RAPID COMMUNICATIONS IN MASS SPECTROMETRY

Rapid Commun. Mass Spectrom. 2010; 24: 1763–1769

Published online in Wiley InterScience (www.interscience.wiley.com) DOI: 10.1002/rcm.4574

Application of selected ion flow tube mass spectrometry

to real-time atmospheric monitoring
Barry J. Prince1, Daniel B. Milligan1 and Murray J. McEwan1,2*
1
Syft Technologies Ltd., 3 Craft Place, Christchurch, New Zealand
2
Department of Chemistry, University of Canterbury, PB4800, Christchurch, New Zealand
Received 21 February 2010; Revised 7 April 2010; Accepted 8 April 2010

Data are presented for real-time atmospheric monitoring of volatile organic chemicals (VOCs) in air
using selected ion flow tube mass spectrometry (SIFT-MS) technology. These measurements were
made by one of the new generation of SIFT-MS instruments. Results are shown for five VOCs that
were continually monitored from a stationary sampling point over a 4-day period: ethene, ethanol,
1,3-butadiene, benzene and toluene. All analytes except ethene in the study have at least two
simultaneous and independent measures of concentration. These results demonstrate the great
advances in SIFT-MS that have been made in recent years. 1,3-Butadiene is measured at a concen-
tration of 9 pptv with a precision of 44%. For a 1-s integration time, a detection limit of 50 pptv is
achieved. Instrument sensitivities are reported for all five analytes. Copyright # 2010 John Wiley &
Sons, Ltd.

Volatile organic chemicals (VOCs) in the earth’s atmosphere Thus, to some extent, PTR-MS and GC provide complemen-
are emitted from a variety of man-made and natural sources tary data.
and their concentrations can be affected by a number of A related technique to PTR-MS is selected ion flow tube
different chemical and physical processes. The ability to mass spectrometry (SIFT-MS). SIFT-MS provides several
measure the concentrations of these VOCs accurately, advantages over PTR-MS.
selectively, and rapidly can dramatically help in our efforts
1. Whereas PTR-MS utilises only the reactions of H3Oþ, the
to understand and characterise the sources and sinks for
ion source in a SIFT-MS instrument produces three
individual VOCs.1
reagent ions for chemical ionisation: H3Oþ, NOþ
Traditionally, atmospheric VOC concentrations have been
and Oþ 2 . These ions are directed through a quadrupole
monitored using gas chromatography (GC) and GC/mass
mass filter where one is selected for reaction with the
spectrometry (MS) methods.2 However, over recent years
sample enabling clean reaction between one reagent ion
measurements of atmospheric compounds have benefited
and the analyte as well as rapid switching between
from the application of real-time mass spectrometric
reagent ions. The availability of NOþ and Oþ 2 enables
techniques, in particular proton transfer reaction mass
the measurement of compounds that do not react
spectrometry (PTR-MS).3–5 In PTR-MS the sample is
with H3Oþ (e.g., light hydrocarbons and many haloge-
continuously drawn into a drift-tube reactor where the
nated species) and also facilitates the identification of
VOCs are ionised by reaction with hydronium ions (H3Oþ).
compounds that cannot be differentiated on the basis
The principal advantages of PTR-MS over GC methods are
of H3Oþ reactions alone. Whereas H3Oþ almost always
two-fold. First, PTR-MS measurements can have a temporal
reacts by proton transfer, Oþ 2 usually reacts by charge
resolution of the order of 1–10 s for concentrations in the 10–
transfer or dissociative charge transfer and NOþ reacts by
100 parts-per-trillion by volume (pptv) concentration range.
a number of mechanisms including charge transfer,
This enables monitoring of atmospheric conditions where
adduct formation and hydride abstraction. The switching
VOC concentrations are rapidly changing (such as close to an
time of the mass filter is sufficiently fast that essentially
emission source). Secondly, the sample is drawn directly into
simultaneous measurements with all three of these
the reaction chamber without the need for any pre-treatment
reagent ions can be carried out.
or pre-concentration, so the integrity of the sample is much
2. The ionisation is softer in a SIFT-MS reactor (flow tube)
less likely to be degraded as a result of the mechanism of
than in a PTR-MS reactor (drift tube). PTR-MS product ion
sampling.
distributions measured for a range of compounds6–8
The principal disadvantage of PTR-MS compared with GC
reveal different fragmentation patterns and generally a
techniques is the lack of measurement specificity. Com-
higher degree of fragmentation than observed for the
pounds can be identified solely on the basis of the mass of the
same compounds when analysed using SIFT-MS.9 Blake
product ions formed upon reaction of H3Oþ with the analyte.
et al.5 note that the increased fragmentation observed in
PTR-MS arises due to the higher collision energies in the
*Correspondence to: M. J. McEwan, Department of Chemistry,
drift tube (
0.2 eV), which are substantially greater than
University of Canterbury, PB4800, Christchurch, New Zealand.
E-mail: murray.mcewan@canterbury.ac.nz the thermal collision energies (
0.038 eV) in a flow tube.

