been introduced.
Production of ions and atoms.
Many basic questions concerning the pro-
cesses that convert a drop (or particle) of
sample to free atoms and ions have long
been unanswered. How long does it take
to completely desolvate a drop in the
plasma? How long does it take to vaporize
the remaining analyte particle? What are
the ideal properties of the sample aerosols Figure 2. Images of Sr ion clouds in the ICP showing the production and
for ICP spectrometry? diffusion of ions detected at different times relative to a reference signal.
Empirical optimization has led to the The time-integrated image of Sr emission is shown at the left.
use of finer aerosols and lower solution
transport rates into the plasma than is
typical of flame spectrometry. One group nisms for excitation and ionization are of lead to biased time-integrated measure-
found that emission intensity correlated great interest because equilibrium-based ments that would appear to deviate from
with the volume of aerosol drops with di- expressions do not correctly predict ex- LTE.
ameters less than 8 um but not with the perimentally measured emission intensi- Refined models for excitation and ion-
total volume of aerosol entering the ties. If the ICP were in LTE, relative emis- ization are being combined with models of
plasma {11). Some aerosol drops with sion intensities and the extent of ioniza- sample decomposition and gas dynamics
initial diameters of 10-15 um were found tion would be easy to predict. This would to quantitatively describe ICP signals, and
to be incompletely desolvated, even in the have implications on semiquantitative experimental measurements to effectively
analytical zone of the plasma (12). analysis using ICP-OES, on choosing in- test and adjust the models—particularly
If individual drops of sample could be ternal standards, and on predicting and using a combination of laser-induced fluo-
introduced into the ICP, the desolvation correcting spectral interferences. The Ar rescence and emission imaging of individ-
and vaporization processes could be sepa- ICP appears to be in partial LTE (15), ual atom and ion clouds produced by the
rated in time and space, and the rates of close enough for a qualitative understand- MDMI—are being made.
vaporization, atomization, and ionization ing but not for quantitatively accurate pre- The flow of plasma gas (including ana-
processes could be determined. A group of dictions of excitation and ionization. lyte ions) through the sampling orifice is
rocket scientists has designed a monodis- What could cause deviations from controlled by the predominant species in
perse dried microparticulate injector (13), LTE? If emission of light depopulates ex- the ICP, neutral Ar atoms. The gas rapidly
or MDMI, that can be used to reproducibly cited states at a significant rate (compared expands, and all of the species move at
introduce individual, monodisperse drops with nonradiative de-excitation by elec- nearly the same velocity, independent of
of user-selectable size into the ICP (14). tron-excited atom or ion collisions), LTE mass.
The rates of production of atoms and predictions will be erroneous; even simple Flow through the skimmer is also prob-
ions as well as diffusion can be determined collisional-radiative models dramatically ably dominated by the flow of neutral Ar
from the time-gated laser-induced fluores- improve predictions of excitation and ion- atoms, which is consistent with the mea-
cence images of individual atom and ion ization (16), and further improvements sured linear dependence of ion kinetic ener-
clouds (Figure 2). Time-integrated mea- are being made (17). gies on mass downstream of the skimmer
surements as a function of height in the Mass transport, likely to occur consid- (19). Charge separation could be caused by
ICP can also be used to investigate these ering the concentration gradients in the an increase in electron mobility as the gas
processes, because height in the plasma ICP, could also produce non-LTE behav- expands or the effect of the electric field
can be related to time through the use of ior. Although specific reactions such as produced by the first ion-optic lens, result-
measured gas velocities. Finally, the initial Penning ionization or ion exchange could ing in a positive ion beam. The location and
appearance of emission can be used to indi- also lead to deviations from LTE, except time required for charge separation could
cate when desolvation is complete and ana- in a few specific cases (18) this does not have important implications on ion trajecto-
lyte particle vaporization begins. appear to be happening. Finally, time- and ries and detection efficiency.
Analyte excitation/ionization space-dependent fluctuations in plasma Once a positive ion beam is formed,
and ion transport. Only excited atoms conditions caused by cooling by desolvat- the ion trajectories depend on the voltage
or ions produce emission. The mecha- ing droplets or vaporizing particles could gradients within the ion optics. The accel-

