Anal. Chem.

1985, 57, 2049-2055 2049

Table I. Control Plasma Data Values obtained by the two methods were not significantly
different (p = 0.788, paired t test for equality of means).
assay day at 75 ng/mL at 700 ng/mL
ACKNOWLEDGMENT
1° 71.30 ± 12.03% 691.22 ± 3.17% We acknowledge the assistance of H. Harpootlian and R.
2 76.18 ± 12.22% 703.62 ± 5.47%
C. Thomas, Drug Metabolism Research, The Upjohn Co., in
3 75.72 ± 12.97% 690.92 ± 3.48%
between-day6 74.40 ± 3.62% 695.25 ± 1.04% preliminary GC/MS studies.
0
Mean ± relative standard deviation of three replicates at each
Registry No. Acivicin, 42228-92-2.
concentration. 6 Mean ± relative standard deviation of daily LITERATURE CITED
means.
(1) Poster, D. S.; Bruno, S.; Penta, J.; Nell, G. L; McGovren, J. P. Cancer
Clin. Trials 1981, 4, 327-330.
Table II. Comparison of GC/MS and Microbiological (2) O’Dwyer, P. J.; Alonso, . T.; Leyland-Jones, B. J. CUn. Oncol. 1984,
2, 1064-1071.
Assays for Quantitation of Plasma Levels in a Cancer (3) Houchens, D. P.; Ovejera, A. A.; Sheridan, . A.; Johnson, R. K.; Bog-
Patient Receiving 18 (mg/m2)/day as a 96-h Constant Rate den, A. E.; Nell, G. L. Cancer Treat. Rep. 1979, 63, 473-476.
Intravenous Infusion (4) Nell, G.L; Berger, A. E.; Bhuyan, B. K.; Blowers, C. L; Kuentzel, S. L.
in "Advances In Enzyme Regulation"; Weber, G., Ed.; Pergamon Press
acivicin concn, (ng/mL) New York, 1979, Vol. 17, pp 375-398.
(5) Denton, J. E.; Lul, M. S.; Croki, T.; Sebolt, J.; Weber, G. Life Sci.
time, h GC/MS microbiological 1982, 30, 1073-1080.
(6) Maroun, J.; Makysmiuk, A.; Ersenhauer, E.; Stewart, D.; Young, V.;
During Infusion Pater, J. Proc. Am. Soc. Clin. Oncol. 1984, 3, 218.
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(7) Weiss, G. R.: McGovren, J. P.; Schade, D.; Kufe, D. W. Cancer Res.
12 250 150 1982, 42, 3892-3895.
48 340 320 (8) Srldhar, K. S.; Ohnuma, T.; Chablnian, A. P.; Holland, J. F. Cancer
Treat. Rep. 1983, 67, 701-703.
60 320 350
(9) Murphy, W. K.; Burgess, M. A.; Valdivieso, M.; Bodey, G. P. Proc. Am.
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72 390 360 Soc! Clin. Oncol. 1982, 1, 23.

96 310 380 (10) Earhart, R. H.; Koeller, J. M.; Davis, T. E.; Borden, E. C.; McGovren, J.
P.; Davis, H. L; Tormey, D. C. Cancer Treat. Rep. 1983, 67,
Postinfusion 683-692.
(11) McGovren, J. P.; Nell, G. L; Sem, P. C. C.; Stewart, J. C. J. Pharma-
0.5 300 320 col. Exp. Ther. mi, 216, 433-440.
1 290 310 (12) McGovren, J. P.; Stewart, J. C.; Elfring, G. L; Smith, R. B.; Soares, N.;
4 230 250 Wood, J. H.j Poplack, D. G.; VonHoff, D. D. Cancer Treat. Rep. 1982,
66, 1333-1341.
6 210 200
(13) Rosenblum, M. G., M.D. Anderson Hospital and Tumor Institute, Hous-
12 150 130 ton, TX, personal communication.
18 90 70 (14) Ames, . M., Mayo Clinic, Rochester, MN, personal communication.
(15) Yamamoto, S.; Kiyama, S.; Watanabe, Y.; Maklta, M. J. Chromatogr.
1982, 233, 39-50.
Within-day precision ranged from 12.03% to 12.97% (relative (16) Hanka, L. J.; Gerpheide, S. A.; Spieles, P. R.; Martin, D. G.; Belter, P.
standard deviation) at 75 ng/mL and from 3.17% to 5.47% A.; Coleman, T. A.; Meyer, H. F. Antimlcrob. Agents Chemother.
1975, 7, 807-810.
at 700 ng/mL. Recoveries from the control standards ranged (17) Kelly, R. C.; Schletter, I.; Stein, S. J.; Wlerenga, W. J. Am. Chem.
from 95.1% to 101.6%. Soc. 1979, 101, 1054-1056.
Table II shows a comparison of the GC/MS and microbi- (18) “Technical Bulletin”; Aldrich Chemical Co.; Milwaukee, WI.

ological assays for measurement of during and posfinfusion

acivicin plasma levels in a cancer patient treated with 18 Received for review February 22,1985. Accepted May 20,
(mg/m2)/day for 4 dáys by constant rate intravenous infusion. 1985.