Copyright # 2010 John Wiley & Sons, Ltd.

1764 B. J. Prince, D. B. Milligan and M. J. McEwan
3. For compounds such as formaldehyde and hydrogen
cyanide that have proton affinities close to that of water,
the possibility of back reactions between the protonated
analyte and water in the sample must be considered. Blake
et al. note5 that the rates of these back reactions are
temperature-dependent. Thus, in a PTR-MS experiment
where the effective temperature is of the order of 1000 K,
these back reactions proceed at a much higher rate, which
can make the measurement of these compounds difficult if
not untenable. In SIFT-MS where the ion-molecule reac-
tion of the reagent ion and analyte typically takes place at
room temperature, compounds such as formaldehyde can
be easily measured.
In spite of the advantages of SIFT-MS, the technique has
been little used for atmospheric measurements due to
insufficient instrument sensitivity delivered by the available
SIFT-MS instrumentation. The results presented here
demonstrate that recent advances in SIFT-MS technology
have vastly improved the achievable limits of detection.
Measurement sensitivities equivalent to those observed with
the latest PTR-MS instruments are reported, enabling the
real-time monitoring of a selection of VOCs in air with parts-
per-trillion level precision. These increases in sensitivity
coupled with the simultaneous measurement of several
reagent ions make SIFT-MS a powerful tool for atmospheric
monitoring applications. It should, however, be noted that
although most volatiles are amenable to measurement by
SIFT-MS using the three reagent ions H3Oþ, NOþ and Oþ 2,
there are a few exceptions. These exceptions include
nitrogen, oxygen and hydrogen plus the noble gases, helium
and argon, and a few other species that are unreactive to the
reagent ions such as SO2 and CO.
EXPERIMENTAL
All the data presented in this paper have been measured
using a Voice2001 selected ion flow tube mass spectrometer
(Syft Technologies, Christchurch, New Zealand). The
Voice2001 is the third-generation selected ion flow tube
mass spectrometer from Syft Technologies, being smaller,
lighter, and significantly more sensitive than earlier instru-
ments such as the Trans-SIFT10 and the Voice1001.11,12 The
Voice2001 has dimensions of 875D  725W  900H mm and
it weighs 212 kg inclusive of all pumps. It has integrated
caster wheels thus making it easy to move and relocate. It can
also be easily transported between sites. The instrument is
powered from a single 10 A, 240 V mains supply and it can
run as a turn-key device without requiring an external
control PC to be connected. The basic layout of components
in the Voice2001 is presented in Fig. 1.
Reagent ions are generated in a microwave discharge,
which acts on an air/water mix at a pressure of approxi-
mately 0.4 Torr to generate the three reagent ions of most
utility for SIFT-MS measurements: H3Oþ, NOþ, and Oþ 2.
These ions are extracted into the upstream chamber
maintained at a pressure of
5  104 torr, using a 70 L/s
turbomolecular pump. The reagent ions pass through an
array of electrostatic lenses and the upstream quadrupole
Copyright # 2010 John Wiley & Sons, Ltd.
Figure 1. Schematic diagram of the Voice 2001.
mass filter, and those not rejected by the mass filter are
passed into the flow tube where they are carried along in a
stream of helium. The upstream quadrupole mass filter can
rapidly (<1 ms) switch between the available reagent ions
allowing a single measurement to use all available reagent
ions essentially simultaneously. This allows the possibility of
multiple independent measurements of the concentration
and consequent identification of analytes. The increased ion
signals of the Voice2001 over the Voice1001 are largely the
result of improved flow conditions within the flow tube and
the downstream chamber, and improvements in the ion
optics.
The predictability of SIFT-MS reaction rates and reaction
products arises from the fact that chemical ionisation of the
sample takes place in the absence of strong field gradients. To
minimise field effects in the Voice2001 the electric potential
of the flow tube can be adjusted to lower the field gradients at
the entrance and exit of the flow tube and optimise the
efficiency of ion transmission. The flow tube is pumped by a
35 m3/h scroll-type dry pump resulting in a typical gas flow
of 360 sccm for the helium carrier and a sample flow of the
order of 20 sccm. These flows result in a total flow tube
pressure of approximately 0.65 Torr and a reaction time of