Analytical Chemistry News & Features, August 1, 1996 471 A


Report

which ion-electron charge separation oc- the plasma. A combination of modeling


curs is critically important and needs fur- and experimental measurements are
ther theoretical and experimental investi- needed to assess these effects.
gation. Models are needed that can ac- Changes in die amount of aerosol enter-
count for the charge separation, its effect ing die plasma can have dramatic affects.
on ion trajectories, and the effects of colli- Vertical emission profiles can shift, and the
sions in the region where charge separa- emission intensity per microgram of ana-
tion occurs. Improved understanding of lyte entering the plasma can change by as
ion transport should lead to improved sen- much as a factor of 50,000. Large changes
sitivity and reduced matrix effects. in ion kinetic energy have also been ob-
served as aerosol loading is varied (19).
Sample effects Some aerosol drops survive even in die
Many of the fundamental processes can normal analytical zone of die ICP (22,23).
be affected by the sample in surprisingly Each drop and vaporizing particle acts as a
dramatic ways. The sample solvent or dis- heat sink that affects a surprisingly large
solved solids can affect the plasma tem- volume of the plasma (12), and average
perature and electron concentration. temperatures in this locally cold region can
Background species can be formed from be more than 1500 K cooler than the sur-
reactions between analytes and solvent or rounding plasma (24). Because the volume
Figure 3. Effect of 0.11 Ml NaCI on plasma species. of plasma affected by a single drop is so
t h e production of Sr ions. Accurate analysis requires that the large, relatively small numbers of incom-
(a) Measured by laser-induced fluorescence and sensitivity (signal per unit analyte concen- pletely desolvated drops can affect the num-
Sr ion excitation, and (b) determined from the ber of atoms and ions in the observation
ratio of emission-to-laser-induced fluorescence.
tration) be constant for the sample and
Emission and fluorescence values were the calibration standards. However, varia- volume (both increase, almough atoms
determined for an entire ion cloud and integrated tion in the sample matrix, including acid increase more dramatically), die fraction
in all directions to obtain a single total value. tiiat are excited (which decreases), and the
concentration or identity, the presence of
small amounts of organic solvent, and fraction that are transported from die
eration of ions attributable to the electric high concentrations of almost any ele- plasma to die detector of die mass spec-
fields produced by the ion optics is depen- ment, can affect sensitivity. trometer (which also decreases).
dent on kinetic energy, so ions with differ- Effect of sample solvent on the Organic solvents cause their own
ent energies then move with different ve- plasma. The effect of aqueous aerosol on unique set of effects on plasma characteris-
locities. Ion focusing is mass dependent if the plasma is much different than the effect tics and analytical signals. Electron concen-
ion kinetic energies are mass dependent. of water vapor, although both can be signifi- trations and temperatures are reduced, and
When a large number of positive ions cant (21). In general, temperatures and a 500-W increase in applied power may be
exist in a small volume, "space charge" can electron number densities increase when necessary to compensate for solvent-in-
result in a loss of sensitivity. Positive ions water vapor is added to a dry Ar ICP. In duced cooling. Because organic solvents
(in the absence of electrons) repel each contrast, temperatures and electron num- typically have higher volatilities than water,
other and cause defocusing of the ion ber densities decrease when die amount of organic solvent vapor loading may be 10
beam. Alternatively, space charge can be water aerosol entering the plasma is in- times larger than that of aqueous samples.
viewed as a radial electric field imposed by creased. Organic solvents generally cause a The maximum tolerable load for many or-
the positive ion beam, which can become as dramatic cooling of the plasma, but their ganic solvents is more dependent on volatil-
large as the electric field produced by an effect depends on die relative amounts of ity than on the nature of the solvent
ion lens and cause the beam to become carbon and oxygen. With a typical nebuliz- The solvent vapor, unlike aerosol, can
defocused. The ion current through the er/spray chamber, approximately 20 mg of diffuse outside of die center channel of the
first ion lens past the skimmer is 100-1000 water vapor and 5-25 mg (uL) of water plasma, perhaps even before entering die
times smaller than predicted by gas dynam- aerosol enter the plasma per minute. plasma, and die distribution of solvent into
ics alone, consistent with space-charge ef- The power required to convert the wa- different regions of the plasma cantiiusbe
fects. Lighter ions (having lower kinetic ter vapor and sample aerosol into free at- very important. The carbon-to-oxygen ratio
energies) will move farther out of the cen- oms and ions (30-50 W) could be a signifi- of the solvent is important, apparently re-
ter of the beam than will heavy ions. Be- cant fraction of the power available in the gardless of the chemical form of oxygen
cause space-charge effects are mass depen- center channel of the ICP (about 100 W) if and carbon that are introduced into the
dent, isotope ratios could be biased toward heat transfer is relatively slow. Although plasma (25).
the higher mass ion. hydrogen and oxygen atoms produced Background and spectral over-
An ion trajectory model that includes from water vapor account for < 2% of the laps. In ICP-OES, little can be done to
space charge has been developed, al- atoms in the plasma, the decomposition reduce continuum background emission
though it is limited to ion currents far be- products of the water vapor could affect without a radical change, for instance,
low those expected (20). The location at the thermal and electrical conductivity of viewing emission after expansion into a