Optical Imaging Spectrometers

John W. Olesik1 and Gary M, Hieftje*
Department of Chemistry, Indiana University, Bloomington, Indiana 47405

Two optical systems for acquisition of two-dimensional Images
are described. The systems, respectively, an electronic
slitless spectrograph and a monochromatic Imaging spec-
trometer, both usé a Czerny-Turner monochromator for
spectral discrimination. A silicon Intensified target vidicon
detector provides quantitative Images In time-integrated or
timé-resolved modes. By use of simple single-lens Image-
transfer optics with a monochromator, spatial resolution on
the order Of 0.3 mm Is attainable. Applications of the Imaging
spectrometers for spatial mapping of Inductively coupled
plasmas and flames are Illustrated.
1
Present address: Department of Chemistry, Venáble and Kenan
Laboratories 045A, University of North Carolina, Chápel Hill, NC
27514.
Spatial resolution in two or three dimensions in needed for
many optical spectroscopic measurements. Sources for atomic
spectrometry including flames, arc and spark discharges, and
inductively coupled plasmas (ICP) all exhibit spatial hete-
rogeneity (1-6). In order to understand and ultimately control
the processes involved in conversion of sample material to
emitting or absorbing atoms, spatial maps of ground-state and
excited-state species are required. Similarly, studies of com-
bustion systems such as internal combustion engines (7,8),
gas turbine engines, or laboratory flames (9,10) often employ
spatially resolved optical probes (11) of atomic and molecular
species.
Many analytical samples also exhibit chemical or physical
spatial heterogeneity (12, 13). Therefore, analysis of the
sample must include a description of the analytes that are

