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Detection of Toluene, Methanol and

Formaldehyde Using Corona Discharge
Ion Mobility Spectrometry
a a a a a
Shu Li , Jian Jia , Xiaoguang Gao , Xiuli He & Jianping Li
a
State Key Laboratory of Transducer Technology, Institute of
Electronics, Chinese Academy of Sciences, Beijing, China
Accepted author version posted online: 21 Feb 2012.Version of
record first published: 30 May 2012.

To cite this article: Shu Li , Jian Jia , Xiaoguang Gao , Xiuli He & Jianping Li (2012): Detection of
Toluene, Methanol and Formaldehyde Using Corona Discharge Ion Mobility Spectrometry, Analytical
Letters, 45:8, 841-849

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 Analytical Letters, 45: 841–849, 2012
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ISSN: 0003-2719 print=1532-236X online
DOI: 10.1080/00032719.2012.655680

Environmental Analysis

DETECTION OF TOLUENE, METHANOL AND

FORMALDEHYDE USING CORONA DISCHARGE
ION MOBILITY SPECTROMETRY

Shu Li, Jian Jia, Xiaoguang Gao, Xiuli He, and Jianping Li
Downloaded by [York University Libraries] at 02:43 26 April 2013

State Key Laboratory of Transducer Technology, Institute of Electronics,

Chinese Academy of Sciences, Beijing, China

Polluted air, indoors, and outdoors, that contains hazardous matters or contaminants cre-
ates a hazard to general health. Ion mobility spectrometry is a very promising method for
the detection of air pollutants. In this work, the experimental parameters of corona dis-
charge ion mobility spectrometer (CD-IMS), such as the discharge distance, the drift tube
temperature and the drift gas flow rate, are discussed and determined in terms of stable ioni-
zation and better reactant ion peak quality. The optimal conditions of the CD-IMS are
applied to the detection of toluene, methanol and formaldehyde with the detection limits
of 7.8, 11.3, and 4.6 ppbv, respectively. This provides an alternative and sensitive method
for detection of air pollutants.

Keywords: Air pollutant detection; Corona discharge ionization; Ion mobility spectrometry

INTRODUCTION
Exposure to indoor air pollution from the tobacco smoke, cooking and heating
appliances, and vapors from building materials, paints, and furniture is a significant
public health hazard worldwide. Long-term touch of air pollutants, (e.g., toluene,
methanol, and formaldehyde), causes damage to the liver, hemopoietic system,
and immune system (Heck, Casanova, and Starr 1990; Jacobsen and McMartin
1986; McMartin, Ambre, and Tephly 1980; Miyagi et al. 1999; Yucel et al. 2008).
And, they are even thought to be carcinogens (Loeser 1983; Soffritti et al. 2002).
Therefore, there is an increasing need for indoor environmental monitoring.
A number of methods have been reported for the detection of indoor air pol-
lutants (APs) including UV-spectrophotometry (Dupuit et al. 2000), chemilumi-
nescence (Collins, Latturner, and Rosepehrsson 1995), Fourier transform infrared
spectroscopy (Esler et al. 2000), and gas chromatography (Nilsson et al. 2005).

Received 29 July 2011; accepted 2 October 2011.

This work is supported by the National Natural Science Foundation of China (Grant No.
60901048).
Address correspondence to Jianping Li, State Key Laboratory of Transducer Technology, Institute
of Electronics, Chinese Academy of Sciences, Beijing 100190, China. E-mail: jpli@mail.ie.ac.cn

841
 842 S. LI ET AL.

