Sensors and Actuators B 176 (2013) 985993

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Sensors and Actuators B: Chemical

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Detection of explosives by plasma optical emission spectroscopy

Jane H. Fujiyama-Novak a , Chethan Kumar Gaddam a , Debanjan Das a , Randall L. Vander Wal a, ,
Benjamin Ward b
a
Dept. of Energy and Mineral Engineering & The EMS Energy Institute, The Pennsylvania State University, State College, PA 16802, USA
b
Makel Engineering, Inc., Cleveland, OH 44128, USA

a r t i c l e i n f o a b s t r a c t

Article history: A new pre-concentration/separation system coupled to a micro-hollow glow discharge (MHGD) plasma
Received 10 July 2011 detector is demonstrated for the analysis of explosives. The detector and spectrometer are miniaturized
Received in revised form 14 August 2012 and eld-portable. Separation eliminated air interferences while pre-concentration improved detection
Accepted 27 August 2012
limits for TATP (triacetone triperoxide) and DNT (dinitrotoluene). In the analysis step, a temperature
Available online 6 September 2012
ramp desorbed the two explosives into an entraining Ar ow. Optical emission spectroscopy (OES) was
applied to detect the plasma generated atomic and diatomic radicals using a spectrometer at atmospheric
Keywords:
pressure. For both test species, the detection limits reached values lower than 5 ppb. The effect of an at-sea
Plasma
Glow-discharge
environment was also evaluated. Such a detector system is very promising for the detection of explosives
Optical emission spectrometry due its small size, high sensitivity and selectivity.
Explosives 2012 Elsevier B.V. All rights reserved.
TATP
DNT
TNT

1. Introduction achieve statistically meaningful detection, pre-concentration offers

Three goals for sensors are sensitivity, selectivity and stability.
Sensitivity equates to low detection limits. Explosives are partic-
ularly challenging in this regard as they typically have very low
vapor pressures, e.g. 2 104 Torr for TNT at 25 C [1]. By compar-
ison triacetone triperoxide (TATP) has a vapor pressure of 0.05 Torr
at 20 C, enabling relative ease of detection. Moreover its precur-
sor, acetone, has a vapor pressure of 77 Torr at 20 C. Nevertheless,
real detection environments will not present such an equilibrium
vapor pressure. Instead of being open to the ambient, explosives
likely will be concealed or otherwise contained. Additionally, large
standoff detection is highly desirable. These factors then drastically
lower the partial pressure or ambient concentration at the detec-
tor location. For detection in the eld, such as by unmanned aerial
vehicles (UAVs), concentrations are subject to varying atmospheric
conditions. In fact at particular times and locations, detection
could fail simply because of transient environmental factors (e.g.
being upwind). Therein sampling is highly desirable and pseudo-
continuous monitoring rather than instantaneous measurement is
the better strategy for detection and prevents false negatives.
Given the likely possibility of concentration uctuations and low
vapor pressures in real environments, coupled with sampling to
Corresponding author. Tel.: +1 814 865 5813; fax: +1 814 865 3248.
E-mail address: ruv12@psu.edu (R.L. Vander Wal).
enhanced detection limits and accuracy. In general such detection
limits are reciprocally related to pre-concentration time. In a mon-
itoring mode pre-concentration times can extend from minutes to
hours. Periodic release of collected analyte then determines the
sampling interval. In reality pre-concentration times should be
as long as possible to prevent false negative detection.
Selectivity is a second key sensor metric. A limitation of
chemical-sensors based upon metal oxides is their lack of chem-
ical specicity. To distinguish oxidizing or reducing gases requires
either additional elements and/or further modication of individ-
ual elements, thereby establishing an electronic nose. It is desired
that a sensor could discriminate against other organics such as
ambient fuel or organic solvents in general and for explosives in
particular.
Stability is also a key sensor metric, particularly with respect
to explosive detection. Elaborate molecular recognition schemes
using uorescence quenching have been developed for TNT detec-
tion but such bio-based sensors are limited to one-time use [2].
Binding of the TNT is irreversible and sensor regeneration is dif-
cult. Moreover many such systems are solution based, an approach
not well suited for vapor phase detection [35]. In general any
sensor for monitoring and sampling over long durations must be
renewable, ideally self-regenerating.
Large platform analytical equipment such as gas chromatogra-
phy (GC) [6,7], high-performance liquid chromatography (HPLC)
[8], mass spectrometry (MS) [9,10] and inductively coupled plasma

0925-4005/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2012.08.063
986 J.H. Fujiyama-Novak et al. / Sensors and Actuators B 176 (2013) 985993
atomic emission spectrometry (ICP-AES) have been used to ana-
lyze chemicals in the environment. However, due to their large
power requirements and supporting high carrier (gas or liquid)
ows or pumping apparatus, these analytical instruments are too
large and heavy for eld-portable use. One such use would be the
maritime inspection in vessels potentially carrying explosives. The
development of a very compact electronic sniffer to be mounted
on shipboard-launched UAVs will provide vital remote inspection
capabilities for Navy and Coast Guard vessels or shipping containers
in ports.
Optical emission spectroscopy (OES) based on plasma excitation
is a useful detection method due to its linearity, sensitivity and
because of the possibility of element-specic detection [1114].
Eijkel et al. reported 600 ppm methane using a glow discharge
contained within a microchannel etched on a glass chip [15]. A
pulsed high-voltage plasma between opposing wires contained
within a capillary tube was reported by Jin and others [13] for
organic vapor detection using CH* emission at 431.2 nm. The
authors achieved a detection limit of 0.2 ppm for dimethyl sulf-
oxide (DMSO). Using a microhollow cathode discharge (MHCD),
Miclea et al. demonstrated detection of ferrocence vapor with a
limit of 500 ppb [16] and later detection limits by OES for Cl and F
[from Freons] of 20 ppb using a MHCD and miniaturized Echelle
spectrometer [17]. More recently Mitra and Gianchandani inte-
grated a pulsed microdischarge within a MEMs conguration for
analysis of hydrocarbon vapors. Using a two-electrode congura-
tion, isopropyl alcohol was detected at 100 ppm using CH* emission
and with a 3-electrode FlashFET conguration, acetone vapor in
air ambient at 501000 ppm using CN* emission at 388.1 nm [18].
