Sparks 19965

Published 1996
Chapter 5
Inductively Coupled Plasma Emission

Spectrometry and Inductively Coupled
Plasma-Mass Spectrometry
PARVIZ N. SOLTANPOUR, Colorado State University, Fort Collins,

Colorado
GREG W. JOHNSON, Matheson Gas Products, Longmont, Colorado
STEPHEN M. WORKMAN,Analytical Technologies, Inc., Fort Collins,

Colorado
J. BENTON JONES, JR., Macro-Micro Analytical Services, Athens, Georgia
ROBERT O. MILLER, University of California, Davis, California
The application of inductively coupled plasma-atomic emission spectroscopy

(ICP-AES) to the analysis of soil and biological materials was reviewed in 1982
for this book series (Soltanpour et aI., 1982). Over the last 14 yr many studies in
soil science have incorporated data obtained on ICP-AES instrumentation, and
many advances in the ICP-AES field have been made. In addition, inductively
coupled plasma-mass spectrometry (ICP-MS) has become commercially avail-
able. The purpose of this chapter is to review basic ICP principles; highlight
some of the applications of ICP-AES in the study of soils; and present an
overview of some of the instrumental features, capabilities, and limitations of the
ICP-MS for application to soil science work.
Relatively new developments in ICP-AES include: suspension nebuliza-
tion analysis of clays (Laird et aI., 1991); interfacing ICP spectrometers with
flow injection analyzers for automatic dilution, calibration, separation, concen-
tration, standard additions and many other operations (Greenfield, 1983;
LaFemiere et aI., 1985); interfacing ICP-AES with liquid chromatographs for
concentration and speciation of elements (Roychowdhury & Koropchack, 1990);
high salt neulizers to prevent clogging of nebulizers (Legere & Burgener, 1985);
successful use of concentration and elimination or reduction of spectral interfer-
ence techniques such as chelation/solvent extraction (Huang & Wai, 1986;
Copyright 1996 Soil Science Society of America and American Society of Agronomy, 677 S.
Segoe Rd., Madison, WI 53711, USA. Methods of Soil Analysis. Part 3. Chemical Methods-SSSA
Book Series no. 5.
91
92 SOLTANPOUR ET AL.
Bradford & Bakhtar, 1991); use of computer programs such as orthogonal poly-
nomials (Hassan & Loux, 1989), simplex optimization (Belchamber et aI., 1986),
and that recommended by Taylor and Schutyser, 1986, for optimization of spec-
trometer operating conditions and automatic correction for spectral interferences;
and compilation of ICP emission lines (McLaren & Berman, 1985; Boumans,
1984; Parsons et aI., 1980).
The ICP-MS technique has been developed over the last 20 yr, particular-
ly by Houk et ai. (1981) who showed suprathermal ionization in an ICP Ar plas-
ma. Within about the last 10 yr it has become possible to apply the method to
routine analytical concentration determinations. Several review articles docu-
ment the ICP-MS developmental milestones (Beauchemin, 1989; Hieftje &
Vickers, 1989; Douglas, 1989; Houk & Thompson, 1988; Houk, 1986; Gray,
1985; Douglas & Houk, 1985). Between 1986 and 1988, ICP-MS enjoyed a
surge of popularity. According to Cresser et ai. (1988), the late AR. Date attrib-
uted the success of ICP-MS to spectral simplicity, very high sensitivity, and iso-
tope ratio capability. Cresser attributes the following quote to Date (1986), "ICP-
MS is the greatest thing to happen to atomic spectroscopy since chopped light."
Each year since 1986, papers dealing with ICP-AES and ICP-MS analysis of
environmental samples including soil samples have been reviewed by Malcolm
S. Cresser, and coworkers (Cresser et aI., 1986, 1988, 1989, 1990, 1991, 1992;
~bdon et aI., 1987). Another source of information for the ICP-MS analysis of
geological and inorganic materials is the biennial review publication appearing
in Analytical Chemistry (Jackson et aI., 1989, 1991). The ICP Information
Newsletter publishers an ICP bibliography each January (Barnes, 1992) and-
like the Cresser review-abstracts papers on ICP-MS presented at national and
international conferences.
An inorganic mass spectrometry, ICP-MS, and x-ray fluorescence spec-
trometry review has been published yearly since 1988 (Ure et aI., 1988; Bacon
et aI., 1989, 1990, 1991). A text on applications of ICP-MS was edited by Date
and Gray (1989), and a compilation of 21 selected papers from the Second
International Conference on Plasma Source Mass Spectrometry held at Durham
University, 24 to 28 Sept. 1990, was edited by Holland and Eaton and published
as a bound volume (1991). A comprehensive book on ICP-MS and its applica-
tions has been written by Jarvis (1992).
Isotopes of 71 naturally occurring elements can be monitored using con-
ventional positive ion, solution nebulization ICP-MS. Accuracies of theconcen-
trations estimated using these measurements at the Division of Agriculture and
Natural Resources (DANR) Analytical Lab at the University of California,
Davis, using internal standard corrections, are typically within 2.5% of the true
concentrations in favorable cases. For about 70% of these elements, more than
one stable isotope occurs in nature. Thus, analyses can be done for them using
isotope ratios and/or isotope dilution. Isotope ratios show precision of 0.1 to
0.3% (Gregoire, 1989). Concentrations calculated using the method of isotope
dilution (Fasset & Paulsen, 1989) are generally within 1% of their true concen-
trations; a higher accuracy and precision than ICP-MS analyses done without the
use of stable isotope addition (Viczian et aI., 1990; Van Heuzen et aI., 1989,
Garbarino & Taylor, 1987; McLaren et aI., 1987; Dolan et aI., 1990).
ICP EMISSION SPECTROMETRY 93
Concentrations for 13 other nuclei that are not naturally occurring also can be
estimated using the ICP-MS (Brown et aI., 1988; Igarashi et aI., 1990; Kim et aI.,
1989a,b, 1991).
While elemental coverage and detection limits under relatively ideal con-
ditions are excellent, there are some problem areas in ICP-MS that must be
investigated before deciding whether or not the ICP-MS technique "will work for
you (Hieftje, 1992)." While most of the following problems have been overcome
or circumvented to meet analytical needs in selected instances, the statements
that follow are generally valid for a generic, normal resolution (i.e., peak widths
between 0.5 and 1.0 dalton), normal aqueous aerosol generation ICP-MS:
1. Although the ICP-MS has been found to be satisfactory for soils work,
compared to ICP-AES the accuracy and precision of ICP-MS data are approxi-
mately three times worse. However, for concentrations determined from isotope
dilution/ratio measurements, precision and accuracy is somewhat better
(Gregoire, 1989; Dolan et aI., 1990; Taylor et aI., 1991).
2. Isobaric overlaps (spectral interferences) occur with some regularity for
elements between approximately 28 to 80 daltons, and do occur throughout the
mass range. They are a result of a common unit mass shared by more than one
element, doubly charged ions overlapping an isotope with half the unit mass of
the doubly charged species (Vaughan & Horlick, 1986), elemental oxide, ele-
mental hydride, and/or elemental hydroxide ions overlapping isotopes of other
elements (Vaughan & Horlick, 1986; Munro et aI., 1986; Date et aI., 1987; Gray,
1986), and background spectral problems (Vaughan & Horlick, 1986; Gray,
1986; Tan & Horlick, 1986). The isobaric interferences involving O2 can be
eliminated using techniques such as electrothermal vaporization (ETV) atomiz-
ers or Laser ablation sample aerosol production (Gregoire, 1989).
3. Ion response is significantly suppressed by matrix elements. The thresh-
old matrix element values are low compared to emission suppressions noted for
ICP-AES. Nonspectroscopic interferences result from excessive dissolved solids
in the test solutions. For a number of reasons, the analyte ion arrival rate at the
detector (i.e., analyte response) is suppressed under these circumstances
(Beauchemin et aI., 1987; Olivares & Houk, 1986; Douglas & Kerr, 1988;
Gregoire, 1987a,b; Hieftje, 1992). Although the onset of suppression is usually
observed in the neighborhood of 100 to 500 mg L-l at the DANR Analytical Lab,
Gregoire (1989) indicated somewhat higher levels using the same instrument
model/manufacturer (i.e., Perkin-Elmer SCIEX 250).
4. The ICP, generated in Ar with normal aqueous solution nebulization,
may be unable to produce measurable amounts of positive ions for some analytes
that could be of interest, e.g., F, CI, and/or S. However, the halogens can be deter-
mined in the negative ion mode (Hieftje et aI., 1988; Chisum, 1992). Sulfur can
be detected if the water is removed from the sample prior to injection of dry
aerosol into the ICP and/or a high resolution ICP-MS is available (Douhitt,
1994a,b). Some water vapor can be removed from the sample aerosol using a
cooled spray chamber (Hutton & Eaton, 1987). Water can be completely sepa-
rated from the S using an electrothermal atomizer (Gregoire, 1989) or partially
removed using nebulization-desolvation equipment (Veillon & Margoshes,
1968).
94 SOLTANPOUR ET AI...
Fig. 5-1. Magnetic fields (H) and eddy currents (shaded)

generated by high-frequency currents (I) flowing
through coil (reproduced from Fassel & Knisely, 1974,
with permission obtained from the publishers of
H
Analytical Chemistry).
5. The cost of instrumentation, operation, and maintenance for ICP-MS are

generally higher than those for ICP-AES, leading to higher cost per analyte con-
centration determination. We calculate that the cost per analyte concentration
determination for an off-the-shelf ICP-MS is about two and one-half times that
of a state-of-the-art automated sequential scanning ICP-AES instrument, using
the same depreciation schedule for both instruments: Gregoire (1989) points out,
however, that the relative cost of analysis using ICP-MS is low relative to other
methods capable of producing data on individual isotopes. Similarly, the sample
throughput is about a factor of five greater for ICP-MS than obtainable by these
other isotope methods.
6. Finally, while multielement capability exists for the ICP-MS, true simul-
taneous multielement analysis does not (Hieftje, 1992). For an ICP-AES simul-
taneous multielement system, adding more analytes does not require longer mea-
surement times per sample to preserve detection limits. For the ICP-MS howev-
er, adding additional analytical isotopes requires a longer analysis time per sam-
ple to avoid detection limit and/or precision degradation.
INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION

SPECTROMETRY AND INDUCTIVELY COUPLED
PLASMA-MASS SPECTROMETRY
Instrumentation
Inductively Coupled Plasma Generation
The ICP is produced by passing initially ionized Ar gas through a quartz
torch located inside a Cu coil connected to a radio frequency (RF) generator. The
RF generator provides up to 3 kW forward power (in most commercial units) at
a frequency of 27.1 MHZ. "The high-frequency currents flowing in the Cu coil
generate oscillating magnetic fields whose lines of force are axially oriented
inside the quartz tube and follow elliptical closed paths outside the coil," Fassel,
1977. The Cu coil-torch assembly is shown schematically in Fig. 5-1 (Fassel &
OPTICAL EMISSION SPECTROMETRY
E
E
...J
5 TEMPERATURE (K)
u ( IO%)
a
<{
25 6000
0
...J 20 6200
w
>
0
15 6500
CD 6800
<{ 8000 (ESTIMATE)
..... 10000
:J:
(!)
iii
:J:
SAMPLE AEROSOL
Fig. 5-2. Temperatures in the plasma as measured by the spectroscopic slope method (reproduced
from Fassel, 1977, in Pure and Applied Chemistry, with permission obtained from Pergamon Press
Ltd., Oxford).
Kniseley, 1974). Electrons and ions passing through the oscillating electromag-
netic field flow at high acceleration rates in closed annular paths varying in their
direction and strength, resulting in electron acceleration on each half cycle.
Collisions between accelerated electrons and ions, and ensuing unionized AI gas
cause further ionization. The collisions cause ohmic heating and, when measured
spectroscopically, give thermal temperatures ranging from 6000 to 10 ooooK
(Fig. 5-2; Fassel, 1977).
The quartz torch has three concentric channels. The outer channel conducts
AI gas at about 15 to 17 L min-I to the plasma to sustain the plasma and to iso-
late the quartz tube from high temperatures. The innermost channel is for intro-
duction of sample into the plasma. The middle channel conducts the auxiliary AI
gas at about 1 L min-I and is used in ICP-AES only when starting the plasma or
for organic samples, and is routinely used for all types of samples for ICP-MS
(Fig. 5-3; Fassel & Knisely, 1974). The ICP has an annular, or donut, shape
when it is viewed from above. The hole has a lower temperature than the donut
and, once the flow of vaporized sample carried in a flow of nebulizer argon is
established, offers less resistance to the sample injection. The sample is injected
into the plasma by using Ar carrier gas at a rate of about 1 L min- 1 for ICP-AES
work. For ICP-MS work the aerosol flow is approximately 1.5 L min-I.
Properties of Inductively Coupled Plasma