0003-2700/85/0357-2049S01.50/0 © 1985 American Chemical Society

2050 · ANALYTICAL CHEMISTRY, VOL. 57, NO. 11, SEPTEMBER 1985
present, the concentration or amount, and their spatial lo-
cation within the sample. Optical techniques based on
fluorescence, absorption, scattering or other processes could
be used to obtain the desired information as a chemical image
(14) .
A number of approaches have been used previously to ob-
tain spatial resolution with optical probes. Point-by-point
measurements can be made in order to construct a complete
map. The required optical system and its calibration are
relatively simple. Also, a low-cost, sensitive detector such as
a photomultiplier can be used. However, the measurement
process is slow if a large number of spatial positions must be
viewed sequentially. For example acquisition of a 500 X 50
array of points with a 1-s per point integration time would
require 6.9 h.
If the chemical spatially resolved measurements are based
on atomic or molecular emission or absorption, tomography
(15) or Abel inversion (16,17) of the laterally resolved, line-
of-sight data is required to obtain three-dimensional or radially
resolved data. Both techniques require a large number of
line-of-sight intensity values to be obtained. The Abel in-
version technique also has a number of experimental re-
quirements such as cylindrical or spherical symmetry, posi-
tional stability, and a lack of self-absorption (18).
Probes based on fluorescence (19-22) or saturated ab-
sorption (23-25) can obtain three-dimensional spatial reso-
lution directly, in a point-by-point manner. These methods
use a combination of imaging on the entrance slit of a
monochromator and the incident laser beam size or the overlap
of two crossed beams, respectively, to provide spatial resolu-
tion. While these methods do not require Abel inversion for
three-dimensional resolution, they can be time-consuming due
to the point-by-point mapping. Long acquisition times are
often required in order to obtain good signal-to-noise ratio
because of the low duty cycle of the pulsed laser sources.
Linear photodiode arrays (LDA) (26, 27) and intensified
LDAs (28) have been used to view a one-dimensional slice of
light from atomic or combustion sources. The LDA-based
systems can result in a reduction in the acquisition time of
up to a factor equal to N, the number of detector elements.
However, because the LDA has a lower gain than a photo-
multiplier tube and requires a longer acquisition time for a
good signal-to-noise ratio, the factor of N may not be achieved.
If the entire two- or three-dimensional image could be
detected simultaneously, there would be a greater reduction
in acquisition time. Also, nonreproducible or transient systems
such as turbulent combustion or high-energy plasmas could
be studied.
Experimental systems which simultaneously acquire data
in two dimensions have been developed. If an interference
filter provides sufficient spectral discrimination, a two-di-
mensional imaging detector, such as a vidicon, can be used.
Radially resolved emission data can be obtained using Abel
inversion, if the necessary conditions (18) are met.
Similarly, three-dimensional spatial resolution can be ob-
tained directly by using a thin sheet of exciting radiation or
a multipass cell and monitoring the resulting fluorescence
(29-32) or Raman (33,34) signal. Two spatial dimensions are
then viewed simultaneously by an imaging detector while the
resolution in the third dimension is provided by the width of
the narrow sheet of exciting radiation. However, the inter-
ference filter possesses a number of limitations as a spectral
discriminator. A different filter is required for each spectral
line or band. Further, the spectral band-pass (10 nm, typi-
cally) may be too large for many applications such as moni-
toring atomic emission lines in electrical discharges.
In this paper we describe two optical systems using
monochromator-based spectral discrimination which provide
Figure 1. Electronic slitless spectrograph: A, aperture; L, lens; M1,
spectrograph collimating mirror; G, grating; M2, spectrograph focusing
mirror.
l·— fu —H
U
LI
SOURCE
_ß_---- -- 0- 1--------- '
'
= 4
Ml
n -
4=-
-
_
u _
"
-
_ M2
Q VIDICON
---0- Ui 3
L2
DISPLAY |— fL2 H MONOCHROMATOR
Figure 2, Monochromatic imaging spectrometer: L1, collimating lens;
focal length of lens L1; S1, entrance slit; M1, M2, concave mirrors;
fL1,
G, grating; S2, exit silt; L2, focusing lens; fL2, focal length of lens L2.
detection of two-dimensional images. A “slitless spectrograph”
can be used to obtain simultaneously both spectral resolution
and two-dimensional imaging. In this arrangement, the usual
entrance slit is removed from the spectrograph. A demagnified
image of the source is formed at the object plane of the
spectrograph and effectively serves as the entrance slit. A
photographic plate has been used as the detector previously
(35). However, the acquisition of quantitative data from the
photographic plate is complicated by its nonlinear response
and time required for point-by-point densitometry. In the
present article, an electronic slitless spectrograph (ESS)
is described (shown in Figure 1) that provides quantitative
two-dimensional data directly by using a silicon intensified
target (SIT) vidicon detector. Further, the inherent tempo-
rally resolved readout or time-gating capability of the SIT
vidicon can be used to provide time resolution from seconds
to microseconds (36-38).
Unfortunately, the electronic slitless spectrograph suffers
from a tradé-off between spectral and spatial resolution. In
order to obtain high spectral resolution (a small band-pass),
narrow slits should be used, requiring great demagnification
of the source. However, because the obtainable spatial res-
olution should be limited by the smallest detector element,
the limiting resolvable distance in the source will be increased
as the source image size is decreased. Conversely, as the source
image size is increased to improve spatial resolution, the ex-
perimental band-pass is increased, degrading the spectral
resolution.
If the image of the source is totally out of focus at the
entrance and exit slits of a monochromator, Bind reconstructed
after passing through the exit slit, the spectral and spatial
resolution can be controlled independently. The mono-
chromatic imaging spectrometer (MIS) described here
(shown in Figure 2) is based on this idea using a Czerny-
Turner monochromator. Light from the source is collimated
before being fed into the monochromator. When the distance
from Ml (normally the collimating mirror) to the grating is
equal to the focal length of Ml, an image of the source is
formed on the grating. The light is recollimated by M2
(normally the focusing mirror) before passing through the exit
slit. Secondsury optics re-form the image of the source outside
of the monochromator, where the imaging detector is placed.
The experimental band-pass is controlled by the entrance and
exit slit widths, the grating angles, and the focal length of the
 ANALYTICAL CHEMISTRY, VOL. 57, NO. 11, SEPTEMBER 1985 · 2051

monochromator. The spatial resolution is determined by the WAVELENGTH (nm)