Recently OES was applied to detection of halogenated hydrocar-
bons using the Cl emission line using a RF-driven MHCD with limits
reported for Freon of 15 ppb for Cl based upon a calibration curve
[19]. Each of these demonstrations used a ber-optically coupled
miniature spectrometer for resolving the OES. Yet despite these
impressive limits, these are energetic plasmas (on a microscale) due
to repetitive initiation of electrical breakdown that can introduce
spectral interpretation difculties, cause electrode erosion, and are
not steady-state plasmas. Detection of low vapor pressure com-
pounds, such as explosives with such plasma-based systems in eld
applications has remained elusive.
One such reason is due to spectral interferences. Anghel et al.
[20] described the air interfering effects with their helium plasma
torch. The authors explained that the back-diffusion effect of air on
the discharge results in atomic emission lines of oxygen, O I at 777
(5 P5 S0 ) and 844 (3 P3 S0 ) nm, hydrogen H at 656 nm (3n 2n)
and molecular bands from NO, OH, N2 and N2 + . The wavelength
range 200300 nm is dominated by the NO molecular -bands (226,
236, 247, 258 and 271 nm). NO is presented due to the chemical
conversion of N2 and O2 [21]. The OH radical is the result of the
dissociation of H2 O molecules with accelerated electrons or long-
lived species present in the plasma, especially helium metastables,
He*m [22]. The nitrogen molecules are mainly represented by the
emission of the second positive system of N2 (315, 337, 357 and
380 nm) and the rst negative system of N2 + (391.44 nm). The for-
mation of N2 + is attributed to Penning ionization of N2 with helium
metastables [23]. With plasma discharges in air generating excited
species with atomic and molecular bands at UV, detection of com-
pounds at this wavelength range will be difcult. As a solution, a
separation system could eliminate the air components.
A second, perhaps more perplexing issue in detecting explosives
is their extremely low vapor pressure. Yet dilution within open
environments and other environmental factors as indicated may
well obscurate detection. For these reasons a sampling and precon-
centration approach is warranted. Precedence for pre-separation
includes studies by Eijkel, using direct current microplasma [12],
Bessoth et al., using a dc-driven plasma [24], Duan and Jin using
a capillary discharge [25]. In a sophisticated arrangement using
a DBD plasma coupled with diode laser atomic absorption of Cl,
Br, F and S atoms as an element specic detector for gas chro-
matography, Kunze et al. showed low to high picogram/second
detection of various halogenated and sulfur containing compounds
[26]. Applying OES using a photodiode array, Guchardi and Hauser
demonstrated detection of oxygen, hydrogen and SO2 species
within helium carrier and mixture separation of carbon-containing
species CH4 , CO and CO2 with detection limits ranging from 1 to
10 ng. Notably all species were as chromatograms with comparison
to TCD [27]. A relevant review may be found elsewhere [28].
In this article we describe the development and demonstrate the
capability of just such a sensor system, featuring a miniature plasma
coupled to a pre-separation system. Plasmas are well known for
their analytical utility and we enhance this capability using a pre-
concentrator for TATP to achieve ppb detection limits and in parallel
eliminate air interference. The plasma is based upon a micro-hollow
glow discharge (MHGD) that dissociates molecules and electroni-
cally excites the atomic and diatomic radical constituents. Despite
differences in terminology, approaches with other plasmas can lead
to an arc or spark and at least two of the aforementioned references
directly reference the sputtering action or erosion of the electrodes
in their plasma conguration [15,18]. By its operation the MHGD
plasma generates reactive ions, metastables and energetic elec-
trons that maintain its operation free of contamination, permitting
long-term use by providing device stability.
2. Materials and methods
High purity argon (99.999%, Praxair) and dried air (99.0%, Prax-
air) were used as plasma gases. Triacetone triperoxide (TATP)
standards were obtained from AccuStandard Inc. (New Haven, CT,
USA). Materials were supplied as 0.1 mg/ml solutions in acetoni-
trile. Dinitrotoluene (DNT) was obtained from Aldrich and used as
received.
2.1. Experimental setup
Fig. 1 shows the experimental setup where the MHGD geom-
etry has been applied to owing gases. It consists of gases, a
multi gas programmer, a pre-concentration system described in
the next section, a chamber with a MHGD element, dc power supply
and spectrometer for capturing atomic/molecular optical emission.
High purity argon is used as the working gas; and the ow rate was
regulated using MKS mass ow controllers and Multi Gas Program-
mer. The argon gas ow rate was restricted to 2 l/min or less at
standard conditions (293 K, 0.1 MPa). A HP 6525A high voltage dc
power supply with a ballast resistor is applied for the excitation and
sustaining of the discharge working with 1.01.2 kV operational
range and current values less than 12 mA.
The development of a permanent and steady glow discharge
depends in greater part on the quality of the metalized disc ele-
ments. The original design and demonstration of these units was
reported by Schoenbach et al. [29]. Their motivation and tests,
along with those following with advancements were toward UV
light sources [30], not analytical chemistry and molecular detec-
tion, our purpose as herein summarized. Rather than laser or
micro-drilling through refractory metal foils [29], we used a screen-
printed process starting with nickel paste lms supported on an
alumina dielectric (with laser drilled hole) that were then red,
together as a unit. Fig. 2 shows two different designs for the elec-
trodes, the circular and spiral geometries. Difculties such as short
lifetime of the electrode or the instability of the plasma glow dis-
charge were found when using the circular electrode. On the other
hand, the spiral nickel screen-printed alumina discs exhibited a
 J.H. Fujiyama-Novak et al. / Sensors and Actuators B 176 (2013) 985993
Fig. 1. Schematic diagram of the experimental setup.
substantial longevity increase, on the order of days due to their
smaller electrode area and consequent lower capacitance features.
Microplasmas such as these offer the key advantage of operation
at atmospheric pressure [31] by virtue of microscaling the relevant
physical dimensions. Yet characterization of the plasma envi-
ronment (energetic species concentrations, electron energy, etc.)
becomes highly challenging with modeling offering key physical
insights [32]. Nevertheless, as a DC operated plasma, it nominally
offers a steady-state energetic environment with other plasma
parameters such as energy density and IV characteristics being
well-characterized [31].