The ICP generated, as discussed above, has unique physical properties that
make it an excellent source for elemental vaporization/atomization/ionization/
excitation. For ICP-AES, the aerosol droplets containing the analyte are desol-
vated, the analyte salts/oxides are vaporized, and the analyte is atomized at the
high temperature region of the plasma near the Cu coil (Fig. 5-2). An initial radi-
ation zone (IRZ) has been defined by Koirtyohann et al. (1980) as the zone that
Fig. 5-3. Typical quartz torch and inductively coupled

plasma configuration. Flow A is auxillary flow used
mf m ARGON PLASMA
@ @ SUPPORT FLOW
for organic samples (reproduced from Fassel &
Knisely, 1974, with permission obtained from the r
AEROSOL CARR IER
publishers of Analytical Chemistry). ARGON FLOW
begins in the sample aerosol channel inside the load coil for ICP-AES. The IRZ
extends upward to 1 or 2 mm above the load coil, taking on the appearance of an
amber "bullet" during nebulization of soil, plant and water samples. The CaO
molecules on the surface of the "bullet" emit an amber colored radiation which
changes to a deep blue- or purple-colored radiation further downstream as emis-
sion from Ca atoms and ions dominate. The blue/purple region is termed the nor-
mal analytical zone (NAZ), and is the region in which the analyte emission is
observed by the spectrometer. Color photographs illustrating the appearance of
the IRZ and NAZ while nebulizing an elevated concentration of Y into an ICP
have recently been published for ICP-AES (Winge et ai., 1988), which clearly
define these critical regions. The NAZ is 15 to 20 mm above the coil, or about
14 to 19 mm above the tip of the IRZ, in an environment relatively low in back-
ground emission.
The background emission consists of Ar lines and some weak band emis-
sion from OH, NO, and CN molecules present in the plasma (Ward, 1978a). By
the time the decomposition products of the sample reach the NAZ, they have had
a residence time of about 2 ms at spectroscopically measured temperatures rang-
ing from about 8000 to 5000 K (Fassel, 1977). The residence time and temper-
0
ature experienced by samples introduced into the plasmas are about twice as
large as those in the hottest flames, e.g., N20-C2H2. The high temperature and
residence time combination, at the sample aerosol flow rates typical for the ICP-
AES, lead to complete sample vaporization and atomization in contrast to flames
that require releasing agents for refractory compounds (Larson et ai., 1975).
Once the free compounds, atoms, and ions are formed in ICP-AES, they are in a
chemically inert environment in contrast to highly reactive combustion flame
environments. Ionization interferences are generally negligible in ICP-AES.
Self-absorption (a phenomenon responsible for the flattening of the standard
curve at high analyte concentrations) is practically absent, which leads to a wide
linear dynamic analytical range of three to five decades. No sampling or skim-
mer cones are used in the ICP-AES, and therefore contamination from them is
absent.
For ICP-MS, the vaporization and atomization begin at approximately the

same location relative to the load coil as do these processes in the ICP-AES, in
a relatively hot region of the plasma near the Cu coil (Fig. 5-2). Compared to
ICP-AES, however, the flow of sample and/or auxiliary argon are increased, so
that the IRZ extends further from the downstream part of the load coil. Sample
aerosol and/or auxiliary Ar flow rates used for ICP-MS work must be higher than
used for ICP-AES to obtain an analytically useful population of ions (Winge et
aI., 1991), while keeping the sampling cone a safe distance from the load coil to
prevent arcing between the cone and the load coil. The IRZ extends well beyond
the downstream side of the load coil. The water droplets produced in a conven-
tional concentric nebulizer, although apparently extremely few in number com-
pared to the total number of aerosol droplets produced, can survive the rigorous
desolvationlatomization conditions generated by the ICP (Winge et aI., 1991).
Although the downstream side of the load coil-to-IRZ tip distance varies from
one lab to another,.it is generally between 10 and 20 mm. Unlike ICP-AES, this
leaves much of the analyte vaporization and atomization to be done in regions
beyond the hottest parts of the ICP in the ICP-MS case. The sampling cone ori-
fice defines the NAZ in the ICP-MS (Fig. 5-4), and can be another 0- to 10 mm
downstream from the tip of the IRZ. In the DANR Analytical Lab, the IRZ
extends approximately 19 mm downstream from the spectrometer side of the
load coil and the. sampler cone orifice is positioned 0 to 3 mm downstream from
the IRZ tips which results in placement of the NAZ a total of between 19 to 22
mm from the nearest surface of the load coil. Most of the particle beam is sucked
through the sampling cone into the intermediate vacuum region of a differential-
ly pumped aperture. The tip of a second cone, called the skimmer, is immersed
in what is termed a barrel shock (Gray, 1989) that results from supersonic expan-
sion of the plasma gas as it passes from atmospheric pressure through the sam-
pling cone orifice into a vacuum of about 1 torr. The kinetic temperature of the
gaseous particles at the tip of the skimmer cone has been measured to be 2200 K 0
(Lim et aI., 1989). Although the position of the sampler with respect to the
extended IRZ of the ICP is adjusted before each analytical run to achieve maxi-
mum ion arrival rate at the detector, it also is sampling aerosol that has under-
gone solute vaporization and atomization reactions outside the hottest regions of
the ICP. This is thought to contribute to the appearance of more molecular ions
in the mass spectra and higher susceptibility to nonspectroscopic matrix effects
than if the aerosol flow rate and/or auxiliary Ar flow rate could be slowed down
enough to put the IRZ back to within 1 or 2 mm of the downstream side of the
load coil. However, this is not possible because of the arcing that occurs between
the load coil and the metallic sampling cone in instances in which the cone is
placed too close spatially to the load coil.
In summary, the NAZ is much closer to the tip of the IRZ in ICP-MS (~1O
mm) than the NAZ is to the tip of the IRZ in ICP-AES (14-19 mm). The closer
proximity used for the ICP-MS measurements increases the concentration of ions
to a level at which they are analytically useful; but, to prevent arcing between the
load coil and the metal sampler cone, high flow rates for the nebulizer and/or
auxiliary gases must be used to push the IRZ tip away from the load coil. Thus,
analyte solute vaporization and atomization occur in a region of the plasma with
A. rep Spatial Configuration for Ato'llic Emission Spectroscopy
1001"= =",'" " ,
Load Coil
B. rcp Spatial Configuration for Mass Spectrometry
Key: Pressures PI' p,. and p,: Cones S, and S,:
p,=760 torr S,=Sampling Con,
p,=1.2 torr S,=Skimmer Com
p,=10. 7 to 10" torr
Fig. 5-4. Spatial nomenclature for ICP (adapted from Koirtyohann, 1980), where IRZ denotes the
Initial Radiation Zone. In agronomic work, it likely will appear red to pink in color due to emis-
sion of CaO and CaOH molecules. NAZ denotes Normal Analytical Zone, the location of the NAZ
depending on whether analytical measurements are being perfonned for AES (A) or MS (B).
cooler excitation and gas temperatures than the ionization temperatures.

Undoubtedly, the requirement for high ion density at a distance well downstream
from maximum gas and excitation temperatures promote formation of metal
oxide ions and nonspectroscopic matrix element supression effects that are
observed in the ICP-MS. A number of modifications that will be mentioned
below, most involving variations on the usual sample introduction techniques,
have been found to significantly reduce these problems.
Sample Introduction Systems

Nebulizers. Nebulizers are devices used for the injection of the sample
into the plasmas. There are three general types of nebulizers-pneumatic nebuliz-
ers, Babington style nebulizers, and ultrasonic nebulizers (USN's) (Thompson &
Walsh, 1983). The pneumatic type uses the Venturei effect to draw sample solu-
tions into the spray chamber. The Babington requires a pump to deliver the solu-
tion to a pinhole orifice from which Ar gas is emerging at high velocity. The
USN also requires a pump to deliver the solution, this time to a vibrating plate.
There are two common types of pneumatic nebulizers: cross flow and con-
centric. For the cross flow, as the solution emerges from the rigid capillary tube
carrying the sample solution, another tube positioned at a right angle blasts Ar
past it to shear off fine aerosol particles. The cross-flow nebulizers are often
made of highly corrosion-resistant capillary metal tubes, e.g., Pt-Ir alloy. One
capillary carries Ar at approximately 1 L min- 1 and the other, sample solution.
The orientation of the tips is fixed by the manufacturer, and may include a sap-
phire edge at the tip of the solution tube to produce a fine, uniform mist out of
approximately 10% of the solution drawn in. The cross-flow systems in the
authors' laboratories have held up to the most demanding applications for 2 or 3
yr with no sign of degradation.
The concentric flow (Meinhardt type) glass nebulizers are routinely used
at the DANR Analytical Lab for both ICP-AES and ICP-MS work. These are
made entirely of glass in a "T" type configuration. The main barrel of the nebu-
lizer consists of a fine glass tube tapered to capillary size. The capillary portion,
measuring 2.5 cm. in length, carries the sample solution and is through a tube
joined in a "T" shape to this barrel. The Ar pressure can be anywhere from 124
kPa to 345 kPa (18-50 psi), resulting in flow rates of between approximately
0.75 to 1.5 L min- 1. The open ends of the argon tube and the capillary tube meet
at a taper, and a fine mist is produced as the Ar (flowing concentrically around
the capillary) shears off small fragments of water droplets at the capillary tip.
These nebulizers are very steady and, like the cross-flow type, produce aerosol
from about 10% of the solution going through the tip.
The cross-flow and concentric nebulizers easily clog with high salt solu-
tions. Soltanpour et a1. (1979a) treated 1 M NH4HC0 3-O.005 M DTPA (diethyl-
enetriaminepentaacetic acid) soil extracts with 0.5 M HN0 3 to overcome clog-
ging. However, the Colorado State University Soil Testing Laboratory
(CSUSTL) presently uses a Legere 1 teflon nebulizer (Legere & Burgener, 1985)
attached to a peristaltic pump; eliminating the need for acid pre-treatment.
Wolcott and Butler (1979) designed a pneumatic nebulizer that could aspirate
solutions containing up to 36% suspended solids. To overcome differences in
surface tension, density, and viscosity, the analyst can use a peristaltic pump to
introduce sample solutions into the nebulizer (Beasecker & Williams, 1978). For
concentric nebulizers, care must be taken to eliminate small insoluble particles
from test solutions that would otherwise clog the capillary. If a particle becomes
lodged in the capillary or between the capillary and the tapered tip, then great
care must be exercised while removing the blockage to avoid breaking the frag-
ile glass tubing. One method is to carefully remove the nebulizer from the Ar and
sample delivery tubes and squirt acetone from the nebulizer tip into the barrel
while tapping with a finger, and then force Ar through the tip into the barrel
while continuing to tap2.
1 Distributed by Burtec Instrument Corporation, Post Office Box 235, Delmar, NY 12054.
2 Petrie, K., Precision Glassblowing of Colorado, Englewood, CO.
In Babington nebulizers (Suddendorf & Boyer, 1978), aerosol is produced

by pumping sample solution into a V-groove and rupturing the cohesiveness of
the liquid stream as it flows over a small hole in the groove from which Ar gas
is flowing. Glass frit nebulizers and the like (e.g., the Hildebrand nebulizeil) use
the same principle as the Babington except with a multitude of orifices. These
nebulizers can be used for high salt solutions. Since no constricting orifices are
needed to produce aerosol, they are relatively clog free. For pneumatic and
Babington nebulizers, larger droplets settle out in the spray chamber and drain
off, leaving the finer aerosol droplets suspended in the flow stream of argon for
transport to the plasma.
In USN's, transducers are used to produce the sample aerosol. USN's
improve the detection limit of ICP spectrometers by one- to two orders of mag-
nitude compared with pneumatic enbulizers (Olson et aI., 1977). A three- to four-
order of magnitude improvement in ICP-MS detection limits has been noted
using the USN with a high resolution, double focusing, ICP-MS instrument
(Tsumura & Yamasaki, 1991). The USN's are operated with a sample aerosol
desolvation system that follows aerosol production by the transducer. The
aerosol desolvation system is a heating assembly followed by a condenser col-
umn. Thus, factors involved in improved analytical performance of the ICP-MS
with use of the USN observed in the latter reference (1991) are: (i) improved
sample transport to the plasma, (ii) reduction in water vapor present in the
aerosol introduced to the plasma (Hutton & Eaton, 1987), (iii) reduction in the
amount of O2 and OH- present as reactive gases in the differentially pumped
interface (Gregoire, 1989; Lim et aI., 1989; Veillon & Marghoshes, 1968), and
(iv) reduced background as a result of reduced O2 and OH- levels in the spec-
trum (Gregoire, 1989). Coupled with the high resolution characteristic of the
double focusing MS, detection limits achieved by Tsumura and Yamasaki (1991)
are in the low parts per quadrillion range.
Pneumatic and Babington nebulizers are the most commonly encountered
ways of enabling a sample to be injected into an ICP, and are used with both ICP-
AES and ICP-MS instrumentation. Some of the alternate methods of sample
aerosol production and/or sample injection which also are applicable to both
ICP-AES and ICP-MS techniques are (i) hydride generators (Workman &
Soltanpour, 1980; Thompson et aI., 1978a,b; Ek et aI., 1991), (ii) LASER abla-
tion (Denoyer, 1991; Hager, 1989; Abell, 1991; Denoyer et aI., 1991; Pearce et
aI., 1992), (iii) high performance liquid chromatography (HPLC), including ion
chromatography (Braverman, 1992), (iv) liquid-liquid solvent extraction (Plantz
et aI., 1989; Serfass et aI., 1986), (v) flow injection (FI) analysis (Thompson &
Houk, 1986; Dean et aI., 1988), (vi) ETV (Gregoire, 1989; Denoyer & Stroh,
1992; Denoyer et aI., 1991), (vii) aerosol desolvation (Veillon and Margoshes.
1968), (viii) DIN4, (ix) direct insertion devices (Gervais & Salin, 1991), and (x)
ultrasonic nebulizer systems (Olson et aI., 1977). Hydride generators (see sec-
tions "Hydride and Mercury Vapor Generators" and "Determination of Ultratrace
Levels of Arsenic, Selenium, and Mercury by Use of Hydride-Mercury Vapor
3 Leeman Labs Inc., Lowell, MA.

4 CETAC Technologies, Inc., Omaha, Nebraska.
Generator"), direct injection (see "Direct Injection Nebulizers"), LASER abla-

tion systems (see "LASER Sampling of Solids") and flow injection principles
(see "Special Apparatus") are discussed below, other systems are described in the
above references.
Hydride and Mercury Vapor Generator. Certain elements, when

reduced by NaBH4' form gases that can be directly introduced into the plasma.
Among these elements, As, Sb, Bi, Se and Te are reduced to form volatile
hydride gases, while Hg is reduced to its volatile elemental form. This method of
sample introduction greatly improves the detection limits of these elements com-
pared with pneumatic nebulization due to an improvement in sample delivery
and a decrease in matrix effect. Thompson et al. (1978 a,b) simultaneously deter-
mined As, Sb, Bi, Se, and Te by use of ICP-AES and a hydride generator. Studies
at the CSUSTL have indicated that by reducing As and Se to their hydrides and
Hg to its vapor form and introducing these gases into the ICP, they could be
quantitatively detected at 1.0, 0.5, and 0.5 )1g L-t, respectively (Workman &
Soltanpour, 1980). Recently, Ek et al. (1991) have used an analogous system
with ICP-MS instrumentation to improve Se detection limits to 0.05)1g L-I.
LASER Sampling of Solids. Many solid samples are difficult or time con-
suming to put into solution, e.g., soils and ceramics. Sometimes the elemental
composition of grain features and small inclusions in the solid are of greater
interest than the overall composition, e.g., minerals. To save time in sample pre-
treatment and to permit feature analysis, surface sampling methods using a
LASER have been developed (Denoyer, 1991; Hager, 1989; Abell, 1991; Denoy-
er et al., 1991b; Pearce et al., 1992). LASER ablation can be used in conjunction
with ICP-AES, but mostly the ablated aerosol is injected into an ICP and the ions
produced are subsequently detected using a mass spectrometer. At least two of
the current manufacturers of ICP-MS instrumentation market a LASER ablation
accessory5. The accessory is equipped with a NdYAG (Nd-Y-Al-Garnet) LASER
and an ablation stand. The ablation stand has an X-Y-Z translational specimen
stage that is moved either with joystick control or rastered under computer con-
trol. Vendor software supports time-resolved data acquisition and semiquantita-
tive analytical reports. LASER repetition rates are adjustable from a single shot
to hundreds of bursts per second. Beams can be used in a de focused mode to
cover approximately 1 mm of surface area, or sharply focused to less than 0.02
mm (Pearce et al., 1992). The time durations and number of repeating shots can
be selected by the operator. The amount of energy per pulse is variable. There is
a threshold energy required to fire the LASER. The upper limit on repetition rate
and energy per pulse is set either by the limitations of the LASER output or the
window material degradation threshold. A typical pulse can be as short as a few
nanoseconds (Q-switched) and delivers approximately 0.1 J of energy.
In operation, the sample argon to the ICP is momentarily interrupted while
the ablation stage cover is removed, the sample specimen placed on the teflon
ablation stage, and the ablation cover replaced. The sample Ar flow is resumed,
5 Fisons Instruments Inc., Danvers, MA 01923; Perkin-Elmer Sciex, Norwalk, cr 06859-0215.

