focal point
BY M. W. BLADES
Atomic Mass
Spectrometry
INTRODUCTION
he use of atomic mass spectrom-
T etry has grown enormously dur-
ing the past two decades. Com-
pared with most optical methods,
atomic mass spectrometry offers lower
detection limits (ppt to ppq) and broad
elemental coverage, with the addition-
al capabilities of providing isotopic
abundance information and internal
standardization through isotope dilu-
tion. The growth in the use of atomic
mass spectrometry is directly related to
the development of reliable instrumen-
t a t i o n - p r i m a r i l y commercial instru-
ments for inductively coupled plasma
mass spectrometry (ICP-MS), glow
discharge mass spectrometry (GD-
MS), laser sampling mass spectrome-
try, and secondary ion mass spectrome-
try (SIMS).
Koppenaal ~ defines atomic mass
spectrometry as "the mass spectromet-
ric measurement of atomic (as opposed
to molecular or polyatomic) ions, for
the primary purpose o f elemental
and/or isotopic composition determi-
nations". The term inorganic mass
spectrometry is also sometimes used to
refer to these same areas of interest. 2
The essential distinction seems to be,
in a sense, territorial. Atomic mass
spectrometry can be thought of as
being used primarily for the same pur-
pose for which "traditional" optical
spectrometric methods have been
12A Volume48, Number11,1994
UNIVERSITY OF BRITISH COLUMBIA,
VANCOUVER, BRITISH COLUMBIA
used--the determination of the partial
or complete elemental content of a
sample. Common techniques that have
been and are still being used for this
purpose include flame and furnace
atomic absorption spectroscopy and
plasma emission spectroscopy. To
some extent, these "traditional" meth-
ods are being displaced by the new and
powerful mass spectrometric analogs.
Photons are out, ions are in!
A generic atomic mass spectrometer
is depicted schematically in Fig. 1.
Common to all the techniques is an at-
omization/ion source and a mass ana-
lyzer. For some techniques (e.g., reso-
nance ionization mass spectrometry)
an additional or supplementary ioniza-
tion source may be used between the
primary atomizer/ionizer and the mass
analyzer to improve the ionization effi-
ciency and, hence, lower the detection
limits or improve the selectivity.
Some atomization/ionization sources
that can be used for atomic mass spec-
trometry are outlined in the left-hand
box in Fig. 1. The bottom three (in ital-
ics) are potential ion sources but have
not yet been reported as being success-
fully coupled to a mass analyzer. The
common mass analyzers are listed in
the right-hand box in Fig. 1.
In theory, any combination of source
and analyzer is possible, and many of
the possible combinations have been
investigated. However, in practice,
only a few of these combinations are
DEPARTMENTOF CHEMISTRY,
V6T I ZI, CANADA
common; the discussion below will
focus on these. Spark source mass
spectrometry will not be included in
the discussion because, although it was
a very important method for direct
solids analysis in the 1960s and 1970s,
it has gradually been replaced by the
methods discussed below. Also, ther-
mal ionization mass spectrometry
(TIMS) and accelerator mass spec-
trometry (AMS) will not be included
although both are very sensitive meth-
ods for elemental analysis. There is an
excellent paper in this issue of Applied
Spectroscopy that provides a brief in-
troduction to TIMS and discusses its
application to environmental monitor-
ing. 3
LASER MICROPROBE MASS
SPECTROMETRY
The unique characteristics of laser
microprobe mass spectrometry
(LMMS) are the low detection limits,
the potential for highly localized anal-
ysis, and the lack of a need for sample
pretreatment prior to analysis. Al-
though the method has been known
since the early 1960s, 4 the most signif-
icant event in its evolution was the in-
troduction of commercial equipment by
Leybold-Heraeus some 15 years ago.
