Anal. Chem.
1994,66, 3916-3924
Particle Beam Aqueous Sample Introduction for Hollow
Cathode Atomic Emission Spectroscopy
Jianzhang You, James C. Fanning, and R. Kenneth Marcus'
Department of Chemistry, Howard L. Hunter Chemical Laboratory, Clemson University,
Clemson, South Carolina 29634- 1905
The design and preliminary operating characteristics of a
particle beam/hollow cathode atomic emission spectrometry
(PB/HC-AES) device is described. By use of a high-efficiency
thermal-concentric nebulization system coupled to a particle
beam LC/MS interface, analyte particles originating in aqueous
solution are introduced into a heated hollow cathode glow
discharge for subsequent vaporization and excitation. The
Thermabeam (Extrel Corp.) interface permits liquid introduc-
tion in either flow injection or chromatographic mode. Helium
and argon are evaluated as discharge gases over a range of
pressures and discharge currents, with He chosen as the most
appropriate for subsequent analytical studies. Nebulization
temperature, liquid (solvent) flow rate, and vaporization
temperature are evaluated in order to determine their effects
on analyte emission characteristics. Optimized sample in-
troduction and He plasma operation conditions are employed
to study the analytical characteristics of the PB/HC-AES
system. Background equivalent concentrations (BECs) for
Na and Cs (as nitrates) in aqueous solutions are 0.53 and 0.74
ppm, respectively. Subsequent studies of cesium at ppm levels
in diluted (1OOOX) simulated nuclear waste solutions (5.0 M
NaNO3 and 0.1 M KOH) indicated that the addition of excess
chloride as a counterion, rather than nitrate, greatly enhances
-
detectability. BEC values for Cs in aqueous solution were
lowered by a factor of 10, while for the diluted simulant the
values were lowered by >lOOX, with detection limits in the
latter found to be -8 ppb.
Glow discharge (GD) devices have become valuable tools
for direct solids elemental analysis of a wide variety of
materials, from bulk metals to thin-film systems.' Glow
discharges provide efficient atomization, excitation, and
ionization of sample material and have been employed
extensively in atomic absorption, emission, and mass spec-
trometric studiese2 In addition to the analysis of metals and
alloys, sample preparation methodologies have been developed
for the analysis of nonconducting powders by compaction in
a conducting host m a t r i ~ .More
~ recently, radio frequency
glow discharge devices have been developed for the direct
analysis of electrically insulating materials without matrix
m~dification.~ The use of radio frequency power has widened
(1) Harrison, W. W.; Barshick, C. M.; Kiingler, J. A.;Ratiiff, P. A,; Mei, Y. Anal.
Chem. 1990, 62, 943-949A.
(2) Marcus, R. K. Glow Discharge Spectroscopies; Plenum Press: New York,
1993.
(3) Dogan, L.; Laqua, K.; Massmann, H. Specfrochim. Acta, Part 8 1972, 278,
65-88.
(4) Marcus, R. K. J . Anal. At. Spectrom. 1993, 8, 935-943.
3910 Analytical Chemisrty, Vol. 66, No. 22, November 15, 1994
the range of applications of the devices to virtually any solid
sample type, making them among the most diverse of the
solids analysis techniques.
Paralleling the developments in other areas of atomic
spectrometry, where techniques best suited for aerosol/vapor
introduction are being investigated with solids introduction
schemes, many laboratories are now looking for efficient means
of applying GD sources to the analysis of solution-based
samples. A long-term goal in this laboratory is the develop-
ment of a single spectrochemical device for the analysis of
solid and solution samples. Solution samples have been
analyzed indirectly with glow discharge devices through the
sputter atomization of solution residue~.~-IOIn this method,
aliquots of the sample solution (1-100 pL) are applied to the
cathode (either a planar or hollow cathode) surface and dried
under an infrared lamp. The resultant residue is atomized by
cathodic sputtering with the atomic population sampled by
atomic a b ~ o r p t i o n ,emission,'
~.~ fluorescence,8 or mass spec-
t r o m e t r i e ~ .The
~ ? ~GD
~ methods for solution residue analysis
have been overshadowed by flame atomic absorption and
plasma emissiontechniques because of their wide applicability,
sensitivity, and high sample throughput.
In order to improve the sample throughput of GD devices
for solution sample analysis, it is desirable to have some means
of continuous, or at least segmented, flow for sample
introduction. Furthermore, if a glow discharge source were
attached to the end of a liquid chromatography (LC) column,
species could be separated and introduced into the excitation
region for subsequent analysis by optical or mass spectrometries
(MS). Because of the low pressures and powers employed in
GD devices (resulting in T,,, <lo00 Kl1 ), the discharges are
quite inefficient at aqueous sample desolvation and vaporiza-
tion in comparison to atmospheric pressure flames and plasmas.
Even if solvent evaporation could be achieved within the
discharge volume, the presence of water-related gaseous species
(assuming aqueous sample introduction) in the plasma can
cause band emission in AES and lower the metastable atom
populations in the negative glow region, quenching analyte
( 5 ) Bruhn, C. G.; Harrison, W. W. Anal. Chem. 1978,50, 16-21.
(6) Chakrabarti, C. L.; Headrick, K. L.; Bertels, P. C.; Back, M. H. J. Anal. At.
Specrrom. 1988, 3, 713-723.
(7) Chen, F.; Williams, J. C. Anal. Chem. 1990, 62, 489-495.
(8) Smith, B. W.; Omenetto, N.; Winefordner, J. D. Spectrochim. Acta, Part 8
1984, 398, 1389-1393.
(9) Jakubowski, N.; Stuewer, D.; Tolg, G. Spectrochim. Acta, Parr 8 1991,468,
155-163.
(10) Barshick, C. M.; Duckworth, D. C.; Smith, D. H.J. Am. SOC.MassSpectrom.
1993, 4, 47-53.
(11) West, C . D.; Human, H. G. C. Spectrochim. Acra. PartB 1976,318,81-92.
0003-2700/94/0366-39 16$04.50/0
0 1994 American Chemical Society
ionization.12 Therefore, any liquid sample introduction