and the portion of the sample to be ablated is located within the ocular of a light
microscope. The specimen is focused using the X-Y-Z movement of the sample
stage. The computer is notified of impending analysis, and the LASER fired.
Preablation times, LASER repetition rates and LASER power per pulse are some
of the more important variables.
The detection limits of metals in the solid are usually less than 1 mg kg-1.
The dry sample aerosol produced by the laser bursts is free of many of the recom-
bination polyatomic ions that would ordinarily accompany a major element (M)
in a nebulized sample (e.g., MO+, MW, MOH+, see Date et al., 1987). Argide
polyatomic ion species, e.g., MAr+, may persist however. Sample analysis rate
can be rapid, but depends on the analytical objectives and the variability between
samples. The accuracy of the analyses are highly dependent on the availability of
certified materials of composition similar to the sample. At ultralow concentra-
tions, memory effects must be taken into consideration. For example, assume a
Au nugget is to be ablated to determine approximate elemental composition. On
the next sample an elemental assay is requested on a metallic inclusion in a piece
of quartz for Au content. To reduce the Au background between the two samples,
the entire ICP-MS system should be shut down to permit thorough cleaning of
the sample and skimmer cones, the ICP torch, and aerosol carrier line from the
LASER stand, and the interior of the glass sample stage cover. Cleaning the glass
sample stage cover is probably the most critical because the interior of the
LASER ablation window becomes coated with a metallic film of elemental com-
position generally representative of the ablated sample, and reablation of the film
can occur during ablation on subsequent samples. Thus, for the analysis problem
at hand, the total analysis time can be a few minutes or a few hours depending
on whether the quartz piece can be run ahead of the Au nugget, and, more gen-
erally, what the detection limit and accuracy requirements are.
Direct Injection Nebulizers. Direct Injection Nebulizers (DIN) provide
for the direct injection of microvolume aqueous liquid samples into the base of
torch plasma using fused silica capillary tube and a high pressure HPLC type
pump. It can be utilized on either ICP-AES or ICP-MS instrumentation. Direct
injection nebulizers is uniquely suited for the determination of nebulizer memo-
ry-prone mass isotopes of B, Hg, I, C, S, and Br or where sample volume is lim-
ited. Studies of Smith et al. (1991) have shown it capable of detecting as little as
1 nglg of B in biological materials using ICP-MS. Powell and Boomer (1995)
have shown that the technique under optimal conditions accurately capable of
detecting Cr at the 30 ngIL concentration range for multiple Cr(lll) and Cr(VI)
species. In addition, the technique provides the fast sample wash-out and high
sample through-put.
Spectrometers
Atomic Emission Spectrometry. Atoms of elements in a sample when
excited emit light of characteristic wavelengths with an intensity directly pro-
portional to the element concentration. The light is focused on the entrance slit
of the spectrometer to illuminate the diffraction grating. The diffraction grating
separates light into its component wavelengths of lines (spectrum). The spectral
line of an analyte passes through the aperture of an exit slit and strikes a photo-
multiplier tube. Photomultiplier tubes produce signals directly proportional to

the intensity of the spectral line. The signal is fed to the readout system, which
displays intensities, concentrations, or both. Readout systems are computer con-
trolled. The computer stores the intensities of standards and uses these data to
calculate the concentrations of unknowns. Systems are available that check cali-
bration curve accuracy periodically, so that if the quality control (QC) limits are
exceeded, the system automatically updates the calibration6 If the system is
equipped with tandem nebulizers7, one nebulizer could be shut down by the com-
puter if indications are that it is clogged or another irrecoverable error has
occurred, leaving the second nebulization system to finish running the samples.
If the sensitivity is degraded beyond prescribed limits, or if the run is finished,
there are commercially available systems that shut down the ICP generator, Ar
flow, and other system functions automatically.
Two types of spectrometers are commonly used (Slavin, 1971, p. 53-80):
(i) direct-reading polychromators (direct readers), and (ii) scanning monochro-
mators. Some systems are equipped with both spectrometers.
Direct readers are designed to reduce the possibility of unwanted light
reaching the photomultiplier tubes. The refractor plates used for fine alignment
of the spectral lines also are filters that exclude stray light and/or radiation in
unwanted orders of diffraction. The photomultiplier tube-exit slit assemblies are
protected by light shield and the internal surfaces of the spectrometer are black-
ened to reduce reflections.
Scanning monochromators use a variety of techniques to make a wide
range of useful analytical wavelengths accessible. Fixed or movable gratings,
single or multiple detectors, and movable entrance and exit slits are a few of the
options available among a variety of manufacturers. The scanning is computer
controlled, fast and accurate.
Direct readers have the advantage of being faster if concentrations are
being determined on more than a few elements per sample, and a smaller sample
volume is required in these circumstances compared with scanning monochro-
mators. The disadvantage of direct readers is their fixed wavelengths. In contrast,
scanning monochromators allow the analyst to scan the entire spectrum and
choose the most useful line (see "Selection of Wavelength"). For laboratories
engaged in both routine and research activities, a spectrometer with both a scan-
ning monochromator and a polychromator is the best system.
The manufacturers of spectrometers usually provide the required software
(computer programs) for the operation of the spectrometer. These programs
enable the computer to do many tasks automatically. Through computer program
commands, modem spectrometers are able to perform standardization, normal-
ization of standard solution readings, correction of the interelemental spectral
interferences, printing data, etc. When a spectrometer is purchased, such factors
as computer size, available software, speed of the printer, automatic interele-
mental spectral interference corrections, and other computer-related factors
should be considered in addition to optical system factors.
6 (f. Zalinski, personal communication)

7 (G. Coleman, personal communication)
Inductively Coupled Plasma-Mass Spectrometry. There are at least five

manufacturers of ICP-MS instruments. Three produce quadrupole spectrometers,
one manufacturer produces a high-resolution double-focusing mass spectrome-
ter, and one manufacturer produces both quadrupole and double-focusing mod-
els. The normal peak widths on quadrupoles are typically one-half to 1 dalton
across the mass range: 6 to 250 daltons. This is sufficient to separate to the
response baseline isotopes differing in one atomic mass unit that may differ up
to a factor of 2 x 107 in concentration in the sample. The high resolution double-
focusing electrostatic-magnetic sector mass spectrometers are capable of achiev-
ing a resolution of 50 000. Note that the resolution, R, is defined as being equal
to M, the mass of interest, divided by 11M, the peak width at 5% of the peak
height, or R =M/I1M. The resolution of the double-focusing system can be used
to avoid isobaric overlaps that occur on unit resolution units in many instances.
However, the analytical sensivity is inversely proportional to the resolution, and
the cost of a double-focusing unit is about three times the cost of a quadrupole
equipped unit. All manufacturers make extensive use of computers for instru-
ment control and data processing.
Among the common features of commercially available ICP-MS systems
are the following: (i) An ICP is used as the ionization device; (ii) The ions are
sampled at atmospheric pressure and detected at high vacuum, requiring a dif-
ferentially pumped interface at an intermediate .vacuum; typically 1 torr (1/760
atmosphere); (iii) The pressure is very low inside the spectrometer that produces
the mass-to charge separation, typically 10-4 to 10-7 torr; (iv) The systems are
highly automated, with computers used for instrument control and data process-
ing; (v) The systems all have rapid sequential multiisotope capability, and are
able to quantitatively analyze isotopes for more than 70 elements; (vi)
Measurements are sequential in nature. Spectrometers do not as yet exhibit true
simultaneous multielement capability; (vii) Detection limits are in the low part-
per-trillion range (ng L-1) for generic ICP-MS units and low part-per-quadrillion
range (pg L-1, see, for example, Tsumura & Yamasaki, 1991) for many elements
using high-resolution and ultrasonic nebulization, but degrade as a result of sev-
eral factors including the number of elements in the analytical suite, the com-
plexity of the sample composition, and the amount of dissolved solids in the ana-
lytical test solutions. Several after-manufacture, add-on accessories are available
for ICP-MS and ICP-AES, i.e., ultrasonic nebulizers (USN), DIN, high-perfor-
mance liquid chromatographic (HPLC) systems, Fl accessory, hydride genera-
tion equipment, ETV accessory, and LASER ablation solid sampling equipment.
Analytical Capabilities
Selection of Wavelength
The number and wavelengths of spectral lines generated by de-excitation
of atoms depends on their electron configuration. The theory and explanation of
atomic emission make for exciting reading but are beyond the scope of this dis-
cussion. Those wishing to explore spectral theory more thoroughly can read
Boumans' (1966) book on the subject.
For the analyst using the spectrometric technique, line selection becomes a
matter of finding the most useful line, sufficiently intense to be easily detected
with a minimum of spectral interference from other spectral lines and back-
ground. Line selection can be a difficult process requiring careful examination of
the spectrum. In some instances, the most useful lines may lie outside the spec-
tral range of the spectrometer or fall in areas of high background. If an analyst
wants to measure the concentration of an element such as S that emits the most
suitable radiation for analytical purposes in the ultraviolet (UV), then that ana-
lyst should have a vacuum or Ar-purged spectrometer available to him because
much of the radiation in the UV spectrum, including UV emission lines of S, is
efficiently absorbed by 02.
For some elements, only one or two useful lines are available, whereas
other elements offer several useful lines.
Winge et at. (1979) determined the relative intensities of atomic and ionic
lines of elements excited in ICP. This information is partially reproduced in Table
5-1.
Table 5-1. Prominent lines of the elements emitted by the ICP. The list is arranged alphabetically
with the lines of each element listed in order of decreasing I..JIb ratio (adapted from Winge et aI.,
1979).
Estimated
*
detection
Element S of It Wavelength I..JIb Concentration Iimi~ Comments#
nm l1g/mL
Ag I 328.068 38.0 10.0 0.007
I 338.289 23.0 10.0 0.01
II 243.779 2.5 10.0 0.1
II 224.641 2.3 10.0 0.1
II 241.318 1.5 10.0 0.2
II 211.383 0.9 10.0 0.3
II 232.505 0.7 10.0 0.4
II 224.874 0.6 10.0 0.5
II 233.137 0.5 10.0 0.6
AI 309.271 13.0 10.0 0.02 OH band, NRtt
309.284 13.0 10.0 0.02 OHband, NR
396.152 10.5 10.0 0.03
237.335 10.0 10.0 0.03 NR
237.312 10.0 10.0 0.03 NR
226.922 9.0 10.0 0.03 NR
226.910 9.0 10.0 0.03 NR
308.215 6.6 10.0 0.04 OHband
394.401 6.3 10.0 0.05
236.705 5.8 10.0 0.05
226.346 5.0 10.0 0.06
221.006 4.8 10.0 0.06
257.510 4.0 10.0 0.08
As 193.696 56.0 100.0 0.05
197.197 39.0 100.0 0.08
228.812 36.0 100.0 0.08
200.334 25.0 100.0 0.1
189.042 22.0 100.0 0.1
(continued on next page)
Table 5-1. Continued.

Estimated
detection
Element S of It Wavelength IJ1b* Concentration limit1l CommentS#
nm llg!mL
234.984 21.0 100.0 0.1
198.970 16.0 100.0 0.2
200.919 6.1 100.0 0.5
278.022 5.7 100.0 0.5
199.048 5.5 100.0 0.5
B 249.773 63.0 10.0 0.005
249.678 53.0 10.0 0.006
208.959 30.0 10.0 0.01
208.893 25.0 10.0 0.01
Ba II 455.403 230.0 10.0 0.001
II 493.408 130.0 10.0 0.002
II 233.527 75.0 10.0 0.004
II 230.424 73.0 10.0 0.004
II 413.066 9.1 10.0 0.03
II 234.758 7.8 10.0 0.04
II 389.178 5.2 10.0 0.06 H 388.905
II 489.997 3.7 10.0 0.08
II 225.473 2.0 10.0 0.2
II 452.493 1.9 10.0 0.2
Be II 313.042 110.0 1.0 0.0003 OHband'
I 234.861 96.0 1.0 0.0003
II 313.107 41.0 1.0 0.0007 OHband
I 249.473 8.0 1.0 0.004 Group NR**
I 265.045 6.4 1.0 0.005 Group NR
I 217.510 2.5 1.0 0.01 NR
I 217.499 2.5 1.0 0.01 NR
I 332.134 1.4 1.0 0.02 Group NR
I 205.590 0.7 1.0 0.04 NR
I 205.601 0.7 1.0 0.04 NR
Bi I 223.061 87.0 100.0 0.03
I 306.772 40.0 100.0 0.08 OHband
I 222.825 36.0 100.0 0.09
I 206.170 35.0 100.0 0.09
I 195.389 14.0 100.0 0.2
I 227.658 12.0 100.0 0.3
II 190.241 10.0 100.0 0.3
I 213.363 10.0 100.0 0.3
I 289.798 9.0 100.0 0.3
I 211.026 7.8 100.0 0.4
Ca II 393.366 89.0 0.5 0.0002
II 396.847 30.0 0.5 0.0005 H 397.007
II 317.933 1.5 0.5 0.01 OHband
I 422.673 1.5 0.5 0.01
Cd II 214.438 120.0 10.0 0.003
I 228.802 110.0 10.0 0.003
II 226.502 89.0 10.0 0.003
I 361.051 1.3 10.0 0.2
I 326.106 0.9 10.0 0.3
I 346.620 0.7 10.0 0.4
I 231.284 0.5 10.0 0.6