4 ms. The quadrupole power supplies are compact and
based on planar transformer technology operating at
2.0 MHz.
The downstream detection chamber, pumped with a 260
L/s split-flow turbomolecular pump, contains the down-
stream analysis quadrupole mass filter and the electron
multiplier. Signal levels of 10 million counts per second (cps)
for each of the reagent ions are typical. Ions are detected
by pulse counting the output from a continuous dynode
electron multiplier. To enable a linear instrument response
for signals in excess of 107 cps these high reagent ion signal
levels are attenuated by a known factor (
20  ) by detuning
one of the downstream electrostatic lenses. The standard
downstream quadrupole has a mass range of m/z 1–250.
Rapid Commun. Mass Spectrom. 2010; 24: 1763–1769
DOI: 10.1002/rcm
 Application of SIFT-MS to real-time atmospheric monitoring 1765

Air analyses means that Rþ þ

1 and R2 are approximately zero. The value of c1
In this study five analytes, 1,3-butadiene, benzene, toluene, and c2 are chosen to give the best fit of Eqn. (2) to data
ethanol and ethene, were quantified in air by utilising the collected using an apparatus designed by Syft Technologies
following SIFT reaction chemistry: that enables the relative humidity of an analytical standard to
be varied from 0 to 100% at
358C.
Toluene Linearity measurements were carried out on samples
prepared by static dilution. Two Air Liquide certified gas
C7 H 8 þ H 3 O þ ! C7 H 9 þ þ H 2 O
mixtures were used (Air Liquide, Auckland, New Zealand).
C7 H8 þ NOþ ! C7 Hþ
8 þ NO
þ
The first contained acrolein (1.05 ppmv), 1,3-butadiene (1.05
ppmv), toluene (1.06 ppmv), and ethanol (1.05 ppmv) in
C7 H 8 þ O þ þ
2 ! C7 H 8 þ O 2
nitrogen, each with an accuracy of 5%. The second
contained benzene (2.16 ppmv) and ethene (2.06 ppmv), in
1,3-Butadiene: nitrogen, each with an accuracy of 10%.
C4 H6 þ NOþ ! C4 Hþ Sample concentrations at
100 ppbv, 10 ppbv and 1 ppbv
6 þ NO
were prepared sequentially by injecting 100 mL of each
C4 H 6 þ O þ þ
2 ! C4 H 6 þ O 2 dilution (gas syringe; SGE, Ringwood, Victoria, Australia)
into 1 L of nitrogen in a Tedlar1 bag. Sample concentrations
Benzene lower than 1 ppbv were made by first preparing an
1 ppbv
sample by injecting 1 mL (SGE gas syringe) of the certified
C6 H6 þ NOþ ! C6 Hþ
6 þ NO
standard into 1.0 L of nitrogen in a Tedlar1 bag and then
C6 H6 þ NOþ þ M ! C6 H6 :NOþ þ M carrying out sequential dilutions on that sample as for the
C6 H 6 þ O þ þ higher concentration samples. The estimated accuracy of the
2 ! C6 H 6 þ O 2
dilutions prepared in this way is 10% per dilution step.
Outdoor air measurements were performed on air
Ethanol
sampled at 6 m above ground level and 2 m above the level
C2 H5 OH þ H3 Oþ ! C2 H7 Oþ þ H2 O of the roof of the Syft Technologies building in Christchurch,
New Zealand. The air was drawn through a 25 mm diameter,
C2 H5 OH þ NOþ ! C2 H5 Oþ þ HNO
9-m long copper tube by a 10-cm, 25-W fan. The transit time
of sample through this sampling tube was determined to be
Ethene approximately 7 s.
C2 H 4 þ O 2 þ ! C2 H þ
4 þ O2

