Microchemical Journal 108 (2013) 117123

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Application and optimization of headspace solid-phase microextraction (HS-SPME)

coupled with gas chromatographyame-ionization detector (GCFID) to determine
products of the petroleum industry in aqueous samples
Maciej Tankiewicz a,, Calum Morrison b, Marek Biziuk a
a
Department of Analytical Chemistry, Faculty of Chemistry, Gdask University of Technology, ul. G. Narutowicza 11/12, 80-233 Gdask, Poland
b
School of Science, University of the West of Scotland, Paisley Campus, Paisley PA1 2BE, UK

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

Article history: A simple and solvent-free analytical method has been optimized for the determination of hydrocarbons (C6C20)
Received 19 July 2012 from products of the petroleum industry in aqueous samples. Extraction and analysis were carried out using
Received in revised form 2 October 2012 headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled with ame-ionization de-
Accepted 18 October 2012
tector (GCFID). A ZB-5 capillary column (30 m0.25 mm inner diameter, 0.25 m lm thickness) was used for
Available online 26 October 2012
GC separation and a 100 m polydimethylsiloxane (PDMS) ber was used to isolate the analytes. Parameters of
Keywords:
HS-SPME, analytes desorption and GCFID were selected and an analytical procedure is proposed. Under the op-
Headspace solid-phase microextraction timum conditions the limits of detection were in the range of 2.013 g L1 and the relative standard deviations
(HS-SPME) were between 2.6 and 14%. The developed analytical method was successfully applied to the analysis of water
Gas chromatography contaminated by unleaded petrol and unltered water used to extinguish a simulated re.
Petroleum products 2012 Elsevier B.V. All rights reserved.
Hydrocarbons (C6C20)
Water samples

1. Introduction sample loss and improving detection limits. Numerous extraction

The continuous development of human activities means that the
environment is increasingly exposed to organic pollutants which nd
their way into watercourses. One of the most serious threats exists
from products of the petroleum industry which can result in environ-
mental contamination and toxicity to life. Products of the petroleum
industry can also constitute a re hazard and may be used as accelerants
by arsonists to increase the rate and intensity of a re [1,2]. The most
commonly used accelerants are liquids, particularly petrol, diesel,
kerosene and complex mixtures of hydrocarbons obtained from the
fractional distillation of crude oil due to their low cost and ready
availability [38].
Hydrocarbon products which originate from the petroleum industry
are complex in terms of chemical composition and pose analytical chal-
lenges in terms of extraction and analysis. For example accelerants may
be composed of hundreds of compounds and analysis of these products
may be complicated after a re by the presence of pyrolysis products
formed from the combustion of common household items including
plastics, woods and carpets [9]. Therefore, it is necessary to prepare
samples for analysis by isolating the components from a complex ma-
trix and enrichment prior to nal determination. Ideally, this approach
should minimize any possible background interferences, while avoiding
Corresponding author. Tel.: +48 58 347 21 10; fax: +48 58 347 26 94.
E-mail address: maciej.tankiewicz@gmail.com (M. Tankiewicz).
techniques are available often using liquidliquid extraction (LLE).
Commonly used solvents for extraction are dichloromethane [10],
ethers and carbon disulde [1114]. Although LLE is relatively sim-
ple and inexpensive, it has many drawbacks, among them the need
to use large quantities of solvents. In order to achieve the desired
enrichment factor, the excess solvent requires removal by evapora-
tion, and extract cleanup may also be necessary. Additionally, there
is a risk of emulsions forming during agitation. This technique is useful
for extracting empty containers and for small samples [15]. Huang et al.
[16] applied a second form of solvent extraction for arson debris using su-
percritical uid extraction (SFE). The recoveries of various ignitable liquid
residues from carpet were above 80% with a low degree of co-extraction
of interfering compounds. Other traditionally used sample preparation
techniques are steam and vacuum distillation, which have been applied
to complex matrices. Steam distillation [17] is used for large amounts of
ignitable liquids in samples and commonly, the extraction solvent is
n-hexane, which provides high recovery efciency. Vacuum distillation
is useful in the case of fragile samples such as burned documents. Howev-
er, the time of distillation and use of hazardous solvents outweigh the
benets [2]. In addition the pre-concentration of analytes on activated
charcoal strips (ACS) [18,19] and Tenax GC [20,21] have been the most
commonly used sorbents for evaluation, but may require the use of
hazardous solvents and/or additional thermal desorption equipment.
Single-drop microextraction (SDME) is a simple, inexpensive meth-
od of preparing samples with analyte isolation and preconcentration