2.2. Pre-concentration system
The operation of the plasma in air background yields high inten-
sity emission bands from NO, N2 and OH species. The concentration
Fig. 2. Micro-hollow glow discharge (MHGD) element: (a) photograph of nickel
screen-printed alumina discs with the spherical and spiral-geometry electrodes;
and (b) description of the MHGD elements dimensions.
987
of these species is large in air, so (1) they can quench emission of a
minor constituent or (2) contribute interfering transitions that will
overlap the atomic and molecular species of the analyte, reducing
the analytical ability of the plasma detector to identify the com-
pound. In addition, comparing to inert gases such as helium and
argon, the plasma stability is markedly less when the background
is air.
In order to eliminate the interfering bands from air species,
a pre-concentration/separation system was developed and inte-
grated with the MHGD element chamber. At its core is a stainless
tube (length 100 mm, OD 6.4 mm) packed with 1 g high surface area
stationary phase. Two valves control the entrainment of the sam-
ple in air or the argon gas carrier into the column. These valves also
control the gas destination: waste or MHGD element. The objective
is to immobilize the analyte on the surface of the packing material
and as result air gases, such as N2 and O2 , precursors to NO, N2 and
OH species, can be separated from the analyte and later eliminated
from the column using an inert gas purging at room temperature.
In parallel, the packing material is able to concentrate the analyte
in the column thereby augmenting the amount of the compound
that will reach the detector, increasing the limit of detection (LOD)
for our microplasma spectrometer.
Fig. 3 shows the schematic of our developed pre-
concentration/separation system. The U-shaped column was
packed with 0.5 g of HayeSep Q 80-100 mesh from Supelco.
HayeSep porous polymer is a poly (divinylbenzene) adsorbent
and the co-elution of the light gases occurs in this material at fast
rates. As a result these light gases can be removed by switching the
valve to waste. On the other hand heavier organic compounds are
adsorbed in the pores of the HayeSep, and they can be desorbed
sequentially by increasing the temperature.
In Fig. 3 two ow states are illustrated: Fig. 3a represents
the sampling process when the analyte is concentrated in the
stationary-phase of the column and separated from the air gases
(N2 , O2 , CO2 , Ar); and Fig. 3b shows the thermal desorption of the
analyte, in argon atmosphere, which vapor phase elutes from the
column and reaches the MHGD element. As a result, the only emis-
sion molecular bands and atomic lines seen in the spectrum will
Fig. 3. Schematic of pre-concentration/separation system: (a) Position 1 corre-
sponds to the elimination of air-component gases and low-boiling point organic
solvents and pre-concentration of analytes; and (b) Position 2 corresponds to the
elution of the concentrated analytes at higher temperatures in an inert gas atmo-
sphere.
988 J.H. Fujiyama-Novak et al. / Sensors and Actuators B 176 (2013) 985993
be generated by dissociation/excitation of the analyte and the inert
gas argon.
The pre-concentration/separation system was coupled to the
MHGD chamber. Prior to perform the experiments with the ana-
lytes, the entire column was heated up to 200 C using a silicone
bath. We observed no emission lines or bands from the packing
material or off-gases potentially generated during the heating pro-
cess, merely the argon lines. This indicated that the porous polymer
did not undergo thermal degradation at 200 C.
2.3. Emission spectrum measurements
The light emitted from the plasma jet was collected by an
Ocean Optics optical ber (F1000-UV-VIS-SR) connected to a col-
limating lens (74-UV UV/VIS) and guided to the Ocean Optics
Maya2000 Pro Spectrometer with back illuminated CCD (grating:
Holographic HC1 300 g/mm; slit width: 0.025 mm) This spectrome-
ter uses a linear CCD-array detector for simultaneous acquisition of
the whole spectrum from 200 to 1100 nm with a nominal resolution
of 0.48 nm.
3. Results
In recent times, TATP (triacetone triperoxide) has been one of
the primary tools of terrorism. According to the press report, TATP
has been implicated in recent bombings throughout the world
[33,34]. The high vapor pressure (7 Pa at ambient conditions) [35]
makes its detection in post-detonation residue more difcult, and
emphasizes the importance of developing analytical methods with
low limit of detection.
Due to its volatility and instability, triacetone triperoxide is
only available commercially as a dilute solution to be used as an
analytical standard. Some studies reported the analysis of TATP
using direct injection of TATP dissolved in an organic solvent by
GC/MS (gas chromatography/mass spectrometry) [36] and LC/MS
(liquid chromatography/mass spectrometry) [37] with nanogram-
detection limits. Nevertheless both analytical instruments are very
heavy and require well-controlled laboratory conditions in which
to operate. As an alternative, in this article we described the method
development of TATP by means of a highly portable micro-hollow
glow discharge (MHGD) plasma technique and its limit of detection
(LOD).
As described before, TATP standard is commercially available
as a dilute solution, dissolved in acetonitrile (Accu Standard,
0.1 mg/ml). Acetonitrile has a lower boiling point (82 C) compared
to TATP (97160 C), therefore the separation of the TATP from the
acetonitrile is feasible. Variables such as stationary phase mass,
tube diameter, gas carrier ow and elution time were studied in
order to dene the most satisfactory conditions for TATP analysis.
Initially, we determined the elution time necessary to eliminate
most of the acetonitrile at room temperature. For this test, 300 l
of pure acetonitrile was added to the column prior to the test. Argon
gas as carrier owed into the column. Fig. 4 shows the acetonitrile
spectrum at the start of argon purge as well after 15 min. The ordi-
nate axis of the graphic is linearly scaled and the two spectra are
offset (arbitrarily) for clarity, in Fig. 4 and subsequent OES gures.
Due to the difference in the concentration of the species during the
elution process, we have normalized most of the spectrum inten-
sities with respect to the Argon line intensity at 696 nm, which is
given a relative intensity value of 1.