optics outside of the monochromator, the detector, and the
fidelity of the entire optical system.
EXPERIMENTAL SECTION
Electronic Slitless Spectrograph Optics (Figure 1). A
Jobin-Yvon (Model HR-1000) 1-m Czemy-Tumer monochromator
was used with a 2400 lines/mm holographic grating. The source
(described below) was imaged onto the normal position of the
entrance plane with a magnification of 0.2 by a plano-convex
quartz lens (7.5 cm focal length, Oriel Corp.). The lens aperture
was adjusted (1.5 mm, typical) to provide a detectable signal
without vidicon saturation. The entrance slit was fully opened
(2 mm) to allow a 10 mm wide portion of the plasma to be viewed.
A silicon intensified target vidicon (Princeton Applied Research
Corp., Model 1205D) was mounted onto the camera port of the
monochromator. Lens L was repositioned each time the wave-
length was changed in order to compensate for chromatic aber-
ration. The correct focal position was determined by backlighting
a precision screen target and positioning lens L for best image
fidelity. The vidicon-reported spatial position was calibrated by I—I—I I—I—I
backlighting with diffuse light a target having millimeter divisions. 3 0 3 3 0 3
A reference target which was 10 mm above the ICP load coils was LATERAL POSITION (mm)
backlit to determine the vertical position of the detected source
image. Figure 3. Laterally and vertically resolved emission due to the sodium
o lines emitted by an Inductively coupled plasma as reported by the
Monochromatic Imaging Spectrometer Optics (Figure 2).
electronic siltless spectrograph. Experimental conditions were as
A Heath (Model EU-700) 0.35-m Czerny-Turner monochromator
follows: ICP, low flow (5.9 L/mln coolant), low power (300 W); de-
was used with a 1200 lines/mm grating. Light from the source
tection, 15 frames summed in memory, 48 tracks over the 10 mm
(flame or ICP) was collimated by either of two plano-convex fused detector height, collected tracks 10-48 (observing heights in the ICP
silica lenses: 35-cm focal length (Oriel) or 25.4-cm focal length from 8 mm below the top of the load coil to 32 mm above the load
(Esco Products, Model A120100, Sl-UV grade). Light passing coil), channels 200-299.
through the monochromator was reimaged by a 15-cm focal length,
plano-convex, fused silica lens (Oriel, Model 4177, UV grade
research quality) onto the face of the vidicon. This lens (L2) was dance-matching unit (Plasma-Therm, Inc., Model PT/AMN/
RCM), a conventional-sized, water-cooled three-turn load coil,
placed on a stage which could be translated along the optical axis and a low-flow, low-power torch design (43). Power and argon
without opening the enclosure between the monochromator and
the detector housing. Lens LI was mounted on an optical rider
flow rates are listed with each example described in the text.
(39,40) which was easily and precisely translated along the optical
Air-Acetylene Flame. The flame was supported on a mod-
axis. The slit widths were set depending on the signal intensity
ified (44) Meker burner. Air and acetylene flow rates were ap-
and desired spectral resolution. The lens apertures were set to proximately 16 L/min and 2.4 L/min, respectively.
provide detectable signals without saturation of the detector RESULTS AND DISCUSSION
(typcially 1 cm or less).
Lens LI was positioned at a distance from the source calculated Electronic Slitless Spectrograph. The horizontal axis
to be its focal length at the particular wavelength passed through of images detected through the electronic slitless spectrograph
the exit slit. Lens L2 was then positioned for best resolution of is a function of both wavelength and lateral position within
an image formed by backlighting a 250- or 325-µ screen with the light source; the vertical axis is simply height within the
diffuse light. The vidicon-reported distances were calibrated as source for a stigmatic spectrograph. Images of the emitted
described above. sodium D lines from a nebulized solution of sodium chloride
Optical Multichannel Analyzer (OMA). A Model 1205 introduced into an inductively coupled plasma are shown in
OMA system (Princeton Applied Research Corp.) was used in-
cluding Model 1205A console with optional two-dimensional scan Figure 3 and illustrate this behavior. When radiation consists
card and Model 1205D silicon intensified target vidicon. For of wide bands or continuum radiation, the wavelength and
time-gated experiments, a high-voltage pulser (PARC Model 1211) lateral spatial information overlaps. For example, the back-
was used to gate the vidicon intensifier. The SIT vidicon was ground continuum emission from the ICP cannot be laterally
cooled to approximately -40 °C with dry ice (PARC Model 1212 resolved. Molecular bands could also not be laterally resolved
cooled housing), for some experiments. if the distance along the focal plane is of the same order of
Specific experimental conditions used for each detected image magnitude as or larger than the spatial lateral distance within
will be listed with the experimental results. the light source. Allemand (45) has described a subtractive
Quantitative intensity data are provided by the vidicon. double monochromator arrangement which overcomes this
However, the sensitivity is a function of the particular resolution
element, called a pixel, or spatial position on the detector face. problem.
The relative standard deviation in response is specified to be The trade-off between spectral and spatial resolution is
±10%. The response could be measured experimentally (36,37, governed by the size of the demagnified image which acts as
41) and experimental data corrected for pixel-to-pixel variation the entrance slit. For Figure 3, the effective entrance slit width
by ratioing. was approximately 1.2 mm, as defined by the width of the Na
Data Acquisition System The data acquisition and control
.
emission plume in the ICP and the demagnification. At 589
system consisted of a DEC MINC-11 laboratory minicomputer, nm the reciprocal linear dispersion of the spectrometer is
Z-80 microprocessor (to generate A/D conversion trigger signals
for each of the detector elements, or pixels, whose signals were approximately 0.4 nm/mm, resulting in a band-pass of 0.5 nm.
to be digitized and stored) and a circuit to enable/disable the
The observed spatial resolution will be a function of the
electron-beam readout in the vidicon and triggering of the detector limiting resolution, optical aberrations, and the size
high-voltage pulser for time-gated detection. The data acquisition
of the final image. Each pixel of the vidicon is approximately
and control system is described in detail in ref 42. 25 µ in diameter. However, blooming (36, 37) results in a
Inductively Coupled Plasma System. The ICP system smearing of the detected image; the resulting vidicon-limited
consisted of a 2.5-kW, 40.68-MHz crystal-controlled power supply resolution is approximately 10-15 line pairs/mm for valleys
(Plasma-Therm, Inc., Model HLF-2000D), an automatic impe- with 50% the intensity of the peak signal.
2052 · ANALYTICAL CHEMISTRY, VOL. 57, NO. 11, SEPTEMBER 1985
