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Manuscript_630d5da4c87736ea2a20717fb6b9ee39

Headspace Analysis of Potassium Chlorate using On-Fiber SPME

Derivatization Coupled with GC/MS
Janet M. Crespo Cajigas1, Luis Perez-Almodovar1, Lauryn E. DeGreeff2*,

1University of Puerto Rico, PR-108, Mayaguez, P.R. 00682; 2Chemistry Division, U.S. Naval
Research Laboratory; 4555 Overlook Ave. SW, Washington, D.C. 20375
*Corresponding author:
Dr. Lauryn E. DeGreeff
U.S. Naval Research Laboratory
4555 Overlook Ave. SW
Washington D.C. 20375
P: (202)767-4256
F: (202)767-1716
lauryn.degreeff@nrl.navy.mil

Abstract
Potassium chlorate is a powerful oxidizer salt that, when mixed with a fuel source, has been used
as a homemade explosive (HME). As an inorganic salt, potassium chlorate has no appreciable
vapor pressure under ambient conditions and requires temperatures exceeding 300 °C for
decomposition. However, detection of potassium chlorate by trained canines has been
demonstrated, implying that it exudes a vapor signature with one or more volatile compounds,
although no such species have been confirmed to date. In this work, solid-phase microextraction
with a novel on-fiber derivatization reaction was used to interrogate the headspace of several
potassium chlorate samples of varying purity, as well as that of related chlorinated salts and
explosive mixtures. This analysis showed the presence of few volatile species in the headspace
of potassium chlorate other than vaporous chlorine, detected as the derivatized product, chloro-2-
propanol. Relative amounts of chloro-2-propanol could be compared between potassium chlorate
variants, and could be detected in the presence of other volatile species associated with the fuels.

Keywords
Solid phase microextraction, on-fiber derivatization, homemade explosives, potassium chlorate,
chlorine detection

Introduction
Over the last two decades the availability of military and commercial explosives for illicit
purposes has diminished due to increased security worldwide, as well as depletion of unsecured
reserves of munitions in the Middle East. At the same time, access to the internet has given
potential hobbyists and terrorists an endless amount of information on formulation and synthesis
of homemade explosives (HMEs). Furthermore, many HMEs are relatively simple mixtures of
oxidizer and fuel, many of which can be derived from commercial products. These factors have
led to an increased number of HME-related incidents over this period [1]. Unfortunately, there

© 2019 published by Elsevier. This manuscript is made available under the Elsevier user license
https://www.elsevier.com/open-access/userlicense/1.0/
has not been a proportionate increase in fundamental research on such materials, hindering
development of new approaches for detection of HMEs. As a result, detection methods are still
not as numerous or robust as those found for traditional explosives [2], such as TNT. In this
work, a new analytical method to examine the headspace of chlorine was developed, and will be
described herein, detailing its use in analyzing the headspace of potassium chlorate, a compound
used in HME formulation.

Potassium chlorate is a powerful oxidizer commercially available in pyrotechnics and certain

household products. Currently, there are no known methods of vapor detection for potassium
chlorate, outside of canine detectors. Detection is challenging as it is an inorganic salt with no
appreciable vapor pressure, and unlike ammonium nitrate, another known HME oxidizer, it is not
known to readily dissociate producing vaporous products under normal ambient conditions [3,
4]. Nevertheless, Lazarowski and Dorman [5] showed that trained canines can reliably find
potassium chlorate alone and in mixtures with fuels suggesting the presence of some associated
volatile compounds composing the odor. It is generally assumed that canines detect such low
volatility compounds via associated volatile compounds, known as the vapor signature, that are
attributable to manufacture byproducts or decomposition of the materials. This is known to occur
with other low volatility compounds, such as with explosives like RDX (1,3,5-Trinitro-1,3,5-
triazinane), or with narcotics like cocaine, both of which exude characteristic vapor signatures
that canines are able to detect as a proxy for the target material [6, 7]. A similar strategy could
be used for instrumental vapor detection where the detector is tuned to identify associated
vaporous compounds available at a higher abundance than the lower-volatility parent molecule.