Upon starting the argon purge, Fig. 4a shows strong emissions
of CH (B2 -X2 ) and CH (A2 -X2 ) radicals with nominal band-
heads at 387 and 431 nm respectively; and C2 radicals (d3 g -a3 a
triplet Swan band systems) with vibrational bands occurring at 473,
516 and 563 nm. These bands are characteristics of hydrocarbons
Fig. 4. Spectrum of acetonitrile at initiation of argon purge and after 15 min (red
trace). At the start of argon purging, the spectra are dominated by molecular bands
from N2 (C3 u -B3 g ) at 358 nm, CN (B2 + -X2 + ) at 387 nm, CH (B2 -X2 ) at
389 nm, CH (B2 -X2 ) at 387 nm, CH (A2 -X2 ) at 431.25 nm, C2 Swan band
(d3 g-a3 a) at 473, 516 and 563 nm (corresponding to v v 10, 00 and 01
vibrational bands, respectively), H at 656 nm (3n 2n) and Ar I [2 (3/2)0 2 {3/2)] at
696 nm. Thereafter only the Ar I line remains (blue trace). (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of
this article.)
[38]. Acetonitrile presents the additional bands of CN (B2 + -X2 + )
at 387 nm, N2 (C3 u -B3 g ) at 358 nm and H at 656 nm (3n 2n).
By means of Fig. 4 we conrmed that most of the acetonitrile
was eluted from the column after 15 min of gas purging, with
only argon Ar I [2 (3/2)0 2 {3/2)] at 696 nm being observed in the
200700 nm wavelength range. Consequently 15 min was adopted
as equilibrium time in order to separate acetonitrile from TATP in
the following experiment.
3.1. Detection of TATP diluted in acetonitrile
Initially 300 l of TATP diluted in acetonitrile (0.1 mg/1 ml) was
added to the column by means of a microsyringe and for 15 min air
was eluted into the column. This procedure aims to simulate the
sampling process that would occur in a UAV or similar platform for
detecting TATP highly diluted in air with other organic chemicals
present at higher concentrations.
Fig. 5 shows the spectra at different points of time and temper-
ature for the TATP standard solution in acetonitrile. After 15 min of
air purging (Position 1, Fig. 5a) at room temperature for the elim-
ination of the greater part of acetonitrile, argon was introduced
for some minutes in the column in order to obtain a sustained
and stable plasma discharge; and the temperature was heated
up to 85 C. Fig. 5a shows the saturated spectrum of the resid-
ual acetonitrile that was not desorbed from the column at room
temperature and subsequently eluted at 85 C. After some seconds,
the spectrum did not present any bands arising from acetoni-
trile, indicating complete solvent removal from the column. Fig. 5b
illustrates the spectrum of TATP eluted at higher temperature
(160 C); a spectrum very different from that of acetonitrile. The
most characteristic molecular bands and atomic lines of TATP
are the C2 Mulliken band system (D1 u + -X1 g + ) at 231 nm, OH
(A2 + -X2 ) at 310 nm, H atomic line at 656 nm (Fig. 5b), and
oxygen atom O I (5 P5 S0 ) line at 777 nm (Fig. 6). The presence
of the Mulliken band at 231 nm and the atomic H line at 656
that also appear in the spectrum obtained at 85 C suggests that a
portion of the TATP was eluted together with the acetonitrile at this
 J.H. Fujiyama-Novak et al. / Sensors and Actuators B 176 (2013) 985993
Fig. 5. Spectrum of (a) acetonitrile eluted from the column at 85 C and (b) TATP
collected at 160 C. The most characteristic bands and lines of TATP are the C2 Mul-
liken band (D1 u + -X1 g + ) at 231 nm, OH (A2 + -X2 ) at 310 nm and H at 656 nm.
(For interpretation of the references to spectra in this gure legend, the reader is
referred to the web version of this article.)
temperature. Spectral bands from OH (A-X), N2 (C-B), CN (B-X) and
H-atoms are indicators that some residual air and water also des-
orbed from the column at 85 C. This spectral comparison shows
a clear need for pre-separation of TATP from other organic com-
pounds and air components.
As a test for the chemical distinctiveness of the TATP spectrum
as generated by the microplasma, we carried out an analysis of the
TATP solution deposited upon a conducting backing plate as a sur-
rogate cathode for the MHGD plasma unit. Prior to the analysis the
solvent (acetonitrile) was evaporated at room temperature and the
spectrum was collected with the solid TATP microcrystals sand-
wiched between the conducting plate and the spiral disc electrode.
Fig. 7 illustrates the comparison between the spectra of solid TATP
deposited on a backing plate and the TATP vapor eluted from the
column. The main bands and lines characteristic of TATP, described
Fig. 6. Spectrum of TATP collected at 160 C (spectral range 750800 nm) with the
oxygen O I (5 P5 S0 ) line at 777 nm. (For interpretation of the references to spectra
in this gure legend, the reader is referred to the web version of this article.)
989
Fig. 7. Spectrum of TATP: (a) solid deposited upon a conducting plate and (b) vapor
eluted from the pre-concentration/separation column. (For interpretation of the ref-
erences to spectra in this gure legend, the reader is referred to the web version of
this article.)
previously, are observed in the two spectra, conrming similarity
of the MHGD environment in both batch and dynamic sampling
modes in addition to conrming that the OES plasma spectrum is
a representative TATP indicator. Moreover, the spectral similarity
suggests that no signicant chemical modication (e.g. polymer-
ization) of TATP occurred using the pre-concentration/separation
system.
The limit of detection (LOD) for TATP was determined by con-
tinuous monitoring of the TATP hydrogen H line eluted from the
column at high temperatures until there were no more character-
istic bands and lines of TATP in the spectrum. In order to clarify the
LOD calculation, an example of one of the runs is presented: dur-
ing the elution time of 150 s, more than 100 spectra were recorded.
After the baseline subtraction process, the intensity values referring
to the H atomic line at 656 nm of all spectra were summed and the
total value is 1,837,512 counts. This intensity value corresponds
to the amount of TATP added to the column (30 mg). Assuming
that TATP is an ideal gas, the volume of vaporized TATP is equal to
3.02 l. Considering 150 s as the elution time, and an average argon
ow rate of 0.75 l/min, the total volume of the carrier gas was 1.87 l.