approach must include a high-efficiency desolvation step and
subsequentsolvent vapor removal prior to analyte introduction
to the discharge source. Complications due to solvent
background and its effects on spectral quality are also major
concerns when one is attempting to introduce liquids into
conventional (organic) mass spectrometric ion sources.13 For
these reasons, it is logical to pursue methods of liquid sample
introduction that have been developed for liquid chromatog-
raphy/mass spectrometry (LC/MS) for the coupling of LC
(or other liquid delivery systems) with the glow discharge.
The implementationof LC/MS approaches to liquid sample
introduction into GD devices were first described by Brackett
and Vickers in 1983.14 That source provided continuous
sample introduction into a glow discharge with a chain
conveyor, wherein the sample was deposited on the moving
chain (straight wire and link types), passed through a reduced
pressure oven to affect solvent evaporation, and then passed
across the GD cathode. In this way, the metal chain became
part of the cathode and the analyte residue was sputter-ablated.
Difficulties in reproducibility in the initial studies were
overcome by use of a bead chain, as this allowed for even
segmentation of the sample on each of the beads? The latter
studies suggested that liquid delivery rates of up to 200 pL
min-I could be tolerated before excessive solvent loading of
the plasma led to instabilities. A sputter atomization step
was confirmed by the fact that little correlation was found
between detection limits (ranging from 0.8 to 3.2 pg mL-I for
Pb, Cd, B, and Cu) and compound volatility. Alternatively,
compound decomposition in the desolvation furnace, resulting
in memory effects, was found to be an important consideration.
In consideringalternativeintroduction schemes, the results
of Brackett and VickersI4J5further point to the need to employ
an interface that has a very high efficiency for solvent vapor
removal. Particle beam devices are finding increased usage
in mass spectrometric analyses of LC separations because of
their ability to operate at reasonable liquid flow rates while
subsequently removing solvent vapors to levels that permit
electron impact ionization.16J7 In this laboratory we have
employed a particle beam LC/MS interface (Thermabeam,
Extrel Corp., Pittsburgh, PA) for liquid sample introduction
into a GD device. The Thermabeam utilizes a thermal-
concentric nebulizer to convert the eluent from the LC column
into a finely dispersed aerosol. The aerosol is desolvated and
passed through a momentum separator, producing a particle
beam that is directed into the source volume. A previous
study illustrated the feasibility of the particle beam introduc-
tion approach for aqueous sample analysis by glow discharge
atomic emissionspectrometry.'* In that work, analyte particles
were effectively collected on a planar cathode and the atomic
population was produced through cathodic sputtering. The
analytical sensitivity of this approach was limited to the single
ppm level due to the inefficient, nonquantitative sample
(12)Hess, K. R.;Harrison, W. W. Anal. Chem. 1988,60,691-696.
( I 3) Covey, T.R.;Lee, E. D.; Bruins, A. P.; Henion, J. D. Anal. Chem. 1986,58,
1451 A-1461A.
(14)Brackett, J. M.; Vickers, T. J. Specfmchfm.Acta, Part B 1983,38B,979-985.
(1 5) Brackett,J. M.; Vickers,T. J. Spectrochim. Acfa. Parr B 1984,39B,837-841.
(16)Willoughby, R. C.; Browner, R. F. Anal. Chem. 1984.56.2626-2631.
(17)Singh, R. P.; Brindle, I. D.; Jones, T. R. B.; Miller, J. M.; Chiba, M. J. Am.
Sa.Mass Spectrom. 1993,4,898-905.
(18)Strange, C. M.; Marcus, R. K. Spcfrochim. Ada, Parr B 1991,46B,517-
526.
t hv
N ~ ~ Cathode
Hollow
~ ~ ,
Macor
'a'
Particle
\ Themoblock
Assembly
Beam t
Discharge
Gas
Figure 1. Diagrammatic representation of the plasma source region
of the particle beam/hollow cathode glow discharge atomic emission
device.
ablation and by losses in the diffuse plasma structure. Analyte
emission intensities were found to optimize under those
conditions wherein the aluminum target was heated through
sputtering, rather than those conditions which produce
optimum photon emission from the plasma glow.
We present here a preliminary evaluation illustrating the
practicality of interfacing a particle beam device with a heated
hollow cathode (HC) glow discharge and the subsequent
measurement of the atomic population by emission spec-
trometry (PB/HC-AB). By use of the heated hollow cathode
volume, the analyte particles are vaporized into the gas phase
as free atoms. The influence of discharge gas identity (Ar or
He), vaporization temperature, and discharge conditions are
evaluated for sodium and cesium analytes. The practical
application of the particle beam approach is illustrated by the
analysis of cesium at ppm levels in diluted simulated nuclear
waste solutions containing initially high levels of salt ( 5 M
NaN03 and 0.1 M KOH). Signal suppression induced by
the presence of the salt is overcome by the addition of small
amounts of HCl. Data presented here suggest that the PB/
GD-AES approach may indeed be a viable technique for the
elemental analysis of volume-limited or chromatographically
introduced samples.
EXPERIMENTAL SECTION
Glow Discharge Source. A diagrammatic representation
of the hollow cathode source region of the particle beam/
hollow cathode glow discharge interface is shown in Figure
1. The hollow cathode is contained within a stainless steel
block (termed the thermoblock) which is mounted onto a 6
in. diameter flange, within a stainless steel five-way cross.
Use of the cross allows for placement of the optical sampling
window, vacuum pumping port, discharge gas inlet, electrical
feedthroughs, and particle beam interface on the appropriate
flanges. The plasma is operated by using helium or argon as
the discharge gas with the bulk chamber pressure monitored
by means of a thermocouple gauge (DV-4D, Teledyne

