2220

Anal. Chem. 1988, 60,2220-2227

coprecipitated lead), the typical lead isotope pattern could

not be detected systematically. It is thus obvious that, at least
for this system, the distribution of a minor element within
a particle has a significant influence on the relative intensity
of its mass peaks observed at high laser irradiance.
This so-called geometry effect on useful ion yield was already noticed by Bruynseels and Van Grieken (10).Studying
carbon bilayers, consisting of a layer of natural carbon and
a second one enriched in 13C,they found ion extraction from
the side of the sample facing the mass spectrometer to be
promoted. The effect seemed to be the most pronounced at
laser intensities near the threshold value for sample perforation. For the lead-coated calcite particles, it is rather difficult to verify this decrease of the geometry effect with increasing laser intensity. This is due to the fact that changes
in laser power density at the sample arise from variations in
both laser beam intensity and focusing conditions, and, as
mentioned earlier, particles are unfavorable samples for reproducible focusing.

CONCLUSION
In the laser desorption mode, the signal from lead adsorbed
on calcite particulates is so enhanced relative to the one of
coprecipitated lead that LAMMA allows unambiguous differentiation between surface enriched and homogeneously
distributed lead down to 100 ppmw or lower. Knowledge
about the elemental distribution within particles is of interest,
e.g. to assess their eventual environmental impact.
Even when the laser intensity increases, such that the entire
particle is ablated, differences between lead signals of corresponding adsorbed and coprecipitated lead particles persist.

This implies that, whenever semiquantitative analysis is

considered, the distribution of the element of interest within
the particle should be taken into account. Moreover, one also
has to be aware of this geometry effect when performing
standardization procedures using vacuum deposition of a thin
film onto the sample, as applied by e.g. Schroder et al. (11).

ACKNOWLEDGMENT
We thank Luc Van Vaeck for valuable discussions.
LITERATURE CITED
Nmssner, R.; Klockow, D.; Bruynseels, F. J.; Van Weken, R. E. Int. J .
Environ. Anal. Chem. 1985. 22, 281-295.
De Waele, J. K.; Vansant, E. F.; Van Espen, P. J.; Adams, F. C. Anal.
Chem. 1983, 55, 671-677.
De Waele, J. K.; Gijbels, J. J.; Vansant, E. F.; Adams. F. C. Anal.
Chem. 1983, 55, 2255-2260.
Otten, Ph. M.; Bruynseels, F. J.; Van Grieken, R. E. Bull. SOC.Chim.
Be@. 1986, 95, 447-453.
Bruynseels, F. J.; Van Grieken, R. E. Atmos. Envkon. 1985, 79,
1969-1970.
Denoyer, E. E.; Van Grieken, R. E.; Adams, F. C.; Natusch, D. F. S.
Anal. Chem. 1982. 54, 26A-41A.
Van Espen, P. J.; Van Vaeck, L.; Adams, F. C. I n Thkd International
Laser Microprobe Mass Spectrometry Workshop, 1986, Antwerp, Belgium, Aug 26-27, 1986.
Fulghum, J. E.; Bryan, S. R.; Llnton, R. W.; Bauer, C. F.; @MIS,D. P.
Environ. Sci. Technol. 1988. 22, 463-467.
Bruynseels, F. J.; Van Grleken, R. E. SpeclrocMm. Acta, Parts 1983,
388,053-050.
Bruynseels, F. J.; Van Grieken. R. E. Int. J . Mass Spectrom. Ion
Processes 1986, 74, 161-177.
Schriider, W.; Frings, D.; Stmve, H. Scannlng Electron Mlcrosc. 1980.
I I , 647-654.

RECEIVED
for review November 2,1987. Accepted May 16,
1988. This work was partially supported by the Belgian
Ministry of Science Policy under Contract 84-89/69.

Atmospheric Sampling Glow Discharge Ionization Source for

the Determination of Trace Organic Compounds in Ambient Air
Scott A. McLuckey,* Gary L. Glish, Keiji G. Asano, and Barry C. Grant
Analytical Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831

A new atmospheric sampling ion source, based on the establlshment of a glow dlscharge In amblent alr drawn into a
region of reduced pressure, Is described. The source is shnpie, rugged, and relatlvely maintenancefree, exhlbits a very
short memory, and is extreme& wnsltive for compounds wlth
hlgh proton affinities, hlgh electron afflnitles, hlgh gas-phase
acidities, and/or low Ionization potentlals. The effects of
dlscharge voltage and Ion source pressure on the nature of
the mass spectra observed are descrlbed. These operating
parameters affect the absolute number of Ions observed and,
particularly for positive ions, affect the distribution of the
reagent lons and the degree of fragmentetlon. For Illustrative
purposes, the limit of detectlon and dynamlc range of the ion
source coupled wlth a mass spectrometer are discussed for
2,4,6-trlnltrotoluene. For the present system, a detection hit
of 1-2 parts per trMion and a Unear dynamk range of at least
6 orders of magnitude are observed.