Currently, Gas chromatography (Elke et al. 1998) and the spectrophotometric

method (Gayathri and Balasubramanian 2000) are often used for toluene and for-
maldehyde analysis. Although these methods are capable of isolating, detecting,
and quantifying toluene and formaldehyde with detection limits of 0.1–10 ppbv, they
are complex and time-consuming. Therefore, a sensitive and rapid method capable
of detecting different air pollutants is desirable.
Ion mobility spectroscopy (IMS) is an analytical method that is ideally suitable
for the detection of trace amounts of the specific compound in a gaseous mixture
(Eiceman and Karpas 2005; St. Louis and Hill 1990). In general, 63Ni ionization
source has been used for most IMS instruments. However, due to the requirement
of a regular leak test as well as special safety regulations and the demand of extend-
ing the types of analytes, alternative sources have been developed. These include cor-
ona discharge ionization (Tabrizchi, Khayamian, and Taj 2000), photoionization
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(Leasure et al. 1986), electrospray ionization (Wittmer et al. 1994), and surface ioni-
zation (Wu et al. 1999). Among these ionization methods, corona discharge ioniza-
tion has received much attention for its high efficiency and simplicity.
Corona discharge is one kind of electrical discharge developed by the ionization
of the gas surrounding a sharp conductor. It occurs when the electric field is strongly
non-uniform but insufficient to cause complete electrical breakdown. Corona dis-
charge ion mobility spectrometry (CD-IMS) was first described in 1994 by Wittmer
et al. (1994). In this literature, corona discharge was a by-product produced by elec-
trospray ionization when a high voltage was applied to the spray needle. The CD-IMS
was systemically designed and optimized by Tabrizchi et al. (2000). According to Tab-
rizchi et al., it has both a better sensitivity and a higher signal-to-noise ratio relative to
the 63Ni source that was achieved. In addition, Borsdorf et al. (2000) demonstrated
that when using a corona discharge such as an ionization source, aromatic com-
pounds and alkanes were more easily ionized than using a 63Ni source.
In this work, a CD-IMS method for the detection of toluene, methanol, and
formaldehyde is proposed. The working parameters, such as discharge distance, drift
tube temperature, and the drift gas flow rate, are analyzed. With appropriate para-
meters, toluene, methanol, and formaldehyde can be detected with an acceptable
detection limit.

EXPERIMENTAL
Instrumentation
The IMS system was constructed in our laboratory. The corona discharge
source is of needle-to-mesh geometry which includes a sharp tungsten needle, a tar-
get electrode of metal mesh and a DC high voltage power supply (30 kV, 1 mA). The
drift tube is constructed from stacked stainless steel rings, separated by Teflon insu-
lators and electrically connected by a series of mega-ohm resistors.
The ion gate of Bradbury-Nielson type is located at the entrance of the drift
region. The Faraday plate detector is connected to a current to voltage amplifier with
a gain of 109 V=A. Figure 1 shows the schematic diagram of this system.
The temperature of the drift tube could be adjusted from room temperature to
200
C. Compressed nitrogen (99.999%) is used as carrier and drift gas. The
 DETECTION METHOD OF AIR POLLUTANTS USING CD-IMS 843

Figure 1. Schematic diagram of the CD-IMS.

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determined experimental conditions for the detection of toluene, methanol and

formaldehyde are given in Table 1.

Sample Preparation
A flask (750 cm3) is filled with nitrogen and used for the exponential dilution
(Arce et al. 2008). A small volume (1 mL) of a liquid sample is then introduced into
the flask through the septum using a micro-syringe. It is assumed that the liquid sam-
ple evaporates completely and behaves like an ideal gas. The initial gas sample in the
flask is diluted by continuous nitrogen introduction with a gas flow of 300 mL=min.
The concentration decreases due to dilution with nitrogen and can be calculated as
follows:

tc
Cg ¼ C0 e V t ð1Þ

where (C0) is the initial concentration of the gaseous sample after injection, (vc) is the
gas flow in mL=min, V represents the volume of the flask, and t stands for the
elapsed time after injection. If there is no absorption of sample on the glass wall

Table 1. Determined experimental conditions for the detection of toluene, methanol,

and formaldehyde

Parameter Setting

Ionization voltage (kV) 2.5–3.0

Discharge distance (cm) 1.4
Ionization region length (cm) 2
Drift tube length (cm) 5.5
Drift electric field (V=cm) 370–390
Inner diameter of drift tube (cm) 1.6
Flow rate of carrier gas (mL=min) 300
Flow rate of drift gas (mL=min) 800
Drift tube temperature (
C) 80
 844 S. LI ET AL.

or tube-connecting materials, the calculation of the concentration (Cg) is reasonable

at a certain time during the experiment.

Chemicals and Reagents

Toluene and methanol in analytical grade were purchased from Beijing Chemi-
cal Reagent. Formaldehyde solution was purchased from Sinopharm Chemical
Reagent Corp. Deionized water was used without further purification. The com-
pressed nitrogen is filtered with a 13X molecular sieve trap before it is entered into
the IMS drift region in order to remove water vapor or other contaminants.