Consequently, the total intensity detected by the spectrometer can
be correlated to the volume of TATP (3.02 l) diluted in 1.87 l of
carrier gas.
By denition [39] the limit of detection (LOD) is the lowest con-
centration level that can be determined and is typically determined
in the region where the signal to noise ratio (S/N) is greater than
5. The average noise level of the spectrometer was found to be 584
counts; therefore the LOD can be calculated by rst determining
the signal level with S/N = 5, 584 counts 5 = 2920 counts and the
volume of TATP to produce a signicant signal (VAS) according to
Eq. (1):
3.02 l 2920 count
VAS = = 0.0048 l = 4.8 nl (1)
1, 837, 512 count
990 J.H. Fujiyama-Novak et al. / Sensors and Actuators B 176 (2013) 985993
If the volume of the system was 1.875 l, the LOD for TATP will be
calculated by Eq. (2):
0.0048 l 106
LOD = = 0.0025 ppm = 2.5 ppb (2)
1, 875, 000 l
Based upon the ratio of the spectral acquisition time to the total
time required for that plus CCD readout and data display, the so-
called duty cycle is <1. Therein only a portion of the plasma signal
is acquired during each detection (i.e. spectral acquisition) cycle.
With longer sampling duration and/or shorter readout and elim-
ination of screen display during the elution time, the duty cycle
could be signicantly improved with a commensurate lowering of
the calculated detection limit to sub-ppb levels.
3.2. Detection of DNT
Commercial standards of TNT explosive are only found as a
dilute solution; therefore for the experiments described in this
report we used pure DNT as a surrogate for 2,4,6-trinitrotoluene.
2,4-Dinitrotoluene has a high boiling point (250300 C) that
exceeds the stationary phase temperature limit (275 C). Conse-
quently, to demonstrate the separation concept for the analysis
of DNT, the packing (stationary phase) of the separation col-
umn was replaced by glass wool. Prior to the analysis, 5.7 mg
of 2,4-dinitrotoluene was added to the column and immediately
thereafter connected to the plasma chamber. Argon gas was eluted
into the column at ow rate of 2 l/m and the plasma was generated
with an applied voltage of 1200 V. In order to reach higher tem-
peratures, the column and the entire gas line was wrapped with a
heating tape, thereby avoiding any condensation process in the gas
line; and the temperature was kept higher than 300 C.
Fig. 8 shows the spectra of DNT eluted at different times from
the column. The ordinate axis is linear and the spectra at different
times are labeled and offset for clarity, but otherwise are scaled
similarly, each having been normalized as described previously. At
5 s, DNT spectrum was observed with its characteristic bands from
Fig. 8. Spectra of DNT eluted from the column at 300 C at different elution times.
The spectra are dominated by molecular bands related to the C2 Mulliken band
(D1 u + -X1 g + ) at 231 nm, OH (A2 + -X2 ) at 310 nm, N2 (C3 u -B3 g ) at 337 and
358 nm, CN (B2 + -X2 + ) at 387 nm, CH (B2 -X2 ) at 389 nm, CH (B2 -X2 ) at
387 nm, CH (A2 -X2 ) at 431.25 nm, C2 Swan band (d3 g -a3 a ) at 473, 516 and
563 nm, Na I (2 P0 2 S) at 589 nm, H at 656 nm (3n 2n) and Ar I [2 (3/2)0 2 {3/2)]
at 696 nm. (For interpretation of the references to spectra in this gure legend, the
reader is referred to the web version of this article.)
C2 (d3 g -a3 a ) at 473, 516, 563 nm, CH (A2 -X2 ) at 431 nm,
CH (B2 -X2 ) at 386 nm, CN (B2 + -X2 + ) at 387 nm, N2 + (B-X) at
356 nm, NH (A3 -X3  ) at 336 nm, Na I (2 P0 2 S) at 589 nm and H
(3n 2n) line 656 nm. Afterward, these band and line intensities
decreased as seen in the spectrum recorded after 240 s from the
start of the DNT elution. After 480 s, the spectrum did not present
the CN (B-X) characteristic bands of DNT, indicating the complete
desorption of the chemical from the column. The intensity of CN
(B-X) band at 387 nm, after baseline subtraction, was used to cal-
culate the DNT LOD. During the elution time of 480 s, 430 spectra
were recorded and the calculated limit of detection (LOD) for dini-
trotoluene is 9.5 ppb. Similar comments as made with regard to the
sampling duration in connection with the TATP detection limit also
apply to the calculated LOD for DNT.
3.3. Effect of the seawater in the detection of TATP
In plasma emission spectroscopy, radiative emission species is
directly related to the electron energy distribution and metastables
that promote molecular dissociation and fragment electronic exci-
tation. The presence of different species has the potential to affect
these dominant plasma processes, thereby modifying the dissoci-
ation and excitation process of the main analyte. For detection in
the eld, such as by unmanned aerial vehicles (UAV) in maritime
airspace, it is relevant to evaluate the effect of sodium chloride in
the dissociation process of TATP and verify if the salt can interfere
with the quantication of the explosive.
Initially we placed a slight quantity of NaCl on the copper back-
ing plate; a spectrum of this compound is shown in Fig. 9. It is
characterized by means of an intense emission line of sodium D
(the current spectral resolution did not permit resolution of the
familiar doublet pair). Additionally, a few excited species such as
OH (A-X) generated from air contaminants are present in the spec-
trum. It is quite possible that some water vapor may have been
retained upon the MHGD chamber walls although it was initially
purged with argon for 10 min.
To better simulate the detection of TATP in a maritime airspace,
replicated seawater (3.5 wt.% NaCl in water) drops were placed on
a backing plate. Just as with electronegative compounds, easily
Fig. 9. Emission spectrum of sodium chloride (NaCl), Na I (2 P0 2 S) at 589 nm and
Ar I [2 (3/2)0 2 {3/2)] at 696 nm with the OH (A2 + -X2 ) at 310 nm generated from
water vapor. (For interpretation of the references to spectra in this gure legend,
the reader is referred to the web version of this article.)