Momentum
Stage 1 Stage 2
Pump Pump
Flgure 2. Complete Thermabeam nebullzer and partlcle beam Interface coupled to the heated hollow cathode glow discharge atomic emission
source.
Hastings-Raydist, Hampton, VA). The discharge is powered
by a Kepco (Flushing, NY) Model BHK 2000 supply operating
in a constant-current mode.
The implementationof the heated hollow cathode discharge
volume is integral to the enhanced performance over the
previous PB/GD approach. The titanium hollow cathode (3
mm diameter, 17 mm length) is housed within the 28 X 28
X 60 mm3 stainless steel thermoblock, heated by a pair of
commercially available cartridge heaters (Model SC 25 15,
Scientific Instrument Services, Ringoes, NJ) which are
powered by a laboratory transformer. In this way, the
temperature of the hollow cathode can be regulated up to 220
OC, as measured by a W-Re thermocouple. Desolvated
analyte particles are introduced to the thermoblock through
the momentum separator (described in the next section)
through a 1.5 mm diameter orifice, wherein they collide with
the heated wall and are vaporized. Volatilized analyte is then
swept into the hollow cathode discharge by a perpendicular
flow of discharge gas and subjected to excitation collisions
within the discharge. The separation of the vaporization and
excitation processes allows for optimization of each without
compromise to theother, which was not thecase in the previous
studies.'*
Particle Beam Interface. Figure 2 is an expanded drawing
of the Thermabeam/glow discharge interface geometry. The
Thermabeam is a particle beam type of LC-MS interface
that employs a thermal-concentric nebulizer to generate a
finely dispersed aerosol, a heated expansion (spray) chamber
for desolvation of the solvent, and a momentum separator to
inject dry particles of the analyte into the source volume. The
liquid sample is passed into the nebulizer through a fused
silica capillary (0.15 mm i.d.) within a stainless steel capillary
(0.50 mm i.d.). Helium gas is passed through the steel tubing
and flowsaround the capillary tip and thus forms a concentric
nebulizer. A potential difference between the ends of the
stainless steel tubing resistively heats the tubing, effectively
heating the He nebulizer gas, adding a thermal component
to the nebulization action at the tip. The aerosol is introduced
3918 A n a ~ c a l l m l s t t y Vol.
, 66, No. 22, November 75, 1994
To
Monochromator
5-way Cross
c-----
Source Housing
U
t
Discharge
Gas
directly into a stainless steel desolvation chamber (3.4 cm i.d.,
10.1 cm long) that is encircled by electrical heating tapes.
The desolvated aerosol passes through a two-stage momentum
separator that "skims" light-weight gas molecules from the
flow and also serves as a differential pumping device to obtain
a beam consisting only of particles. The interface is flange
mounted opposite from the GD source, with the exit aperture
fitted into the side of the thermoblock, -14 mm from the
heated surface. No attempt has been made to modify the
commercial particle beam nebulizer or momentum separator.
Solution Preparation and Delivery. For the purposes of
evaluatingthe feasibility of the particle beam/hollow cathode
coupling,aqueous stock solutions of NaN03 and CsNO3 were
prepared with deionized, distilled water from reagent grade
inorganic salts. Simulated nuclear waste solutions were also
prepared from reagent grade salts, having a nominal com-
position of 5.0 M NaN03 and 0.1 M KOH. The solvent
delivery system was a Waters (Division of Millipore, Milford,
MA) Model 5 10 high-performance liquid chromatography
pump. The solutions were passed through a 0.76 mm 0.d.
stainless steel tubing with no attempt made at performing
chromatographic separations. Solution flow rates are adjust-
able at intervals of 0.1 mL min-' up to a maximum of 1.5 mL
m i d . Throughout these studies, samples were introduced
into the flowing aqueous solvent stream in a flow injection
mode, with 200 pL injection volumes.
Optical System. Atomic emission produced from within
the hollow cathode discharge was focused by a plano-convex,
fused silica lens onto the entrance slit of a scanning mono-
chromator. The spectrometer employed is a 0.24 m Czerny-
Turner mount having a 2400 gr/mm holographic grating
(Digikrom 240, CVI Laser Corp., Albuquerque, NM).
Spectral scanning, wavelength selection, and slit widths are
easily controlled via the monochromator control interface
provided by the manufacturer. A photomultipliertube (RCA
1P28) and analog photometer (Model 110, Pacific Instru-
ments, Concord, CA) are employed to detect and record
spectral intensities. Emission intensity data are recorded by
an X/Y recorder (Model 200, Houston Instruments, Austin,
TX), with transient peak heights used in all tabulations and
calculations.