Though the literature to date has not identified any headspace products from potassium chlorate
salt, we hypothesize chlorine as a suspected headspace component based on preliminary research
by Steven and Glover [8], where chlorine was detected in the headspace of potassium chlorate
using selected ion flow tube - mass spectroscopy (SIFT-MS). Chlorine, however, is not
amenable to either solid phase microextraction (SPME) or gas chromatography / mass
spectrometry (GC/MS), though these techniques are generally the primary tools in the
characterization of vapor signatures. In order to allow characterization of the chlorine content of
chlorate salt headspaces, a method for derivatization of chlorine gas to a SPME and GC-
amenable species was required.
While the authors are unaware of a previously reported standard procedure for derivatization of
chlorine for GC analysis, a method has been reported by Esposito, et al. for the analysis of
ethylene oxide (EtO) by GC using sampling tubes containing charcoal coated with hydrobromic
acid (HBr) [9]. In this method EtO reacts with HBr to produce 2-bromoethanol. Later, Tsai, et
al. [10] published a method adapting this derivatization reaction to SPME, a static sampling
technique, with analysis by GC/MS. This method utilized a technique called sequential, on-fiber
derivatization where the SPME fiber was first exposed to the derivatizing agent, HBr, then
exposed the analyte of interest, EtO. The product, 2-bromoethanol, was then formed on the fiber
and desorbed for subsequent analysis by GC/MS.
The authors implemented a similar reaction in reverse using propylene oxide in place of ethylene
oxide, which is a gas at room temperature and highly toxic. The resulting reaction, given in
Figure 1, uses propylene oxide as the derivatizing agent for available chloride, yielding chloro-2-
propanol. This product is easily extracted and detected by SPME-GC/MS.

It was hypothesized that, should chlorine be present in the headspace of solid potassium chlorate,
it could be measured using sequential on-fiber derivatization with propylene oxide as the
derivatizing agent. Using this method, the headspace of potassium chlorate was interrogated for
the presence of chloride, from vaporous HCl or Cl2 with ambient water, in addition to other
volatile species comprising the vapor signature of potassium chlorate. This technique was used to
measure relative quantities of chloride present from several sources of potassium chlorate,
related salts, and potassium chlorate-based homemade explosives.

Material and Methods

Materials
The headspaces of potassium chlorate salts as well as related chlorine salts were analyzed.
“Laboratory-grade” potassium chlorate, potassium chloride, potassium perchlorate, and sodium
chlorate were purchased from Millipore Sigma and were at least 99% pure. Additional
“industrial-grade” potassium chlorate was purchased from a pyrotechnic chemical supply
company (Skylighter) containing 0.2% anti-caking agent (undefined by manufacturer).
“Clandestine” potassium chlorate was harvested from matchstick heads (Diamond Greenlight
Strike-on-the-Box Matches) using a clandestine method described elsewhere [11]. The
derivatizing agent, propylene oxide (≥99.5%), and the internal standard, 1-octanol (≥99%), were
both purchased from Millipore Sigma.
The headspaces of potassium chlorate explosive mixtures were also analyzed. These included
the industrial-grade potassium chlorate mixed with petroleum jelly or vegetable oil (purchased
from local supermarket).

Explosive handling
WARNING! Potassium chlorate mixed with a fuel source can be an explosive hazard. Proper
handling, storage, and disposal precautions should be taken. Mixtures were prepared in static
dissipative vials using wooden spatulas for stirring. The vials were then placed in a headspace-
sampling chamber developed by the U.S. Naval Research Laboratory for explosives testing [12].
All preparation and testing took place behind Explosive Personnel Shields (certified to a net
explosives weight of 10.0 g). All extraction and analysis procedures were the same as that used
for the other samples, and will be discussed below.

Headspace Extraction
The presence of chlorine in the headspace of potassium chlorate was investigated using on-fiber
SPME derivatization by propylene oxide to produce chloro-2-propanol. For the sequential on-
fiber derivatization followed by externally sampled internal standard, 2.0 mL of the derivatizing
agent, propylene oxide, and the internal standard, 1-octanol, were deposited into separate vials,
and were allowed to equilibrate for a minimum of 1 hr.

To first test the derivatization mechanism and subsequent extraction and detection methods,
fibers containing the derivatizing agent were exposed to a source of pure chlorine vapor. For this
purpose a chlorine vapor permeation tube certified to 29 ng/L at 40 °C was purchased from KIN-
TEK Analytical, Inc. The tube was placed in a FlexStream Modular Gas Standards Generator
oven (KIN-TEK Analytical, Inc.) set to 40 °C. The vapor from the permeation tube was diluted
with clean and dry house air at a flow rate of 1 L/min. 1 L of the dilute chlorine mixture was
collected into a 1 L Tedlar Air Sample Bag (SKC Inc.) with a single polypropylene fitting (SKC
Inc.) resulting in a chlorine vapor concentration of 29 ng/L in the bag. Headspace extraction was
carried out using PDMS/DVB/CAR SPME fibers (1 cm length, 50/30 µm thickness, Millipore
Sigma). Fibers were first inserted into the headspace of the propylene oxide vials for 15 s. They
were then removed and inserted through the septa in the Tedlar bag fitting for an extraction time
of one hour. Extraction took place immediately after the bag was filled, as to minimize loss of
chlorine through the Tedlar bag. Separate, clean Tedlar bags were also filled with clean room air
and clean air from the permeation tube oven for comparisons and measurement of the chlorine in
the background.