 J.H. Fujiyama-Novak et al. / Sensors and Actuators B 176 (2013) 985993
Fig. 10. Emission spectra of NaCl and TATP: (a) backing plate with dried seawater
only; (b) TATP eluted from the column at 160 C and the backing plate loaded with
the dried seawater; and (c) TATP eluted from the column at 160 C. (For interpreta-
tion of the references to spectra in this gure legend, the reader is referred to the
web version of this article.)
ionized materials such as alkali elements can substantially alter
the plasma characteristics and stability. Prior to the analysis, the
system was heated on a hot plate to evaporate the water and form
NaCl microcrystals upon the backing plate. This backing plate was
placed against the spiral disk electrode in the MHGD chamber.
Next, 300 l of TATP standard solution was added to the devel-
oped pre-concentration/separation system packed with HayeSep
Q and connected to the chamber. For 15 min dried air was eluted
into the column, removing the solvent and thereafter the air was
replaced by argon gas at an initial ow rate of 1 l/min. Shortly
thereafter, the column was immersed into a silicone oil bath at
160 C with the plasma generated using an applied voltage of
1.1 kV.
Fig. 10 shows the spectrum of (a) backing plate with dried sea-
water, (b) TATP eluted from the column at 160 C and the backing
plate loaded with the dried seawater, (c) TATP eluted from the col-
umn at 160 C. It is clear that the spectra of TATP in the presence
or absence of salt are similar. It was found that the intensity of
some bands and lines were slightly modied due to the presence
of additional compound NaCl. However, the main radical emission
bands and atomic lines characteristic of TATP, the C2 Muliken band
at 231 nm, H (I) line at 656 nm and O I line at 777 nm (not shown in
Fig. 10) are well pronounced.
In the spectrum of NaCl (Fig. 10a), there is a minor hydrogen
line emission that is most probably generated from physisorbed
water in the surrogate seawater sample. The H atomic line
intensity at 656 nm is used for the limit of detection of TATP,
and we concluded that water would present a signicant spec-
tral interference for the detection of this explosive without
pre-separation.
On the other hand, our pre-concentration/separation column
allows the initial elution of water at a temperature of 100 C,
and at modestly higher temperatures TATP leaves the column. In
real environments the salt would be retained by the stationary
phase, thereby afrming that TATP can be separately character-
ized, without the water H-atom interference arising from water.
As illustrated in Fig. 9, the Na I line is emitted at 589 nm and
991
therefore did not interfere with the characteristic bands and lines
of TATP.
The limit of detection (LOD) for TATP in the presence of sea-
water was determined by continuous monitoring of TATP eluted
from the column at high temperatures until there were no more
characteristic lines or bands of TATP in the spectrum. During the
elution time of 120 s, 104 spectra were recorded. A detection limit
of 2.2 ppb (v/v) for TATP could be achieved.
4. Discussion
In the MHGD, a few hundred volts applied across the electrodes
cause breakdown of the gas and formation of energetic ions, elec-
trons and other species. In a traditional glow discharge, positive
ions are accelerated across the cathode dark space and collide with
the cathode surface, resulting in physical sputtering. In this man-
ner, the sample is atomized and introduced into the discharge. As
the sputtered atoms diffuse into the negative glow, they may be
ionized by electron impact and Penning ionization. Use of a noble
gas can enhance these effects. Our use of the backing plate as sur-
rogate cathode mimics this conguration while the open-hollow is
rather different.
In either conguration the key to plasma analysis in general
and the proposed MHGD in particular is that the atomic emission
serves to identify the sample composition [40]. As it is not in ther-
mal equilibrium but relatively cold [41], the emission features
are correspondingly narrow, aiding identication and selectivity.
The low electron densities and energies within the negative glow
region result in minimal Bremstrahlung continuum background
while providing high signal-to-noise.
The combination of sample atomization and electronic exci-
tation is a powerful combination for direct solids analysis or
deposited particulate, as demonstrated. In fact this approach is
used commercially where the plasma provides sample atomiza-
tion for subsequent analysis by mass spectrometer [42]. In this
approach a particular advantage of the MHGD is the immunity
to sample spatial/geographic uniformity and quantity. Spatially
inhomogeneous deposition is entirely acceptable with precollec-
tion. Other sensor approaches for detecting explosive vapors have
relied upon spectrometric methods and ion detection methods
[43]. Spectrometric (in situ gas-phase) methods such as multi-pass
infrared absorption or cavity ring-down spectroscopy achieve high
sensitivity (ppm or ppb levels respectively), by selective detec-
tion of NO2 stretching modes. Such approaches however lose
selectivity by targeting specic functional groups. Ion mobility
methods have been rated for minimal mass of detectable mate-
rial, picogram or lower for TATP, but not concentration. Moreover
denitive detection requires an additional mass spectrometer with
the added equipment complexity, power and operational burden.
A pre-concentration system as illustrated here adds additional
degrees of freedom to achieve selectivity and sensitivity. Coupling
with the MHGD links the pre-concentrators sensitivity gain with
micro-plasma eld portability and optical emission spectroscopy
selectivity.
The present system serves as proof-of-concept for a miniatur-
ized system to be on-board a UAV. The present system response was
on the order of several tens of seconds. Suitable scaling to a micro-
capillary as the concentration column will reduce this sampling
time interval to a sub-second scale, thereby permitting pseudo real-
time analysis. In addition to the determination of organic vapors,
the detector is also applicable to the analysis of solids and aerosols
in a static-sampling mode. We project that the detection sensitivity
of the explosives using the described technique can be improved
by increasing the duty cycle of the detector, using a more efcient
992 J.H. Fujiyama-Novak et al. / Sensors and Actuators B 176 (2013) 985993
column heat exchanger and applying an automated system for the
interchange of gas ows.
5. Conclusion
Based on our studies we developed a new technique for the
detection of explosives such as TATP and DNT by means of
micro-hollow glow discharge (MHGD) plasma spectroscopy. A pre-
concentration column that in parallel separates the air-component
gases and low-boiling point solvents from the explosives allows
the detection of the compounds of interest in trace levels. The limit
of detection achieved for DNT is 9.5 ppb and for TATP is 2.3 ppb
(v/v). The miniaturized system is well suited for explosive detection
in unmanned aerial vehicles (UAVs) due to its small size, demon-
strated high sensitivity and specicity for these two explosives
within air maritime environments.