RESULTS AND DISCUSSION .-c,

Role of Discharge Parameters. As in the case with all GD v)
C
Q,
devices, the parameters of discharge current and pressure,
along with the discharge gas identity, play key roles in the -
c,
C

observed emission characteristics of the PB/HC-AES system.

Different from other GD sources, though, is the fact that the
atomic population in the plasma need only to be excited, rather
than also being produced by sputtering. In this evaluation,
both helium and argon were investigated as discharge gases,
as they represent the most commonly applied gases for hollow
cathode emission and mass spectrometric applications, re-
spectively. The primary difference lies in the ability of He
to excite atoms to high-lying levels due to its higher ionization
potential and the resultant higher discharge voltages, while
Ar is a much better sputtering gas while still efficiently
exciting/ionizing most elements of the periodic table. Of
particular interest in the comparison of the two gases was the
response of analyte emission intensities over a range of
discharge conditions and the relative complexityof the emission
spectra.
Figure3 illustrates theresponseofNa (I) 589.0nmemission
intensity over a range of discharge conditions for the (a) He
and (b) Ar discharge gases. Throughout this study, the
NaNO3 concentration was maintained at a value of 0.1%,
with a liquid flow rate of 0.5 mL min-l. As seen in both plots,
thedischarge current has a direct effect on emission intensities,
reflecting the typical response of electron number densities
found in hollow cathode discharges. l 9 A proportional response
of analyte emission to increases in discharge current is not
generally observed in glow discharges where sputtering effects Figure 3. Effect of discharge pressure and current on Na (I) 589.0
are involved,20q21even though electron densities do increase.22 nm emission intensity for (a, top) heliumand (b, bottom)argondischarge
gases: 0.1 % NaN03 solution; 0.5 mL min-I solution flow rate.
The respective responses to changes in discharge gas pressure
are very different for He and Ar, with the former showing a
more well-defined range of optimum operation. A comparable case in the previous studies of the PB/GD combination,'* the
set of experiments employing Cs as the analyte yielded similar overall magnitude of band emission is not prohibitively high,
response characteristics. The differences between the gases roughly of the same magnitude as the Na (I) 589.0 nm emission
are likely explained by the physical nature of the plasmas, from the 10 ppm N a N 0 3 test solution. The low amounts of
wherein the energy within the negative glow (and indeed the band structure are a testament to the efficiency of the
shape) of the He plasma is more concentrated within the center desolvation and particle beam separation characteristics of
of the cathode, while the Ar plasma is visually more diffuse. the Thermabeam interface. Neither the atomic or molecular
Studies by Kirichenko et al.23in hollow cathode discharges spectral contributions of the discharge gases nor the residual
have found as well that differences exist in plasma shapes and water are considered detrimental. Given the possible wide
character between He and Ar plasmas. range of excitation energies that might be presented in
The spectral comparison between He and Ar lies in the applications of this particle beam/hollow cathode device, a
overall spectral complexity due to the gases themselves. With decision has been made to employ solely He as the discharge
respect to atomic transition overlaps, He produces a far simpler gas.
spectrum than Ar, particularly in the spectral region between Role of Nebulization Parameters. As with any technique
400 and 500 nm. On the other hand, the higher excitation wherein solution nebulization is employed, one must be
energy afforded by He does tend to produce slightly more concerned with the role that solution/solvent introduction has
band emission from OH' and air-related species. As was the on plasma performance. In the Thermabeam interface, the
key parameters affecting nebulization efficiency are the
(19) Howorka, F.; Pahl, M. Z . Naturforsch. Teil A 1972, 27, 1425. temperature at the nebulizer tip and the liquid flow rate. In
( 2 0 ) Boumans, P. W. J. M.Anal. Chem. 1972, 44, 1219-1228.
(21) Leis, F.; Broekaert, J. A. C.; Laqua, K. Spectrochim. Acta, Part E 1987,428,
practice, He nebulization gas flow rate and the desolvation
1169-1 176.
(22) Fang, D.; Marcus, R. K. Spectrochim. Acta, Parr E 1990,458, 1053-1074.
(23) Kirichenko, V. I.; Tkachenko, V. M.; Tyutyunnik, V. B. Sov. Phys. Tech Phys.
1976, 21, 1080-1086.
-
chamber temperature are also important. Previous experience
has suggested that He flow rates over 50 mL m i d do not
substantially affect nebulization characteristics, while opti-