0026-265X/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.microc.2012.10.010
118 M. Tankiewicz et al. / Microchemical Journal 108 (2013) 117123
taking place in a single step [22]. This technique was applied by Xiong
et al. [23] to determine light hydrocarbons C6C12 in petroleum and
aqueous samples. Under optimum extraction conditions (1.5 L
drop of n-hexadecane, 30 min extraction of 5 mL aqueous sample
and stirring at 1000 rpm at room temperature) limits of detection
(LODs) were in the range of 0.264.33 g L 1 and relative standard
deviations (RSD) were 3.86.1%. In comparison with traditional
LLE, the ratio of solvent to sample is small, and SDME is easily ap-
plied. However, some disadvantages have been noted and included:
the difculty of achieving a stable organic drop, air bubble formation,
equilibrium process is slow resulting in time-consuming extraction
in most cases.
Solid-phase microextraction (SPME) was developed in 1989 [24]
and is a solventless extraction and which has been used to identify pe-
troleum products in real arson-suspected re debris samples [9,2533].
SPME is an excellent alternative for traditional extraction techniques,
and can be divided into Direct Immersion (DI-SPME) and Headspace
(HS-SPME) types, depending on where the ber is situated. Many of
the advantages of SDME also apply here, for example SPME reduces
the extraction time by 1020 min in comparison with activated char-
coal strips (ACS) [34], shows greater sensitivity in detecting gasoline
in a study at levels where other passive methods have failed [29] and
is unaffected by interferences from the pyrolysis products of wood
and plastics [35]. In addition headspace sampling eliminates interfer-
ences, can be used when aqueous media are present and has the ability
to be used in the eld. Therefore in re investigation, HS-SPME is poten-
tially useful due to complex matrix composition and potentially high
water content. DI-SPME has been applied to the recovery of accelerants
and explosives from aqueous samples [36,37], but a SPME method has
not been reported so far. Water samples represent 5% of all samples
for re investigation [9] and liquid matrix membrane SPME has been
applied to complex and dirty matrices [38]. Direct-contact SPME has
been applied to soil by Yoshida et al. [39], with the technique also
used for identication of ignitable liquids from human skin [27]. The
SPME method, compared with traditional LLE, limits loss of petroleum
products during the sampling procedure since the process incorporates
extraction, concentration and injection into a single step, which, in turn,
makes it more time efcient. Additionally, the HS mode provides a lon-
ger lifetime of the ber and protects the ber from any adverse effects
that may occur due to non-volatile, high molecular weight substances
in the real samples. This allows determination of petroleum products
in low levels of concentrations with greater accuracy and precision.
The objective of this study was to develop and apply a procedure
to determine products of the petroleum industry in aqueous samples
using headspace SPME with a ber for sampling and GCFID for anal-
ysis. Parameters of extraction (time, temperature, agitation rate, con-
tent of salt), and the time and temperature of desorption in the gas
chromatograph injector were selected. The procedure was validated
and applied to analyze water contaminated by unleaded petrol and
water used to extinguish a simulated re.
2. Materials and methods
2.1. Reagents and chemicals
Hexane (99%), o-xylene (98 +%), m-xylene (98 +%), p-xylene
(98 +%), nonane (99%), decane (99 +%), undecane (99%), dodecane
(99%), pentadecane (99%), hexadecane (99%), eicosane (99%) and
sodium chloride were purchased from Sigma-Aldrich (Poole, UK).
Toluene (99%), methanol and ethyl acetate were supplied by Fisher
Scientic (Loughborough, UK). Tetradecane (99%) was purchased
from Koch-Light Laboratories Ltd. (Colnbrook, UK) and unleaded
petrol from local Shell station (Paisley, UK). All reagents, except pet-
rol, were of analytical or higher grade and solvents were of HPLC
grade. The water used in this study was obtained from an ultrapure
water purication system Elgastat, Elga Ltd. (Bucks, UK).
A standard stock solution was prepared by dissolving hexane, tol-
uene, o-xylene, m-xylene, p-xylene, nonane, decane, undecane,
dodecane, tetradecane, pentadecane, hexadecane and eicosane in a
mixture of ethyl acetate and methanol 10:90 (v/v) at the concentra-
tion 2000 mg L 1 and stored at 4 C. The standard aqueous samples
were produced by spiking puried water with the standard solution
at different concentration levels. For optimization of HS-SPME, the
working solutions were prepared by spiking puried water with
the standard solution at 10 mg L 1 concentration level for each
hydrocarbon.
2.2. Real water samples
To verify the suitability of the developed analytical procedure two
types of real water samples were used. Firstly, tap water contaminated
by unleaded petrol 0.1% (v/v) was used to examine the applicability of
the HS-SPME method for samples containing high concentrations of dif-
ferent hydrocarbons. Water from reghting was used in this study to