To prepare the potassium chlorate samples, 4.0 g of potassium chlorate (laboratory-grade,

industrial-grade, clandestine), or related salts was placed into individual 20 mL headspace vials
with septa (Headspace Screw-Tread Vials, 18 mm; Restek Co.). All samples were allowed to
equilibrate in the closed vials for a minimum of 24 hours under ambient conditions. All samples
were prepared in replicates of five including blank vials. Headspace extraction was again carried
out using PDMS/DVB/CAR SPME fibers. After the fibers were exposed to the propylene oxide
derivatizing agent, they were then removed and reinserted into the headspace of the sample vials
for a given amount of time. Extraction times ranging from 30 min to 17 hours were tested.
Finally, the fibers were exposed to the headspace of the internal standard for 5 seconds. Chlorine
vapor data was reported as the ratio of the peak area of derivatized chlorine (chloro-2-propanol)
to the peak area of the internal standard (1-octanol).
The internal standard was sampled sequentially on-fiber in a manner similar to the derivatizing
agent. This method of an externally sampled internal standard (ESIS) was first published by
MacCrehan et. al. and was shown to improve reproducibility of replicate measurements by an
order of magnitude. The use of an ESIS minimizes the effects of fiber-to-fiber variation, fiber
deterioration, and instrument drift, each of which can result in poor reproducibility and an
inability to make equitable comparisons between multiple sample sets [13]. Similar to this
research, Lubrano et. al. combined sequential on-fiber derivatization with an externally sampled
internal standard, and also showed improvements in reproducibility [14].
For the explosives samples, the mixtures were prepared in the static dissipative vials and were
left to equilibrate open in the sealed headspace sampling chamber for 24 hours. Following
equilibration, the orifice atop of the sampling chamber was opened and the SPME fiber was
immediately inserted through the top of the chamber, placing the fiber immediately above the
open vial. The sampling and derivatization methods remained the same with an equilibration
time of 17 hours.

Instrument Analysis
For analysis, fibers were thermally desorbed in the inlet of a gas chromatograph (GC; Agilent
6890; Agilent Technologies) for 4 min at 260 oC. Propylene oxide was discovered to remain
absorbed to the SPME fibers even after 4 minutes of thermal desorption. As such, following
desorption of the analytes, the fibers were inserted into 1.5 mL of methanol for 30 seconds and
baked for three minutes in the GC inlet at 260 oC. This process was repeated twice for each fiber
to ensure complete removal of residual propylene oxide. As methanol is water-soluble organic
solvent, no or minimal additional wear to the SPME fiber was noted due to the cleaning process.

Separation occurred on a “Rtx-Volatile Amine” capillary column (30 m, 0.32 mm I.D., Restek;
Bellefonte, PA) at a flow rate of 2 mL/min and a split ratio of 10:1. Oven temperature started at
35 °C (held for 0.50 min) and increased to 240 °C (held for 3.0 min) at 40 °C/min. Analytes were
detected by an Agilent 5975 mass selective detector (MS; Agilent Technologies). The MS
source was maintained at 230 ºC and the scan range was (m/z 30-300).

Results and Discussion

Results from the preliminary proof-of-concept experiment to test the derivatization and
extraction method using a standard chlorine vapor mixture (prepared in Tedlar bag as described
above) are given in Figure 2 as the extracted ion chromatogram for the m/z 45 ion. The chloro-2-
propanol peak was identified by the NIST Mass Spectral Library and confirmed by comparison
to a chloro-2-propanol standard. Chlorine was detected at low levels in both the Tedlar bag and
the permeation tube oven; however, the amount of chlorine recovered from the chlorine vapor
sample was notably much greater.
Headspace analysis of the three potassium chlorate variants, laboratory-, industrial-, and
clandestine-grades, were compared prior to addition of derivatizing agent in Figure 3. The only
major contributor to the headspace of any sample was acetic acid found solely in the clandestine
sample. While the source of the acetic acid is unknown, it is likely attributable to the breakdown
of the wood in match tips used in preparation of the clandestine-grade material. Low levels of
additional volatile species, likely impurities from packaging or manufacturing, were detected and
are listed in Table 1.
Table 1. Headspace components detected above three potassium chlorate variants, industrial-grade, laboratory-grade, and
clandestine, without derivatizing agents.
Industrial
Lab Grade Clandestine
Headspace component: Grade
Methoxy-2-propanol acetate x
Nonanal x x
Carbon disulfide x
Acetid Acid x
Methoxy-phenyl-oxime x
Acetamine x
Triethylamine x
Hexanal x