Analytical Chemistry. Vol. 66, No. 22, November 15, 1994 3919
mum desolvation efficiency (>95%) can be achieved with
chamber wall temperatures of >220 "C.18 The role of
nebulization (tip) temperature was assessed by use of a
thermocouple attached at the exit end of the stainless steel
capillary. This temperature is not the temperature directly
applied to the solvent but a measure of the heating of the He
nebulizer gas. Helium, having a very high thermal conduc-
tivity, transfers the heat to the fused silica capillary indirectly
heating the solvent. Additional thermal energy is imparted
as the hot He gas passes the silica capillary exit, producing
the combination thermal-concentric nebulization character.
Figure 4a depicts the observed, integrated Na (I) 589.0 nm 0.0I ' I ' I , I , I , I
160 180 200 220 240 260
emission intensity as a function of the nebulizer tip tempera-
ture. As would be expected, the efficiency of nebulization (as Tip Temperature ('C)
observed through emission intensity) increases with tempera-
ture, up to a maximum of 220 "C. Above temperatures of
220 OC,the nebulizer begins to sporadically eject solvent and
vapor from the silica as vaporization appears to occur from
within the capillary rather than at the end. Additionally,
clogging of the capillary becomes an issue for high-solids
(>O. 1%) solutions. For the remainder of the studies described
here, a nebulizer tip temperature of 220 "C is maintained.
Similar to other nebulizer-based solution introduction
schemes, the liquid flow rate is a critical parameter as it will
ultimately limit both the nebulization efficiency and the
response of the source (plasma/flame) characteristics. More
so than any other source, the effect of introduced solvent vapors
into the hollow cathode region can be detrimental, even at Flow Rate (ml/min)
very low (C10 ppm) levels.12 As seen in Figure 4b, the response
of integrated Na (I) intensity is inversely related to increases
in solvent delivery rate. The reasons for this response can be *.O 1
evaluated in terms of the nebulization, desolvation, and 1.8-
particle/vapor introduction stages. In the nebulization step,
higher flow rates would be expected to lower the efficiency 1.6-
as more thermal energy is required for aerosol generation.
This was evident by the fact that the current passing through 1.4-
the steel heating capillary had to be increased with increasing
flow rate in order to maintain a constant tip temperature of 1.2-
220 OC. Even though the temperature was held constant, the
1 .o-
reduced residence time of the solution in the capillary and in
the aerosol generation region at the tip would be expected to
lower the overall efficiency. Likewise, heavy solvent load
0.0
100
I
150 200 250 300
within the desolvation chamber resulted in a need to increase
Block Temperature ("c)
the heating current there to maintain a constant temperature.
Figure 4. Roles of nebulization and vaporization parameters on Na
Although the walls of the chamber were kept hot, surely the (I) 589.0 nm emission Intensity (0.1 % NaN03solution): (a, top) nebulizer
desolvation step also suffers at high flow rates. Finally, in the tip temperature: (b, middle) solvent flow rate; (c, bottom) vaporization
event of reduced desolvation efficiency, more water vapor temperature.
would be expected to pass to the discharge, quenching the
plasma energetics. This effect is the least likely culprit as no and nebulizer gas flow rates, nebulizer temperature, and solvent
(expected) change in discharge voltage was observed under identity (volatility).
these conditions. This observation is consistent with the One additional experimental variable involved with the
previous studies and confirms the excellent vapor-filtering particle beam interface is the vaporization temperature that
characteristics of the particle beam interface. While more the introduced particles experience. The previous studies
detailed studies of the nebulization and desolvation qualities showed quite clearly that the the inherent sputtering in the
of the Thermabeam device are in order, it has been generally glow dischargedevice occurred at rates insufficient to maintain
observed that moderate flow rates of -0.5 mL min-' are less the temporal quality of flow injected or chromatographically
susceptible to clogging and will be employed throughout the introduced analytes; Le., the residence time was too long.
remainder of the work presented here. Future studies will Thermal vaporization has long been employed in organic LC/
include a thorough evaluation of the relationship between liquid MS applicationsof particle beam devices.I6 The present design

3920 AnalyticalChemistry, Vol. 66,No. 22, November 75, 1994

 I I I
0.0 1 .o 2.0
Time (min)
Flgure 5. Temporal profile of Na (I) 589.0 nm emission intensity for
a 200 pL injection of a 10 ppm Na solution: solution flow rate, 0.5 mL Na Concentration (ppm)
min-I.
8
y - 0.86 + 1,17x RAZ - 0.961