Figure 4. Images detected by (A) electronic slitless spectrograph and
(B) monochromatic imaging spectrometer due to backlighted test target.
The target line spacing in line pairs per millimeter is (1) 2.24, (2) 2.00,
(3) 1.78, (4) 1.59, (5) 1.41, (6) 1.26, (7) 2.00, (8) 2.24, (9) 2.52, (10)
2.83, (11) 3.17, (12) 3.56, and (13) 1.00.
Optical aberrations include chromatic aberration, coma,
astigmatism, and spherical aberration (46,47). Loss of image
fidelity due to chromatic aberration is eliminated by repo-
sitioning the lens for each significant change in wavelength.
The source must also be repositioned if the magnification is
to be held constant since the effective focal length of the lens
is a function of wavelength. Coma introduced by the Czer-
ny-Turner monochromator is small due to the arrangement
of mirrors. The lens will introduce little coma since it is used
on axis. However, the coma will increase for portions of the
object which are removed from the optical axis. The most
significant aberration expected to be introduced by the ESS
optical system is astigmatism. Astigmatism is minimized by
use of small off-axis angles for the concave monochromator
minors. It is also possible that the grating acting as a nonideal
plane mirror will result in a loss of image fidelity.
As can be seen from Figure 4A, a resolution (horizontal)
of approximately 2 line pairs/mm in the source was observed
in the present system with valley intensities 50% of peak
intensities reported by the ESS. The most significant limi-
tation on spatial resolution is the detector. If a perfect image
were produced with a magnification of 0.2, the detector-limited
resolution would be 2 to 3 line pairs/mm. The experimental
measure of resolution indicates that the detector is the most
significant limitation on the detected image resolution. The
vertical resolution was further limited by the detector, in
particular, by the number of tracks used. Because our ap-
plications demanded a higher spatial resolution in the hori-
zontal than in the vertical dimension, 32 to 96 tracks (vertical
resolution elements) were used compared to 500 horizontal
channels. As a result, the vertical resolution obtained is 5 to
15 times poorer than the horizontal resolution.
Of course, the detector-limited spatial resolution could be
improved by using auxiliary optics to magnify the images at
the spectrometer focal plane onto the faceplate of the vidicon.
Allemand’s subtractive double monochromator based elec-
tronic slitless spectrograph (45) uses a 20-fold demagnification
of the source and subsequent 20-fold magnification, apparently
with good fidelity.
The sensitivity of the electronic slitless spectrograph is high.
For example, a 1.5-mm aperture was used for the images
detected in Figure 3. Moreover, the sensitivity of the SIT
vidicon was reduced by more than 2 orders of magnitude so
that it was similar to that provided by an unintensified vidicon.
Although a large sodium concentration was used (350 ppm),
detection of the emission image with a small light collection
angle (effective //# is 50) and no intensification demonstrates
the high sensitivity of the system. With an increase of the
intensifier voltage to its typical value, a similar signal would
be obtained for a solution of less than 4 ppm. For more dilute
solutions, the lens aperture could be increased.
The ability to use a small-aperture light-collection system
provides two advantages. Aberrations, such as spherical
aberration, are minimized and the depth of field is large. This
characteristic is advantageous when observing sources with
a large depth along the optical axis and when Abel inversion
is to be used to transform the laterally resolved intensity data
into radially resolved information.
Monochromatic Imaging Spectrometer. The spatial
resolution provided by the monochromatic imaging spec-
trometer (Figure 2) is determined by the image magnification,
aberrations, and the detector resolution but is independent
of the spectral resolution. In turn, the image magnification
is controlled by the collimating and reimaging optics. For
example, if the light is collimated entering and exiting the
monochromator, the magnification is equal to the ratio of the
focal lengths of the collimating to reimaging lenses. In fact,
in our system the distance from mirror Ml (normally colli-
mating mirror of the monochromator) to the grating is ap-
proximately 34 cm while the distances from the slit to the
mirror and the mirror focal length are 35 cm. Therefore, an
intermediate source image is formed 1 cm past the grating and
approximately 34 cm in front of mirror M2. As a result, a
virtual image is formed approximately 1240 cm in front of
mirror M2. The virtual image then acts as an object for the
reimaging lens, L2. Because the object distance is large
compared to the focal length of L2, the distance from L2 to
the image it forms is similar to that if the light incident on
L2 were collimated (15.2 cm rather than 15.0 cm).
Caution must be exercised when the collimating and reim-
aging optics are configured with a particular monochromator.
Field-limiting and vignetting effects are especially important
and often subtle. For example, the size of the intermediate
image must not be larger than the grating or the grating will
act as a field stop and part of the image will be lost. The
magnification of this intermediate image is controlled by the
ratio of the focal length of monochromator mirror Ml to that
of lens LI. Also, as the grating angle is changed, the effective
width of the grating perpendicular to the optical path is al-
tered.
Vignetting effects might occur also at the slits of the
monochromator if the light is not collimated at that point.
The effect can be very subtle and will result in changes in the
light-gathering efficiency with position within the optical
source. Vignetting by the slits is minimized by placing the
external lenses as close to the slits as is practical.
One might be tempted to pay little attention to the distance
of lens LI from mirror Ml since the light is collimated by LI.
However, a field-limiting effect can occur if the aperture of
lens LI is imaged near the intermediate or final source image.
For example, if lens LI were placed 2 m from mirror Ml, the
lens aperture would be focused 42 mm past mirror Ml, or 7
cm past the grating. The demagnified (0.21X) image of the
lens aperture would then act as a field stop for the interme-
diate image of the source formed near the grating. Again, this
effect is minimized by placing LI as close to the entrance slit
as possible.
A number of aberrations must be considered when assessing
the spatial resolution provided by the MIS. In particular, one
must not overlook the aberrations introduced by the mono-
chromator and the external optics. Loss of image fidelity due
to chromatic aberration is minimized by repositioning the two
lenses for each wavelength. Astigmatism caused by the
monochromator will be significant due to the relatively large
off-axis mirror angles used in the Heath 0.35-m monochro-
 ANALYTICAL CHEMISTRY, VOL, 57, NO. 11, SEPTEMBER 1985 · 2053