A schematic diagram of a "typical"
time-of-flight/laser microprobe mass
spectrometry (TOF-LMMS) instru-
ment is provided in Fig. 2. For obtain-
ing inorganic mass spectra, the output

Sample
Introduction
P Ion Source
k Mass
Inductively Coupled Plasma (ICP)
Microwave Induced Plasma (MIP)
DC-Glow Discharge (GDL)
rf-GIow Discharge (rf-GDL)
Spark Source (SS)
Laser Ablation/Ionization
Ion-beam
Electrnspray
rf-Capacitively Coupled Plasma (ocCCP)
Capacitive Microwave Plasma (CMP)
Direct Current Plasma (DCP)
Fla. I. A generic atomic mass spectrometer. The bottom three ion sources, given in
italics, have not yet been reported as being successfully coupled to a mass analyzer.
of a pulsed, frequency-quadrupled
Nd:YAG laser (266 nm) is directed
onto the sample and focused to a spot
size of between 0.5 and 2/xm in diame-
ter. Pulse energies from 100/zJ to 20
mJ are used for ablation and provide ir-
radiances of between 2 × 1011 and 4 X
l 0 j4 W c m -2 at the sample. This tech-
nique is closely related to laser desorp-
tion mass spectrometry (LDMS),
which is used to obtain mass spectra
from nonvolatile organic solids. 5'6 In
fact, the two techniques share identical
instrumentation. The essential differ-
Sampling
Laser
Ion Detector I
bIon Optics-Ion Extraction
Sample
Fla. 2. Schematic diagram of a TOF/laser microprobe mass spectrometer instrument.
Analyzer k Ion detection
and Readout
I of asbestos fibers; and for the study of
Magnetic Sector Mass Spectrometer
Quadrupole Mass Filter
Time-of-Flight Mass Spectrometer
Quadrupole Ion Trap
Fourier Transform Mass Spectrometer
ence is that a laser energy of 10 to 1000
nJ is normally used for LDMS, yield-
ing power densities at the surface of
the sample of 2.12 X 107 to 2.12 × 108
W cm -2.
LMMS is used for a variety of inor-
ganic applications. It has been used in
plant and animal biology studies for
the determination of the distribution of
elements in biological tissue at the cel-
lular and subcellular level; for research
in metallurgy, geochemistry, and soil
science; for the determination of ionic
contaminants in semiconductor mate-
Reflectron
Time-of-Flight
Mass Spectrometer
rials and the micro-analysis of inte-
grated circuits; for the characterization
environmental aerosols.
Because the sampling and ionization
step takes place in a very short time pe-
riod in LMMS, the mass analyzer must
be capable of "capturing" the entire
mass range of interest without scan-
ning. As a result, the most popular
mass analyzer for LMMS has been the
time-of-flight system. There are, how-
ever, limitations to TOF spectrometers
for this application, one of which is re-
lated to the limited mass resolution,
which prevents the unambiguous inter-
pretation of mass spectra. Fourier
transform mass spectrometers (FTMS)
coupled with laser sampling offer far
higher mass resolution and accurate
mass assignment. Van Vaeck's re-
search group at the University of
Antwerp has developed a FTMS-
LMMS system using externally gener-
ated ions injected into the FTMS cell. 7
They have used this instrument for in-
organic microanalysis of mineralogi-
cal samples, thin films, and com-
pounds deposited from solution. These
authors also demonstrated the possibil-
ity of performing inorganic speciation
with this instrument. Binary salts of
MX, yielded ions such as (MX,)mM +
and ( M X n ) m X - , whereas oxy-salts like
MOX provided cluster ions built from
MO and X moieties. Another benefit of
FTMS-LMMS is that it can be used to
study the time of ion formation with re-
spect to the arrival of the laser pulse.
For example, Van Vleck et al. 7 have
shown that ion formation can take
place up to several hundred milisec-
onds after the arrival of the laser pulse.
This factor is one further shortcoming
of the TOF spectrometer in this appli-
cation.
Laser sampling mass analysis has
the potential for remote sampling ap-
plications and is being investigated for
deployment in space, either from sur-
face rovers or from satellites, for deter-
mination of the elemental composition
of planetary bodies. De Young and
Situ s described an instrument in which
a Nd:YAG laser was used to sample
and ionize a "lunar simulant" material.