calculate the recovery of analytes and check the impact of pyrolysis
products on analytical results and the SPME ber. For this purpose, a
simulated re on a small scale was performed in the laboratory. The fol-
lowing frequently occurring household materials were added to the
re: plastic, wood, paper, pieces of carpet, glass, cotton garments and
rubber products. To extinguish the re 2 L of tap water was used,
which was then stored unltered at 4 C.
2.3. HS-SPME procedure
HS-SPME extraction was performed using a Supelco (Bellefonte,
USA) manual holder containing a ber assembly with a 100 m polydi-
methylsiloxane (PDMS) coating. The ber was conditioned in the injec-
tion port of a gas chromatograph at 250 C for 30 min prior to use and
blank desorption was performed. 2 mL of aqueous sample (standard
or real) was placed in 4 mL glass vial with PTFE/silicone septa, which
contained 10% (w/v) sodium chloride salt. The ber was exposed to
the headspace of a sample, kept at a selected temperature for a set
time, retracted into a needle, and introduced into the injection port of
gas chromatograph. Extraction was supported by magnetic stirring at
the highest possible level. A ber blank experiment was performed to
ensure that there were no contaminants on the ber.
For optimization of HS-SPME process, the factors affecting extrac-
tion efciency (headspace volume, extraction time, temperature,
sample ionic strength and agitation speed) were investigated.
2.4. Gas chromatography ame-ionization detector (GCFID)
HP5890 series II gas chromatograph equipped with a split/splitless
injector coupled with a ame-ionization detector connected to an
Agilent 3396 series 3 integrator was used. Analytes were desorbed
from the ber in a gas chromatograph splitless injection port. The injec-
tion port was tted with a 0.75 mm i.d. injection liner (Supelco) with
the splitsplitless purge valve opened at 1 min after injection. The de-
sorption temperature and time of analytes were optimized. The depth
of the SPME needle in the injection port was also selected (3 cm) and
controlled. The injector temperature was 260 C. The chromato-
graphic column used was Zebron ZB-5 (30 m 0.25 mm 0.25 m
of 5% phenyl95% dimethylpolysiloxane) supplied by Phenomenex
(USA). Helium (CP grade, 99.999%) was used as a carrier gas and was
supplied by BOC Gases Europe (Guildford, UK). The ow of carrier gas
was 1 mL min1, with constant ow conditions being observed
throughout. The temperature program was as follows: 40 C (hold
2 min), 10 C min1 to 70 C, 5 C min1 to 90 C, then 25 C min1
to 270 C (hold 1 min). The detector temperature was 300 C. For conr-
mation of the developed analytical methodology a second fused silica
column was also used: Equity-1 capillary column (30 m0.25 mm
0.25 m lm thickness) supplied by Supelco.
 M. Tankiewicz et al. / Microchemical Journal 108 (2013) 117123
3. Results and discussion
3.1. Gas chromatography (GC) separation
Since hydrocarbons C6C20 are apolar compounds columns with
apolar properties were selected for this study. In order to achieve sepa-
ration of all analytes and appropriate peak shapes a temperature pro-
gram was optimized. Firstly, an experiment with a constant increasing
of temperature was performed in order to obtain the retention times
of analytes, and then introduced three different temperature ramps in
order to achieved full separation of analytes. Unfortunately, no separa-
tion of p-xylene and m-xylene was achieved. Both compounds were elut-
ed from the column at the same time. This is caused by these analytes
having a similar boiling point. However, separation from o-xylene was
achieved successfully. Therefore, in further analysis both p-xylene and
m-xylene compounds were treated as one analyte p-(m)-xylene. The
ow rate of carrier gas was also optimized. Conditions of 1, 2 and
4 mL min1 were tested and a ow rate of 1 mL min1 gave the best
results.
3.2. Desorption of analytes
Hydrocarbons C6C20 were isolated into the PDMS ber coated
from the headspace of an aqueous standard sample of 10 mg L 1 of
each analyte and desorbed for 3, 5 and 7 min at injector temperatures
ranging from 210 to 270 C (10 C increments) with measurement of
peak areas; 5 min desorption at 260 C was sufcient to remove all
analytes from the ber and was selected for further analysis. Under
these conditions the desorption process from the ber was performed
twice for each extraction event. Standard samples of three different
concentrations of each hydrocarbon, i.e., 10, 1, and 0.1 mg L 1,
were analyzed. Peak areas of particular hydrocarbons on the second
desorption chromatograms were never larger than 0.5% of those
obtained in the rst desorption. This suggests that only trace, if any,
amounts of extracted C6C20 remained on the ber after the rst de-
sorption event and can be neglected as they are smaller than the ex-
perimental errors.
3.3. Optimization of HS-SPME conditions
HS-SPME is an equilibrium process that involves the partitioning of
analytes from aqueous phase to the gas phase and into the polymeric
phase according to their partition coefcients. Thus, the optimization
of parameters that inuence the partition of hydrocarbons C6C20 be-