50 ppm Co 50 ppm Co
mator compared to the 1.0-m JY monochromator used in the
700 ppm No
ESS. Coma introduced by the Czerny-Tumer monochromator
will be small.
A measure of the observed lateral spatial resolution obtained
with our system is indicated by detecting the image of a
backlighted test target as shown in Figure 4B. The image
magnification was approximately 0.42. The observed reso- —
14.2 -

lution is better than 3.5 line pairs/mm with valley intensities

50% of peak intensities reported by the MIS. If perfect image
fidelity were obtained, a vidicon-limited resolution of 4 to 6
line pairs/mm would be expected. While the spatial resolution
could be improved by increasing the magnification of the
image, a smaller portion of the source would then be detected
by the 10 X 12 mm vidicon active area. The usable size of
the vidicon is further limited by distortion effects which are
most severe near the edges (36, 37). The vertical spatial
resolution is limited by the number of tracks (lateral slices)
which are used to read out the vidicon signal. When the
maximum number of tracks is used (256 in our system), the
vertical resolution is approximately 2 times poorer than the
lateral resolution. Typically, 32 to 96 tracks were used and
provided a vertical spatial resolution of 0.3 to 0.1 mm at the
vidicon or 0.6 to 0.2 mm in the source when a magnification
of approximately 0.5 was used.
The optical fidelity could be improved in a number of ways.
The most significant aberration is probably astigmatism. A
monochromator with smaller off-axis mirror angles (such as
the 1.0-m monochromator used for the ESS) would produce
less astigmatism (46,47), Also, it is possible to compensate
for astigmatism by using collimating and reimaging mirrors
in an over-under arrangement with the appropriate off-axis
angle in place of the lenses (46,47). The all-reflective optical
system would also suffer no chromatic aberration.
The importance of the characteristics of the monochromator
used to process two-dimensional images was illustrated when
a concave grating monochromator with large off-axis angles
(a Jobin-Yvon H-20) was used. With lenses placed close to
the entrance and exit slits, an image of the source was pro-
duced on the grating. While the image fidelity appeared
adequate when zero-order light was passed through the exit
slit, the spatial resolution degraded as the wavelength and the
grating angle were increased.
The sensitivity of this system is less than the electronic
slitless spectrograph since smaller slit widths are employed.
However, the sensitivity was sufficient to require introduction
of a 1.6 optical density neutral density filter when Ar 415.9-nm
light was viewed from a 300-W ICP. Further, light from the
Ar 415-nm line was detected during time-gated operation using
a gate width of 50 µß each 5 ms (a duty cycle of 0.01). Signals
from a 500 ppm solution of sodium introduced through a
pneumatic nebulizer required introduction of a 1.0 optical
density neutral density filter to prevent detector saturation.
Therefore, similar signals would be obtained from a 50 ppm
solution of sodium without the neutral density filter.
The monochromatic imaging spectrometer is somewhat
similar in principle to the molecular optics laser examiner
(MOLE) system (48, 49). However, the MOLE system em-
ploys a double monochromator with concave gratings for
spectral resolution and imaging of the entrance slit on the focal
plane. In contrast to the MIS, the internal optics of the
MOLE monochromator are not used to collimate light from
the source or reimage collimated light from the monochro-
mator. Therefore, the lenses used to image the source on the
grating and transfer that image outside of the monochromator
must be placed as close as possible to the entrance and exit
slits in order to minimize vignetting. Since light fed to the
entrance slit of the MIS is collimated and light exiting the
monochromator is nearly collimated, it is not imperative that
-5 0 5
LATERAL POSITION (mm)
Figure 5. Laterally and vertically resolved Ca I (422.7 nm) emission
from a low-flow, low-power ICP. ICP and detector parameters are
listed in Figure 3.
Ill
>
I-
<
-I
111
IE
Figure 6. Spatially resolved, time-integrated Na emission from a ni-
trogen-sheathed, air-acetylene flame. Sodium was introduced as 60
µ diameter droplets of 50 ppm NaCI at a rate of 496 Hz. Detection
conditions were as follows: 20 frames summed in memory (40 s total);
64 tracks total; collected signal from tracks 6-35 and channels 136—
296; vidicon cooled with dry ice. The 0 to 7 and 0 to 15 scales indicate
the relative intensity of tracks 11 and 21.
the external optics be placed close to the slits. (However, the
external optics must then be large enough to prevent field-
limiting effects as discussed above.) As a result, simple
spherical mirrors could be used as the external optics for the
MIS to provide an all-reflective optical system or compensate
for astigmatism. Such an arrangement could not be used with
the MOLE.
Applications of Imaging Spectrometers to the Spatial
Mapping of Atomic Sources. The imaging spectrometers