The resulting ions were collected in an
ion trap at the distance of 11.1 m away
APPLIEDSPECTROSCOPY 13A
focal point
from the ionization point and subse-
quently analyzed by means of a TOF. A
paper in this issue discusses this inter-
esting space-age application of
LMMS.9
Laser ablation ion-trap mass spec-
trometry has been investigated by Gill
and Blades. 10They ablated and ionized
pin-shaped conductors and noncon-
ductors placed inside the ion trap,
which was used as both a trap and a
mass spectrometer. The use of an ion-
trap mass spectrometer allows collec-
tion and storage of ions generated by
several laser pulses, thus offering the
potential for enhancing sensitivity for
trace elemental analysis. For example,
ions generated from successive firings
of the laser may be stored and integrat-
ed inside the trapping volume to en-
hance the signal-to-noise ratio during
readout. The disadvantages of this
technique include a restricted sample
(pin) geometry, a limited dynamic
range resulting from space charge ef-
fects inside the trapping volume, and
possible sample matrix interferences.
Additionally, sampling and ionization
are not independent since they result
from the same laser pulse.
A very useful variant of straightfor-
ward LMMS is the combination of
laser sampling and resonance ioniza-
tion. 11.12 Resonance ionization has
been used for many years for ultratrace
atomic analysis. 13'14The ion yield effi-
ciency for LMMS is typically in the
range of 10 -2 to l 0 -3, and the sensitivi-
ty of LMMS is often limited by back-
ground signals from the matrix. By
tuning a second laser to a resonance
transition of desorbed neutrals, one can
use resonance ionization to enhance
the ionization efficiency for selected
species so that a detection limit of sub-
ppb can be achieved. For even better
selectivity and sensitivity, multiphoton
ionization can be used. Alimpiev et
al. 15have described the use of laser ab-
lation combined with a two-color (1 +
1) resonant multiphoton ionization
(REMPI) technique to determine the
concentration of B, Al, Fe, and Cr at
the ppb level in semiconductor sam-
ples. Under conditions of strong satu-
ration of both transitions, the ioniza-
tion efficiency was estimated to be
about unity.
14A Volume 48, Number 11,1994
The characteristics of LMMS that
make it useful are its microsam-
pling capability, low detection limits
( - - 1 0 -2° g), minimal sample prepara-
tion requirement, and ability to per-
form molecular analysis. The biggest
downfall of the technique is the diffi-
culty of quantitation and sample-to-
sample reproducibility. There is hope
that, when an adequate understanding
of the fundamental physics and chem-
istry of the ablation process is attained,
the technique will mature into a routine
quantitative analytical tool.
INDUCTIVELY COUPLED
P L A S M A MASS
SPECTROMETRY
In his 1988 fundamental review,
Koppenaal listed 123 references to
plasma source mass spectrometry; in
1990 there were 163 and in 1992 there
were 291.1'16'17 The majority of these
papers dealt with inductively coupled
plasma mass spectrometry (ICP-MS).
This "explosive growth ''18 is indicative
of the tremendous appeal of ICP-MS
for elemental analysis. There have
been several recent reviews of ICP-
M S , 18-2° and the detailed description of
ICP-MS already offered in these re-
views will not be repeated here.
A schematic diagram of a "typical"
quadrupole ICP-MS instrument is pro-
vided in Fig. 3. Nebulized sample solu-
tion that is transported to the plasma is
often desolvated and is then atomized
and ionized in the ICE The resulting
atomic ions are extracted from the
plasma tailflame into a vacuum enclo-
sure with the use of a combination of
sampling and skimmer cones. The ions
are then focused and transmitted to the
mass spectrometer. The mass-analyzed
ions are subsequently detected, and ei-
ther they are counted individually or
the ion current they produce is record-
ed in an analog fashion.
The four most important attributes
of ICP-MS that make it attractive to
analytical chemists are:
1. Ability to accommodate solution
samples easily.
2. Low detection limits.
3. Broad elemental coverage.
4. Isotopic analysis capability.
Detection limits for most elements in
the periodic table are in the 0.001 to
0.05 ppb range, the exceptions being
the halogens, P and S. For rapid quali-
tative analysis of aqueous samples,
ICP-MS is unequaled. It can provide a
quick assessment of the elemental
composition of a sample from Li
through U in a few seconds.