tween the headspace and the solution are very important. For
HS-SPME, the critical factors that affect extraction efciency include
headspace volume, extraction time, temperature, sample ionic strength
and agitation speed. All of these were taken into consideration in
this study. Each data point is the average of three independent
measurements.
3.3.1. Effect of headspace volume
Firstly the effects of the water sample and headspace volume were
studied. The experiment was performed using 4 mL vials and the vol-
ume of water was increased from 1 to 3 mL (headspace volume from
3 to 1 mL). A standard solution with the concentration of 10 mg L 1
for each analyte was analyzed twice. The extraction time was 30 min
at the ambient temperature and desorption time was 5 min at 260 C.
Little effect of the ratio of sample volume to headspace volume on the
extraction efciency was observed. The optimum detector response
was found to be 2 mL of spiked water sample with 2 mL of headspace
volume and so was used for subsequent analysis.
3.3.2. Extraction time
An evaluation experiment was performed using different extrac-
tion times from 5 to 60 min at the ambient temperature. The time
119
required for the extraction process is one of the most important
parameters, which should be investigated, because HS-SPME is an
equilibrium process of analytes between the ber coating and vapor
phase. In this study the selected time periods were 5, 15, 30, 45 and
60 min. Each data point is the average of three independent measure-
ments. The areas of peaks obtained for each hydrocarbon with the
different extraction time are presented in Fig. 1.
The best extraction efciency for all studied hydrocarbons was
observed when a longer extraction time was used. Improved results
were achieved up to 45 min, except toluene, for which there were
no differences between the 30 and 45 min extraction times. Based
on the experimental results, the extraction time giving the highest re-
sponses was 45 min. After this time the extraction efciency de-
creased, except in the case of tetradecane, pentadecane, hexadecane
and eicosane. For these hydrocarbons slightly better efciency was
observed after 60 min. This may be due to their lower diffusion coef-
cient and higher molecular mass than other hydrocarbons. The ex-
traction process time of 45 min was therefore chosen.
3.3.3. Extraction temperature
The extraction temperature affects the efciency of the extraction
process by controlling the diffusion rate of hydrocarbons into the coat-
ing of the ber. The inuence of temperature on the area of peaks for
each analyte was investigated varying the temperature of extraction
between 23 C and 90 C with a constant extraction time of 45 min. In
this experiment room temperature, 45, 65 and 90 C were chosen for
investigation. The detector responses (areas) for each hydrocarbon
with different extraction temperatures are presented in Fig. 2.
As can be seen in Fig. 2 the higher the extraction temperature is
above room temperature the lower the efciency of the extraction.
The results showed that increasing the temperature causes lower de-
tector responses (areas) for all hydrocarbons, except tetradecane,
pentadecane, hexadecane and eicosane. For these analytes the
highest extraction efciency was observed at 65 C. The optimum
extraction efciency was achieved at ambient temperature and was
selected for the subsequent experiments.
3.3.4. Salt addition
The inuence of sodium chloride (NaCl) salt additives to the
HS-SPME procedure was investigated by comparing the extraction ef-
ciency of samples with different concentrations of NaCl. In this study
5, 10 and 20% (w/v) of salt was used. Higher salt content has not been
taken into consideration because of problems with dissolving NaCl.
Fig. 3 presents the effect of NaCl additives on detector responses
(areas).
The addition of salt into the aqueous sample prior to the extraction
process increased the ionic strength of the solution. As a consequence,
the diffusion of the analytes into the headspace is favored and extrac-
tion time is reduced. As can be seen in Fig. 3 a slight increase in peak
areas was observed with the increasing of NaCl concentration up to
10%. For higher content of NaCl the extraction efciency decreased.
Thus, the optimum concentration of salt for the extraction of hydrocar-
bons was 10% (w/v) and was chosen for further analysis.
3.3.5. Magnetic stirring
Magnetic stirring accelerates extraction and shortens the time
needed to reach thermodynamic equilibrium between the aqueous
and the headspace phase. For headspace, stirring should be vigorous
and constant to provide excellent reproducibility. Generally, the larger
the agitation, the faster the mass transfer between the aqueous phase
and the headspace. The stirring speed range studied was 01000 rpm.
From the obtained results it can be stated that extraction efciency
was poor without stirring and the detector responses (areas) were
higher for each analyte when the stirring rate increased. An optimal
stirring speed of 1000 rpm (the highest possible level) was used in
120 M. Tankiewicz et al. / Microchemical Journal 108 (2013) 117123