Preliminary analyses were conducted with the industrial-grade potassium chlorate using the
sequential on-fiber derivatization method, demonstrating the successful derivatization of chlorine
product in the sample (Figure 4). In addition to chlorine, the sample was discovered to contain
unanticipated amounts of bromine, detected as bromo-2-propanol. Chloro-2-propanol eluted at a
retention time of 3.9 min and bromo-2-propanol eluted at 4.5 min.
Peak area was examined as a function of fiber exposure time to determine optimal extraction
time (Figure 5). A small quantity of chloro-2-propanol was identified above the blanks, but this
was significantly lower than that found above the potassium chlorate samples. It did not appear
that equilibrium was reached even after an overnight extraction. For this reason, the maximum
extraction time of 17 hours was chosen for future analyses. The long SPME equilibration time
could be due to the low level of chlorine present or the rate of the mechanism producing the
chlorine, or a combination of both.

The amount of chlorine in the headspace of each potassium chlorate variant, as well as related
chlorine salts, were compared using a ratio of the chloro-2-propanol peak area over the peak area
of 1-octanol, the internal standard (Figure 6). All potassium chlorate samples had significantly
more chlorine than the blank vials (Figure 6A; one-tailed t-test, 99+ % confidence). The
industrial-grade sample was found to contain the greatest amount of chlorine in its headspace,
followed by clandestine, and then laboratory-grade. The differences in quantity of chlorine
measured from the three sources was likely due to differing purities and surface area, with the
laboratory-grade being the most pure and the clandestine having the lowest surface area (due to
imperfect grinding of the material). Interestingly, when measuring the chlorine above other
chlorinated-salt samples, only the potassium chlorate was statistically greater than the blank
(Figure 6B). While there does appear to be less chlorine in the sodium chlorate sample compared
to the blank, this difference was not statistically significant, though it could be due to
sequestration of the background chlorine by the solid salt sample. As the mechanism for chlorine
production from potassium chlorine is currently unknown, it is also not known why significantly
more chlorine is present in the headspace of potassium chlorate than other related salts.

Finally, Figure 7 gives chromatograms of the headspace above two potassium chlorate-based
explosives. Figure 7A depicts potassium chlorate mixed with vegetable oil. The derivatized
chlorine, chloro-2-propanol, can be identified at approximately 3.9 min (see m/z 45 extracted ion
trace), in addition to many volatiles associated with the vegetable oil. The C6-C10 aldehyde
series associated with the vegetable oil [15] and labelled in the figure can be detected with no
inference from the derivatizing agent. Likewise, Figure 7B includes the chromatogram of the
headspace from potassium chlorate mixed with petroleum jelly. Again, chloro-2-propanol is
detected at approximately 3.9 min (as shown in the m/z 45 extracted ion trace) in addition to
phenyl ethyl alcohol, a common volatile associated with the odor of petroleum jelly.

Conclusions
Potassium chlorate is not expected to decompose in temperatures under 356 °C [4], and to this
date no headspace components have been confirmed that could be utilized for vapor detection.
However, the novel derivatization method described here was shown to enable characterization
of halogen content in the headspace of potassium chlorate and other salts by SPME-GC/MS.
With the use of on-fiber derivatization, chlorine, as well as bromine, was detected at different
levels in the headspace of several variants of potassium chlorate, but not related chlorinated salts.
Additionally, chlorine was detected in potassium chlorate – based explosive mixtures at the same
time as other, underivatizated volatile species associated with the fuels.

The described analytical approach can be applied in future research to elucidate the species and
origin of chlorine in the headspace of potassium chlorate, and, in turn, potentially exploit this for
detection purposes. Results from this study have potential applications that include improving
non-contact vapor detection of low vapor pressure explosive and chemicals as well as
implications for canine detection.

Acknowledgements
The authors would like to acknowledge the Office of Naval Research for the funding for this
research, as well as the Naval Research Laboratory’s NREIP and HBCU-MI summer internship
programs. The authors would also like to thank Christopher Katilie and Dr. Alison Simon for
their assistance and input on this project.