472 A Analytical Chemistry News & Features, August 1, 1996


vacuum. However, automated chemometric reduces the analyte transport rate. Al- excited when high concentrations of EIEs
means of subtracting background and si- though the drop size distribution of the are present in the sample. This is one rea-
multaneous detection of background and primary aerosol shifts to only slightly son EIE effects in ICP-OES are often less
analyte signals are improving in accuracy. It larger diameters as the acid concentration severe than in ICPMS. There is a shift in
is likely that models for ICP-OES will even- is increased, the average tertiary aerosol the relative number of atoms and ions
tually allow spectral overlaps to be quantita- drop size decreases, implicating pro- towards atoms in the presence of high
tively predicted. The use of solid-state de- cesses within the spray chamber (27). It concentrations of EIEs, but the increase
tectors that view multiple emission lines for is not clear why this occurs. Sulfuric and in the number of atoms is too small to ac-
each element should lead to improvements phosphoric acids cause more severe ef- count for the entire decrease in the num-
in handling spectral overlaps, including fects than do hydrochloric and nitric ac- ber of ions.
automated selection of background correc- ids, although each behaves uniquely. The Matrix effects in ICPMS are caused by
tion methods and parameters. relative magnitude of the acid effects is a combination of decreases in ion concen-
Although isobaric overlaps (from iso- critically dependent on the plasma and tration in the plasma and changes in the
topes of different elements with an isotope sample introduction conditions used. fraction of ions transported from the ICP
at the same nominal mass) in ICPMS are Surprisingly small changes in acid con- to the MS detector. According to theoreti-
easily predicted, spectral overlaps from centration can be important when the acid cal calculations and experimental mea-
molecular ions (such as ArO+, ArH\ refrac- concentration is low (28). Changing the surements, there is no mass dependence
tive oxides, and organic molecular ions) are HC1 concentration from 10"4 or less to to EIE effects in the plasma itself (33);
more problematic. It is not yet clear if mo- 10"3 % v/v can result in a 20% increase in rather, the mass-dependent portion of EIE
lecular ions are formed primarily by ion- signal, and a similar change in HC104 con- effects in ICPMS appear to be caused by
molecule reactions or by ionization of neu- centration can cause a 30% decrease in space-charge effects. Instruments de-
tral molecules. The molecular species could signal. Furthermore, the effects can be signed to reduce space-charge effects
be formed in the ICP (but not seen in ICP- highly element-dependent (29). show less severe EIE chemical matrix
OES because molecules are weak emitters effects with a weaker dependence on
and the continuum background is high), mass (34,35). The magnitude of the EIE
near the sampling orifice, or in the expan- Fundamental effect is less severe for matrix elements
sion region. Molecular oxide ions have with high ionization energies, such as Se
lower kinetic energies than do elemental processes can be or As, than for matrix elements with lower
ions of similar mass (19), which is consis- ionization energies.
tent with the formation of molecular oxide affected by the sample Measurements to separately assess the
ions in locally cool regions of the plasma,
such as those near incompletely desolvated in surprisingly effect of matrix on plasma properties and
conversion of drops into free atoms and
droplets or vaporizing particles.
Two approaches to overcoming molec-
dramatic ways. ions are now being made. Some initial re-
sults using the MDMI are shown in Figure
ular ion spectral overlaps in ICPMS con- Small amounts of organic solvent in an 3. The entire ion cloud is within the laser
tinue to evolve: use of high-resolution aqueous sample can have a significant beam and optical collection volume so that
mass spectrometers or means to eradicate effect on analyte signals. For example, the total number of ions produced can be
or reduce polyatomic ion signals by using one drop of acetone added to 50 mL of an calculated as a function of the location of
cryogenic desolvation, addition of xenon aqueous sample produced a 15% decrease the center of the cloud. The presence of Na
or other gases, and a carbon center tube. in analyte signal, because the fraction of in the sample causes an earlier appearance
Solvent composition. The solvent ions that were excited decreased more of ions (lower in the ICP), probably be-
can affect analyte sensitivities because of than the 11% increase in analyte transport cause of faster vaporization, but it takes
changes in the analyte transport rate into rate (30). Further investigation of aerosol longer from the initial appearance of ions
the plasma resulting from changes in aero- generation, modification, and transport, as until the analyte is completely ionized
sol properties, differences in the chemical well as plasma-sample interactions, is (reaching a steady value). Excitation is dra-
composition of the sample and the aerosol essential. matically affected by the presence of NaCl
that reaches the ICP, or matrix-induced Dissolved solids. Analyte signals in the sample, as determined from emis-
variations in the plasma itself. Large varia- can also be affected by the presence of sion-to-fluorescence ratios.
tions in acid concentration or the use of high concentrations (> 10 mM for ICP- This is consistent with the observation
organic rather than aqueous solvent will, OES, > 1 mM for ICPMS) of any element of increases in electron concentration,
not surprisingly, affect analyte signals. that is efficiently ionized, as most are, in electron temperature, and in some cases,
However, changes in acid concentration the ICP. Efficiently ionized elements gas temperature by using Thomson scat-
from one sample to the next can cause (EIEs) generally cause a decrease in the tering (36). When these experiments are
large, transient variations in analyte signals number of analyte ions in the analytical combined with atom emission, fluores-
that may occur in a matter of minutes (26). zone of the ICP as measured by laser-in- cence imaging, and laser light scattering,
A large increase in acid concentration duced fluorescence (31,32). At the same the effect of matrices on each fundamental
(such as from 1% to 20% v/v nitric acid) time, a larger fraction of analyte ions is process can be assessed.