The vast majority of commercial
ICP-MS instruments employ a quadru-
pole mass filter since these devices
offer a good balance between cost and
performance. They have several limi-
tations, however, the most severe
being the lack of simultaneous ion
monitoring and the relatively low reso-
lution. The resolution difficulty has
been addressed primarily through the
use of magnetic sector instruments. Si-
multaneous ion monitoring is impor-
tant for accurate measurement of iso-
topic abundances and for precise
application of isotope-dilution meth-
odology. In a paper in this issue, War-
ren et al. 21 approach the problem by
splitting the ion beam and using two
quadrupole mass filters. Another ap-
proach for simultaneous ion monitor-
ing that has been explored is the use of
TOF mass spectrometers for ICP-MS.
The TOF approach offers high
throughput (which counters its rela-
tively low duty cycle) and simultane-
ous ion extraction from the ICP. 22 Duty
factor in the ICP-TOF instrument is
further improved by the use of orthog-
onal ion extraction, in which the slow-
ly moving ion beam from the ICP is ac-
cumulated and pulsed as a packet into a
TOF flight tube oriented perpendicu-
larly to it. Alternative approaches for
simultaneous ion monitoring are the
use of a magnetic sector instrument
with an imaging detector 21 or the use of
a hybrid mass spectrometer. An inter-
esting example of the latter type of in-
strument has been published by Bari-
naga and Koppenaal, 23 who have
coupled a quadrupole mass filter with
an ion-trap mass spectrometer. The
quadrupole mass filter was used as a
bandpass or notch filter to remove ma-
trix species, and the ion-trap was used
as the mass spectrometer. An advan-
tage of this instrument was an apparent
reduction in spectral interferences
caused by polyatomic ions.
While its positive attributes are ob-

Quadrupole Mass Filter
I J ~ Ion Lenses
Skimmer Cone
"- SamplingCone
ICP Torch
FIe. 3. Schematicdiagram of a quadrupole-based inductively coupled plasma mass
spectrometer.
vious, there are some negative aspects
to ICP-MS, and this concern is where
much of the current research work in
the area is being directed. Isobaric
overlaps from molecular species
formed in the plasma or, more likely,
during the extraction stage are one of
the most serious problems. The most
commonly encountered species are ox-
ides of the various elements in the sam-
ple and plasma gas. Their impact on
the mass spectrum is a complex func-
tion of solution composition, plasma
operating characteristics, and instru-
mentation used. Matrix interferences
arise from components in the sample
that cause depressions or enhance-
ments in the measured signal. The
most ubiquitous of these is the "mass-
dependent interference" caused by
space charge effects in the extracted
ion beam. 24'25 Space charge effects are
caused by the mutual repulsion of ions
of like charge in the skimmed ion
beam. The effect is dependent on the
total ion beam current and on the na-
ture of the ions in the beam; hence
lighter ions, such as Li, are affected to
a greater extent than heavier ions.
The most common means of sample
introduction in ICP-MS is using solu-
tion nebulization with a pneumatic
nebulizer. An active area of interest in
ICP-MS is the development, character-
Ion Detector
ization, and application of alternative
methods for sample introduction. Pop-
ular methods that have been extensive-
ly evaluated to date are itemized
below.
Electrothermal Vaporization, Elec-
trothermal vaporization (ETV) ICP-
M S 26-29 is a technique in which a
graphite furnace is used to vaporize the
sample prior to its transport to the plas-
ma. It provides microsampling capabil-
ity and a partial reduction of interfer-
ences from oxides since the solvent is
removed prior to the atomization step.
In this issue, Gray et al. discuss meth-
ods for enhancing sensitivity and stabil-
ity for (ETV)-ICP-MS. 3°
Flow Injection. Flow injection
(FI) 31'32 also permits small samples to
be introduced into the ICP and offers a
convenient and rapid means of au-
tomating sample handling and pre-
analysis sample preparation chemistry.
The coupling of flow injection with an
ICP is relatively simple. The outlet of
the FI apparatus is connected directly
to the nebulizer inlet. A paper by Dad-
farnnia and McLeod in this issue 33 dis-
cusses the use of flow injection for pre-
concentration of uranium in natural
waters.