Acknowledgment
The work was supported through a Phase II STTR with the U.S.
Navy Naval Air Warfare Center (NAVAIR), Contract No. N68335-08-
C-0020.
References
[1] R.L. Woodn (Ed.), Trace Chemical Sensing of Explosives, Wiley, New York,
2007.
[2] E. Ehrentreich-Forster, D. Orgel, A. Krause-Griep, B. Cech, V.A. Erdmann, F. Bier,
F.W. Scheller, M. Rimmele, Biosensor-based on-site explosives detection using
aptamers as recognition elements, Analytical and Bioanalytical Chemistry 391
(2008) 17931800.
[3] Q. Lu, G.E. Collins, M. Smith, J. Wang, Sensitive capillary electrophoresis
microchip determination of trinitroaromatic explosives in nonaqueous elec-
trolyte following solid phase extraction, Analytica Chimica Acta 469 (2002)
253260.
[4] J. Wang, S. Thongnamdee, On-line electrochemical monitoring of (TNT) 2,4,6
trinitrotoluene in natural waters, Analytica Chimica Acta 485 (2003) 139144.
[5] K. Masunaga, K. Hayama, T. Onodera, K. Hayashi, N. Miura, K. Matsumoto,
K. Toko, Detection of aromatic nitro compounds with electrode polarization
controlling sensor, Sensors and Actuators B 108 (2005) 427434.
[6] M.E. Walsh, Determination of nitroaromatic, nitramine, and nitrate ester explo-
sives in soil by gas chromatography and an electron capture detector, Talanta
54 (2001) 427438.
[7] R. Batlle, H. Carlsson, P. Tolback, A. Colmsjo, C.J. Crescenzi, Enhanced detection
of nitroaromatic explosive vapors combining solid-phase extraction-air samp-
ling supercritical uid extraction, and large-volume injection-GC, Analytical
Chemistry 75 (2003) 31373144.
[8] R. Batlle, H. Carlsson, E. Holmgren, A. Colmsjo, C.J. Crescenzi, On-line coupling
of supercritical uid extraction with high-performance liquid chromatography
for the determination of explosives in vapour phases, Journal of Chromatogra-
phy A 963 (2002) 7382.
[9] S.A. McLuckey, G.L. Gush, K.G. Asano, Coupling of an atmospheric-sampling ion
source with an ion-trap mass spectrometer, Analytica Chimica Acta 225 (1989)
2535.
[10] S. Boumsellek, S.H. Alajajian, A. Chutjian, Negative-ion formation in the explo-
sives RDX PETN, and TNT by using the reversal electron attachment detection
technique, Journal of the American Society for Mass Spectrometry 3 (1992)
243247.
[11] A.J. McCormack, S.C. Tong, W.D. Cooke, Sensitive selective gas chromatography
detector based on emission spectrometry of organic compounds, Analytical
Chemistry 37 (1965) 14701476.
[12] J.C.T. Eijkel, H. Stoeri, A. Manz, A molecular emission detector on a chip employ-
ing a direct current microplasma, Analytical Chemistry 72 (2000) 25472552.
[13] Z. Jin, Y. Su, Y. Duan, A low-power atmospheric pressure, pulsed plasma source
for molecular emission spectrometry, Analytical Chemistry 73 (2001) 360365.
[14] R. Pereiro, T.K. Starn, G.M. Hieftje, Gas-sampling glow discharge for optical
emission spectrometry. Part II: Optimization and evaluation for the determi-
nation of nonmetals in gas-phase samples, Applied Spectroscopy 49 (1995)
616622.
[15] J.C.T. Eijkel, H. Stoeri, A. Manz, A molecular emission detector on a chip employ-
ing a direct current microplasma, Analytical Chemistry 71 (1999) 26002606.
[16] M. Miclea, K. Kunze, U. Heitmann, S. Florek, J. Franzke, K. Niemax, Diagnostics
and application of the microhollow cathode discharge as an analytical plasma,
Journal of Physics D 38 (2005) 17091715.
[17] M. Miclea, K. Kunze, J. Franzke, K. Niemax, Plasmas for lab-on-chip applications,
Spectrochimica Acta, Part B 57 (2002) 15851592.
[18] B. Mitra, Y.B. Gianchandani, The detection of chemical vapors in air using
optical emission spectroscopy of pulsed microdischarges from two- and three-
electrode microstructures, IEEE Sensors Journal 8 (2008) 14451454.
[19] C. Meyer, R. Heming, E.L. Gurevich, U. Marggraf, M. Oksuss, S. Florek, J. Franzke,
Radiofrequency driven and low cost fabricated microhollow cathode discharge
for gaseous and atomic emission spectroscopy, Journal of Analytical Atomic
Spectrometry 26 (2011) 505510.
[20] S.D. Anghel, A. Simon, T. Frentiu, Spectroscopic investigations on a low power
atmospheric pressure capacitively coupled helium plasma, Plasma Sources Sci-
ence and Technology 17 (2008) 045016.
[21] R. Brandeburg, J. Ehlbeck, M. Stieber, T. Woedtke, J. Zeymer, O. Schluter, K.-D.
Weltmann, Antimicrobial treatment of heat sensitive materials by means of
atmospheric pressure RF-driven plasma jet, Contributions to Plasma Physics
47 (2007) 7279.
[22] I.E. Kieft, E.P.v.d. Lann, E. Stoffels, Electrical and optical characterization of the
plasma needle, New Journal of Physics 6 (2004) 149.
[23] R. Rahul, O. Stan, A. Rahman, E. Littleeld, K. Hoshimiya, A.P. Yalin, A. Sharma,
A. Pruden, C.A. Moore, Z. Yu, G.J. Collins, R.F. Optical, electrical characteristics
of atmospheric pressure open-air hollow slot microplasmas and application
to bacterial inactivation, Journal of Physics D: Applied Physics 38 (2005)
17501759.