follows this lead as the analyte particles are introduced

perpendicularly to the hollow cathode axis, flash vaporized, 6-
and swept by the discharge gas flow into the plasma. In such
an approach, the temperature within the thermoblock is key
4-
to efficient particle vaporization and analyte introduction.
Figure 4c illustrates the role of block temperature on the
integrated Na (I) intensity under the nebulization conditions
2-
described above. As can be seen, the vaporization process is
highly dependent on temperature. This is the expected
response characteristic as the particles would require some I
O ! ' , ' I ' I ' I ' ! '
minimum energy for volatilization, with the efficiency 0 1 2 3 4 5 6
increasing to the point of completevaporization. Interestingly,
the response shows a rollover at the highest temperatures, Cs Concentration (ppm)
rather than the expected plateau. The reasons for this response Figure 6. Analytical response curves obtained for aqueous (a, top)
are not clear at this point and require further evaluation. It NaN03(589.0 nm) and (b, bottom) CsN03 (852.1 nm) solutions. Error
bars representthe range of values obtainedfor three consecutive 200
seems obvious that the absolute threshold temperature pL inJections.
(analogous to an appearance temperature in GF-AAS) will
be a function of the sample particle identity and could affect
and also having established its feasibility for proposed
substantial matrix effects. Future studies will look at this
chromatographic applications, an evaluation of the basic
variable for a wide range of metal/anion combinations. Given
calibration characteristics was in order. Initial efforts focused
the nature of the response curve, it seems apparent that the
on the generation of working curves for simple solutions of
highest practical temperature will allow for the most uniform
aqueous Na and Cs, each in the form of nitrates. Shown in
sample introduction.
Figure 6 are the obtained calibration curves (transient peak
An important characteristic of any proposed chromato-
height) over concentration ranges of between 0.001 and 10
graphic detector is a low degree of dispersion as indicated by
ppm for sodium (a) and 0.05 and 5 ppm for cesium (b).
the temporal response of the detected signal. Evidence of the
Indicated on the respective plots are the least-squares linear
flow dispersion induced by the particle beam introduction is
regression data as well as the sample-to-sample variability
provided in Figure 5. Shown is a strip chart trace of the
obtained for triplicate injections. While these preliminary
signal generated by the injection of 200 pLof NaN03 solution,
calibration plots cover limited concentration ranges, reasonable
which was 10 ppm in Na. The 0.5 mL min-' flow rate
linearity is observed, particularly in the case of sodium.
corresponds to an ideal signal transient time of 24 s. As can
Background equivalent concentrations calculated from the
be seen, the temporal profile exhibits a very sharp leading
working curves were also encouraging. In comparison to the
edge, with the signal approaching the baseline level in -20
initial work with the planar glow discharge arrangement,24
s. It is suggested from this response that the volatilization
the sodium sensitivity is quite good with a BEC = 0.5 ppm,
process is relatively free from memory effects and that the
with the BEC from the cesium regression equal to 0.7 ppm.
particle and vapor transport processes do not suffer from
From these preliminary calibration data, detection limits (DL
excessive dead volume. In addition, the plasma stability of
= hblank/m, nblank = 10) are calculated to be 0.05 and 0.1
the current design is very good as well. This transient signal
ppm, respectively for Na and Cs. Given the rather early stage
illustrates the desired response qualities necessary for future
of instrument development, and a rather simplistic optical
implementation of this device in chromatographic sampling
and detection system, we consider these to be quite reasonable
applications.
figures of merit. It should be emphasized that while cesium
Analytical Characteristics. Having optimized the plasma
and nebulization characteristics of the PB/HC-AES device, (24) Strange, C. M. Masters Thesis,Clemson University, Clemson, SC, 1992.

Analytical Chemistry, Vol. 66, No. 22, November IS, 1994 3921
is in general a strong emitter at the 852.1 nm wavelength, its 4
analytical characteristics in atomic emission spectrometry are y = 0.22+ 2.56e-2x R A 2 = 0.974

poor due to the very low responsivity of photomultiplier tubes

and low transmission characteristics of optical spectrometers
that are designed for optimum performance at wavelengths
below 500 nm (as is the instrumentation employed here).
Further analytical evaluation into the possible applicability
of the PB/HC-AES approach was pursued by way of a
collaborative project with the Westinghouse Savannah River
Co. (Aiken, SC) at the Savannah River Site (SRS), where
a major nuclear waste disposal program is underway. The
primary waste mixture has an approximate bulk makeup of
5 M NaN03,O. 1 M KOH (pH 14) with most heavy metal ions 0 20 40 60 80 100 120
precipitated as hydroxides or oxides. The primary radioactive Cs Concentration (ppm)
species present in the solution is I3'Cs at a concentration of
-20 ppm. The objective of the collaborative project was for
the inorganic chemist (J.C.F.) to develop methods to efficiently
remove Cs+ from solution. In order to assess the respective
efficiencies of the developed procedures in simulated waste
I y = 1.14 + 1.88e-Zx RA.2 = 0.994

solutions, in-house analytical methods were needed.

The bulk solution is obviously quite caustic and would be
classified in most instances as having a high degreeof dissolved
solids. The combination of high alkalinity, high solids, and
having a high concentration of easily ionizable elements (EIEs)
poses particular challenges for traditional atomic spectrometric
methods such as flame AAS or ICP emission or mass
spectrometries. 'The high solids content would generally
dictate a minimum dilution factor of lOOX for standard 0 20 40 60 80 100 120
pneumatic nebulization systems, though the high level of EIEs Cs Concentration (ppb)
would dictate this step as well, even for nebulizers with high
solids capabilities. The constricted nature of the fused silica 2.61 I