Estimated
detection
Element S of It Wavelength l,/lb* Concentration Iimit~ Comments#
nm llg/mL
479.992 0.5 10.0 0.6
Co II 238.890 50.0 10.0 0.006
II 228.616 43.0 10.0 0.007
II 237.862 31.0 10.0 0.01
II 230.786 31.0 10.0 0.01
II 236.379 27.0 10.0 0.01
II 231.160 23.0 10.0 0.01
II 238.346 21.0 10.0 0.01
II 231.405 18.0 10.0 0.02
II 235.342 17.0 10.0 0.02
II 238.636 14.0 10.0 0.02
II 234.426 14.0 10.0 0.02
II 231.498 13.0 10.0 0.02
II 234.739 13.0 10.0 0.02
Cr II 205.552 49.0 10.0 0.006
II 206.149 42.0 10.0 0.007
II 267.716 42.0 10.0 0.007
II 283.563 42.0 10.0 0.007
II 284.325 35.0 10.0 0.009
II 206.542 31.0 10.0 0.01
II 276.654 22.2 10.0 0.01
II 284.984 21.0 10.0 0.01
II 285.568 16.0 10.0 0.02
II 276.259 15.0 10.0 0.02
II 286.257 15.0 10.0 0.02
II 266.602 14.0 10.0 0.02
II 286.511 14.0 10.0 0.02
II 286.674 13.0 10.0 0.02
I 357.869 13.0 10.0 0.02
Cu I 324.754 56.0 10.0 0.005 OHband
II 224.700 39.0 10.0 0.008
I 219.958 31.0 10.0 0.01
I 327.396 31.0 10.0 0.01
II 213.598 25.0 10.0 0.01
I 223.008 23.0 10.0 0.01
I 222.778 19.0 10.0 0.02
II 221.810 17.0 10.0 0.02
II 219.226 17.0 10.0 0.02
I 217.894 17.0 10.0 0.02
I 221.458 13.0 10.0 0.02
Fe II 238.204 65.0 10.0 0.005
II 239.562 59.0 10.0 0.005
II 259.940 48.0 10.0 0.006
II 234.349 29.0 10.0 0.01
II 240.488 27.0 10.0 0.01
II 259.837 24.0 10.0 0.01
II 261.187 24.0 10.0 0.01
II 234.810 23.0 10.0 0.01 NR
II 234.830 23.0 10.0 0.01 NR
II 258.588 20.0 10.0 0.02
II 238.863 20.0 10.0 0.02

108 SOLTANPOUR ET AL

Estimated
detection
Element S of It Wavelength IJ1bt. Concentration limit~ Comments#
nm JlglmL
II 263.105 19.0 10.0 0.02 NR
II 263.132 19.0 10.0 0.02 NR
II 274.932 19.0 10.0 0.02
II 275.574 16.0 10.0 0.02
II 233.280 15.0 10.0 0.02
II 273.955 15.0 10.0 0.02
Ga I 294.364 64.0 100.0 0.05
I 417.206 45.0 100.0 0.07
I 287.424 38.0 100.0 0.08
I 403.298 27.0 100.0 0.01
I 250.017 16.0 100.0 0.2
II 209.134 11.0 100.0 0.3
I 245.007 10.0 100.0 0.3
I 294.418 9.4 100.0 0.3
I 271.965 5.7 100.0 0.5
I 233.828 3.9 100.0 0.8
I 265.987 3.6 100.0 0.8
Hg II 194.227 120.0 100.0 0.03
I 253.652 49.0 100.0 0.06
I 296.728 1.7 100.0 1.8
I 435.835 1.1 100.0 2.7
I 265.204 0.7 100.0 4.3
I 302.150 0.6 100.0 5.0
I 365.483 0.3 100.0 10.0
In II 230.606 47.0 100.0 0.06
I 325.609 25.0 100.0 0.1
I 303.936 20.0 100.0 0.2
I 451.131 16.0 100.0 0.2
I 410.176 6.4 100.0 0.5 H 410.174
I 271.026 5.4 100.0 0.6
I 325.856 5.0 100.0 0.6
II 207.926 4.2 100.0 0.7
I 256.015 4.2 100.0 0.7
I 293.263 2.0 100.0 1.5
II 197.745 1.7 100.0 1.8
I 175.388 1.6 100.0 1.9
K 404.721 0.7 1000.0 42.9
404.414 NM 1000.0 NM AR404.442
Li 460.286 3.5 100.0 0.9
323.263 2.8 100.0 1.1 OHband
274.118 1.9 100.0 1.6
497.170 1.4 100.0 2.1
256.231 0.7 100.0 4.3
413.262 0.4 100.0 7.5 NR
I 413.256 0.4 100.0 7.5 NR
Mg II 279.553 195.0 1.0 0.0002
II 280.270 100.0 1.0 0.0003
I 285.213 19.0 1.0 0.002
II 279.806 2.0 1.0 0.02
I 202.582 1.3 1.0 0.02
II 279.079 1.0 1.0 0.03

Estimated
*
detection
Element S of It Wavelength IJlb Concentration Iimit~ Comments#
nm llg/mL
I 383.826 0.9 1.0 0.03
I 383.231 0.7 1.0 0.04
I 277.983 0.6 1.0 0.05
II 293.654 0.5 1.0 0.06
Mn II 257.610 220.0 10.0 0.001
II 259.373 190.0 10.0 0.002
II 260.569 145.0 10.0 0.002
II 294.920 39.0 10.0 0.008
II 293.930 29.0 10.0 0.01
I 279.482 24.0 10.0 0.01
II 293.306 22.0 10.0 0.01
I 279.827 18.0 10.0 0.02
I 280.106 14.0 10.0 0.02
I 403.076 6.8 10.0 0.04
II 344.199 6.6 10.0 0.05
I 403.307 6.3 10.0 0.05
II 191.510 5.8 10.0 0.05
Mo II 202.030 38.0 10.0 0.008
II 203.844 24.0 10.0 0.01
II 204.598 24.0 10.0 0.01
II 281.615 21.0 10.0 0.01
II 201.511 16.0 10.0 0.02
II 284.823 15.0 10.0 0.02
II 277.540 12.0 10.0 0.03
II 287.151 11.0 10.0 0.03
II 268.414 10.0 10.0 0.03
II 263.876 8.0 10.0 0.04
II 292.339 8.0 10.0 0.04
Na I 588.995 101.0 100.0 0.03 AR588.859
I 589.592 43.0 100.0 0.Q7
I 330.237 1.6 100.0 1.9
I 330.298 0.7 100.0 4.3
I 285.301 1.1 1000.0 27.3 NR
I 285.281 1.1 1000.0 27.3
II 288.114 0.6 1000.0 50.0
Nb II 309.418 83.0 100.0 0.04 OHband
II 316.340 75.0 100.0 0.04 OHband
II 313.079 60.0 100.0 0.05 OHband
II 269.706 43.0 100.0 0.Q7
II 322.548 42.0 100.0 0.Q7 OHband
II 319.498 41.0 100.0 0.Q7 OHband
II 295.088 40.0 100.0 0.08
II 292.781 40.0 100.0 0.08
II 271.662 34.0 100.0 0.09
II 288.318 31.0 100.0 0.1
II 210.942 31.0 100.0 0.1
II 272.198 30.0 100.0 0.1
II 287.539 28.0 100.0 0.1
Ni II 221.647 29.0 10.0 0.01
I 232.003 20.0 10.0 0.02
II 231.604 19.0 10.0 0.02

Estimated
*
detection
Element S of It Wavelength IJlb Concentration limit'!! Comments#
nm llglmL
II 216.556 17.0 10.0 0.02
II 217.467 13.0 10.0 0.02
II 230.300 13.0 10.0 0.02
II 227.021 12.0 10.0 0.03
II 225.386 12.0 10.0 0.03
I 234.554 9.5 10.0 0.03
II 239.452 7.8 10.0 0.04
I 352.454 6.6 10.0 0.05
I 341.476 6.2 10.0 0.05
P I 213.618 39.0 100.0 0.08
I 214.914 39.0 100.0 0.08
I 253.565 11.0 100.0 0.3
I 213.547 8.5 100.0 0.4
I 203.349 7.4 100.0 0.4
I 215.408 7.2 100.0 0.4
I 255.328 5.2 100.0 0.6
I 202.347 3.8 100.0 0.8
I 215.294 3.4 100.0 0.9
I 253.401 3.0 100.0 1.0
Pb II 220.353 70.0 100.0 0.04
I 216.999 33.0 100.0 0.09
I 261.418 23.0 100.0 0.1
I 283.306 21.0 100.0 0.1
I 280.199 19.0 100.0 0.2
405.783 11.0 100.0 0.3
224.688 3.0 100.0 0.3
368.348 8.6 100.0 0.3
266.316 7.7 100.0 0.4
239.379 6.3 100.0 0.5
363.958 5.2 100.0 0.6
247.638 5.1 100.0 0.6
S 180.669 30.0 100.0 0.1 Vac.line
181.979 30.0 100.0 0.1 Vac. line
Sb 206.833 91.0 100.0 0.03
217.581 68.0 100.0 0.04
231.147 49.0 100.0 0.06
252.852 28.0 100.0 0.1
259.805 28.0 100.0 0.1 NR
259.809 28.0 100.0 0.1 NR
217.919 19.0 100.0 0.2
195.039 18.0 100.0 0.2
213.969 16.0 100.0 0.2
204.957 15.0 100.0 0.2
214.486 12.0 100.0 0.3
209.841 8.7 100.0 0.3
203.977 6.6 100.0 0.5
220.845 6.5 100.0 0.5
287.792 4.7 100.0 0.6
Se 196.026 40.0 100.0 0.08
203.985 26.0 100.0 0.1
206.279 10.0 100.0 0.3

Estimated
*
detection
Element S of It Wavelength IJlb Concentration Iimit~ CommentS#
nm I!glmL
207.479 1.9 100.0 1.6
199.511 0.6 100.0 5.0
Si 251.611 250.0 100.0 0.01
212.412 180.0 100.0 0.02
288.158 110.0 100.0 0.03
250.690 100.0 100.0 0.03
252.851 95.0 100.0 0.03
251.432 79.0 100.0 0.04
252.411 75.0 100.0 0.04
221.667 72.0 100.0 0.04
251.920 61.0 100.0 0.05
198.899 50.0 100.0 0.06
221.089 47.0 100.0 0.06
243.515 36.0 100.0 0.08
190.134 23.0 100.0 0.1
220.798 23.0 100.0 0.1
205.813 23.0 100.0 0.1
Sn II 189.989 120.0 100.0 0.03
I 235.484 31.0 100.0 0.1
I 242.949 31.0 100.0 0.1
I 283.999 27.0 100.0 0.1
I 226.891 25.0 100.0 0.1
I 224.605 25.0 100.0 0.1
I 242.170 19.0 100.0 0.2
I 270.651 18.0 100.0 0.2
I 220.965 16.0 100.0 0.2
I 286.333 14.0 100.0 0.2
I 317.505 14.0 100.0 0.2 OH band
Sr II 407.771 72.0 1.0 0.0004
II 421.552 39.0 1.0 0.0008
II 216.596 36.0 10.0 0.008
II 215.284 29.0 10.0 0.01
II 346.446 13.0 10.0 0.02
II 338.071 8.8 10.0 0.03
II 430.545 4.8 10.0 0.06
I 460.733 4.4 10.0 0.07
II 232.235 2.9 10.0 0.1
II 416.180 2.4 10.0 0.1
Te 214.281 73.0 100.0 0.04
225.902 17.0 100.0 0.2
238.578 17.0 100.0 0.2
I 214.725 14.0 100.0 0.2
I 200.202 12.0 100.0 0.3
I 238.326 11.0 100.0 0.3
I 208.116 11.0 100.0 0.3
I 199.418 6.3 100.0 0.5
I 225.548 2.7 100.0 1.1
I 226.555 2.7 100.0 1.2
Ti II 334.941 79.0 10.0 0.0004
II 336.121 57.0 10.0 0.0005
II 323.452 56.0 10.0 0.005 OHband

Estimated
detection
Element S of It Wavelength 1r/1b+ Concentration Iimit1l CommentS#
nm ~g!mL
II 337.480 45.0 10.0 0.007

II 334.904 40.0 10.0 0.008
II 308.802 39.0 10.0 0.008 OHband
II 307.864 37.0 10.0 0.008 OHband
II 338.376 37.0 10.0 0.008
II 323.657 30.0 10.0 0.01 OHband
II 323.904 29.0 10.0 0.01 OHband
II 368.520 26.0 10.0 0.01
TI II 190.864 74.0 100.0 0.04
I 276.787 25.0 100.0 0.1
I 351.924 15.0 100.0 0.2
I 377.572 13.0 100.0 0.2
I 237.969 7.0 100.0 0.4
I 291.832 2.9 100.0 1.0
I 223.785 2.2 100.0 1.4
I 352.943 1.7 100.0 1.8
I 258.014 1.7 100.0 1.8
V II 309.311 60.0 10.0 0.005 OHband
II 310.230 47.0 10.0 0.006 OHband
II 292.402 40.0 10.0 0.008
II 290.882 34.0 10.0 0.009
II 311.071 30.0 10.0 0.01 OHband
II 289.332 29.0 10.0 0.01
II 268.796 29.0 10.0 0.01
II 311.838 25.0 10.0 0.01 OHband
II 214.009 20.0 10.0 0.02
II 312.528 20.0 10.0 0.02 OHband
II 327.612 19.0 10.0 0.02
II 292.464 18.0 10.0 0.02
II 270.094 17.0 10.0 0.02
Zn I 213.856 170.0 10.0 0.002
II 202.548 75.0 10.0 0.004
II 206.200 51.0 10.0 0.006
I 334.502 2.2 10.0 0.1
I 330.259 1.3 10.0 0.2
I 481.053 1.3 10.0 0.4
I 472.216 0.7 10.0 0.4
I 328.233 0.6 10.0 0.5
I 334.557 0.4 10.0 0.8
I 280.106 0.4 10.0 0.8 NR
I 280.087 0.4 10.0 0.8 NR
Zr II 343.823 42.0 10.0 0.007
II 339.198 39.0 10.0 0.008
II 257.139 31.0 10.0 0.01
II 349.621 30.0 10.0 0.01
II 357.247 30.0 10.0 0.01
II 327.305 25.0 10.0 0.01
II 256.887 22.0 10.0 0.01
II 327.926 21.0 10.0 0.02
II 267.863 20.0 10.0 0.02