The detection of trace quantities of organic compounds in

ambient air is a commonly encountered problem often re-

quiring both high specificity and low detection limits. For

example, the detection of organic explosives in ambient air
requires detection limits in the parts per trillion range (or
lower) along with high specificity to minimize false positives
(I). The method of choice for many trace analyses of constituents present in ambient air is the combination of a sensitive ionization method with mass spectrometry.
Several approaches have been taken in ionizing compounds
present in ambient air. One approach is to leak air into the
mass spectrometer and ionize by electron bombardment (2,
3). Air may be leaked into the system directly or through a
selective membrane that passes certain organic compounds
more readily than the normal constituents of air.
A widely used approach is to ionize at atmospheric pressure
by using either a @ emitter such as 63Ni( 4 , 5 ) or a corona
discharge (6-9)as a source of ionizing electrons. Both methods
are commonly referred to as atmospheric pressure ionization
(API). A number of reviews are available that describe API
as a sensitive means for detecting trace quantities of certain
organics in air (6, 10,11).
Several characteristics are usually desirable for an ion source
intended for monitoring trace organics in ambient air. These
include the following: low detection limits for the compounds

0003-2700/88/0360-2220$01.50/00 1988 American Chemical Society

ANALYTICAL CHEMISTRY, VOL. 60, NO. 20, OCTOBER 15, 1988 2221

of interest, fast response, minimal memory effects, minimal

interferences from compounds that may also be present, the
possibility of analyzing for either positive or negative ions,
low maintenance requirements, and a wide dynamic range.
Other characteristics may also be important, depending upon
the particular application. For example, the capability of
analyzing for a wide variety of compounds may be very important in many instances. In some cases, however, it may
be desirable to ionize only particular types of compounds.
Each of the approaches to ionizing trace organics in ambient
air mentioned above has its own unique set of characteristics.
For example, electron impact ionization has the advantage
of allowing for the analysis of a wider range of compounds than
the API approaches but is not well-suited for the analysis of
negative ions. API has been shown to be extremely sensitive
for many types of compounds but can be highly subject to
chemical interferences. The chemical interferences may
compete for charge, resulting in poor ionization efficiency for
the species of interest, or may complicate the mass spectrum
by showing, for example, extensive clustering.
This paper describes an ion source designed for analysis
of trace quantities of organic vapors in ambient air. This
method appears to have a set of characteristics superior to
those of previous methods for many atmospheric monitoring
applications. This ion source is based on the establishment
of a glow discharge in a region of reduced pressure with ambient air as the discharge support gas. Ionization occurs, as
with conventional chemical ionization, primarily through
ion-molecule reactions. In this case, however, the discharge
supplies the ionizing electrons, and compounds present in the
sampled air serve as the reagent molecules. This ion source
has proven to be very sensitive for a variety of heteroatomcontainingorganic molecules. It has a number of features that
make it useful as an ion source for continuous monitoring of
ambient air for trace organic contaminants.
The use of glow discharges, and other types of discharges,
to form ions in mass spectrometry is hardly new. Much of
the early work in mass spectrometry was done with electrical
discharges (12,13). In recent years, inductively coupled
plasmas (14-16) and microwave-induced plasmas (17,18) have
been used as ion sources for elemental analysis. Ionization
by glow discharge, usually with argon as the support gas, has
recently been developed for analysis of inorganic solids (1g21).
In this case, the sample is used as the cathode of the discharge
so that neutral sample atoms sputtered by cation bombardment are ionized in the plasma primarily via Penning ionization and charge transfer. In organic mass spectrometry, the
corona discharge at atmospheric pressure, as mentioned above,
has been used in API. Discharge ionization is currently used
in some liquid chromatography/mass spectrometry (LC/MS)
thermospray interfaces as an auxiliary method for forming
ions that do not readily ionize under normal thermospray
conditions (22-24), and a chemical ionization source for
LC/MS based on a glow discharge has been reported (25).
Several groups have reported the use of a Townsend discharge
in a chemical ionization source to allow for the use of oxygen
as the reagent gas in negative chemical ionization (26, 27).
The development of the ion source described here is
noteworthy in its use of a glow discharge, supported by untreated atmospheric gases at reduced pressure, as a rugged,
reliable, maintenance-free, and, in many cases, extremely
sensitive means for monitoring trace species in ambient air.
The purpose of this paper is to describe the source, its operation, and its characteristics, particularly with respect to
the ion source pressure and discharge voltage, the two major
operating parameters. For any particular ambient air analysis
problem, the detection limit, sensitivity, and dynamic range
of the ion source/mass spectrometer combination for the