Analytical Chemistry News & Features, August 1, 1996 4 7 3 A


Report
Must Reading!
The Internet: Future progress (12) Olesik, J. W.; Fister, J. C. Spectrochim.
Acta 1991,46B, 851-68.
A Guide for Improvements in ICP-OES and ICPMS
performance, reliability, accuracy, and
(13) French, J. B.; Etkin, B.; Jong, R. Anal.
Chem. 1994, 66, 685-91.
Chemists ease of use depend on further fundamen- (14) Olesik, J. W.; Hobbs, S. E. Anal. Chem.
tal research. Sample introduction systems 1994, 66,3371-78.
(15) Blades, M. W.; Caughlin, B. L.; Walker,
are likely to be dramatically improved by Z. H.; Burton, L. L. Prog. Analyt. Spectrosc.
investigation of aerosol generation pro- 1987,10, 57-109.
cesses and sample-plasma interaction. (16) Burton, L. L.; Blades, M. W. Spectrochim.
Acta 1990,45B, 139.
Intelligent instruments based on diag- (17) Fey, F.H.AG.; Benoy, D. A; de Regt,
nostic signals could warn the operator, J. M.; van der Mullen, JAM.; Schram,
D. C. Spectrochim. Acta B 1993,48B,
not only if the instrument is malfunction- 1579.
ing but also if a particular sample is likely (18) Farnsworth, P. B.; Smith, B. W.; Ome-
to suffer from an analysis error, by identi- netto, N. Spectrochim. Acta 1991,46B,
fying changes in the aerosol transport rate 843-50.
(19) Tanner, S. D.J. Anal. At. Spectrom. 1993,
or the extent of ionization and excitation 8,891-97.
in the plasma. Problem samples could (20) Tanner, S. D. Spectrochim. Acta 1992,
then be reanalyzed by using matrix- 47B, 809-23.
(21) Long, S. E.; Browner, R. F. Spectrochim.
This timely book presents the basics matched standards or standard additions. Acta 1988,12,1461-71.
of the Internet along with instruc- Alternatively, the instrument could force (22) Cicerone, M. T; Farnsworth, P. B. Spec-
tions on becoming an information plasma conditions to be the same, regard- trochim. Acta 1989,44B, 897.
provider on the Internet. In a (23) Olesik, J. W.; Smith, L. J.; Williamsen,
less of the sample matrix, to eliminate the E.J. Anal. Chem. 1989, 61,2000-08.
stepwise and thorough manner it de- potential error.
scribes how to use the major Internet (24) Hobbs, S. E.; Olesik, J. W. Spectrochim.
Acta 1993, 48B, 817-33.
resources, including e-mail, electronic Progress has already been made to- (25) Weir, D. G.; Blades, M. W.J. Anal. At.
lists, Gopher, FTP, and the World ward this goal. For example, Mermet (37) Spectrom. 1994, 9,1311-22.
Wide Web and gives useful informa- has described a set of diagnostic signals (26) Maessen, F.J.M.J. Spectrochim. Acta
tion specific for chemists, such as 1982,37B, 517.
that can be used to determine if a nebu-
Web addresses, electronic mailing (27) Canals, A; Hernandis, V.; Todoli, J. L.;
lists, Gopher sites, and FTP sites. lizer is likely clogged, if the applied power Browner, R. F. Spectrochim. Acta 1995,
Also includes a brief history and over- has drifted, if the spectrometer is drifting, 50B, 305-21.
view of the Internet, and describes or if the window to the spectrometer is (28) Marichy, M.; Mermet, M.; Mermet, J. M.