Estimated
detection
Element S of It Wavelength IJIb + Concentration limitll CommentS#
nm llg!mL
II 272.261 16.0 10.0 0.02
II 273.486 14.0 10.0 0.02
II 274.256 14.0 10.0 0.02
II 270.013 12.0 10.0 0.03
II 350.567 12.0 10.0 0.03
II 355.660 12.0 10.0 0.03
II 348.115 12.0 10.0 0.03
II 256.764 11.0 10.0 0.03
II 272.649 11.0 10.0 0.03
II 330.628 11.0 10.0 0.03
II 316.597 11.0 10.0 0.03 OH band
II 318.286 11.0 10.0 0.03 OHband
II 328.471 10.0 10.0 0.03
II 274.586 10.0 10.0 0.03
II 275.221 10.0 10.0 0.03
II 357.685 10.0 10.0 0.03
t S of I = state of ionization. Symbols I, II, and III indicate that the spectral lines originate from the
neutral atom, singly ionized, and doubly ionized states, respectively.
+ InlIb =ratio of net analyte intensity to background intensity.
Concentration = concentration of the single element analyte solution used for the wavelength
scans from which the prominent lines were determined.
11 Detection limits estimated from the IJIb ratios using the formula: DL =O.03C/(IJIb) where C is
concentration of analyte.
# Includes interference information when a component of the background spectrum overlaps an
analyte line (e.g., the Ba 389.178-nm line is located on the H 338.905-nm line) or when an ana-
Iyte line is located in complex molecular band system (e.g., the OH 306.36-nm system) where
band components may cause spectral interferences. The notation of molecular bands does not pre-
clude the use of analyte wavelengths within the band region.
tt NR = not resolved. This description indicates components of an unresolved pair of lines.
+:!: Group NR indicates components of an unresolved group (three or more lines). Only the wave-
length of the strongest line is listed.
Vacuum lines for S require either a vacuum or an Ar purged spectrometer, see "Selection of
Wavelength."
Selection of Isotope
Ideally, the most abundant isotope is selected for an element because it
usually will produce the strongest signal to background ratio. Thus, the analyst
obtains the lowest detection limit, the best accuracy, and the best sensitivity.
However, the analytical isotope selection process can be complicated by the
presence of isobaric interference from atomic and molecular ions originating
from the plasma, the solvent, and the reagents used to prepare the test solutions
as well as from nonanalyte sample elemental constituents (Vaughan & Horlick,
1986; Munro et ai., 1986; Date et ai., 1987; Gray, 1986; Tan & Horlick, 1986).
In the isotope selection process the following are considered: analytical isotope
abundance, background isobaric species, and isobaric species resulting from
sample solution composition. Relative abundance of the isotopes of all natural
elements are given by Date and Gray (1989). Tables by Holden and Walker
(1972) and Weast and Astle (1979) contain not only the naturally occurring iso-
114 SOLTANPOUR ET AL
topes but those produced as a result of man's activities as well. These are useful
when used with the relative abundances in accurately calculating atomic masses
of the elements, and by themselves for those considering high resolution, double-
focusing ICP-MS.
Detection Limits (Inductively Coupled Plasma-Atomic Emission

Spectrometry)
Detection limit is defined as the analyte concentration equivalent to two
times the standard deviation of the background beneath the analyte line.
However, concentrations five times the detection limits are generally required for
quantitative measurements. Hence, the latter is referred to as "quantitative detec-
tion limit."
From the definition, it is obvious that detection limits are a function of
excitation source and sample matrix as they affect the intensity of background
radiation. The detection limits are also affected by sample delivery efficiency.
Detection limits are further affected by operational parameters of plasma spec-
trometers; such as power, height of observation, and the flow rate of sample car-
rier gas. The optimum operational parameters are often different for different
groups of elements, and therefore, one should select compromise operational
parameters for simultaneous multielement analysis.
Winge et at (1979) calculated the ICP detection limits of different ele-
ments (Table 5-1), assuming that the standard deviation of the background is
approximately 1% of the background signal level and that the detection limit is
three times the standard deviation of the background. The formula used for these
calculations is given in the footnote under Table 5-1. These values can be used
as first approximation in the absence of measured values for detection limits.
Table 5-2 gives the measured ICP detection limits of some elements in
pure water, in 10% HCl, and in a solution containing major elements of a typical
arid region soil digest (assuming a dilution factor of 50). The pure water values
were obtained from literature (Robin, 1979). Other values were determined at the
CSUSTL. The blank or 0 concentration solutions were analyzed 10 times to
determine the standard deviation of the background signal at the wavelength of
the elements of interest. These standard deviations were multiplied by two and
changed to their apparent concentration equivalents using appropriate calibration
curves. These values are called detection limits by definition.
The detection limits in 10% HCl solution are given for those elements for
which the CSUSTL ICP spectrometer has channels. The simulated soil digest
was prepared in a 10% HCl solution containing AI, Fe, K, Na, Ca, Mg, Ti, Mn,
and P; therefore, the detection limits for these elements are not given in the third
column of Table 5-2.
It should be emphasized that the two last columns of Table 5-2 represent
detection limits that are more realistic and could be obtained under outline con-
ditions. The detection limits close to those in 10% HCI are probably obtainable
for soil water extracts, NH4HC03-DTPA extracts, and other extracts of low back-
ground. However, for total soil digests, the last column of Table 5-2 is more real-
istic. It seems detection limits get poorer by one order of magnitude from soil
extracts to total soil digests.
Table 5-2. Detection limits in an ideal solution (pure water), 10% HCl, and in a simulated arid soil
digest.
ICP
Element Ideal solutiont 10% HCl:j: Simulated soil digest
l1g!mL
Ag 0.004
AI 0.0002 0.03
As 0.04 0.02 0.7
Au 0.04
B 0.0007 0.002 0.03
Ba 0.00002 0.001 0.001
Be 0.0004
Bi 0.05
Ca 0.00002 0.002
Cd 0.002 0.001 0.006
Ce 0.0007
Co 0.003 0.01 0.02
Cr 0.0003 0.003 0.01
Cu 0.0001 0.003 0.01
Fe 0.0003 0.003
Ga 0.0006
Hf 0.01
Hg 0.001 0.02 0.2
In 0.03
K 0.1
La 0.00005
Li 0.0003
Mg 0.00001 0.0004
Mn 0.00006 0.001
Mo 0.0002 0.004 0.02
Na 0.0002 0.01
Nb 0.00007
Ni 0.0004 0.005 0.009
p 0.02 0.03
Pb 0.002 0.03 0.07
Pt 0.08
Sb 0.2
Se 0.02 0.2
Si 0.01
Sn 0.03
Sr 0.00002 0.0006 0.007
Ta 0.002
Ti 0.00007 0.002
U 0.03
V 0.0002
W 0.0007
Zn 0.002 0.002 0.008
Zr 0.0004
t Data from Robin (1979).
:j: Data from CSUSTL.
Data from CSUSTL. Simulated soil digest contained 10% HCl and the following elements at the
given concentrations in micrograms per milliliter: AI = 1500, Fe = 500, K = 400, Ca = 200, Na =
200, Mg = 100, Ti = 60, Mn = 20, P = 15.
116 SOLTANPOUR ET AI...
Table 5-2 reveals the deterioration of the detection limits due to interele-
ment spectral interferences. For example, in the case of As, a detection limit of
0.7 ppm is shown. This detection limit will preclude determination of As in total
soil digests using direct nebulization. In this case, As is separated from major soil
constituents by the hydride generation technique (see "Determination of
Ultratrace Levels of Arsenic, Selenium, and Mercury by Use of Hydride-
Mercury Vapor Generator"). When interelemental interference is not as severe as
in the case of As, other correction techniques can be used (see "Correction for
Interferences (Inductively Coupled Plasma-Atomic Emission Spectrometry),,).
Detection Limits (Inductively Coupled Plasma-Mass Spectrometry)

Detection limits are one to three orders of magnitude lower by ICP-MS
than by ICP-AES for most elements measurable by both techniques. However,
there are a few key analytes of interest in soil and plant analysis that exhibit bet-
ter detection limits by ICP-AES than by ICP-MS; including S and Ca. A list of
ideal detection limits has been compiled by Date and Gray (1989). Some of the
detection limits listed by them can be lowered if necessary by adopting strict
cleanliness procedures to reduce analyte contamination in reagents and glass-
ware. Detection limits also can be improved by using mass spectrometers capa-
ble of resolution equal to or better than 3500 (Tsumura & Yamasaki, 1991;
Bradshaw et aI., 1989). In addition, detection limits could be reduced by increas-
ing the duty cycle on the analytical mass. This could be done by using time of
flight mass spectrometers instead of quadrupole mass spectrometers (Hieftje,
1992).
Net analytical signal for generic ICP-MS, in units of analyte response per
unit analyte concentration, decrease rapidly with increasing matrix element con-
centration and commence being degraded at lower matrix element concentrations
in ICP-MS than ICP-AES (Beauchemin, 1989; Houk & Thompson, 1988; Houk,
1986; Gregoire, 1989; Beauchemin et aI., 1987; Douglas & Kerr, 1988; Gregoire,
1987a,b). Thus, comparison of detection limits for the two methods is accurate
for describing analysis of test solutions with total dissolved solids up to approx-
imately 100 to 500 mg L-1, the range depending on several factors including the
mass(es) and ionization potential(s) of the matrix elements (Gregoire, 1989).
This fact, coupled with the outstanding detection limits exhibited by the ICP-MS,
makes it a more natural choice for a chromatographic detector than the ICP-AES.
With continuing interest in chemical speciation, numerous papers and publica-
tions have appeared in the area of ICP-MS involving ion exchange, HPLC,
and/or liquid-liquid solvent extraction prior to detection.
Comparison of detection limits between ICP-MS and ICP-AES must be
done on an analysis by analysis basis. If digestion of solid materials is involved,
the detection limits of ICP-MS and ICP-AES could be about the same because
the ICP-AES can tolerate 10 to 100 times more dissolved solids than the ICP-MS
before the analytical sensitivity becomes adversely affected. Many of the appa-
ratus mentioned in "Special Apparatus (Inductively Coupled Plasma-Mass
Spectrometry" are designed to allow the concentration of matrix element in the
sample solutions to be increased while maintaining the analytical response.
Interferences (Inductively Coupled Plasma-Atomic Emission

Spectrometry)
Solute Vaporation. In emission spectrometry, refractory compounds such
as calcium phosphates or calcium aluminates are vaporized in the excitation
sources and hence interfere with analysis. For example, Johnson (1979) showed
that AI suppresses the Ca signal in DCP emission spectrometry. The solute
vaporization interference is negligible in ICP (Larson et aI., 1975).
Ionization. When atomic or ionic species of an element in a plasma emit

their characteristic line radiation, any shift in the ratio between these two species
causes a shift in the intensity of the atomic and ionic lines. Johnson et ai. (1979b)
reported the enhancement effect of Cs and Li on K, Na, Ba, AI, Cr, etc. in DCP.
This enhancement effect is negligible in ICP when recommended parameters for
power input, observation height, and carrier gas flow rate are used (Larson et aI.,
1975).
Unwanted Radiation. Unwanted radiation refers to that radiation other
than the analyte radiation reaching the analyte detector. In any emission system,
the analyte signal consists of the wanted analyte radiation and the unwanted radi-
ation. The latter may be divided into the following categories (Ward & Myers,
1979):
1. Source background.
2. Extracting solution background.
3. Stray radiation in the spectrometer.
4. Spectral line or band interference.
Source background refers to the radiation originating, for example, from
Ar. This background radiation is very stable in the case of Ar plasmas. Extracting
solution background refers to the continuum originating from the extracting solu-
tion.
Stray light radiation in some direct readers creates the most serious error in
determination of trace metals (U.S. Dep. Commerce Nati. Tech. Inform. Serv.,
1977). Three main sources of stray light are: (i) grating scatter; (ii) reflections
and scatter in the secondary optics, i.e., the region between the exit slits and pho-
tomultipliers; and (iii) general scatter from reflections by internal surfaces of the
direct readers.
The grating scatter is due to the grating imperfections and has been dis-
cussed by Larson et ai. (1976). The degree of stray light interference of the lat-
ter two types depends on the engineering design of the direct readers and could
be reduced significantly by the use of nonreflective coatings, light traps, baffles,
and general optical design (U.S. Dep. Commerce Nati. Tech. Inform. Serv.,
1977).
The spectral line or band interferences arise when there are spectral over-
laps between the analyte and matrix element species. In some instances, matrix
element species may elevate the intensity of the background continuum. The
method used to correct for the spectral overlaps, background elevations, and
stray light interferences is discussed in "Corrections for Interferences
(Inductively Coupled Plasma-Atomic Emission Spectrometry)".
Correction for Interferences (Inductively Coupled Plasma-Atomic