Fig. 1. Effect of extraction time from 5 to 60 min at ambient temperature on extraction efciency: desorption time 5 min at 260 C, concentration of each hydrocarbon 10 mg L1,
n = 3.

the subsequent experiments to ensure the efcient extraction of all
hydrocarbons.
3.4. Method validation
The optimized conditions were used for validating the HS-SPME
method for quantitative analysis of C6C20 hydrocarbons (linear range,
detection limit, and precision). The working standard solutions for the
calibration study were prepared by spiking puried water with the stan-
dard solution in the concentration range of 11000 g L1 for each ana-
lyte. The linear range for hydrocarbons was studied by replicate analysis
of the standard stock solutions. The linear regression values were calcu-
lated with the average peak areas of three replicate injections for each
analyte. Table 1 presents the linear regression for each analyte with coef-
cient of determination in the range from 0.9281 (eicosane) to 0.9983
(nonane).
The calculated calibration curves showed good linearity up
to 500 g L 1 for hexane, nonane, tetradecane, pentadecane and
hexadecane, and up to 1000 g L 1 for toluene, p-(m)-xylene,
o-xylene, decane, undecane, dodecane and eicosane. Coefcient of
variability (percentage of relative standard deviation, CV %) was
the average value of different concentrations of studied hydrocar-
bons in the linear range and was in the range from 0.2% (decane)
to 9.4% (eicosane), which is considered as good method precision.
The sensitivity of the HS-SPME method was considered in terms of
limit of detection (LOD). LODs were calculated from calibration func-
tions [40] using Eq. (1):
3:3 S
LOD 1
b
where S is the residual standard deviation of the calibration function
and b is the slope of the rst linear function. As can be seen in Table 1
the method allows detection of the selected hydrocarbons in water
samples at concentrations lower than 12.5 g L 1. LODs were in the
range from 2.0 g L 1 (eicosane) to 12.5 g L 1 (pentadecane). The