L a s e r Ablation. Laser ablation
(LA) ICP-MS 34-36 sampling offers the
ability to sample solid materials direct-
ly and, with an appropriate sample ma-
nipulation stage, can be used to obtain
spatially resolved elemental concen-
tration information from a sample.
Wang et al: discuss the application of
(LA) ICP-MS to spatially resolved mi-
croanalysis of biological tissue in this
issue. 37
Direct Injection Nebulization. Di-
rect injection nebulization (DIN) ICP-
MS 38 is a method whereby the nebuliz-
er is incorporated directly into the
plasma torch and transports nearly
100% of the aspirated sample into the
plasma. While it has not received
widespread application, it does offer
the advantage of low dead volume for
applications where the ICP is coupled
with liquid chromatography and flow
injection.
ICP-MS has become a very impor-
tant technique in atomic spectrometry,
and, while there are still some short-
comings, it has clearly joined the main-
stream of analytical methods. Some re-
searchers have predicted that it will
completely displace optical emission
and absorption spectrometry, while
others see it as being complementary to
these techniques.
G L O W D I S C H A R G E MASS
SPECTROMETRY
As is the case for LMMS, one of the
chief strengths of glow discharge mass
spectrometry (GDMS) is the ability to
sample solids directly. Glow dis-
charges have been used for atomic
spectrometry for many years. Glow
discharge mass spectrometry was in-
vestigated in the 1960s 39-41 for the
characterization of sputtered materials
and for the analysis of semiconductor
materials using a radio-frequency glow
discharge. There are numerous reviews
of glow discharges for analytical spec-
troscopy and G D M S ; 42-47 all the details
of operation and application certainly
need not be repeated here. During the
mid-1980s there was a strong resur-
gence of interest in the technique as an
alternative to spark source mass spec-
trometry (SSMS) for the following rea-
sons:
1. The ion beam produced by GDMS
is not as erratic as that provided by
APPLIED SPECTROSCOPY 15A
focal point
spark source MS, thus providing
superior signal-to-noise ratios.
2. The glow discharge consumes
much more sample than the spark
source, thus improving the sam-
pling statistics.
3. The ion-energy spread produced
by the GD is much narrower than
that from the spark source; hence,
quadruple mass filters can be used
as the mass spectrometer.
4. The ionization of sample ions is
not as strongly influenced by the
matrix as it is for secondary ion
mass spectrometry, resulting in a
sensitivity variation among the el-
ements of only about one order of
magnitude. 48
Sampling in a glow discharge takes
place when energetic support-gas ions,
formed in the plasma glow adjacent to
the sample, are accelerated toward and
impact with the sample surface. The
impinging ion either back-scatters
from a surface atom or penetrates to a
depth of a few angstroms where its ki-
netic energy can cause surface atoms to
be ejected, provided that the amount of
energy which is transferred exceeds
the binding energy of the surface
a t o m s - - a phenomenon called sputter-
ing. The sputtered atoms diffuse into
the plasma glow, where they are ion-
ized. The ions are extracted from the
plasma discharge through an aperture
into the mass analyzer.
Glow discharges can be formed with
a direct current (dc) or radio-frequency
(rf) power supply. The dc glow dis-
charge is formed between the sample,
which operates as the cathode, and an
anode. There are a variety of geometric
arrangements including the planar
diode in which the anode and cathode
are parallel plates, the hollow cathode,
and the Grimm lamp, which is perhaps
the most useful from a sampling stand-
point because the samples need only be
sufficiently flat and large to form a
vacuum seal.
Several instrumental configurations
are utilized for GDMS. The first com-
mercial instrument employed a reverse
Nier-Johnson double-focusing geome-
try. This arrangement provided a typi-
cal resolution of 8000 for the mass
range from 1 to 280 amu with detection
limits in the range of 1 to 10 ppb (in the
16A Volume 48, Number 11, 1994
solid) for most elements. Quadrupole
mass filters were first used for GDMS
by Coburn and Kay 41 in 1971 and sub-
sequently by Harrison's group. 49'5°
Typically, the quadrupole mass filter
provides unit mass resolution with an
abundance sensitivity (the leakage of
an intense peak into the adjacent chan-
nel 1 amu away) of about 105 to 10 6.