Emission Spectrometry). To correct for solute vaporization effect, the analyst
should add a releasing agent to both sample and standards. For example, to
reduce the effect of AI on Ca, one may add Sr to both the sample and standard
solutions. The Sr will combine with AI and reduce its effect on Ca. To suppress
ionization interference, an easily ionizable element such as Cs or Li is usually
added to standard and sample solutions. These sample pretreatments are not nec-
essary for ICP-AES.
To correct for source and extracting solution background, the analyst will
zero the spectrometer with the blank solution made up of the extracting solution
(blank correction).
The interferences due to stray light, background elevation, and spectral
overlaps could be corrected for if the blank and the sample solutions were iden-
tical in composition except for the analyte. This ideal solution is beyond the prac-
tical realm, especially when a multielement analysis is desired. However, if the
samples are rather uniform in major interfering species, these could be added to
the blank and the standards to compensate for their interference. But addition of
major interfering species to the sample solutions prevents analysts from deter-
mining these elements with other elements simultaneously. This dilemma is
resolved by using a scheme known as interelemental spectral interference cor-
rection, which is discussed below.
Interelemental interference is observed when the analyte detector (channel)
receives signals from the interfering elements.
When the soil water extracts, NH4HC03-DTPA extracts, dilute acid
extracts, and other extracts with low concentrations of interfering element are
analyzed by ICP, the degree of interelemental interference is usually small.
However, a soil analysis for total elemental content results in high concentrations
of interfering elements and correspondingly large interelemental interferences. In
the latter case, one should determine significant interelemental interferences in
sample solutions and correct for them.
To determine the degree of interelemental interference, the spectrometer
should be standardized, a pure solution of interfering (affecting) elements should
be aspirated, and the apparent concentration of the affected elements determined.
When the sample is analyzed, the concentration of the interfering elements is
determined and the necessary corrections made on the apparent concentration of
the affected elements. Computer programs are available for the automatic cor-
rection of the interelemental interference (Dahlquist & Knoll, 1978).
The following example is given to show the use of the interelemental inter-
ference correction method. A synthetic solution containing 1.0 mg L-1 of Pb read
3.66 mg L-1 of Pb when AI, Fe, K, Ca, Na, Mg, Ti, Mn, and P were added to the
Pb solution as 1,500-,500-,400-,200-,200-, 100-,60-,20-, and 15-mg L-1 con-
centrations, respectively. When pure solutions of the above elements at the above
concentrations were aspirated into the plasma, the apparent concentrations of Pb
were 2.62, 0.164, and 0.038 for AI, Fe, and Ti solutions, respectively. Other ele-
ments did not produce any noticeable unwanted radiation at the Pb wavelength
(220.3 nm). Subtracting the above interferences from 3.66 gave a Pb value of
0.84, which is much closer to the true value of 1.0 mg L-1 than the uncorrected
value of 3.66. In this case, the spectrometer was not restandardized before the
high background Pb solution was read. This may explain the reason for obtain-
ing 0.84 value instead of 1.0 for Pb. However, when a solution containing all the
above element concentrations except Pb was aspirated, it gave an apparent Pb
concentreation of 2.80, which is almost identical to the sum of the apparent Pb
concentrations in AI, Fe, and Ti solutions. The above example shows the validi-
ty of interelemental interference correction method discussed above.
Some precautions to be observed in interelemental spectral interference
correction are discussed in the remainder of this section. Care must be taken to
ensure that an adequate rinse between the introduction of each interferential solu-
tion is performed. Pure chemicals such as SpecPure (Curtis Matheson Scientific,
Inc. Chern Pure Brand, Houston, TX) reagents should be used for determination
of interelemental interferences. If the chemicals are not pure, an impurity of ana-
lyte in these chemicals will create rather large errors in the results. For soil HF-
HCI0 4 digests, the interference of major soil constituents on other elements
should be determined. Soil extracts also should be examined for possible
interelemental interferences. These interferences are specific for a given instru-
ment depending on the wavelength used for each element and effective use of
baffles and black interiors to reduce stray light interferences.
In the instrument (Jarrell-Ash Model 975 ICP AtomComp) used at the
CSUSTL, it was found tha~ the following elements significantly interfere with
some trace elements in HF-HCI0 4 soil digests: AI, Fe, Mg, Mn, and Ti. However,
one should be on guard against interference from other elements that may be
found in large quantities in contaminated soils. The interelemental spectral inter-
ferences found in the ICP-AES system mentioned above are shown in Table 5-3.
In the Colorado State University instrument, Ca interference with other elements
is very low in contrast with published reports on another instrument (U.S. Dep.
Commerce Natl. Tech. Inform. Serv., 1977).
The order of elemental correction is important (Marciello & Ward, 1978).
As a general rule, interelement correction should be programmed into the com-
puter in the following order:
1. Major matrix components as interfering elements.
2. In order of magnitude of interference effect for minor matrix compo-
nents.
In correcting for interelemental interference, one should be aware of the
fact that inference per unit concentration of the interfering element may not be
linear. This has been shown to be the case in the particular instrument used for
the Ca interference on As, Se, Pb, and Sn (U.S. Dep. Commerce Natl. Tech.
Inform. Serv., 1977). In this event, curves should be plotted showing the appar-
ent concentration of the affected element as a function of the concentration of the
affecting elements. These curves should then be used to correct for interelemen-
tal interferences. Computer programs and computers interfaced with the direct-
readers capable of performing these tasks wit make the interelemental interfer-
ence corrections easier and much faster.
Another scheme for interference correction, called background correction
by some, is by the use of a device called a spectrum shifter. The spectrum shifter
N
...<=
Table 5-3. Examples of some interelemental spectral interferences observed in an ICP spectrometer at the CSUSTL.
Wavelength (nm)
Affecting 324.7 206.2 x 3 213/6 x 2 202.0 214.4 228.6 267.7 407.7 249.7 455.4 220.3 253.6 193.6 196.0
element Concentration Cu Zn Ni Mo Cd Co Cr Sr B Ba Pb Hg As Se
llg/mL Apparent concentration of affected elements llg/mL
K 400t
Ca 50 0.003
200t 0.002 0.D15 0.024
500 0.004 0.039 0.079
Mg 50 0.007 0.009 0.005 0.004 0.006 0.024 0.054
lOOt 0.012 0.012 0.005 0.008 0.010 0.039 0.043 0.087
200 0.024 0.038 0.008 0..013 0.004 0.066 0.083 0.168
Na 200t
P 15t 0.030
Ti 60t 0.026 0.003 0.111 0.008 0.028 0.038 0.197
Mn 20t 0.002 0.003 0.010 0.D18
Fe 100 0.005 0.006 0.011 0.010 0.008 0.016 0.004 0.285 0.064 1.36 0.053 0.083
500t 0.014 0.021 0.048 0.044 0.046 0.072 0.024 1.32 0.164 6.96 0.250 0.564
1000 0.025 0.040 0.093 0.082 0.088 0.140 0.046 2.51 0.004 0.302 13.1 0.494 1.07
AI 500 0.088 0.002 0.253 0.080 0.008 0.053 0.006 0.006 0.866 0.019 5.96 1.46
rJl
1000 0.002 0.176 0.013 0.517 0.164 0.008 0.016 0.106 0.020 0.012 1.76 0.030 12.2 2.90 0
1500t 0.002 0.261 0.016 0.760 0.242 0.018 0.024 0.156 0.020 0.D18 2.62 0.054 18.0 4.28 ~
High background solutiont 0.046 0.295 0.080 0.807 0.288 0.200 0.074 0.172 1.26 0.023 2.80 6.84 18.2 4.98
~
t Indicates high background solution was made from the elements and concentrations marked by t. All solutions were 10% in HCI. -=0
~
:=
~
>
r
measures the background radiation close to the analyte exit slit. This radiation is
assumed to originate from nonanalyte sources and to increase the radiation at the
analyte wavelength. The average background radiation signal is subtracted from
the signal observed at the analyte wavelength to correct for the interference. This
correction method may be used when the analyst is not aware of all the con-
stituents of the sample or deals with samples of varying matrixes. This correc-
tion method is obviously not valid when the background radiation received at the
analyte wavelength is grossly different from the one measured by the spectrum
shifter.
Interferences (Inductively Coupled Plasma/Mass Spectrometry)

In a concise explanation of interference effects in ICP-MS, Conrad
Gregoire (1989) has divided the subject of interference effects in the ICP-MS
into three areas. These are isobaric interference, nonspectroscopic interference,
and mass discrimination. The isobaric problems were subdivided further into two
categories: (i) Molecular ion interferences including oxide ions, and (ii) Spectral
interferences due to other elements. The nonspectroscopic suppression effects
were discussed in the context of space charge and ionization suppression effects.
Mass discrimination effects were viewed in two categories: (i) Instrumental mass
discrimination, and (ii) Matrix dependent mass discrimination. To the discussion
of nonspectroscopic interference will be added suppressions due to solids depo-
sition on the sampler and skimmer cones and suppressions due to solute vapor-
ization.
Solids Deposition on Sampler and Skimmer Cones. Deposition of solids
on the skimmer and sampler cones can cause unwanted changes in the analytical
response, i.e., reductions in the quantity (ion arrival rate at the detector per unit
analyte concentration in the test solutions) (Douglas & Kerr, 1988). At the
DANR Analytical Lab, long runs involving analytical measurements on plant
digests prepared using a microwave bomb technique (Sah & Miller, 1992) have
been made using the ICP-MS instrumentation. During a run, coatings of calcium
sulfate and oxide on the sampler and skimmer cones occur. Unless the dilution
factors and sample nebulization times of the test solutions are carefully con-
trolled, the solid depositions on the sampler and skimmer cones can result in seri-
ous suppression of analytical response. The coating of the skimmer cone near the
tip, to the point of obstructing the orifice, causes the most serious decrease in
analytical response; which persists independent of matrix element concentration
in the test solution for the duration of the analytical run. The suppression can be
at once eliminated by cleaning the skimmer cone.
Non-Spectroscopic Interferences (Inductively Coupled Plasma-Mass
Spectrometry). Nonspectroscopic interference is the general term adopted in
ICP-MS for describing reduction in analytical response with increasing matrix
element concentration in the test solution. Nonspectroscopic interference is a
complex issue, with several factors contributing to the suppression(s) observed.
To successfully use ICP-MS for soils analysis, the major element concentration
of the solutions must be anticipated to vary widely. Among the several factors
discussed below are: (i) Solute vaporization, (ii) Ionization suppression, and (iii)
Space-charge.
Solute vaporization interference occurs in instances in which the solute
does not have sufficient time and/or the source does not have sufficient energy to
dissociate the solute before the analytical species moves into and through the
region of observation. Typical manifestations of the interference are suppression
and/or increased variability of the analyte signal as a function of increased con-
comitant concentration. For example, Johnson et al. (1979a) showed that AI sup-
presses the Ca signal in a direct current plasma. Winge et al. (1991) published
high-speed photographs providing evidence that species generally associated
with low spectroscopic temperatures can persist through the central channel of
the ICP to enter the sampling cone of the ICP-MS, and discussed similar reports
of unvaporized solvent doing the same. Ionization interferences can be noted for
ICP-MS. Partially ionized elements in an ICP, e.g., Au and B, are susceptible to
ion suppression from fully ionized interferants (smaller effective analyte ion
molar ratio/interferant ion) and less effective in causing ion suppression for fully
ionized analytes (larger analyte ion molar ratio/interferent ion) (Gregoire, 1989).
In ICP-MS measurements, ionization interferences cause suppression of analyti-
cal response (Houk & Thompson, 1988; Tan & Horlick, 1986).
Easily ionized matrix element interference has been recognized in ICP-MS
data. For a given matrix element ion interference, the analytical response for the
lighter atomic mass isotopes are suppressed more than the heavier ones. For a
given analyte, lighter matrix elements suppress the response less than the heav-
ier ones. These trends are consistent with what would be expected from a space-
charge effect (Gregoire, 1989; Hieftje, 1992). Tracing the course of the ions from
the point of ion production in the plasma, the ions that move through the sampler
and skimmer, through the ion optics, and through the quadrupole, are reflected
away from the deflector and accelerated onto the detector. As the particle beam
electrons diffuse out of the beam more quickly than the positive ions-a process
termed ambipolar diffusion (Ahearn, 1972). As a consequence, coulombic repul-
sion spreads the ion beam. The larger ions stay on course better than the lighter
ones. Equivalently, the trajectories of the lighter ions are affected more by the
ions of the heavier mass isotopes than the trajectories of the heavier ions are
affected by the lighter mass isotopes.
In practice, it is difficult to separate the nonspectroscopic interferences.
These can be compensated for by matrix matching, but that seriously limits the
range of matrix element concentration variability between test solutions within
the run. Another approach that has been used successfully by many is the inter-
nal standard calibration method, discussed in "Methods of Correction for
Interferences and Standardization Procedures (Inductively Coupled Plasma-
Mass Spectrometry)."
Mass Discrimination. Gregoire (1989) defines mass discrimination as
bias in ion transmission to the detector the magnitude of which is dependent
upon the mass of the analytical isotope. Further, the effects can be divided into
two categories depending upon the origin of the mass bias. The first category is
referred to as instrumental mass discrimination effects which are the result of
mass discrimination occurring at the interface (sample and skimmer cones), ion
lenses, quadrupole mass filter and detector. Correction factors for instrumental
mass discrimination are normally found by comparing measured isotope ratios to
the known isotope ratio for a substance of known or certified isotopic composi-
tion, and applying the correction to the samples run during the same time.
Instrumental mass discrimination can range from 50% per dalton for light ele-
ments to 2% per dalton for heavy elements.
The other type of mass discrimination results from the presence of matrix
elements, has been reported only twice, and effects only Li and B. Briefly, the
magnitude of the effect is dependent upon five factors:
1. Absolute mass of the analyte.
2. Degree of ionization of the analyte.
3. Difference in mass between the two isotopes.
4. Mass of the matrix elements.
5. Degree of ionization of the matrix elements.
The above dependent factors involved with this effect are very similar to the
space-charge interpretation of analyte response suppression, so for all practical
purposes matrix dependent mass discrimination can be considered a special case
of the more general space-charge effect. The interested reader is referred to
Gregoire (1989) for more details.
Unwanted Ions (Inductively Coupled Plasma-Mass Spectroscopy).
Unwanted ions refer to that part of the ion beam other than the analyte ion part
reaching the detector. In a mass spectrometer system, particularly one operated
with peak widths in the neighborhood of one dalton, the analyte signal may be
accompanied by unwanted ions. These unwanted ions occur as a consequence of
several factors (Gray, 1985; Date & Gray, 1989; Gregoire, 1989; Vaughan &
Horlick, 1986; Munro et aI., 1986; Date et aI., 1987; Gray, 1989; Tan & Horlick,
1986), and include the following:
1. Elemental ions (NM+) of the same unit mass as the analyte isotope
(NN).
2. Elemental hydride (N{N-IMIHV) molecular ions that are of the same
unit mass as the analyte isotope (NA +).
3. Element oxide (N{N-16M160+) molecular ions that are of the same unit
mass as the analyte isotope (NA +).
4. Element hydroxide (N{N-17M1601HV) molecular ions that are of the
same unit mass as the analyte isotope (NA +).
5. Elemental (2NM2+) ions that are doubly charged and twice the unit mass
of the analyte isotope (NA +). Also, for unit resolution spectrometers,
elemental 2N-l)M2+) and (2N+IlM2+) ions must be included as ions that
will overlap, albeit partially with the analytical mass (NA +).
6. Elemental Argide (N{N-36M36Ar}+' N{N-38M38Ar}+' N{N-40M 40 ArV)
molecular ions that are of the same unit mass as the analyte isotope
(NN).
7. Elemental Hydrogen Argide (N{N-37MIW6Ar}+' N{N-39MIH38Ar}+'
N{N-41MIH40ArV) ions that are of the same unit mass as the analyte iso-
tope (NA+).
Methods of Correction for Interferences and Standardization Proce-