(150 wm i.d.) introduction path for the Thermabeam nebulizer,

along with the aforementioned possibility to desolvate along
the capillary path, required that a dilution factor of 500-
lOOOX be employed to efficiently nebulize the test solution in
this case without the deleterious effects of clogging.
The initial analytical characterization was carried out by
generating a working curve for Cs doped into the stock
simulated waste solution (lOOOX dilution). Figure 7a shows
the obtained response curve taken under the same nebulization
and plasma conditions as those employed in the neat solution
in Figure 6b. Immediately obvious in these data is the large
suppression of both the analytical signal intensities as well as
a lowering of the sensitivity (slope) relative to the neat solution
curve, with the background equivalent concentration increasing
to -9 ppm. At this point it is not immediately obvious where
in the complete nebulization/desolvation/vaporization/
excitation sequence that the matrix effect comes into play.
Physical characteristics that might be expected to change
relative to the neat solution include the solution viscosity,
analyte particle size, particle volatility, and, subsequently,
plasma excitation conditions. In a rather simple test to
examine the role of pH in the matrix effect, small aliquots of
HC1 were added to the test solutions and the resultant Cs (I)
emission intensities monitored. It was quickly found that a
5: 1 mixture of the test solution and concentrated HC1produced
a great enhancement in the analyte emission intensity, whereas
the use of H N 0 3 produced no effect at all (even though the
separation solutions were neutralized by the respective acid
additions). These results point to an effect that is more related
2.4-
2.2 -
2.0 -
1 .a-
1.6-
1*2b ' 20 ' 40 ' 60 ' 80 ' 100' * !O
Cs Concentration (ppb)
Flgure 7. Analytical response curves obtained for Cs (I) 852.1 nm
emission in solutions composed of (a, top) 5 M NaN03/0.1 M KOH
matrix (lOOOX dilution in D I H20),(b, middle) aqueous CsN03 with HCI
addition (5:1), and (c, bottom) 5 M NaN03/0.1 M KOH matrix (lOOOX
dilution in DI H20) with HCI addition (51). Error bars represent the
range of values obtained for three consecutive 200 pL injections.
to the final particle characteristics, either size or volatility, as
the chloride ion from HC1 addition is in great excess in
comparison to the nitrate ion within the sample matrix.
Panels b and c of Figure 7 further illustrate the profound
effect of HCl addition (5:1, sample/acid) on the analytical
response of Cs (I) emission for the aqueous CsNO3 and Cs-
doped separation solutions, respectively. Note first the
concentrations depicted in the calibration curves, now in the
ppb range. For the aqueous solution, the slope of the response