References
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[13]
MacCrehan, W. Moore, S. Schantz, M. Evaluating headspace component vapor-time profiles by
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Figure captions:
Figure 1. Derivatization of chloride by propylene oxide yielding chloro-2-propanol.
Figure 2. Extracted ion chromatogram for m/z 45 for three samples; diluted chlorine vapor (Cl2),
Tedlar bag blank, and permeation oven and Tedlar bag blank. The chloro-2-propanol peak is found
at 3.98 min.
Figure 3. Reproduced chromatograms representing the headspace of three potassium chlorate (PC)
variants, industrial-grade, laboratory-grade, and clandestine, without derivatizing agent.
Figure 4. Total ion chromatogram of industrial-grade potassium chlorate headspace with
propylene oxide derivatizing agent. Inset chromatogram shows the extracted ion, m/z 45,
indicating the presence of derivatized chlorine and bromine in the sample headspace.
Figure 5. Amount of derivatized chlorine (chloro-2-propanol) measured above industrial-grade
potassium chlorate (PC) using varying SPME extraction times. Note. Error bars equal one
standard deviation of the average value of at least three replicates; some error bars are within the
size of the marker.
Figure 6. Relative amount of chlorine detected in the form of the derivatized product chloro-2-
propanol from (A) potassium chlorate samples and (B) related laboratory-grade chlorinated salts.
The relative abundance of chlorine in the headspace is measured as the chloro-2-propanol peak
area divided by the peak area of the externally sampled internal standard (A/E).
Figure 1. Total ion chromatogram of the headspace above industrial-grade potassium chlorate /
fuel explosive mixtures. Inset chromatogram shows the extracted ion, m/z 45, indicating the
presence of derivatized chlorine and bromine in the sample headspace. Other volatile species
related to the fuel, (A) vegetable oil or (B) petroleum jelly, are indicated by number.
 4.0E+05

3.0E+05

Abundance
2.0E+05

1.0E+05

0.0E+00
3.5 3.7 3.9 4.1 4.3 4.5
Retention time (min)

Cl2 (29 ng/L) Blank (oven and bag)

Blank (bag only)
 8.0E+06
7.0E+06
Acetic Acid
1-octanol
6.0E+06 (internal
standard)

Abunance
5.0E+06
4.0E+06
3.0E+06
2.0E+06
1.0E+06
0.0E+00
0 1 2 3 4 5 6 7 8
Time (min)

Industrial Grade PC Lab Grade PC Clandestine PC

 Extracted Chromatogram
(m/z 45)
3.0E+05
3.0E+06

Abundance
2.0E+05
2.5E+06 Propylene 1.0E+05
oxide Internal
Abundance
0.0E+00
2.0E+06
standard 3.4 4.4
Time (min)
1.5E+06

1.0E+06
Chloro-2- Bromo-2-
propanol propanol
5.0E+05

0.0E+00
0 2 4 6 8
Time (min)
 1.0E+07

8.0E+06

Peak Area
6.0E+06

4.0E+06 PC
Blanks
2.0E+06

0.0E+00
0 200 400 600 800 1000 1200
Extraction Time (min)
 1.60 0.25
1.40 0.20
1.20
1.00 0.15

A/E
A/E
0.80 0.10
0.60 0.05
0.40
0.20 0.00
0.00

A B
A.) PC and Vegetable oil (TIC) 1. propylene oxide
2. dervatized chlorine
3.0E+06 3. hexanal
6 4. heptanal
2.5E+06 m/z 45 5. octanal
6. internal standard
2.0E+04 7. nonanal
2.0E+06 2 8. decanal

Abundance
1.0E+04
1.5E+06
0.0E+00
3.6 4.1
1.0E+06

1
5.0E+05
4 5 7 8
2 3
0.0E+00
1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9
Time (min)

B.) PC and Petroleum jelly (TIC)

1. propylene oxide
5.0E+06 2. dervatized chlorine
4.5E+06 3. internal standard
m/z 45 3
1.0E+05 4. phenyl ethyl alcohol
4.0E+06
2
3.5E+06
5.0E+04
Abundance

3.0E+06
2.5E+06 0.0E+00
3.6 4.1
2.0E+06
1.5E+06
1
1.0E+06
5.0E+05 4
2
0.0E+00
1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9
Time (min)
 On-fiber Derivatization
Halogens Detected from
Potassium Chlorate

+ +
3.00E+05 Chlorine Bromine
2.50E+05
2.00E+05
1.50E+05
1.00E+05
5.00E+04
0.00E+00
3.4 4.4

1. Headspace of 2. Headspace of 3. Headspace of

derivatizing agent non-volatile salt internal standard
(1-octanol) 4. Desorb both analyte and internal
standard; analysis by gas
chromatography/mass spectrometry