Fig. 2. Effect of extraction temperature from 23 C to 90 C on extraction efciency: extraction time 45 min, concentration of each hydrocarbon 10 mg L1, n= 3.
 M. Tankiewicz et al. / Microchemical Journal 108 (2013) 117123 121

Fig. 3. Effect of content of sodium chloride (NaCl) salt (%) (w/v) on extraction efciency: extraction time 45 min, ambient temperature, concentration of each hydrocarbon
10 mg L1, n = 3.

limits of quantitation (LOQs) dened as 3 times the LOD were analyte-
dependent and they were in the range from 6.1 g L1 (eicosane) to
38 g L 1 (pentadecane).
Reproducibility of the method was examined by extracting ve real
water samples from reghting spiked at two different concentration
levels 40 g L 1 and 200 g L 1 under optimized experimental condi-
tions. As shown in Table 2, RSDs vary between 0.037 (hexadecane) and
0.14 (pentadecane) for the hydrocarbons at the 40 g L 1 concentra-
tion, and between 0.026 (o-xylene) and 0.10 (hexadecane) for the
hydrocarbons at the 200 g L 1 concentration, indicating that the re-
producibility of this extraction method is satisfactory.
The mean recoveries obtained for the studied hydrocarbons
spiked at the two concentration levels 40 and 200 g L 1 in the real
water samples are shown in Table 2. The relative recovery, as deter-
mined by the peak area ratio of real sample to puried water sample
spiked with hydrocarbons at the same concentration level, was
applied because SPME is a non-exhaustive extraction technique in-
stead of an absolute recovery as used in exhaustive extraction tech-
niques. The recovery of analytes at the concentration level of
40 g L 1 ranged between 98% (pentadecane) and 118% (hexane),
except for decane for which the recovery was 93%. For hydrocarbons
C6C20 added to the water samples at the concentration level of
200 g L 1, the recovery was in the range of 87% (undecane) to
117% (hexane). Fig. 4 displays the chromatograms obtained for
water from reghting (a), spiked water from reghting at the
concentration level 40 g L 1 for each analyte (b) and spiked
water from reghting at the concentration level 200 g L 1 for
each analyte (c) using HS-SPMEGCFID.
The conrmation of the developed methodology using an Equity
-1 capillary column (30 m 0.25 mm 0.25 m lm thickness)
was performed, as identication based solely on retention times is in-
sufcient. In this experiment an apolar column was used. Conditions
and parameters during the HS-SPME process and nal determination
by GCFID were the same as outlined previously. From the obtained
results it can be stated that all hydrocarbons were sufciently sepa-
rated, except p-xylene and m-xylene which were eluted from the col-
umn at the same time.
3.5. Applications
The developed procedure was applied to determine the hydrocar-
bons C6C20 in two real aqueous samples. Firstly, tap water contaminat-
ed by unleaded petrol 0.1% (v/v) was used to examine the applicability
of the HS-SPME method for samples containing high concentrations of
different hydrocarbons. Approximately 2 L of unleaded petrol was
added to 4 mL glass vial. The vial was then lled with a volume of tap
water up to 2 mL, which contained 10% (w/v) of sodium chloride salt
and extracted under optimized conditions. Fig. 5 shows the chromato-
gram obtained for the contaminated tap water sample by 0.1% (v/v) of
unleaded petrol using the HS-SPMEGCFID.

Table 1
Basic validation parameters obtained for each hydrocarbon by using HS-SPMEGCFID.

Analyte Retention time Equation Coefcient of Limit of detection LOD Limit of quantication Linearity range Coefcient of
[min] determination R2 [g L1] LOQ [g L1] [g L1] variability CV [%]

Hexane 2.427 y = 2791 x + 42,461 0.9959 2.4 7.3 7.3500 1.8

Toluene 3.931 y = 20,602 x 363,412 0.9864 3.7 11 111000 7.2
p-(m)-xylene 5.910 y = 51,124 x + 182,587 0.9926 6.5 19 191000 1.9
o-xylene 6.429 y = 31,568 x 655,764 0.9859 3.2 9.6 9.61000 1.7
Nonane 6.558 y = 16,891 x + 302,798 0.9983 6.9 21 21500 0.5
Decane 9.025 y = 58,668 x 2,228,190 0.9759 3.6 11 111000 0.2
Undecane 10.876 y = 52,817 x 2,071,517 0.9750 4.5 14 141000 2.5
Dodecane 12.067 y = 52,582 x 3,152,724 0.9618 7.6 23 231000 0.4
Tetradecane 13.702 y = 8305 x + 1,120,376 0.9394 7.2 22 22500 2.8
Pentadecane 14.341 y = 7810 x + 937,236 0.9654 12.5 38 38500 5.0
Hexadecane 14.917 y = 7237 x + 943,146 0.9448 5.2 16 16500 4.3
Eicosane 16.900 y = 964 x + 297,369 0.9281 2.0 6.1 6.11000 9.4
122 M. Tankiewicz et al. / Microchemical Journal 108 (2013) 117123

Table 2 and products of pyrolysis from the different kinds of materials present
Mean recovery and RSD value of selected hydrocarbons C6C20 in real water samples at a re scene did not affect for the results.
from reghting by using HS-SPMEGCFID (n = 5).