RESULTS AND DISCUSSION

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Determination of the CD-IMS Parameters

Discharge distance. The determination of discharge distance is based on the
Paschen law,

Vs ¼ f ðPdÞ ð2Þ

which means that the breakdown voltage (VS) is correlated with the product of press-
ure (P) and electrode distance (d). Different electrode distances also lead to different
kinds of discharges, for example, the dark or Townsend discharge, the glow dis-
charge, and the corona discharge which can be distinguished on the basis of their
current-voltage (I-V) characteristics.
Figure 2(a) shows current=voltage versus the total voltage from the needle to
mesh at different distances. Such an I-V characteristic is similar with that of a corona
discharge (Tabrizchi et al. 2000). The straight lines in Fig. 2(a) are coincident with
the Townsend’s formula I/V(V-VS) for low current self-sustained coronas. The
degrees of fitting for each current voltage plots are all above 0.99. This should be
corona discharge. Meanwhile, in order to get a stable corona discharge, the distance

Figure 2. (a) Discharge current=voltage vs. voltage; and (b) Total ion current as a function of time.
 DETECTION METHOD OF AIR POLLUTANTS USING CD-IMS 845

must be determined when the pressure is approximately invariable in atmosphere

operation. Total Ion Current (TIC) at different distances measured as a function
of time up to 8 min is shown in Fig. 2(b). The discharge voltage is set to obtain
the same value of TIC (Ī2 mA). The ion current produces approximately the same
baseline noise (about 0.7 mA). Randomly spaced positive and negative large spikes
are observed in all four distances especially in 8 mm and 18 mm. The sudden change
in TIC is most likely caused by the disturbance of the carrier gas in the ionization
region. Standard deviation (SD) of TIC at four different distances is calculated,
and at the distance of 14 mm, the SD reaches its minimum of 0.089. Therefore,
the appropriate discharge distance required for the CD-IMS could be set to 14 mm.

Drift tube temperature and the drift gas flow rate. Figure 3(a) shows the
CD-IMS spectra of a reactant ion peak (RIP) collected at different drift tube
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temperatures ranging from 30
C to 150
C. As can be seen from the figure, when
the temperature is low (<50
C), two peaks of multiple water cluster ions are
observed at 6.32 ms and 8.84 ms (30
C), and the intensity of RIP is weak. It enhances
with an increase in drift tube temperatures and remains unchanged after the

Figure 3. (a) Ion mobility spectra; (b) Ratio of peak intensity to PWHM at different drift tube
temperatures; (c) Ion mobility spectra; and (d) Drift time of RIP at different drift gas flow rates.
 846 S. LI ET AL.

temperature increases to 120
C. This can be attributed to the existing multiple water
cluster ions (Hþ(H2O)n, n ¼ 2, 3, 4) at low temperatures. When increasing the tem-
perature, the value of n in Hþ(H2O)n is gradually decreased (from n ¼ 2, 3, 4 to
n ¼ 2, 3) (Kim, Betty, and Karasek 1978). Therefore, the RIP is more concentrated.
On the one hand, high temperatures of the drift tube are necessary to reduce the
number of water molecules (n) in clustered ions; and on the other hand, lowering
the temperature is an effective means to reduce the diffusion of ions that diminishes
the ions lost and leads to smaller peak width at half maximum (PWHM). Hence, the
appropriated temperature should be kept as low as possible but capable of removing
the water clusters of n  4. The ratio of peak intensity to PWHM of the spectra can
be used as a guide of determining temperature and is plotted in Fig. 3(b). The ratio is
enhanced with increasing the temperature and maximized at 80
C; then, it slightly
decreases due to the ion diffusion at the high temperature range. Therefore, the
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appropriate temperature required of the drift tube is 80
C.

The drift gas is intended to maintain a clean gas environment in the drift tube
and to reduce the residual memory effect. Figure 3(c) and (d) show the RIP spectra
and the drift times of RIP collected at different drift gas flow rates ranging from
0 mL=min to 1000 mL=min. As shown in Fig. 3(c) and (d), the drift time of RIP
remains unchanged when the drift gas flow rate is within the range of 400 mL=min
and 800 mL=min. In the upper region (>800 mL=min), the drift time increases
slightly due to the temperature change caused by a cooling effect of the drift gas.