dures (Inductively Coupled Plasma-Mass Spectrometry). The presence of
both isobaric and nonspectral matrix dependent interferences requires special
attention. Several papers describe in more or less detail the procedure used to
correct isobaric overlap (Date et aI., 1987; Tsumura & Yamasaki, 1991; Evans &
Ebdon, 1989; Lam & McLaren, 1990). Methods for correcting for analyte
response changes as a function of time and matrix element concentrations in test
solutions have also been described and evaluated (Doherty, 1989; Thompson &
Houk, 1987; Johnson et aI., 1992a,b). Software issued by the instrument manu-
facturers corrects for isobaric interference, allows periodic update of calibration
data to correct for drift, and includes internal standard correction calculations to
correct for analyte response changes as a function of matrix element concentra-
tion in the test solutions. In addition, several instrument add-ons are available
that tend to reduce the isobaric and/or nonspectroscopic matrix dependent inter-
ferences.
In a correction scheme routinely used at the DANR Analytical Lab
(Johnson et aI., 1992a,b), from two to four levels of analyte concentration
(including 0 ).lg L-1) are prepared in triplicate as calibration standard solutions.
Two- thirds of these are spiked with an appropriate concentration of Y, e.g., 100
and 200 mg L-1. The Y is purchased as the oxide at 99.999% purity and dis-
solved using nitric acid. Single element concentrations of the major concomitants
generally representative of the concentrations anticipated to be found in the sam-
ples are prepared in a similar manner, i.e., with and without Y. The calibration
solutions are run at the beginning of the analytical run sequence and approxi-
mately every 20 to 30 samples thereafter, and again at the end of the run
sequence. Three internal standards are used to cover the instrument mass range.
These are usually Be, In, and Bi, but can be varied as necessary depending on
whether or not any of these are analytes. Data are written on the hard disk of the
computer in a format standardized by the manufacturer (Perkin Elmer Sciex, 500
ICP-MS hardware, 5000 ICP-MS software). The file is copied onto a floppy disc,
transported to an off-line computer, and processed with a BASIC program for
importation into the Quattro Pro spreadsheet by Borland.
Concentrations are estimated by a simple four-step procedure:
1. Zero).lg L-1 response calculated.
2. Isobaric interferences corrected.
3. Analytical response corrected for nonspectroscopic interferences.
4. Concentrations computed.
In the absence of spectral interference, accuracy of measured vs. true con-
centration estimates for the standard concentrations read as samples depend
somewhat on the number of internal standards applied to the data. In step three
above, as many as three internal standards have been applied to data for one ana-
lytical isotope in either a sequential or simultaneous fashion using regression sta-
tistics. Note that interaction terms can be, and are included with the simultane-
ous regression model. Accuracies of measured concentrations improve from
15% to better than 1.5% of the corresponding true concentrations from one to
three iterations using Bi, Be, and In as internal standards. Accuracy is about the
same with sequential vs. simultaneous, but the simultaneous is easier to apply.
Trends for improvement in analytical sensitivities (Skogerboe & Grant, 1970)
were about the same as noted for accuracies. While the isobaric overlap correc-
tion procedure is still being evaluated, it appears that the calibration - subtrac-
tion approach, supplemented by assumptions concerning the natural distribution
of the interfering isotopes where convenient and/or necessary, can yield correc-
tions within 2.5% of the true correction. The accuracy of the final results then
depends on the severity of the specific interference (Johnson et aI., 1979b).
Practical Applications
Grinding Soil Samples
Soil samples should be air dried as close to the time of sampling as possi-
ble (drying and grinding of soil samples are not recommended for Mn and Cr).
Soil samples may contain clods or large aggregates. Many laboratories use auto-
matic grinders to crush soil. Recent studies have shown that the amount of
extractable micronutrients from soils is affected largely by the degree of grind-
ing (Soltanpour et aI., 1976, 1979a); therefore, grinding variables such as force
and time should be standardized. When soils are ground for extractable microele-
ments, care must be taken to avoid excessive grinding. It is important to use
grinders that do not contaminate the soil. At the CSUSTL, a high-density alu-
minum oxide auger made by the Coors Porcelain Co., Golden, Colorado, is
attached to a Nasco-AspIin automatic grinder. The grinder is equipped with a 2-
mm stainless steel sieve. This grinder minimizes the degree of soil contamina-
tion with trace elements. In soil analysis, it is a standard procedure to pass the
soil through a 2-mm sieve after mild grinding. Then all analytical results are
based on a 2-mm soil. For total elemental analysis, the 2-mm soil may be further
ground so that all of it passes through a O.16-mm (lOO-mesh) polyvinyl chloride
(PVC) sieve.
Obtaining Soil Extracts

For simultaneous multielement determination, obviously single-element
extraction solutions are not useful. Therefore, Soltanpour and Schwab (1977)
developed a 1M NH 4HCO T O.005M DTPA (AB-DTPA) solution for simultane-
ous extraction of P, K, Zn, Fe, Cu, Mn and nitrates from soils. This test was mod-
ified by Soltanpour and Workman (1979) to omit C black, which sometimes con-
taminated the sample and adsorbed metal chelates. The above test is routinely
used by the CSUSTL to assess soil fertility of the Colorado farms. After extrac-
tion, ICP-AES is used to simultaneously analyze these extracts for P, K, Zn, Fe,
Cu, and Mn. Experience has shown that AB-DTPA solution should be acidified
to get rid of the carbonate-bicarbonate matrix in order to prevent clogging of the
capillary tip (Soltanpour et aI., 1979b). However, use of high salt nebulizers
(Legere & Burgener, 1985) has obviated the use of acid pretreatment
(Soltanpour, 1991).
Soil water extracts and DTPA extracts (Lindsay & Norvell, 1978) can be
analyzed by ICP-AES. We are analyzing the soil saturation extracts simultane-
ously for Ca, Mg, Na, and K and then calculating the Na absorption ratio. Plant
digests also are analyzed by ICP-AES.
The CSUSTL and many environmental laboratories in the western U.S.
analyze mine overburden and mine spoil materials by use of AB-DTPA and ICP-
AES for P, Zn, Cu, Mn, B, Cd, As, Se, Mo, Pb, Ni, and other elements for screen-
ing these materials for their potential toxicity to plants and their consumers
(Soltanpour, 1991). The AB-DTPA extract is low in Ca, Mg, AI, Fe, Mn and Ti,
which cause interelemental interference, and therefore is well adapted to ICP-
AES analysis. Obviously water extracts are ideal for ICP-AES determinations,
but some elements in water extracts are found in very low concentrations that are
below the ICP-AES detection limits.
Jones (1977) determined Ca, K, Mg, and P simultaneously in the double-
acid extracts of Georgia soils.
The type of vessel and shaker and the speed of the shaker may affect the
amount of some extractable elements, but their effect is small compared with the
grinding variables (Soltanpour et aI., 1976).
For obtaining saturation extracts, refer to Chapter 14 (Rhoades, 1996). For
obtaining double-acid extractions, refer to Chapter 19 (Helmke & Sparks, 1996).
For obtaining Mehlich 3 extracts (a modification of double-acid extract for mul-
tielement extraction) refer to Chapter 19 (Helmke & Sparks, 1996).
Special Equipment
1. Reciprocal shaker.
Reagents
1. Ammonium bicarbonate (NH4HC03).
2. Diethylenetriaminepentaacetic acid (DTPA).
3. Ammonium hydroxide (N~OH).
5. Ammonium bicarbonate-diethylenetriaminepentaacetic acid solution
(AB-DTPA).
To make aIM NH4HCOr -O.OO5 M DTPA solution, add 1.87 g of DTPA
to 800 mL of distilled-deionized water (DDW). Add approximately 2 mL of 1:1
NH40H to facilitate dissolution and to prevent effervescence. Shake until most
of the DTPA is dissolved. Then add 79.06 g of NH4HC0 3, and stir gently until
dissolved. Adjust the pH to 7.6 with NH40H. Dilute the solution to 1.0 L with
DDW. This solution is unstable with regard to pH. If the solution is stored under
about 3 cm of mineral oil, the pH remains stable. However, it is preferable to use
a fresh solution.
Procedure. Weigh 10 g of a 2-mm soil into a 125-mL conical flask. Add
20 ml of AB-DTPA solution. Shake on the reciprocal shaker for 15 min at 180
cycles/min with flasks kept open. Filter the extracts through Whatman no. 42 fil-
ter paper or its equivalent. Take a 2-mL aliquot of the extract, and add 0.25 mL
of concentrated HN0 3 Shake for 10 min to get rid of carbonate-bicarbonate
matrix to prevent clogging of the capillary tip in cross-flow or concentric nebu-
lizers. This solution is now ready for simultaneous multielement determination.
With high-salt nebulizers (Babington type) the acid pretreatment is not required.
Digestion of Organic Matter and Dissolution of Silicates

for Total Elemental Analysis
Digestion (oxidation) of organic matter and dissolution of silicates are nec-
essary steps in bringing all elements into solution. These processes are referred
to as digestion in this chapter. Certainly, it is advantageous to use methods that
yield themselves to multisample rather than single sample digestion. Another
important consideration in choosing a method is preservation of the easily
volatilized elements in the sample. Fusion and other high temperature methods
of digestion lead to the loss of volatile substances such as As, Se, Sb, and Hg.
The method described below avoids the loss of As, Se, and Sb in the presence of
silicates (Bajo, 1978); therefore, we recommend this method. Research is under
way on the use of other methods such as the use of capped polyethylene bottles
for HF digestion of siliceous material (Odegard, 1979; Langmyhr & Paus, 1968;
see Chapter 3, Hossner, 1996). An all-Teflon bomb (Bernas, 1968; Lechler &
Leininger, 1979) has been used for analysis of siliceous material.
Special Equipment
1. Stainless steel perchloric hood.
2. Hot plate.
3. Teflon beaker, 100 mL.
4. Teflon watch cover.
Reagents
1. Perchloric acid (HCI04).
2. Nitric acid (HN03).
3. Hydrofluoric acid (HF).
4. Hydrochloric acid (HCl).
Procedure. Weigh 1.0 g of the lOO-mesh (0.15-mm) soil into a 100-mL
Teflon beaker. Add 10 mL of HN0 3 and 10 mL of HCI04 Cover with a Teflon
watch cover, and heat at 200C for I h. Remove the cover and continue heating
until the volume is 2 to 3 mL. Cool the sample, add 5 mL of HCI04 and 10 mL
of HF, cover with a Teflon watch cover, and heat overnight at 200C. Overnight
digestion is for convenience, but one may terminate digestion as soon as all
siliceous material has been dissolved. Remove the cover, and continue heating
until the volume is 2 to 3 mL. Cool the digest, add 10 mL of 50% HCI, cover,
and heat at 100C for 30 min. Remove from the hot plate, and allow it to cool.
Transfer the solution quantitatively into a 50-mL volumetric flask, and bring to
volume. The solution is then ready for ICP determination.
Comments. The reason a 100-mesh (0.15-mm) soil sample instead of a 2-
mm sample is used in digestion is to speed up the breakdown of silicates. At the
CSUSTL, 2-mm soil samples have been digested with no difficulty when soils
were digested overnight in the presence of HF-HCI04
The HCI04 hood should be washed periodically to remove perchlorates
and to avoid danger of explosion. Do not let HCl04 solution get dry, anhydrous
HCl04 is explosive.
Analysis of Soil Extracts and Digests

Special Apparatus
1. An inductively coupled plasma atomic emission spectrometer.
Special Apparatus (Inductively Coupled Plasma-Mass Spectrometry).
There are several different after manufacture add-ons available for sample
aerosol production and/or introduction for ICP-MS systems from different man-
ufacturers. These include USN, DIN, HPLC systems (Braverman, 1992), FI
accessory (Thompson & Houk, 1986; Dean et aI., 1988; Denoyer & Stroh, 1992;
Denoyer et aI., 1991a), hydride generation equipment (Denoyer & Stroh, 1992a),
ETV accessory (Denoyer et aI., 1991a), and LASER ablation solid sampling
equipment (Denoyer, 1991; Hager, 1989; Abell, 1991; Denoyer et aI., 1991b;
Pearce et aI., 1992). These accessories also are available for use on ICP-AES
instrumentation.
One of the most versatile pieces of equipment in this list is the FI accesso-
ry (Denoyer & Stroh, 1992). There are many possible physical and chemical pro-
cedures that can be combined with the ICP-MS via a flow injection apparatus,
including on-line dilution, isotope dilution, standard additions, hydride genera-
tion, cation exchange, anion exchange, and ETV. The flow injection apparatus
introduces a discrete sample aliquot into a flowing carrier stream for direct
analysis of solutions. Sample volumes for a typical analytical measurement range
from 50 to 500 pL, compared to 1 to 3 mL for continuous solution aspiration.
Full mass scans can be performed on a quadrupole in about 100 ms, or 10 scans
per second. The high scanning speed of the quadrupole allows transient signals
generated by flow injection to be captured and measured. Relative standard devi-
ations are 2 to 5% on replicate injections. Rinse-out times are considerably short-
er for FI-equipped systems than for intermittent nebulization. An impressive
advantage of FI is that it allows analysis of solutions containing approximately
50 times more matrix element concentration than conventional nebulization
equipment for comparable reductions in analytical response due to nonspectro-
scopic matrix dependent interferences; putting the acceptable level of dissolved
solids in the test solutions in the 0.5 to 2.5 g per 100-mL range. Use of the FI
apparatus also reportedly prevents clogging of sampler and skimmer cones while
reducing the amount of solids deposited on them per sample solution. Fourfold
increases in sample throughput per unit have been reported using FI (Dean et aI.,
1988).
Preparation of Stock Standard Solutions. Any emission spectrometric
method compares the emission signals from the sample solutions with that of the
standard solutions to determine the composition of the sample solution.
Therefore it is imperative that extreme care be taken in preparing standard solu-
tions. It is recommended that ready-to-use standard solutions of highest purity be
purchased. In some developing countries these ready-to-use standards may not
be available. Therefore, in the following paragraphs we have described a method
for preparation of standards. All acids used for dissolution should be of high
purity, such as Hi-Pure or Ultrex grade. Water used for dilution should be dis-
tilled-deionized. Table 5-4 adapted from Ward (1978b) can be used for prepara-
tion of solutions containing 1000 mg L-l of an element.
Table 5-4. Primary standard solution preparation (adapted from Ward, 1978).t
Element Compound Weight Solvent
g
AI AI 1.0000 6MHCI
AlCI3 6HzO 8.9481 1MHCI
Sb Sb 1.0000 Aqua regia
SbCI 3 1.8736 1MHCI
As As 1.0000 4MHN03
Asz0 3 1.3203 4MHCI
Ba BaClz* 1.1516 Water
BaC03* 1.4369 0.05MHN0 3
BaN03 1.9029 Water
Be Be 1.0000 0.5MHCI
BeO* 2.7753 0.5MHCI
Bi Bi 1.0000 4MHN0 3
Bi z0 3 1.1149 4MHN03
Bi (N03)3 5HzO 2.3211 1MHN03
B B 1.0000 4MHN03
H3B03 5.7195 Water
Cd Cd 1.0000 4MHN0 3
CdO 1.1423 4MHN03
Ca CaC03 2.4972 0.5MHN0 3
Ca (N03)z 4HzO* 5.8920 Water
Cr Cr 1.0000 4MHCI
CrCI 3 (6H20) 5.1244 Water
Co Co 1.000 4MHCI
CoCl z 6 HzO 4.0373 Water
Cu Cu 1.0000 4MHN0 3
CuO 1.2518 4MHN0 3
In In 1.0000 Aqua regia
Fe Fe 1.0000 4MHCI
Fez03 1.4297 4MHCI
Pb Pb 1.0000 4MHN03
PbO 1.0772 4MHN03
Pb (N0 3)z 2.6758 Water
Li Li zC0 3 5.8241 1MHCI
LiCI 6.1092 Water
Mg MgO 1.6581 0.5MHCI
MgCLz 6HzO* 8.3625 Water
Mn Mn 1.0000 4MHN0 3
MnOz 1.5825 4MHN0 3
Hg HgClz 1.3535 Water + 1 g (NH4)zSzOg
Mo Mo 1.0000 Aqua regia
Mo0 3 1.5003 Aqua regia
Ni Ni 1.0000 4MHCI
NiO 1.2725 4MHCI
NiClzo 6HzO 4.0489 Water
Nb NbzOs 1.4305 Minimum quantity of HF, add 1 M HCI
P NaHzP04 3.8735 Water
NH4HzP04 3.7137 Water
K KCI 1.9067 Water
KZC03 1.7673 1MHCI
Se SeOz 1.4053 Water
Si Na zSi0 3 9HzO* 10.1190 Water
Ag Ag l.OOOO 4MHN0 3
AgzO 1.0742 4MHN03