Detection limits are in the sub-ppm
range (in the solid). A triple-quadru-
pole GDMS system has also been con-
structed for studying the formation of
polyatomic ions, but it appears to offer
little commercial potential. The analyt-
ical capabilities of quadrupole GDMS
and magnetic sector double-focusing
GDMS have been compared. 51 Raith et
al. reported that (l) the magnetic sector
instrument was superior for ultratrace
analysis as a result of its ability to bet-
ter handle isobaric overlaps; (2) the
two instruments were comparable with
respect to relative sensitivity factors;
and (3) quadrupole instruments were
superior for depth profiling because of
their rapid scan capability.
The interest in glow discharge mass
spectrometry is driven by the need for
a fast, sensitive, reliable, relatively in-
expensive method for the characteriza-
tion of metals and semiconductors. 52
For example, Hutton et al. describe the
application of a quadrupole-based
glow discharge mass spectrometer for
the determination of trace impurities in
"pure" copper. 53 GDMS is also ex-
tremely useful for thin-film depth pro-
filing.oEtCh rates of between 0.1 and
1000 A/s are possible, and a depth res-
olution as fine as 0.03/~m has been re-
ported; s4 however, the physical size of
GD sources limits their utility for later-
al resolution. Applications of the tech-
nique include the characterization of
thin coatings on metals and laminated
materials. GD-MS has also been used
for the analysis of compacted powders
and dried deposited solutions. A paper
in this issue investigates the effect of
solution-deposited anions on ion
yield. 5s
An area of current interest is the de-
velopment and exploitation of rf-
G D M S . 56-6° The motivation for this
work is that the use of an rf-GD en-
ables the sputtering of insulators, ce-
ramics, and other electrically noncon-
ducting samples. Myers et al. describe
a novel GDMS instrument utilizing a
TOF in this issue. 61
S E C O N D A R Y ION M A S S
SPECTROMETRY
Since the late 1960s, secondary ion
mass spectrometry (SIMS) has been
acknowledged as one of the most im-
portant techniques for surface analysis
and for elemental imaging. 62'63 The
strong points of SIMS are its outstand-
ing sensitivity, which is in the ppb
range (in the solid), and its extremely
fine lateral-profiling resolution, which
is on the order of 0.1 to 1/xm.
A schematic diagram of a "typical"
SIMS instrument is provided in Fig. 4.
For obtaining mass spectra with this
instrument, a tightly focused beam of
primary ions, such as Cs +, Ga +, Rb +, O +
Ar +, or N +, is directed at the sample
surface at an energy in the range of 20
to 60 keV. The outermost atomic layers
are sputtered by these impacting ions;
these secondary ions are separated by
the mass spectrometer and measured.
There are three types of SIMS mea-
surements:
1. Dynamic SIMS uses a high-inten-
sity beam of O~ or Cs + to etch the
surface at a very rapid rate to ob-
tain concentration depth profiles
at very high sensitivity. It is used
primarily for bulk, high-sensitivi-
ty elemental analysis.
2. Imaging SIMS utilizes a narrow
beam of primary ions (Ga ÷ or In+),
typically < 1 0 /xm in diameter,
and the beam is rastered across the
sample to obtain a topographic
image of the elemental distribu-
tion. It is used primarily to obtain
a "chemical image" of the sample.
3. Static SIMS utilizes a relatively
low intensity ion beam (Ar ÷) to
etch the sample surface at an ex-
tremely slow rate; hence the tech-
nique is used primarily for obtain-
ing chemical information about
the surface monolayer. Static
SIMS not only is useful for mea-
suring elemental concentrations
but also can determine molecular
structure.