Analyte concentrations derived from the NOþ and Oþ2

reactions were determined from Eqn. (1):9

Pþ
A¼ (1)
Rþ c

where A is the analyte concentration, Pþ is the measured

signal of the product ion, Rþ is the measured signal of the
reagent ion (NOþ or Oþ 2 ) and c is a calibration factor
determined from the linearity measurements described
below. For reactions involving H3Oþ allowance has to be
made for the reactions of water vapour in the sample. In
particular, H3Oþ reacts with water to form the cluster
ions H3Oþ.H2O and H3Oþ.2H2O, and these may react with
the same analytes as H3Oþ but at a reduced rate. (We have
determined that the reactions of higher-order cluster ions
need not be considered.) In this case the concentrations are
determined from Eqn. (2):9
Pþ
A¼ (2)
Rþ
0 c0 þ Rþ þ
1 c1 þ R2 c2

where Rþ þ þ
0 , R1 , R2 are the measured signals of the
ions H3O , H3O .H2O and H3Oþ.2H2O, respectively, and
þ þ

c0, c1, c2 are the associated calibration factors for the reactions
of these ions with the analyte A to form the product ion Pþ.
The value of c0 is determined from the linearity measure- Figure 2. Schematic diagram of the sampling system in the
ments described below, since the dry nature of these samples Voice 2001.
Copyright # 2010 John Wiley & Sons, Ltd. Rapid Commun. Mass Spectrom. 2010; 24: 1763–1769
DOI: 10.1002/rcm
1766 B. J. Prince, D. B. Milligan and M. J. McEwan
The Voice200 sample inlet was switched between four
available sample streams (Fig. 2):
1. The outdoor air drawn from just upstream of the fan.
2. The outdoor air drawn from just upstream of the fan and
diverted through a Pt catalyst heated to
3008C to remove
organics. This sample stream was used to determine an
instrument background for all the analytes measured
except toluene, for which an interfering compound was
produced by the Pt catalyst.
3. A cylinder of industrial-grade nitrogen, used to determine
the instrument background for toluene.
4. One of the two certified gas mixtures detailed above.
The instrument was programmed to run a scan of inlet 3
for 2 min (to measure the toluene background) followed by a
scan of inlet 2 for 5 min (to measure backgrounds for ethene,
ethanol, 1,3-butadiene and benzene) and a scan of inlet 1 for
5 min (to measure the outdoor concentration of all five
compounds using all three reagent ions). This series of scans
was repeated continuously and an additional scan was
intermittently made of the two certified gas mixtures through
inlet 4. The scans through inlet 4 (not presented here) were
used to verify that the instrument calibration did not change
for the duration of the measurements.
Figure 3. Linearity plots for the eleven reactions used to monitor the five analytes in this study.
Copyright # 2010 John Wiley & Sons, Ltd.
RESULTS AND DISCUSSION
Linearity plots of the 11 reactions utilised in this work are
shown in Figs. 3(a)–3(e). The extent to which the measure-
ment remains linear at low concentrations depends on the
instrument background. For ethanol, which has a high
instrument background of
12 ppbv, deviations from
linearity are evident for sample concentrations below
2
ppbv. However, for 1,3-butadiene, the instrument back-
ground amounts to
20 pptv and the measurement linearity
extends down beyond 10 pptv. The lowest concentration
measurement shown for 1,3-butadiene in Fig. 3(a) is 9 pptv
with a measurement precision of 4 pptv. The measurement
sensitivities of each of these reactions are presented in
Table 1. The measurement sensitivities for analytes that react
to form a single ion product are typically in the range 50–100
cps/ppbv. Lower sensitivities are observed for reactions
with smaller branching ratios and/or lower reaction rate
coefficients as expected.
To gauge the specificity of the Voice2001 for the detection
of these compounds in outdoor air, a series of measurements
was collected overnight for all 11 reactions listed in Table 1.
The results of these measurements are shown in Figs. 4(a)–
4(d). It is evident that, while the concentration profiles of the
four compounds measured are quite different, there is a high
Rapid Commun. Mass Spectrom. 2010; 24: 1763–1769
DOI: 10.1002/rcm
 Application of SIFT-MS to real-time atmospheric monitoring 1767