[24] F.G. Bessoth, P. Naji, J.C.T. Eijkel, A. Manz, Towards an on-chip gas chromato-
graph: the development of a gas injector and a dc plasma emission detector,
Journal of Analytical Atomic Spectrometry 17 (2002) 794799.
[25] Y. Duan, Y. Su, Z. Jin, Capillary-discharge-based portable detector for chemical
vapor monitoring, Review of Scientic Instruments 74 (2003) 28112816.
[26] K. Kunze, M. Michlea, J. Franzke, K. Niemax, The dielectric barrier dischargea
powerful microchip plasma for diode laser spectrometry, Spectrochimica Acta,
Part B 58 (2003) 14351443.
[27] R. Guchardi, P.C. Hauser, Capacitively coupled microplasma for on-column
detection of chromatographically separated inorganic gases by optical emission
spectrometry, Journal of Chromatography A 1033 (2004) 333338.
[28] M. Miclea, M. Okruss, K. Kunze, N. Ahlman, J. Franzke, Microplasma-based
atomic emission detectors for gas chromatography, Analytical and Bioanalyt-
ical Chemistry 388 (2007) 15651572.
[29] K.H. Schoenbach, R. Verhappen, T. Tessnow, F.E. Peterkin, W.W. Byszewski,
Microhollow cathode discharges, Applied Physics Letters 68 (1996) 1315.
[30] A. E-Habachi, K.H. Schoenbach, Generation of intense excimer radiation from
high-pressure hollow cathode discharges, Applied Physics Letters 73 (1998)
885887.
[31] R.H. Stark, K.H. Schoenbach, Direct current glow discharges in atmospheric air,
Applied Physics Letters 74 (1999) 37703773.
[32] M.J. Kushner, Modeling of microdischarge devices: plasma and gas dynamics,
Journal of Physics D 38 (2005) 16331643.
[33] P. Naughton, TATP is suicide bombers weapon of choice, Times Online July 15
(2005).
[34] M. Townsend, The real story of 7/7, The Observer May 7 (2006).
[35] J.C. Oxley, J.L. Smith, K. Shinde, J. Moran, Determination of the vapor den-
sity of triacetone triperoxide (TATP) using a gas chromatography headspace
technique, Propellants Explosives Pyrotechnics 30 (2005) 127130.
[36] D. Muller, A. Levy, R. Shelef, S. Abramovich-Bar, D. Sonereld, T. Tamiri,
Improved method for the detection of TATP after explosion, Journal of Forensic
Science 49 (2004) 935938.
[37] L. Widmer, S. Watson, K. Schlater, A. Crowson, Development of an LC/MS
method for the trace analysis of triacetone triperoxide (TATP), Analyst 127
(2002) 16271632.
[38] J. Luque, W. Juchmann, E.A. Brinkman, J.B. Jeffries, Excited state density distri-
butions of H, C, C2 , and CH by spatially resolved optical emission in a diamond
depositing dc-arcjet reactor, Journal of Vacuum Science and Technology A 16
(1998) 397408.
[39] Analytical Detection Limit Guidance & Laboratory Guide for Determin-
ing Method Detection Limits, PUBL-TS-056-96, p. 5, http://dnr.wi.gov/org/
es/science/lc/outreach/-publications/lod%20guidance%20document.pdf
[40] R.K. Marcus, Glow Discharge Spectroscopies, Plenum Press Inc., New York, NY,
1993.
[41] K.H. Becker, K.H. Shoenbach, J.G. Eden, Microplasmas, Applications, Journal of
Physics D 39 (2006) R55R70.
[42] R.K. Marcus, M.A. Dempster, T.E. Gibeau, E.M. Reynolds, Sampling and analysis
of particulate matter by glow discharge atomic emission and mass spectrome-
tries, Analytical Chemistry 71 (1999) 30613069.
[43] D.S. Moore, Instrumentation for trace detection of high explosives, Review of
Scientic Instruments 75 (2004) 24992512.
Biographies
Jane Hitomi Fujiyama-Novak received a Ph.D. in polymer engineering at the Uni-
versity of Akron and has a M.S. degree in chemical engineering. She worked as a
research associate for 5 years in polyolen characterization and product develop-
ment. She contributed to the development of re sensors for space exploration and
new coatings for PSP technology at NASA-Glenn Research Center. In the EMS Energy
Institute at the Penn State University, her interests included the synthesis and char-
acterization of nanocarbon-based materials, catalysts, composites, adsorbents and
lubricants as well as the development of atmospheric pressure plasma for optical
diagnostics and analytical applications.
 J.H. Fujiyama-Novak et al. / Sensors and Actuators B 176 (2013) 985993
Chethan Kumar Gaddam was born in Warangal, Andhra Pradesh, India and obtained
his bachelors degree in Chemical Engineering from Osmania University. He began
his research career at Penn State in The Dept. of Energy & Mineral Engineering, study-
ing plasma science under the direction of Dr. Randy Vander Wal. His other interests
include developing plasma sources and processes for surface functionalization of
nanostructures, synthesis of nanostructures and nanoparticles.
Debanjan Das is presently a graduate student at Penn State University in the Dept.
of Energy and Mineral Engineering.
Dr. Randy L. Vander Wal leads a research group with projects in catalysis, energy
storage, tribology & lubrication, sensors and plasma development for analytical
applications. These have included vapor detection, aerosol and liquids analysis
and most recently demonstration of lunar simulant analysis. His other research
993
interests include laser-material interactions for annealing and SERS. Prior programs
have included HRTEM & XPS characterization of aerosols and development of laser-
based diagnostics such as DFWM and LII. He holds a Ph.D. in Physical Chemistry and
has worked at Sandia National Labs and NASA prior to Penn State.
Dr. Benjamin Ward is the senior engineer in charge of sensor development at
Makel Engineering, Inc. (MEI); he has overseen ongoing development efforts in gas
microsensors, microreactors, and system integration targeting aerospace, automo-
tive, and power generation applications in particular. Synergistic activities at MEI
include the development of gas and uid sensors incorporating MEMS processing
and chemically sensitive nanomaterials, smart systems with integrated sen-
sors, and highly efcient microreactors incorporating novel catalysts and reaction
schemes.