ATMOSPCEAE

0.2-0.8 t a l

L/S

5x 1OE-5 ton

1000 L Is

Figure 1. Cutaway side view of the atmospheric sampling glow discharge Ionization source. The source is housed within a Bin. Conflat
flange that has been hollowed out in the center wlth a 13/,in. hole. Four
pumpout ports are drilled from the edge of the flange into the center
hole. Aperture plates A, and A, are attached to either side of the
flange by ngon screws and are sealed by O-rings. Half-plates P, and
P, are used when the discharge is maintained orthogonal to the ion
beam into the mass spectrometer.

compound of interest will determine its applicability. These

ion source characteristics are expected to vary widely with the
nature of the compound. In general, the lowest detection
limits are expected for compounds with high proton affiiities
or low ionization potentials in the positive ion mode and for
compounds with high electron affinities or high gas-phase
acidities in the negative ion mode. We are currently developing procedures to measure these quantities at very low
concentration levels. For illustrative purposes, however, we
discuss results we have obtained in the negative ion mode for
2,4,6-trinitrotoluene.

EXPERIMENTAL SECTION
Apparatus. The atmospheric sampling glow discharge ionization source is incorporated into a 6-in. Conflat flange. A 13/4
in. diameter hole is situated in the center of the flange, and four
1/2-in.ports are drilled through the edge of the flange to the center
hole to allow the center hole region to be pumped. The flange
is bolted to the vacuum chamber housing a mass spectrometer
that is described briefly below. A schematic drawing of the
cutaway side view of the ion source and part of the mass spectrometer is shown in Figure 1. Circular platea Al and A2 are bolted
by nylon screws to the front and back sides of the flange, respectively, and are electrically isolated from the flange by Viton
O-rings. These plates contain apertures in their centers in-line
with the central ion optical axis of the quadrupole mass spectrometer. Although several aperture size combinations have been
tested, the data described herein, unless otherwise noted, were
acquired with the diameters of Al and A2 being 0.2 and 0.8 mm,
respectively. Two half-plates PI and P2are situated opposite one
another within the central region of the ion source flange and are
spaced roughly equidistant from the line formed by the apertures
in Al and A% The distance between the half-plates is ,- 1.5 cm.
The four ports drilled through the edge of the flange are
connected to a 15 L/s roughing pump (conductance limitations
result in a pumping speed of -8 L/s for the source region).
Ambient air is then drawn through the aperture in Al. When an
AI aperture diameter of 0.2 mm is used, air is sampled at a rate
of roughly 5 mL/s. Under these conditions, the pressure in the
central region of the source flange is -0.5 Torr as measured with
a Baratron capacitance manometer connected into one of the
pumpout ports. A valve is situated in the line to the rough pump,

2222

ANALYTICAL CHEMISTRY, VOL. 60, NO. 20, OCTOBER 15, 1988

which allows the pressure in the source flange to be elevated by

reducing the pumping speed. Pressure studies were performed
by replacing AI with a plate with a center hole of 3 mm diameter
and a 1/4-in. Cajon connection welded to the center. A Granville-Phillips leak valve was connected to the Cajon fitting and
was used to vary the gas flow into the source region. The acceesible
pressure range was determined by the ability to sustain a stable
discharge.
The ion source has been evaluated with a tandem mass spectrometer constructed at Oak Ridge (28).Briefly, the instrument
consists of a quadrupole mass filter (Extrel C50 system) as the
first stage mass analyzer followed by a time-of-flight mass
spectrometer. Although extensive MS/MS data have been collected by wing the atmosphericsamplingglow discharge ionization
source, mass spectral data are emphasized here. A 1000 L/s
turbomolecular pump is used to pump the region of the vacuum
system housing the quadrupole mass filter. Under normal operating conditions, viz. the A, diameter is 0.2 mm and the A2
diameter is 0.8 mm, the pressure in the quadrupole region is -5
X
Torr. A Channeltron Model 4873 conversion dynode/
electron multiplier is currently being used as the detector. We
found that noise from photons could be significantly reduced by
moving the conversion dynode from its 45' angle with respect
to the ion beam to make it nearly parallel with the ion beam and
offset by -0.5 cm. The typical background noise level of the
system is in the range of 100-1OOO counts/s. Much of this noise
comes from photons and, perhaps, fast neutrals. We have made
no other efforts to reduce further the background noise due to
neutral species. In a similar system, however, we have incorporated a 180' electric sector, which reduces the background level
by an order of magnitude.
Operating Procedures. The ion source is typically operated
in one of two modes. One approach to forming ions is by establishing a glow discharge with Al and A2 as the electrodes. A
voltage difference between Al and Az of -350 V is sufficient for
a glow discharge to occur. In this mode of operation, P1and Pz
are either removed from the central region of the ion source flange
or are held at the same potential (usuallynear 0 V). Best results,
in terms of observing molecular or pseudomolecular ions, are
obtained when the negative glow of the discharge is nearest to
A,. This situation occurs when A, serves as the cathode and A2
serves as the anode. To optimize the transmission and mass
resolution of the mass spectrometer, Al is normally held at -350
to -400 V and A2 is held near 0 V. Under these conditions, both
positive and negative ions issue from A2. Which ion polarity is
observed is determined by the potentials applied to the mass
spectrometer lenses and the electron multiplier detector.
The other approach to forming ions is to establish a glow
discharge between PIand PSIi.e. orthogonalto the apertures and
ion optical axis of the mass spectrometer. In this case, the voltage
on plate A, is unimportant and the voltage applied to Az is varied
(usually within *15 V) to optimize the extraction of ions from
the discharge and to optimize the performance of the mass
spectrometer. The voltages on the half-plates are each -200 V
and are of opposite polarity.
In both modes of operation the current supplied to the discharge
is typically 3-10 mA, corresponding to a power of 1-4 W. The
former mode is used exclusively when one is analyzing negative
ions. Both modes can be used for positive ions. Unless otherwise
noted, all data were acquired by using the coaxial mode of operation.
Due to the relatively high flow rate through the system, the
ion source responds almost instantaneously to the entry and exit
of samples from the ionization region. Even when large doses
of organic vapors are admitted into the ion source, we observe
no memory effect; i.e. the signals for the compounds drop back
to background levels immediately after the sample is removed.
This is presumably due both to the high flow rate and the fact
that the aperture plates are continuously being bombarded by
ions and/or electrons. We have operated this ion source continuously for months at a time, sampling ambient air with no
noticeable degradation in signal levels. After months of operation
during which large sample doses have regularly been admitted
into the ion source, we begin to observe an increase in the
background noise level (from an increase in chemical noise) by
a factor of -2.