Table 1. Voice2001 measurement sensitivity for the reac- degree of correlation for each compound between the
tions of toluene, 1,3-butadiene, benzene, ethanol and ethene different reagent ions utilised to monitor their concen-
Analyte Reagent ion Product ion Sensitivity (cps/ppbv)
trations. This degree of correlation between the concen-
trations calculated using different product ions provides
Toluene H3Oþ C7Hþ9 69 support for the contention that the compounds being
Toluene NOþ C7Hþ8 92 measured are indeed those listed in Table 1, rather than
Toluene Oþ
2 C7Hþ8 74 other interfering compounds. Unfortunately, ethene is
1,3-Butadiene NOþ C4Hþ 96
6 reactive with only one of the reagent ions and produces a
1,3-Butadiene Oþ
2 C4Hþ6 63
single product ion, so the selectivity of the ethene
Benzene NOþ C6Hþ6 54
Benzene NOþ C6H6.NOþ 24 measurement could not be verified in this way. Nevertheless,
Benzene Oþ
2 C6Hþ6 43 it is clear that ethene is the most likely compound responsible
Ethanol H3Oþ C2H7Oþ 57 for the signal at m/z 28 with the Oþ 2 reagent ion.
Ethanol NOþ C2H5Oþ 51 Having established the linearity and specificity of the
Ethene Oþ
2 C2Hþ4 33 Voice2001 for the measurement of these five compounds,

Figure 4. A comparison of the concentrations monitored (with background subtracted) using multiple
reagent ions for the analytes 1,3-butadiene (a), toluene (b), benzene (c), and ethanol (d).

Figure 5. Typical data recorded for the two VOCs, ethene (a) and 1,3-butadiene (b), over a 90-min period with one
data point recorded every 12 s.

Copyright # 2010 John Wiley & Sons, Ltd. Rapid Commun. Mass Spectrom. 2010; 24: 1763–1769
DOI: 10.1002/rcm
1768 B. J. Prince, D. B. Milligan and M. J. McEwan

Figure 6. Data recorded for the entire 4-day period for all five VOCs monitored. In addition, the wind speed
from the NZ Institute of Water and Atmospheric Research is shown in (c).