how a chemical company has inte- Spectrochim. Acta B 1990,45B, 1195-
becoming fogged. As pointed out by 1201.
grated the Internet into its business
Blades and Weir (1), "Eventually plasma (29) Brenner, I. B.; Mermet, J. M.; Segal, I.;
regimen. Long, G. I. Spectrochim. Acta B 1995,
diagnostics will probably be used interac-
Contents 50B, 323-31.
tively to provide on-line feedback control (30) Olesik, J. W.; Moore, A. W., Jr. Anal.
History of the Internet
Electronic Mail
to compensate for drift, matrix effects, Chem. 1990, 62, 840-45.
The Berkeley Mail Program solvent loading effects, and noise." (31) Gillson, G.; Horlick, G. Spectrochim. Acta
Electronic Lists 1986,41B, 619.
Gopher (32) Olesik, J. W.; Williamsen, E. J. Appl. Spec-
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Electronic Conferencing (1) Blades, M. W.; Weir, D. G. Spectroscopy 1991,45,1395-1407.
Electronic Lists for Chemists 1994, 9(8), 14-21. (34) Turner, P. J. In Applications ofPlasma
Managing the Computational Chemistry (2) Hieftje, G. M.; Galley, P. J.; Glick, M.;
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Steven M. Bachrach, Editor, N o r t h e r n 47B, 3-25. D.J.Appl. Spectrosc. 1994,45,1367-72.
Illinois University (4) Houk, R. S.; Shum, S.C.K.; Wiederin, D. R. (36) Hanselman, D. S.; Sesi, N. N.; Huang, M.;
360 pages (1996) Anal. Chim. Acta 1991, 250, 61-70. Hieftje, G. M. Spectrochim. Acta B 1994,
Clothbound: ISBN 0-8412-3223-7, $29.95 (5) Montaser, A. In Inductively Coupled Plas-
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49B, 495-526.
mas in Analytical Atomic Spectrometry, (37) Poussel, E.; Mermet, J. M. Spectrochim.
Paperbound: ISBN 0-8412-3224-5, $23.95
2nd ed.; Golightly, D. W., Ed.; VCH Pub- Acta 1993,48B, 743.
(plus $3.00 handling)
lishers: New York, 1992.
ORDER FROM (6) OlesikJ.W.^Mfl/. Chem. 1991,63,
American Chemical Society 12 A-21 A. In addition to performingfundamental re-
1155 Sixteenth Street, NW (7) Huang, M.; Hanselman, D. S.; Yang, P.;
Washington, DC 20036 search on plasmas, John W. Olesik does re-
Hieftje, G. M. Spectrochim. Acta 1992, search on CE/ICP, LC/ICP, and ion spray
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1-800-227-5558 (8) Gaillat, A.; Barnes, R. M.; Boulos, M. I. and electrospray MS. Address correspondence
(in Washington, DC 872-4363) about this article to Olesik at Laboratory for
and use your credit card! J. Anal. At. Spectrom. 1995,10, 935.
FAX: 202-872-6067. (9) Canals, A; Hernandis, V.; Browner, R. F. Plasma Spectrochemistry, Laser Spectroscopy
ACS Publications Catalog now /. Anal. At. Spectrom. 1990,5, 61-66. and Mass Spectrometry, Dept. of Geological
available on Internet: (10) Olesik, J. W.; Bates, L. C. Spectrochim. Sciences, 275 Mendenhall Laboratory, 125
Acta 1995,50B, 285-303.
gopher acsinfo.acs.org or
(11) Olsen, S. D.; Strasheim, A. Spectrochim. S. Oval Mall, The Ohio State University,
URL: http://pubs.acs.org Acta 1983,38B, 973. Columbus, OH 43210

474 A Analytical Chemistry News & Features, August 1, 1996

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