Very simple sampling systems have been used to obtain mass

spectra in all cases. For involatile samples, such as the polynitroaromatice, a small quantity of the solid (a few tenths of a
gram) is placed in a vial and vapors above t$e solid are drawn
into the source through the aperture in Al. To facilitate sampling
and to reduce the effect of normal turbulence of the air on the
stability of the signal, one end of a 4 in. long, 1/4 in 0.d. stainless
steel tube, bent to 90, is placed in the vial above the sample and
the other end is placed near the aperture in A,. For volatile
samples, this method is unsatisfactory in that it allows large
quantities of sample to be drawn into the ion source, resulting
in clustering and/or discharge instability. For volatile samples,
a bottle of the sample is placed in a Plexiglass box with a 1/4 in.
diameter, 4 in. long glass tube extending from the side of the box
to the inlet aperture of Al. Vapors from the sample are then drawn
into the ionization region along with ambient air. Depending upon
sensitivity of the ion source for the compound(s) in the sample
and their volatilities, the bottle may or may not be slightly opened.
This method of sampling provides for a steady sample input into
the ion source, but the actual concentrationis generally not known,
especially for volatile samples.
The calibration curve data for 2,4,&trinitrotoluene(TNT) were
obtained by dissolving TNT in acetone and making up a series
of solutions of known concentration. Known quantities of TNT
in solution were introduced onto a small spot within a quartz tube,
which was then introduced into a heated block held at 453 K. The
block was connected to a heated tube directly butted to the inlet
aperture of the ion source. As the TNT vaporized off the tube,
it was drawn into the ion source and the signal intensity at m / z
227 (the molecular anion) was recorded. For all sample sizes up
to 800 ng, greater than 95%of the ThT signal was observed within
-10 s.

RESULTS AND DISCUSSION

At a fiied pressure, the discharge current increases linearly
with the voltage difference between the discharge electrodes.
This behavior is typical for a direct current self-sustained
discharge (29). The form of discharge in the ion source, under
the conditions of -400 V and 3-10 mA, is considered a
"normal" glow discharge, as distinguished from other forms
such as the Townsend discharge and the abnormal glow
discharge often used with hollow cathode glow discharge ion
sources. At a fixed discharge voltage, the discharge current
increases linearly with pressure, or nearly so, over the range
of 0.2-0.8 Torr. At pressures above and below these extremes
the discharge either shuts off or becomes unstable. Although
the discharge current increases with pressure, high ion source
pressures do not necessarily result in greater ion intensities
for the species of interest (see below).
A variety of mechanisms lead to ion formation and transformation in glow discharges (30). The ion-molecule reaction
chemistry can be quite complex, particularly when a mixture
of gases is used to sustain the discharge. However, an important characteristic of this form of discharge with respect
to the ionization of organic molecules is that it is relatively
soft. The electron temperature in the plasma may be several
thousand Kelvin, but the ion temperature is very close to that
of the neutrals. For a given set of A, and A2 aperture sizes,
the two major operating parameters that directly affect both
the absolute and relative abundance5 of the ions that enter
the mass spectrometer are the discharge voltage and the ion
source pressure. These parameters, along with other characteristics of the ion source, are discussed below for positive
ions and negative ions in turn.
Positive Ions. Electron impact ionization near the cathode
is a primary source of positive ions. Many of these ions are
accelerated into the cathode where they liberate electrons,
thereby sustaining the discharge. Positive ions can also be
formed from charge transfer and Penning ionization from
highly excited neutral molecules. As in conventional chemical
ionization, rapid ion-molecule reactions can transform the
ionic product distribution to a set of relatively stable reagent