outdoor air measurements were performed continuously the advances and application of SIFT-MS technology to
over 4 days and nights. The data from approximately 90 min environmental monitoring. Nevertheless, the following
of measurement with one data point every 12 s is presented points are pertinent.
in Fig. 5 for ethene and 1,3-butadiene. As described above, Meteorological data recorded during the period of the
data are collected for the background and sample measure- measurements were surveyed for correlations with the
ments for 5 min each with a cycle time of
12 min. These observed VOC concentrations. The New Zealand Institute of
graphs demonstrate the application of the Voice2001 to the Water and Atmospheric Research provided hourly averages
real-time detection of VOCs with ppt-level resolution. for temperature, humidity, barometric pressure, wind
Figure 6 shows the data from the entire 4-day period for direction and wind speed. Of these data, the most compelling
all five compounds measured. In this data, each point is the
average concentration from a 5-min sample measurement
phase with the background from the preceding background
measurement phase subtracted. The total measurement time
per analyte and the resulting limit of detection for these data
are presented in Table 2. All the measurements reported here
were validated by monitoring an Air Liquide certified gas
mixture of all the analytes.
It is not the purpose of this paper to attempt a detailed
meteorological analysis of the data, but rather to outline

Table 2. Measurement time and corresponding limit of

detection (LOD) for the five compounds measured
Analyte Measurement time per 5-min cycle (s) LOD (pptv)

Toluene 32 35
1,3-Butadiene 32 6.4
Benzene 32 72 Figure 7. A comparison of the measured concentrations of
Ethanol 64 210 1,3-butadiene with ethene and ethanol showing a different
Ethene 32 180
production source for ethanol.
Copyright # 2010 John Wiley & Sons, Ltd. Rapid Commun. Mass Spectrom. 2010; 24: 1763–1769
DOI: 10.1002/rcm
 Application of SIFT-MS to real-time atmospheric monitoring
correlation observed was an inverse relationship between the
wind speed and the concentration of analytes measured.
Surprisingly, the concentrations of the measured compounds
depend even more strongly on the wind speed than on the
time of day. There is insufficient correlation between the
wind direction and our measurements for us to identify
the direction of the source. We take these results to indicate
that the source of these compounds is nearby and the
primary action of the wind is to dilute the compounds
through vertical mixing.
To determine if the five compounds measured originated
from the same source we examined the correlations between
their concentrations. Doing so revealed that the 1,3-
butadiene concentration was highly correlated with ethene,
toluene and benzene, with linear correlation coefficients of
r ¼ 0.93, 0.86 and 0.94, respectively. However, 1,3-butadiene
was poorly correlated with ethanol, with r ¼ 0.46. Correlation
plots for 1,3-butadiene with ethene and ethanol are shown in
Fig. 7. The implication from this data is that the measured 1,3-
butadiene, ethene, benzene and toluene arise from the same
source, but that there is an alternative source contributing to
the measured ethanol levels. The likely source of these
compounds is from combustion engine exhaust emissions. A
major railway yard lies 100 m to the north of the sampling site
and emissions from diesel locomotives have a significant
influence on the nocturnal emissions, as during the night
considerable freight assembly and train traffic occur. Also, at
this time, vehicular street traffic is light.
CONCLUSIONS
The time variation of the concentration of five VOCs emitted
in the vicinity of the Syft Technologies factory were
monitored over several days. The results demonstrate the
real-time monitoring of environmental air using a commer-
cial SIFT-MS instrument. The enhanced selectivity provided
Copyright # 2010 John Wiley & Sons, Ltd.
1769
by the use of multiple reagent ions provides a high level of
confidence in the positive identification of the compounds
measured. The reported sensitivities enable measurements
with single-digit pptv precision. The limit of detection for a
1-s measurement of 1,3-butadiene is 50 pptv, which is
equivalent to the level reported by Knighton et al. using
a modified PTR-MS instrument.13 We also note that both
PTR-MS and, to a lesser extent, SIFT-MS cannot always
distinguish between isomeric species. It is not possible, for
example, to distinguish between 1,2- and 1,3-dimethylben-
zene although SIFT-MS can readily distinguish between
the C3H6O isomers, acetone and propanal. The important
prerequisite for isomeric distinction is that the isomers must
react differently with one of the reagent ions.
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