3922 Analytical Chemistry, Vol. 66, No. 22, November 15, 1994
curve exhibits far better detectability and a > 1OX lower BEC
value (60 ppb) relative to theoriginal data (Figure 6b). Similar
effects were seen as well for HCl addition to the aqueous
NaN03 test solutions. Figure 7c illustrates a much more
dramatic change in response curve for the separation solution
-
case. In this instance, the BEC value decreases by 2 orders
of magnitude, from -9 ppm to 100 ppb. The far better
calibration characteristicsfor the latter case, in which the pH
change and the extent of anion (N03-) compensation are far
greater than for aqueous solution, do not clearly differentiate
the actual mechanism for the removal of the matrix effect.
The definite increase in both Cs (I) and Na (I) emission
intensities upon addition of excess C1- clearly illustrates the
fact that matrix effects exist in either the nebulization,
desolvation, particle transport and vaporization, or plasma
excitation processes. Comparison of the physical character-
istics of the respective chloride and nitrate salts reveals
somewhat surprising qualities. An initial assumption that
the chloride salts have higher volatilities upon impaction in
the heated block was not correct, as the boiling points of the
metal chlorides are substantially higher than the nitrates in
both cases. Therefore one must turn to the possibility of
analyte losses in the desolvation process in the case of the
nitrates. That is, the nitrates are sufficiently volatile that
desolvated salts vaporize enroute to the source volume and
are lost in the momentum separator, as small particles (vapors)
are not efficiently transported. The respective solubilities of
the salts would also point to transport-related phenomena. In
both cases, the chlorides have higher solubilities, and therefore
form larger particles than the nitrates. These transport-related
matrix effects will be assessed in future experiments involving
the collection of solute particles and subsequent microscopic
observation of particle size and densities. Additionally, a far
ranging counterion study is in order to assess the role of anion
identity on plasma excitation efficiency, as this may also
contribute to the observed matrix effect@).
Regardless of the precise mechanism(s) involved, it is clear
that the addition of HCl provides a different counterion
environment for all of the solutions tested in this study. The
sensitivities exhibited here (DLcs = 8 ppb in aqueous CsN03
and 10 ppb for the diluted simulated waste) are indicative of
the effectiveness of the chloride addition in normalizing the
Cs response from vastly different matrices. These detection
limits are difficult to compare with well-established optical
methods of Cs analysis, as “typical” values for ICP-AES and
furnace AAS are not included in general texts. Detection
limits of 8 and 20 ppb can be found for flame atomic emission
and a b s o r p t i ~ n .Characteristic
~~ masses for furnace AAS
are reported to be 0.3 ppb (20 pL samples).25 Figures of
ICP-AES are not widely published due to the aforementioned
difficulties with PMT detection at 852.1 nm and the fact that
Cs is nearly 100%ionized in the plasma, with the ion emitting
in vacuum-UV region of the spectrum. Thompson and
Barnes26have included a detection limit for Cs in a tabulation
listing it in a category of elements with values in the range
(25) Ingle, J. D., Jr.; Crouch, S. R. Spectrochemical Analysis; Prentice Hall:
Englewood Cliffs, NJ, 1988; Chapters 8 and 10.
(26) Thompson, M.; Barnes, R. M. In Inductively Coupled Plasmas in Analytical
Atomic Spectrometry, 2nd ed.; Montaser, A,, Golightly, D. W., Eds.; VCH
Publishers: New York, 1992; Chapter 5, p 265.
Analytical Chemistry, Vol. 66, No. 22, November 15, 1994
of 10-3 1 ppb, in aqueous solution. Depending on the amount
of dilution required to nebulize/atomize the waste solution
effectively, the detection limits for each of these methods are
more or less comparable. In any case, the approach described
here seems to hold a great deal of promise, having sensitivities
comparable to the aforementioned methods, while having the
additional advantage of ready chromatographic sampling
capabilities of relatively small sample volumes (200 pL).
Detailed evaluations of nebulization and transport parameters
are hoped to improve the detection limits reported here as
well as reduce the required sample volumes.
CONCLUSIONS
Preliminary data have been presented illustrating the basic
operating characteristics of the combination of a particle beam
LC/MS interface with a heated hollow cathode discharge
source for the analysis of aqueous samples (PB/HC-AES).
The combination of efficient desolvation and solvent removal
properties of the particle beam interface allows for the
presentation of analyte particles to the hollow cathode source
without the deleterious effects of residual water vapor loading
on the plasma. In addition, the use of an HPLC pump and
flow injection sample introduction illustrate excellent temporal
qualities with regard to future applications as chromatographic
detectors. The use of the heated hollow cathode source to
affect particle vaporization and subsequent analyte excitation
was found to be a far superior approach than the planar cathode
geometry investigated previously.’8
Plasma operation parameters (current and pressure) were
evaluated for their effects on Na (I) atomic emission intensities
for both helium and argon discharge gases. While the emission
intensities derived with the respective gases were relatively
equivalent, the overall spectral purity and ability to excite
high-lying transitions were found to be more advantageous
for the He gas. The nebulization parameters of solution flow
rate and nebulizer tip temperature were investigated, with
low flow rates being found to be more efficient and tip
temperaturesof -220 OC most optimal. Lower temperatures
were found to be less efficient at producing dry aerosols, while
higher temperatures wereapt tocreate clogging in thenebulizer
capillary due to premature desolvation. Evaluation of the
role of particle vaporization temperature indicated that block
temperatures of >-200 OC were required to provide sub-
stantial vaporization. Under the optimized conditions, injec-
tions of Na analyte (10 ppm) exhibited temporal characteristics
that indicated no appreciable dead volume contributions to
band broadening.
The basic analytical characteristics of the PB/HC-AES
approach were evaluated for Na and Cs analytes. Calibration
curves derived from aqueous standards prepared from the
respective nitrate salts exhibit good linearity and calibration
characteristics, with BECs found to be at the tenths of parts-
per-million level. Practical application of the technique was
demonstrated by the analysis of Cs in diluted simulated nuclear
waste solutions, which contained high levels of sodium and
potassium salts. While the heavy salt matrix severelydepressed
theemission characteristics of Cs (even after lOOOX dilution),
it was found that a nominal addition of HCl resulted in
enhanced detectability for both aqueous and separation
solutions. This suggests that chloride ion acts as a preferential
3923
counterion over nitrate and seemingly results in an analyte
particle with more favorable transport characteristics. The
resultant BECs for Cs in aqueous and salt solutions were
reduced by 1-2 orders of magnitude relative to the native
solutions without HC1 addition. Detection limits for Cs in
the diluted separation solution were determined to be 10
-
parts per billion ( 10 ppm in the original sample).
- ACKNOWLEDGMENT
The results presented here give very positive evidence that
of particle beam sample introduction into a heated hollow
cathode device warrants further exploration. The abilities to
work in a flow injection mode with small sample volumes or
to directly sample chromatographic eluents are very attractive
features. Future studies will focus on evaluating the role of
nebulization parameters (liquid and gas flow rates, capillary
size, and solvent makeup) and counterion identity on analyte
response. Ultimately, implementation of ion chromatography
to affect ionic species separations is envisioned. Additional
studies are currently underway to investigate the PB/HC
approach for elemental mass spectrometry. While the
3924 Analytical Chemistry, Vol. 66,No. 22, November 15, 1994
technique described here will not likely supplant current
methods of bulk solution analyses, such as flame atomic
absorption or ICP atomic emission, it is believed that the
unique qualities described here will find selected applications.
Financial support from the National Science Foundation
under Grant CHE-9117152 and the Department of Energy,
Office of Technology Development, through the Westinghouse
Savannah River Co. in cooperation with the South Carolina
Universities Research and Education Foundation is greatly
appreciated. Donation of the Thermabeam nebulizer and
particle beam interface by Extrel, Division of Millipore, is
also appreciated.
Received for review May 3, 1994. Accepted August 18, 1994."
a Abstract published in Advance ACS Absfracfs.October 1, 1994.