ANALYTICAL CHEMISTRY, VOL. 60, NO. 20, OCTOBER 15, 1988

+ve GDMS

0;

air b a c k g r o u n d

320

0.54 torr,

(H20)

"I
(H20) 3Ht
20,

0-'
10

/+

Not (H20) 2Ht

H30t

32

/ +'

(H20) 5Ht

*A
dl

2223

d3

$5

54

f6

$7

Id9

dS

id0

0.2
0.4
0.6
Water clusters/Total ions
Flgure 4. Ratio of protonated naphthalenelnaphthaleene molecular ion
as a function of the ratio of proton hydratesltotai positive ions at an
ion source pressure of 0.54 Torr.

0.0

490 V

0;

0.0

3
13

$5

d4

!6

dS

$7

109
I

1 0

Figure 2. Positive ion background mass spectra observed at an ion

source pressure of 0.54 Torr and at discharge voltages of 320 (top)
and 490 V (bottom).

0.0

? 0.6 -

i
U

2
U
I0 . 4

YX

\ x

U
0

zc

0.2

'X

x\x.

t
0.01

20.0

Flgure 5. Intensities of the naphthalene molecular ion, protonated

naphthalene, and their sum as a function of discharge current at an
ion source pressure of 0.54 Torr.

V
+I
c

5.0
10.0
15.0
Discharge c u r r e n t (mA)

0.0

x- -x---x-x,

X-X

, .

15.0
5.0
10.0
Discharge c u r r e n t (mA)

20.0

Figure 3. Ratio of the sum of the abundances of the proton hydrates

to the total posltive ion intensity as a function of discharge current at
an ion source pressure of 0.54 Torr.

ions that serve as the predominant source of charge for trace

organic molecules in the gas mixture. The trace organic
molecules are therefore primarily formed from either electron
or proton transfer (or both) with the reagent ions.
At a fixed ion source pressure the discharge voltage can be
used to influence the degree to which charge transfer and
proton transfer occur by altering the relative reagent ion
concentrations. Figure 2, for example, compares the positive
background ions observed at discharge voltages of 320 and
490 V, at a source pressure of 0.54 Torr. At 320 V the major
reagent ions are NO+ and 02" and proton hydrates of the form
(H20),H+ where n = 1-5. We have never observed larger

water clusters under any condition, including sampling air

saturated with water vapor. The proton hydrates serve as
proton-transfer reagents whereas 02+'and NO' serve as
charge-exchange reagents. At 490-V, the proton hydrates
largely disappear, leaving almost exclusively charge-exchange
reagents. Figure 3 shows the ratio of the sum of the abundances of the proton hydrates to the total positive ion
abundance as a function of discharge current, demonstrating
a clear trend toward fewer proton-transfer reagent ions as the
discharge current increases. This suggests that products from
proton-transfer reactions are most likely to be observed at low
discharge currents. The major ions formed from naphthalene
demonstrate this. The two major positive ions formed from
naphthalene are observed at mlz 128 and mlz 129, corresponding to the molecular ion and the protonated molecule,
respectively. The ratio of the abundance of the protonated
molecule to that of the molecular ion as a function of the ratio
of proton hydratesltotal ion current is shown in Figure 4.
This plot clearly indicates that proton transfer is maximized
at low discharge currents where the abundances of the proton
hydrates are highest.
The discharge voltage also influences the absolute number
of ions that enter the mass spectrometer. Figure 5 shows the
total mass-analyzed ion current arising from naphthalene, viz.
the sum of the mlz 129 and mlz 128 intensities, as a function
of discharge current along with a plot showing the behavior

2224

ANALYTICAL CHEMISTRY, VOL.