Earliest applications of SIMS uti-
lized the dynamic mode for high-sensi-

Mass
Spectrometer
Ion Gun
~Beam Pulsing
Focusing
Optics
Raster Scanner
FIG. 4. A schematic diagram of a secondary ion mass spectrometer. The electron
flood gun is used to maintain charge balance at the sample.
tivity trace analysis of the chemical
composition of surfaces; this is still an
important application since the detec-
tion limits for many elements are at the
ppb level. This application has been
particularly useful for the measure-
ment of dopant and impurity concen-
trations in semiconductor materials. Of
course, the ability to do elemental
imaging, at a resolution as fine as 0.1
/zm, is the major selling feature of
SIMS. For surface-science applica-
tions there are a couple of reasons why
static-SIMS is preferable to LMMS
and GDMS. First, each area of the sur-
face is probed only once; therefore re-
deposition of sputtered material is not
an issue. Second, it can be operated es-
sentially nondestructively.
E L E C T R O S P R A Y MASS
SPECTROMETRY
Elemental analysis utilizing electro-
spray mass spectroscopy (ES-MS) is a
new method lurking on the horizon.
Electrospray ionization is a means by
which ions can be obtained directly
from solution samples. 64 Small droplets
are formed at the tip of a capillary tube
held at a high voltage (3-4 kV). The
very high electric field between the tip
of the capillary and a counter electrode
causes the droplets to be enriched in
positive electrolyte ions (Fig. 5). As the
droplets that are formed evaporate, the
surface charge on the droplets increas-
es, eventually causing droplet fission
and leading to free ions of the species
Ion Detector
~ Electron
Flood Gun
/----.,
that were originally in the solution.
These ions can be analyzed with a mass
spectrometer. In addition to its obvious
simplicity (no plasma source or ion gun
is necessary), the particular advantage
that electrospray has to offer is that it
can provide speciation information,
since with the proper conditions, the
chemical form of the element (ligands
and oxidation state) is retained by the
gas-phase ions. This issue is becoming
increasingly important in environmen-
tal analytical chemistry; as a result, ES-
MS could be poised to become a very
important method. A paper by Agnes
/ Conductive ~ ~'~1
[ High Voltage
[ Power Supply
I'I'
FIG. 5. Schematicdiagram of the electrospray ion formation process in ES-MS (after
Kebarle and Tang64).
and Horlick in this issue introduces the
method and assesses it for use in atomic
spectrometry. 65
CONCLUSION
Research at universities, govern-
ment laboratories, and instrument
companies has led to the development
of many new ion sources and improved
mass analyzers during the past few
decades. The coupling of these devices
has provided the analyst with new and
very powerful instrumentation for ele-
mental analysis. This short paper has
attempted to outline the characteris-
tics, strengths, and limitations of some
currently popular atomic mass spectro-
metric methods: LMMS, ICP-MS, GD-
MS, SIMS, and ES-MS. As these meth-
ods continue to be improved, detection
limits lowered, and matrix-effects
overcome, the range of applications for
which they are used will expand, and,
as a result, continued growth in atomic
mass spectrometry can be expected for
many years to come.
Finally, on the front cover of this
journal, the reader can find the familiar
logo of the Society for Applied Spec-
t r o s c o p y - - a circle with a white light
beam entering from the top being dis-
persed into the familiar rainbow of col-
ors punctuated with the letters hu. For
generations, analytical spectroscopists
have understood what this m e a n s - -
F
@ ? eee
(~ ~) c~, . . . .
To Mass
Spectrometer
@e@ ss * *
@e e
_-4
APPLIEDSPECTROSCOPY 17A
focal point
" a n a l y t i c a l s p e c t r o s c o p i s t s d o it w i t h
light". These days, however, many
s p e c t r o s c o p i s t s a r e n ' t d o i n g it w i t h
light: t h e y are d o i n g it w i t h i o n s - -
using mass spectrometers. There may
come a time when analytical atomic
s p e c t r o s c o p i s t s w i l l l o o k at t h e l o g o o n
t h e c o v e r o f Applied Spectroscopy as
t h e y w o u l d at a h i s t o r i c a l a r t i f a c t in a
museum. How quaint . . . they used
light!
ACKNOWLEDGMENT
The author acknowledges funding from the
Natural Sciences and Engineering Research
Council of Canada.
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18A Volume 48, Number 11,1994