described above have been used for fundamental investigations
of inductively coupled plasma and flame sources. A contin-
uous detection mode was used to study the effect of the ad-
dition of easily ionizable elements on calcium atom and ion
emission. Figure 5 shows a portion of the detected images
for calcium atom emission.
The vaporization and atomization of sample material in
flames have been studied by introducing monodisperse dro-
plets along a reproducible path into an air-acetylene flame.
This scheme (44,50-53) allows a separation of the vaporization
and atomization processes in time and space, unlike the sit-
uation when an aerosol with a range of droplet sizes is sprayed
into the source. Figure 6 shows the time-integrated detection
of sodium emission from vaporizing particles of sodium
2054 · ANALYTICAL CHEMISTRY, VOL. 57, NO. 11, SEPTEMBER 1985
VERTICAL
O
POSITION
e.5
I-1-1-1-1-1
5 3 I I 3 5 mm
LATERAL POSITION
Figure 7. Spatially resolved, time-gated Na emission. Source and
sample introduction are the same as those listed in Figure 6. Detection
conditions were as follows: 10 frames summed, 32 tracks total;
collected signal from tracks 4-23, channels 159-408, vldicon cooled
with dry Ice, 10 ps gate triggered 0.50 ms after the beginning of
atomization (Indicated by the appearance of emission), stroboscopic
measurement with a total of approximately 5100 gates (individual atom
clouds).
chloride. In order to view directly atom clouds in the flame,
a time-gated detection mode was used. Figure 7 shows atom
clouds detected stroboscopically with a 50-µß time gate. Data
detected in this manner allow the direct measurement of the
flame-gas velocity, particle vaporization rates, and diffusion
rates of the resulting atoms (50-53).
CONCLUSIONS
The imaging spectrometers described here can provide a
quantitative two-dimensional image of optical sources. The
simultaneous detection in two dimensions dramatically re-
duces the time required for many experiments. Some ex-
periments which could not reasonably be done with a
point-by-point detection scheme because of the necessary
acquisition time or source irreproducibility can be performed
with an imaging spectrometer. Radial spatial information
could be obtained by Abel inversion of the laterally resolved
data. The systems described here could also be used with
absorption, scattering, or fluorescence probes with similar
spatial resolution and with spectral resolution far better than
that available from interference filter based systems.
Improvements to the system described here could be ac-
complished with better detectors. The blooming, lag, and
narrow dynamic range of the SIT vidicon (particularly of this
first generation DMA system) limit the performance of the
system. Use of second-generation vidicons or newly developed
charge-coupled device or charge-injection device detectors
would result in improved capabilities.
Changes in the data acquisition system would significantly
improve the overall performance of the imaging monochro-
mators. The vidicon-based system used here was not originally
designed for two-dimensional detection. As a result, the frame
readout time is long (32 ms times the number of tracks) when
a large number of tracks are detected. The computer data
collection system could only store images of 5000 or fewer
detection elements. Video data collection systems using frame
grabbing buffer systems would allow real time signal averaging
and background subtraction. Also, newer versions of the
optical multichannel analyzer are more suited to two-di-
mensional detection than the system used for this work.
If one compares the electronic slitless spectrograph (ESS)
and monochromatic imaging spectrometer (MIS), the ESS is
most useful when spectral and spatial resolution can be traded
for higher sensitivity and when nearby wavelength images do
not overlap. Also, the ESS is a less complicated optical system.
In contrast, the MIS can provide high spectral and spatial
resolution simultaneously if sufficient light is available.
Although the performance of the ESS and MIS described
here are adequate for many applications, work is continuing
(J.W.O.) to further improve and characterize the optical fi-
delity and aberrations of the monochromatic imaging spec-
trometer. Characterizations under way include ray tracing
and third-order aberrations analysis and more complete ex-
perimental measurement of the two-dimensional spatial res-
olution and aberrations including astigmatism, possible field
distortion or curvature, and wavelength (grating angle) de-
pendent effects. Reflective optical systems to compensate for
aberrations such as astigmatism and eliminate chromatic
aberrations are being designed and tested.
ACKNOWLEDGMENT
The work of Ray Sporleder who designed the Z-80 micro-
processor and wrote software for it and Robert Deutsch who
aided in development of the MINC software is acknowledged.
Registry No. Na, 7440-23-5; Ca, 7440-70-2.
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Received for review November 29,1984. Resubmitted May
Controlled Potential Electrolysis Coupled with a Direct Sample