"1

73+

60,NO.20, OCTOBER 15, 1988

376 V

134'

Eo00 -

- 0.6

4000 -

- 0.4

MOO -

- 0.2

I/

mater c l u ~ t e r a

j0.0

a 1 1 ions

0.01
1

0.0

0.2

0.4

0.6

0.6

1.0

Source pressure (torr1

Flgure 7. Total massanalyzed positbe ion current and the ratio of the
sum of the water cluster intenslties/total Ion signal as a functlon of ion
source pressure at a discharge voltage of 375 V.

peatedly observed that the ratio of the fragment ions m / z 91

(C7H7+)to m / z 92 (C7Hs+')increases with the internal energy
of the molecular ion. This ratio has therefore been used to
characterize different methods of ionization and excitation
with respect to the energy deposited into the molecular ion
(31). At low discharge voltage (376 V), conditionswhere water
clusters are abundant, the molecular ion is observed at m / z
134, and the protonated molecule appears at m / z 135.
Daughter ions appear at m / z 89,91,92, and 105. A large peak
is observed at m / z 73, which is due to the protonated tetramer
of water, (H20)4H+.
MS/MS data (not shown here) indicates
that the protonated pentamer of water is also present and
' -7- - 7 ; L - n -7r-%l.-,L
dl --A
accounts for roughly half of the signal at m/z 91. Even with
the contribution to m / z 91 from (Hz0)6H+,the ion at m / z
M/Z
92 is the base peak in the spectrum. At the intermediate
Flgure 6. Mass spectra obtained for n-butylbenrene at discharge
discharge voltage of 392 V, the molecular ion and protonated
voltages of 376,392,and 409 V at an ion source pressure of 0.54
molecule are much diminished relative to the daughter ions.
Torr.
The water clusters drop out of the spectrum, and the ion at
of each ion individually. The total is peaked at a discharge
m/z 91 is made up almost entirely of C7H7+.Greater energy
deposition into the molecular ion is indicated both by its
current of a few milliamperes where the protonated molecule
diminished intensity and by the increase in abundance of
is most abundant. The intensity of the molecular ion, however,
is relatively constant over a range of 1-8 mA until it begins
C7H7+relative to C7H8+'. This trend is further demonstrated
in the spectrum acquired with a discharge voltage of 409 V.
to drop off at discharge currenta in excess of 10 mA. The total
number of positive ions (including the reagent ions) that pass
The molecular ion is no longer observed, m / z 91 dominates
through the quadrupole does not decrease at high discharge
the spectrum, and daughter ions that require greater energies
for formation appear, such as the ion at m / z 65 (formed by
currents but tends to level off. It is unclear whether these
loss of CzHzfrom C7H7+).This example illustrates the general
observations reflect phenomena that occur in the discharge
trend toward the observation of greater fragmentation with
or are due to the mass analyzer and/or the extraction optics
of the mass spectrometer. A decrease in the naphthalene ion
increasing discharge voltage at a fixed pressure. Increased
current with high discharge currents may be due partly,
fragmentation may result, at least in part, from greater energy
deposition on ionization. This can follow either directly, by
however, to the changing nature of the reagent ions in the
source. A t high discharge currents NO+ is as intense as 02+', electron impact, from the greater electron velocities expected
at higher discharge voltages (30),or indirectly, from different
and atomic ions such as N+' and O+' appear. Charge exchange
with these ions may not be as efficient as with 02+'
or more highly excited reagent ions. Spectral changes due to
leading
,
changes in discharge voltage may also result from changing
to fewer naphthalene-derived ions.
the regions of the discharge from which ions are sampled into
The discharge voltage also affects the degree of fragmenthe mass spectrometer.
tation observed in the mass spectrum. For example, Figure
6 shows mass spectra obtained for n-butylbenzene, with P,
Ion source pressure, like the discharge voltage, plays a role
in determining the number of ions observed, the distribution
and P2as the electrodes, a t three discharge voltages and at
of the reagent ions, and the degree of fragmentation. The
a pressure of 0.54 Torr. The n-butylbenzene molecular ion
number of ions formed in the discharge increases with presis a much-studied ion in mass spectrometry, and its fragsure, as indicated by the increase in discharge current with
mentation behavior is well characterized. It has been re-

K'&

409 V

ANALYTICAL CHEMISTRY, VOL. 60, NO. 20, OCTOBER 15, 1988

1
0.2

0.6
0.B
1.0
Source pressure [torr1
Flgure 8. Abundances of the proton hydrates as a function of ion
source pressure at a discharge voltage of 375 V.
0.0