Element Compound Weight Solvent
Na NaCI 2.5421 Water
Na2C03 2.3051 IMHCI
Sr SrC03 1.6849 IMHN0 3
Sr(N03h 2.4152 Water
Te Te02 1.2508 4MHCI
TI Tl20 3 1.1174 4MHCI
TICI 1.1735 Water
Sn Sn 1.0000 4MHCI
SnCI 20 2H 2O 1.9010 4MHCI
Ti Ti 1.0000 4MHCI
V V 1.0000 4MHN0 3
Zn Zn 1.0000 4MHN0 3
ZnO 1.2448 4MHN0 3
Zn (N03h 6H2O 4.5506 Water
t Use 100 to 150 mL of solvent to dissolve and bring to 1 L volume to give a concentration of 1000
mg L-l of element.
:j: Not Specpure materials.
Standardization Procedures (Inductively Coupled Plasma-Atomic

Emission Spectrometry). In calibrating the ICP spectrometer, one should con-
sider the concentration range to be used, the interelement interference correction,
and the stability of the standards. Mixtures of chemicals that cause precipitation
should be avoided. McQuaker et al (1979) devised a calibration scheme for 30
elements that satisfies the needs of analysts in soil, water, tissue, and particulate
matter analysis. In soil analysis, one set of secondary standards is required for
each extracting solution and another set for the total soil digest. In making a mul-
tielement standard solution, one should avoid making solutions containing high
concentrations of affecting and low concentrations of affected elements (see
Table 5-3).
Interelemental effects are measured by using single element solutions pre-
pared with Specpure chemicals. Appropriate computer software is used to cor-
rect for interelemental effects. In case of nonlinear interference, computer soft-
ware should be able to store correction curves for interelemental corrections.
Secondary standards should be made in such a way that standard solutions
match the sample solutions in concentration of acids. For AB-DTPA extracts,
standards should be made in 1 M NH4HCOr O.005 M DTPA solution that has
been neutralized with concentrated HN03 (Soltanpour & Workman, 1981). For
HN03-HCI04-HF digests, standard solutions should be made to contain 5%
(vol/vol) HCl04 and 10% (vol/vol) HCl.
Comments. The operational parameters that have been used with the ICP
spectrometer (Jarrell-Ash 750 AtomComp); Jarrell-Ash Corp., Waltham, MA) at
the CSUSTL are given here to aid in interpretation of data given in Tables 5-2
and 5-3: sample flow rate, 0.7 mLimin; Ar pressure, 550 kPa (80 Ib/in.2); aerosol
carrier Ar flow rate, 1 Llmin; Ar plasma support flow rate, 17 Llmin; capillary
used in cross flow nebulizer, tungsten carbide (o.d. = 0.99 mm, i.d. = 0.25 mm);
height of observation above coil (NAZ), 15 mm; incident power, 1.25 kW;
reflected power, <3 W.
NaBH4
Solution
To
plasma
Sample
60ml coarse
fritted disc
Buchner funnel
Drain
Argon
Pumps l2Imin
Fig. 5-5. The hydride and mercury vapor generator.
It should be noted that the operational procedure of different ICP spec-

trometers cannot be given in a chapter such as this. When a particular ICP spec-
trometer is purchased, usually the manufacturers will train the analysts in opera-
tional procedures and in solving any operational problems that may arise.
Determination of Ultratrace Levels of Arsenic, Selenium, and Mercury

by Use of Hydride-Mercury Vapor Generator
The hydride-mercury vapor generator is used to determine ultratrace levels
of As, Se, and Hg in soil extracts and total soil digests. Pneumatic nebulization
is not useful when levels of these elements are lower than 100 Jlg/L. In contrast,
the hydride-mercury vapor generator will enable the analyst to quantitatively
measure levels as low as 1.0 Jlg/L.
Soil extracts must be pretreated before introduction into the hydride gen-
erator. The oxidation state of the analyte is critical. Selenium (IV) is readily
reduced to the hydride, but Se(VI) is not. Arsenic (III) is more readily reduced
than As(V). Also, organic constituents in the extracts interfere with hydride gen-
eration and should be destroyed. At present, no pretreatment procedure has been
found to simultaneously pretreat extracts for Se and As analysis. The Se pre-
treatment is not effective in reducing As(V) to As(III), and the As pretreatment
reduces Se to the metal form, which will not form the hydride.
The total digest solutions resulting from the procedure given in
"Procedure" should contain only Se(IV) so that no pretreatment for Se analysis
is needed. However, for As determinations the digest solution must be pretreat-
ed.
Mercury may be determined in solutions pretreated for Se or As analysis.
It is recommended that spike recovery studies be performed on the particular
type of solution to be analyzed to verify the accuracy of the technique.
Special Equipment
1. Hydride-mercury vapor generator (Fig. 5-5).
2. Hot water bath.
3. Calibrated 50-mL digestion tubes.

Reagents
1. Concentration hydrochloric acid (HCI).
2. Hydrogen peroxide (H 20 2), 30%.
3. Sodium borohydride (NaBH4) solution: in 1 L of DDW first dissolve
0.5 g of sodium hydroxide (NaOH), then 2.0 g of NaBH4.
4. Potassium iodide-ascorbic acid solution: in 100 mL of DDW, dissolve
10 g of potassium iodide (KI) and 1 g of ascorbic acid.
Description of Generator. The system (Fig. 5-5) consists of three peri-
staltic pumps and a gas-liquid separator. Pump A (head no. 7014, 5.3 mL/min
flow rate) (Curtis Matheson Scientific, Inc., Denver, Colo.) pumps the NaBH4
solution continuously. Pump B (head no. 7016, 20 mL/min flow rate) pumps
either 30-s (lO-mL) aliquots of pretreated sample or 30 s of 0.5 M HCI rinse
between samples. Pump C (head no. 7015, 42 mL/min flow rate) drains the gas-
liquid separator. Argon is forced through the base of it 60-mL coarse-fritted disc
Buchner funnel to strip the gases from the liquid and to carry them into the plas-
ma. A signal is produced whenever a detectable amount of analyte is introduced
into the plasma. Ten-second integrations of the maximum signal are used to cal-
culate concentrations. To begin the integration at the proper time, a chart recorder
is useful initially to observe the signal timing. One sample per minute is usually
analyzed unless a very high concentration is encountered and a long rise period
becomes necessary. Total Se determination in metal-contaminated soils needs
special attention. Banuelos8 noticed Cu-like precipitates, after which Se deter-
minations were not reproducible. The NaBH4 might have been used up by ele-
ments other than Se. Banuelos recommended sample dilution to overcome the
above interference.
Pretreatment of Soil Extracts to be Analyzed for Selenium. The fol-
lowing procedure is used to reduce Se(VI) to Se(IV) and to destroy organic con-
stituents in aqueous solutions before generating hydrides.
Place 15 mL of extracting solution into a 50-mL digestion tube. Add 1 mL
of fresh 30% H20 2, and heat for 20 min in a boiling water bath. Add 10 mL of
concentrated HCI, and heat again for 20 min. Cool and bring the solution to a
final volume of 25 mL with DDW. The solution is now ready to be analyzed for
Se using the hydride-mercury vapor generator. The solutions are approximately
4.8 M HC!. Standards should contain the same acid concentrations.
Pretreatment of Soil Extracts or Total Soil Digests to be Analyzed for
Arsenic. The following procedure is used to reduce As(V) to As(III) before gen-
erating hydrides.
Add 3 mL of potassium iodide-ascorbic acid solution to 10 mL of either
soil extracts previously treated using the procedure in "Pretreatment of Soil
Extracts to be Analyzed for Selenium" or total soil digests from the procedure in
"Procedure." Wait at least 10 min. The solution is now ready for analysis using
the hydride-mercury vapor generator. Standards should contain the same acid
concentration and be treated in the same way as the samples.
8 Banuelos, Gary, USDA-ARS, Fresno, CA.

Quality Cootrol Methods
In ICP-AES and ICP-MS as in any other methods of analysis, the QC

should be an integral part of the procedures used for analysis. The quality of the
analytical work may be checked in several different ways. Use of blind dupli-
cates, check sample, standard reference materials, recovery of added elements,
and interlaboratory comparisons are recommended.
Blind duplicates are samples that are introduced into the laboratory by the
laboratory supervisor or customers. The analysts analyze these samples without
any knowledge of the presence of blind duplicates. A check sample is a sample
that has been analyzed many times by different laboratories and is available in
large quantities. This sample is analyzed with every batch of samples to see if
any gross contamination or error has occurred. Standard reference materials are
materials that have certified analytical values, such as National Bureau of
Standard (NBS) samples. Recently, NBS has been changed to National Institute
of Science and Technology (NIST). Canadian Land Resource Institute,
Agriculture Canada, and the Canada Center for Mineral and Energy Technology
have prepared a few reference soil samples with recommended values for sever-
al elements. One of the best ways to evaluate analytical results is to have sam-
ples analyzed by several reputable laboratories and then to compare the values,
such as in a proficiency testing program. Two programs available are the Western
States Laboratory Proficiency Testing Program and The Soil & Plant analysis
proficiency testing program. Another method of quality control is to add known
amounts of elements to soil digests or extracts and to determine the percentage
recovery of the added element. The best guard against contamination of samples
is maintaining a high standard of cleanliness throughout the laboratory. For a dis-
cussion of QC methods, see Skogerboe and Koirtyohann (1976) and Chapter 2
(Klesta & Bartz, 1996).
SUMMARY
In this chapter we have discussed ICP-AES and ICP-MS. Our experience

and that of the workers who use ICP specrometry for routine analysis have
shown that ICP is a generally superior source in accuracy, precision, detection
limit, freedom from interferences, and dynamic range. Use of automatic sam-
plers, large computers, and the needed software facilitates analysis. One can ana-
lyze a solution for many elements in 1 min with ICP-AES and 2 to 3 min with
ICP-MS. Therefore, large volumes of data can be generated very fast. Isaac and
Johnson (1982) indicate that with ICP-AES one technician can do the same work
that formerly required four technicians. The ICP-MS requires highly trained
technicians and is subject to more pitfalls than ICP-AES. To our knowledge, only
three soil testing laboratories use ICP-MS in contrast with many that use ICP-
AES in the USA. However, for elemental isotope abundance determination the
ICP-MS is the instrument of choice. Thought should be given to the handling and
processing of the data. Interfacing the instrument with larger computers for data
handling and analysis is a must if one contemplates obtaining large volumes of
data. It is recommended that users of ICP-AES and ICP-MS subscribe to the
newsletters available from the manufacturer of their unit and other sources so
that they can be kept abreast of new developments in ICP-AES and ICP-MS.
Journals references and other significant sources of information are given in the
reference section.
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Published 1996

Inductively Coupled Plasma Emission

PARVIZ N. SOLTANPOUR, Colorado State University, Fort Collins,

STEPHEN M. WORKMAN,Analytical Technologies, Inc., Fort Collins,

ROBERT O. MILLER, University of California, Davis, California

The application of inductively coupled plasma-atomic emission spectroscopy

Fig. 5-1. Magnetic fields (H) and eddy currents (shaded)

5. The cost of instrumentation, operation, and maintenance for ICP-MS are

INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION

OPTICAL EMISSION SPECTROMETRY

Properties of Inductively Coupled Plasma

Fig. 5-3. Typical quartz torch and inductively coupled

For ICP-MS, the vaporization and atomization begin at approximately the

A. rep Spatial Configuration for Ato'llic Emission Spectroscopy

1001"= =",'" " ,

B. rcp Spatial Configuration for Mass Spectrometry

Key: Pressures PI' p,. and p,: Cones S, and S,:

p,=760 torr S,=Sampling Con,

p,=1.2 torr S,=Skimmer Com

p,=10. 7 to 10" torr

cooler excitation and gas temperatures than the ionization temperatures.

Sample Introduction Systems

In Babington nebulizers (Suddendorf & Boyer, 1978), aerosol is produced

3 Leeman Labs Inc., Lowell, MA.

Generator"), direct injection (see "Direct Injection Nebulizers"), LASER abla-

Hydride and Mercury Vapor Generator. Certain elements, when

5 Fisons Instruments Inc., Danvers, MA 01923; Perkin-Elmer Sciex, Norwalk, cr 06859-0215.

multiplier tube. Photomultiplier tubes produce signals directly proportional to

6 (f. Zalinski, personal communication)

Inductively Coupled Plasma-Mass Spectrometry. There are at least five

Table 5-1. Continued.

(continued on next page)

Table 5-1. Continued.

(continued on next page)

Table 5-1. Continued.

Table 5-1. Continued.

Table 5-1. Continued.

Table 5-1. Continued.

Table 5-1. Continued.

II 337.480 45.0 10.0 0.007

(continued on next page)

Table 5-1. Continued.

Detection Limits (Inductively Coupled Plasma-Atomic Emission

Detection Limits (Inductively Coupled Plasma-Mass Spectrometry)

Interferences (Inductively Coupled Plasma-Atomic Emission

Ionization. When atomic or ionic species of an element in a plasma emit

Correction for Interferences (Inductively Coupled Plasma-Atomic

Interferences (Inductively Coupled Plasma/Mass Spectrometry)

Methods of Correction for Interferences and Standardization Proce-

Obtaining Soil Extracts

Digestion of Organic Matter and Dissolution of Silicates

Analysis of Soil Extracts and Digests

(continued on next page)

Table 5-4. Continued.

Standardization Procedures (Inductively Coupled Plasma-Atomic

Fig. 5-5. The hydride and mercury vapor generator.

It should be noted that the operational procedure of different ICP spec-

Determination of Ultratrace Levels of Arsenic, Selenium, and Mercury

3. Calibrated 50-mL digestion tubes.

8 Banuelos, Gary, USDA-ARS, Fresno, CA.

Quality Cootrol Methods

In ICP-AES and ICP-MS as in any other methods of analysis, the QC

In this chapter we have discussed ICP-AES and ICP-MS. Our experience

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