Insertion Device for Multielement Determination of Heavy
Metals by Inductively Coupled Plasma Atomic Emission
Spectrometry
Magdi M. Habib and Eric D. Salin*
Department of Chemistry, McGill University, Montreal, Quebec H3A 2K6, Canada
The application of controlled potential electrolysis with both
graphite eléctrodes and a hanging mercury drop electrode as
a separation and preconcentration technique for Inductively
coupled plasma (ICP) atomic emission spectrometry using
the direct sample Insertion device (DSID) Is described.
Heavy metal Ions In aqueous solution are determined. With
a deposition time of 5 min the detection limits under com-
promise conditions are 2.4, 680, 2.0, 175, 25, and 259 ng/mL
for Cu, Pb, Zn, Cd, NI, and Co, respectively. A determination
of Cu at the 63 ng/mL level In artificial seawater (3.5% sa-
linity) was made with a 4% error.
The application of inductively coupled plasma atomic
emission spectrometry (ICP-AES) to the simultaneous de-
termination of major and minor and trace level elements in
various matrices has been well documented (1-5). Pneumatic
nebulization appears to be the most popular method of sample
introduction although the sensitivity attainable is not suffi-
cient for the ICP analysis of many elements which are present
in the nanogram per gram range (6). A number of studies have
concentrated on developing methods for isolating trace ele-
ments from complex matrices including coprecipitation (7),
chelation (8, 9), chromatography (10), and conversion into
hydrides (11). In all of these isolation methods large volumes
of additional chemicals are brought into contact with the
samples and thus may introduce contaminating or interfering
species. In addition, some of these techniques are time-con-
suming and tedious. Ultrasonic nebulizers have demonstrated
improvements in working range by factors of 1.1-12 (12-14)
in various matrices; however, considerable question still exists
about the general reliability and freedom from interferences
of these devices (15).
Separation of heavy metal ions from various matrices by
controlled potential electrolysis is often a very useful method
in trace analysis (16-19). By the use of mercury electrodes,
a number of heavy metals can be deposited even from acidic
aqueous solution because of the broad cathodic potential range
0003-2700/85/0357-2055$01.50/0
2055
13,1985. Accepted May 13,1985. This work was supported
by the National Science Foundation through Grants CHE
82-14121 and CHE 83-20053 and by the Office of Naval Re-
search. Portions of this work were presented at the Tenth
Annual Meeting of the Federation of Analytical Chemistry
and Spectroscopy Societies (Sept 1983, Philadelphia, PA) and
the Thirty-fifth Pittsburgh Conference and Exposition on
Analytical Chemistry and Applied Spectroscopy (March 1984,
Atlantic City, NJ).
(20). This separation technique has found wide application
in the field of atomic spectrometry. Higher sensitivity than
conventional techniques was obtained because of the sample
preconcentration during electrolysis and the potential power
of the technique to separate trace elements from complex
interfering matrices. Electrolysis has been performed on metal
wires (21-25), carbon rods (26, 27), hanging mercury drop
electrodes (28, 29), and tubular pyrolytic graphite-coated
electrodes (30) for spectrochemical applications. The tech-
nique has also been applied to flame AA, using a thin film
of mercury deposited on a wax-impregnated graphite rod (31),
to a direct current arc using a hanging mercury drop electrode
(HMDE) (32) and to a helium microwave induced plasma
(He-MIP) (33). A wall-jet electrochemical cell for precon-
centration of trace metals from flowing streams prior to their
determination by ICP with conventional pneumatic nebuli-
zation was also described (34).
We previously reported preliminary results on controlled
potential electrolysis coupled with ICP-AES for the deter-
mination of copper in aqueous solutions (35). The method
involved the electrodeposition of copper from an aqueous
Solution of copper nitrate onto a piece of spectrographic
graphite electrode previously coated with mercury. After the
completion of the electrolysis the electrode was demounted
from its holder and mounted on the top of the quartz rod of
the direct sample insertion device (DSID) (36). The electrode
was then inductively dried for 1 min at a forward power of
30 W prior to ICP analysis.
This study is an evaluation of this technique for the si-
multaneous determination of heavy metals (Cu, Pb, Cd, Zn,
Ni, and Co) in aqueous solution as well as an evaluation of
the performance with a difficult sample matrix.
EXPERIMENTAL SECTION
Table I lists the principal components of the instrumentation.
Figure 1 is an illustration of the electrochemical cell. The cell
body (a) is made from Teflon and has a volume capacity of 40
mL. The cell lid (b) contains three holes to fit the reference
electrode (c), the working electrode (d), and the auxiliary electrode
(e). The lid also contains two small holes (f) for nitrogen input
&copy; 1985 American Chemical Society