0.4

pressure. Figure 7, however, shows a plot of the total massanalyzed positive ion current as a function of pressure and
indicates a maximum near 0.4 Torr. Much of the decrease
in mass-analyzed ion current probably results from scattering
and neutralization in the high-pressure region just after the
ion exit aperture.
The positive charge distribution among the reagent ions
also changes with pressure but less dramatically than with
discharge voltage. The ratio of the sum of the proton hydrateslall ions does not vary significantly over the pressure
range, but the relative abundances of the different water
cluster ions do. This is shown in Figure 8, which is a plot of
the abundances of the proton hydrates as a function of the
source pressure at a discharge voltage of 375 V. The general
trend shows that larger clusters tend to be formed at higher
pressures, but under these conditions, no water cluster larger
than (HZ0I5H+is detected.
The degree of fragmentation observed in the mass spectrum
at a fixed discharge voltage is inversely related to ion source
pressure. Figure 9, which shows mass spectra acquired from
n-butylbenzene at a discharge voltage of 400 V at several
pressures, illustrates this point. As noted above, the ratio of
the ions at mlz 91 and mlz 92 can be used to indicate changes
in the internal energy distribution of the n-butylbenzene ions
as they are formed. The trend is clear that greater source
pressures tend to decrease internal energies as reflected in the
steadily decreasing ( m / z 91)/(m/z 92) ratio with increasing
pressure. Furthermore, the molecular ion is observable at the
highest source pressure whereas it is essentially absent at lower
pressures, and the fragment ion at mlz 65 from further
fragmentation of C7H7+is only observed at the lowest pressure.
Increasing pressure can reduce ion internal energies both by
reducing the electron velocities in the plasma and via stabilizing collisions.
Negative Ions. Electrons are the major negative charge
carriers in the discharge. Fast electrons (up to a few hundred
electronvolts in energy) arise from electrons generated in the
cathode fall region where most of the potential drop of the
discharge is located. These electrons can ionize molecules,
liberating slow electrons, and themselves are decelerated by
collisions in the gas. Slow electrons can be captured directly
by molecules with positive electron affinities or can be taken
from reagent anions if the relative electron affinities are appropriate (32).Electron transfer and electron capture are the

2225

91.

9'

s
1

92'

M/Z
Mass spectra obtained for n-butylbenzene at ion source
pressures of 0.24, 0.50, and 0.75 Torr and a discharge voltage of 400
Flgure 9.

V.

major mechanisms for anion formation for most compounds

we have investigated. For acidic compounds, proton abstraction is observed to give (M - H+)-.
Unlike the positive ion case, for the compounds we have
studied we have not observed a significant effect of changes
in the discharge voltage or ion source pressure on the degree
of fragmentation in the negative ion mass spectra, nor are the
relative abundances of the reagent ions highly sensitive to
these parameters. The absolute intensity of the negative ions
is, however, highly sensitive to discharge voltage and ion source
pressure. Figure 10 shows the total mass-resolved negative
ion current as a function of discharge current along with the
corresponding data for the molecular anion of T N T when a
sample of TNT was held near the entrance aperture. The two
signals show very similar qualitative behavior.
The major negatively charged reagent ions observed in the
background mass spectrum can vary dramaticallywith relative
humidity and air temperature. In humid room-temperature
air, the major anions are OF*, (H20)Oz-', and (HzO)zO~-'.In
dry heated air, the major peaks are 0-*,Oz-',and NOz-. The
formation of oxygen hydrates in the negative ion mode appears
to be aided by the expansion of the air as it enters the ioni-

ANALYTICAL CHEMISTRY, VOL. 60, NO. 20, OCTOBER 15, 1988

2226

1.0

x 0 -

0.E

6.0 -

0.6 x

I+

1
r(

0.4 0.2 -

--%I
I

0.0

1.0

2.0
3.0
log Nass lpgi

4.0

5.0

Flgwe 12. Analytical curve for 2,4,6trinitrotolueneobtained by plotting

the logarithm of the peak intensity of the anion signal at m / z 227 as
a function of the mass of TNT.

I
I
I
I
I

4000 -

I
I
I

2000 -

I
I

0.0 5.0

J
5.5

6.0 6.5 7.0 7.5

Pressure IxlOE-l torr1

8.0

Flgure 11. Total mass resolved negative ion current observed as a

function of ion source pressure over a range of 0.55-0.80 Torr at a
discharge voltage of 375 V.

zation region through A,. When air first passes through a

heated block and transfer line, the water clusters are no longer
observed. Furthermore, when A, was replaced by a plate with
a 3 mm diameter orifice and air was admitted via a leak valve
for pressure studies, no clusters were observed (in contrast
to the positive ion data). Both sets of reagent ions behave
similarly as the discharge current is varied (see Figure lo),
and both give similar results for the compounds we have
investigated. Provided the electron affinity of the sample
molecule is greater than those of the neutral counterparts to
the reagent ions, electron transfer is facile and anions derived
from the sample are observed.
Figure 11shows a plot of the total mass-resolved negative
ion current observed as a function of pressure over the range
of 0.55-0.80 Torr at a discharge voltage of 375 V. The number
of negative ions drops dramatically below 0.6 Torr, despite
the fact that a stable discharge can be maintained well below
this pressure. Unlike the positive ion results, which show a
maximum in ion current at -0.4 Torr, the maximum negative
ion current is observed between 0.6 and 0.7 Torr. At higher
pressures the negative ion current drops off more slowly. This