Figure 4. IMS spectrum of: (a) RIP; (b) 0.1 ppm toluene; (c) 0.1 ppm methanol; and (d) 0.1 ppm
formaldehyde.
 DETECTION METHOD OF AIR POLLUTANTS USING CD-IMS 847

Table 2. Drift time and reduced mobility of toluene, methanol, and formaldehyde ions

APs Toluene Methanol Formaldehyde

Relative drift time (ms) RIP 5.17  0.40% 5.17  0.48% 5.18  0.55%
monomer 5.93  1.11% 5.66  1.45% 5.60  1.47%
dimer — — 6.28  1.82%
Reduced mobility K0 (cm2=V  s) RIP 2.11 2.11 2.11
monomer 1.84 1.93 1.95
dimer — — 1.74

However, the drift time increases tremendously as the flow rate in the lower region
decreases (< 400 mL=min). This indicates that the composition of reactant ions
becomes complex because more water molecules and other impurities exist in the
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gas environment of the drift tube, especially the ionization region, when the flow rate
is  400 mL=min or lower. Therefore, In order to avoid the temperature change in
the drift tube and make the composition of reactant ions simple, the suitable drift
gas flow rate could be set at  800 mL=min.

Detection of Three Air Pollutants

The IMS spectra of toluene, methanol, and formaldehyde were recorded in a
positive mode with experimental conditions given in Table 1. Three replicates are
taken for each measurement. Blank RIP is shown in Fig. 4(a). In the RIP spectrum,
the reactant ion peaks at 4.69 ms, and 5.17 ms corresponds to water clusters of
NH4þ ðH2 OÞn (n ¼ 0, 1) and Hþ(H2O)n (n ¼ 2, 3) (Kim et al. 1978). An overview of
the spectra of three APs is given in Fig. 4(b)–(d). Every compound generates a
characteristic spectrum and each peak has specific ion mobility. The drift times
extracted from the spectra and calculated reduced mobility (K0) for three APs are
listed in Table 2. Figure 4(b) shows the spectrum obtained for toluene. One of the
peaks is identified as a toluene monomer and has a K0 value of 1.84 cm2 V1 s1
which is consistent with that reported in the literature (Borsdorf et al. 2000).
Figure 4(c) shows the spectrum obtained for methanol. One of the peaks is identified
for a methanol monomer with a K0 value of 1.93 cm2 V1 s1. Figure 4(d) is the spec-
trum obtained for formaldehyde. Two peaks were identified as the monomer and
dimmer of formaldehyde with K0 of 1.95 and 1.74 cm2 V1 s1. In all the measure-
ments, drift times are found to be similar with the difference of <2%.
The peak intensity for a given sample is considered as the response. The
relationships between the response and the concentration for toluene, methanol,
and formaldehyde are shown in Fig. 5. The relationships in the low concentration
range are approximated by a linear function with the slope or sensitivity b. Then
the limit of detection (LOD) may be defined as:

3rblank
LODðresponseÞ ¼ ð3Þ
b

where rblank is the standard deviation of noise signal for a blank spectrum. The
slope (b) for toluene, methanol, and formaldehyde are 0.0029, 0.0025, and 0.0032,
 848 S. LI ET AL.

Figure 5. Relationships between response and concentration of toluene, methanol, and formaldehyde (In
the inset, concentration up to 1000 ppbv).

respectively. The standard deviation of the blank at the drift time range considered is
about 0.0075. The calculated detection limit value for toluene, methanol and formal-
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dehyde are 7.8, 11.3, and 4.6 ppbv, respectively.

CONCLUSIONS
A CD-IMS method for the detection of three APs, toluene, methanol, and for-
maldehyde, has been proposed. Longer discharge distance (14 mm) leads to more
stable corona ionization. Moderate drift tube temperature (80
C) and drift gas flow
rate (800 mL=min) give better quality to the reactant ion peek. With an appropriate
choice of parameters, the detection limits of three APs are 7.8, 11.3, and 4.6 ppbv,
respectively. The method allows a sensitive and rapid APs detection.

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