Analyte Spiked water at Spiked water at 4. Conclusion

concentration 40 g L1 concentration 200 g L1

Recovery [%] RSD (n = 5) Recovery [%] RSD (n = 5) In this study, the HS-SPME method for the extraction and GCFID
Hexane 118 0.039 117 0.041 for the nal determination of the products of the petroleum industry
Toluene 115 0.091 102 0.056 were developed. Extraction conditions were optimized to 45 min,
p-(m)-xylene 101 0.11 106 0.087 2 mL aqueous sample, 10% (w/v) of sodium chloride salt, the highest
o-xylene 107 0.078 101 0.026
possible stirring rate and room temperature. Under the optimized
Nonane 109 0.094 89 0.082
Decane 93 0.10 93 0.043
conditions, the LODs were in the range from 2.0 g L 1 (eicosane)
Undecane 110 0.058 87 0.061 to 12.5 g L 1 (pentadecane). The developed analytical method was
Dodecane 102 0.064 91 0.039 successfully applied to the analysis of water contaminated with un-
Tetradecane 99 0.041 104 0.085 leaded petrol and unltered water used to extinguish a simulated
Pentadecane 98 0.14 111 0.097
re. The results show that the selectivity of developed methodology
Hexadecane 113 0.037 108 0.10
Eicosane 103 0.12 101 0.086 is sufcient to analyze samples of very complex matrices. Pyrolysis
products from differing materials did not affect the results. Therefore,
the HS-SPME can be an effective tool for the sampling of products of
As can be seen in Fig. 5, eight hydrocarbons were detected: hex- the petroleum industry. The developed analytical method here is sim-
ane, toluene, p-(m)-xylene, o-xylene, nonane, decane, undecane and pler, lower cost and less labor intensive, than conventional tech-
dodecane. The results show that the selectivity of the developed niques such as LLE and ACS for the simultaneous determination of
methodology is sufcient to analyze samples of very complex matri- hydrocarbon analytes by GC. The lack of solvents and ability to use
ces and can be used in monitoring studies to control the content of the injection port of a gas chromatograph for thermal desorption
hydrocarbons C6C20 in environmental water samples. makes SPME an ideal sampling device. Additionally, headspace sam-
Water from simulated reghting was used in this study to calculate pling eliminates interference from the complex sample matrix and
the recovery of analytes and checking the impact of pyrolysis products has potential for eld analysis, making it even more attractive for
on analysis results and the SPME ber. In re investigation, HS-SPME use in routine testing.
has been mainly used for accelerants detection from solid material
(re debris). For the aqueous samples, headspace mode has not been Acknowledgments
reported so far. The HS-SPME method, compared to traditional LLE, limits
loss of hydrocarbons during the sampling procedure since the process in- This research work was supported by the system projects:
corporates extraction, concentration and injection into a single step, InnoDoktorant Scholarships for PhD students, IVth edition and
which, in turn, makes it more time efcient. Additionally, headspace sam- The development of interdisciplinary doctoral studies at the Gdansk
pling eliminates interference from the complex sample matrix, including University of Technology in modern technologies. Projects are
suspensions. Fig. 4 illustrates chromatograms obtained for an unltered co-nanced by the European Union in the frame of the European So-
water sample from reghting experiment. This illustrates that matrix cial Fund.

Fig. 4. Chromatograms obtained for water from reghting (a), spiked water from reghting at the concentration level 40 g L1 for each hydrocarbon (b) and spiked water from
reghting at the concentration level 200 g L1 for each hydrocarbon (c) using HS-SPMEGCFID; 1 = hexane, 2 = toluene, 3 = p-(m)-xylene, 4 = o-xylene, 5 = nonane, 6 =
decane, 7 = undecane, 8 = dodecane, 9 = tetradecane, 10 = pentadecane, 11 = hexadecane, 12 = eicosane.
 M. Tankiewicz et al. / Microchemical Journal 108 (2013) 117123
Fig. 5. Chromatogram obtained for the contaminated tap water sample by 0.1% (v/v) of unleaded petrol using the HS-SPMEGCFID; 1 = hexane, 2 = toluene, 3 = p-(m)-xylene, 4 =
o-xylene, 5 = nonane, 6 = decane, 7 = undecane, 8 = dodecane.
The authors thank Mr. C. McGinness, University of the West of Scot-
land, for technical assistance, and are grateful to Mrs. Ailsa Morrison for
assistance with proof reading and constructive comments.
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