may well be due to electron detachment and scattering as the

ions enter and pass through the mass spectrometer.
A measure was made of the ratio of positive ions/negative
ions that pass through the quadrupole a t a source pressure
of 0.6 Torr and a discharge voltage of 375 V. The electron
multiplier voltage was set for both ion polarities at -1.1 kV
while the conversion dynode was held at +4.0 kV for negative
ions and at -4.0 kV for positive ions. Under these conditions,
i.e. nearly optimal for the observation of negative ions, the
total ion current recorded for positive ions was roughly 10
times greater than that for negative ions. The detection
efficiency for negative ions is likely to be less than that for
positive ions so that the actual ratio is likely to be lower than
10.
Although total negative and positive ion currents either
show a maximum or level off with discharge voltage, the
background noise increases linearly with discharge current.
The main source of noise is from photons and, perhaps, fast
neutrals. The main source of noise from charged particles is
electrons, provided there is little chemical noise at the mass
to charge ratio at which the quadrupole is set. (In the positive
ion mode, noise comes almost exclusively from uncharged
particles (photons and fast neutrals) if a portion of the mass
spectrum is chosen where chemical noise is insignificant.)
2,4,6-Trinitrotoluene. The most abundant peak in the
negative ion mass spectrum of TNT, other than those of the
reagent ions, is observed a t m / z 227, corresponding to the
molecular anion. T N T at room temperature is present at a
concentration of 9.5 parts per billion (ppb) on a mol/mol basis
(33) in its saturated headspace vapor. When vapors from
above a solid sample of T N T a t room temperature are drawn
into the ion source, the concentration of T N T vapor is likely
to be lower than 9.5 ppb due to losses in the tubing leading
to the entrance aperture of the ion source and the fact that
an equilibrium between the solid and gaseous phases of TNT
may not be established. When the vapors over solid TNT are
sampled, a t unit mass resolution, the signal at m/z 227 is
slightly in excess of lo6 counts/s and the background count
rate a t m / z 227 averages 2 x lo3 counts/s. Three times the
standard deviation of the noise, which conventionally establishes the limit of detection, is roughtly 150 counts/s above
background. Assuming that a steady-state concentration of
9.5 ppb of TNT gives lo6 counts/s and that the response of

ANALYTICAL CHEMISTRY, VOL. 60, NO. 20, OCTOBER 15, 1988

the ion source is linear with concentration down to that required to give 150 counts/s, the limit of detection for the
concentration of TNT in air is estimated to be 1.4 pptr (parts
per trillion).
Figure 12 shows the results obtained when various amounts
of TNT were deposited onto a glass tube in acetone solutions
and desorbed in a heated block into the ion source. The
logarithm of the peak signal intensity is plotted as a function
of the logarithm of the quantity of TNT. Up to a sample size
of 800 ng the desorption time profiles of the ion current are
very similar (the sample all desorbs within about 10 s), indicating that the concentration of gaseous T N T that enters
the ion source increases with the sample quantity. The response curve indicates good linearity with concentration,
therefore, over at least 6 orders of magnitude. The detection
limit can be estimated from the low side of the response curve
and compared with the 1.4 pptr detection limit obtained from
the extrapolation described above. The width of the desorption profile a t half-height is about 8 s so that the T N T
sample is diluted by the air being drawn into the ion source
during this period. The smallest detectable sample size is 400
fg or 1.8 X
mol, which with a sampling rate of 5 mL/s,
enters the source diluted by 40 mL or -1.6 X
mol of air.
The average concentration is therefore -1 Rptr. This is a
conservative estimate of the true detection limit of the ion
source, since we have made little effort to reduce the noise
level in the line-of-sight geometry of the instrument. Above
a sample quantity of 800 ng the desorption profile begins to
significantly broaden so that the height of the profile is no
longer linear with sample size, and thus neither is the concentration of T N T entering the ion source. This method,
therefore, cannot be used to determine the linearity of response with concentration for sample size greater than 800
ng. An 800-ng sample of T N T entering the ion source over
a period of 8 s gives an average concentration of -2 ppm.
The TNT example is given to show the limits of detection
and sensitivities possible with this ion source for what is
expected to be an optimal case. T N T has a high electron
affinity, and the chemical noise is relatively low throughout
most of the negative ion mass spectrum. We have observed
similar performance for other explosive compounds, which also
have high electron affinities. In the positive ion mode, compounds with high proton affinities and/or low ionization
potentials are readily detected at low levels.

ACKNOWLEDGMENT
We thank Henry S. McKown for his many contributions
to the development of the mass spectrometer and its data
system.

2227

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RECEIVED
for review April 8, 1988. Accepted June 28, 1988.
This research was sponsored by the US.D.O.E. Office of Basic
Energy Sciences under Contract DE-AC05-840R21400 with
Martin Marietta Energy Systems, Inc.