Organic Geochemistry 42 (2011) 316322

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Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem

Optimization of headspace single-drop microextraction technique for extraction

of light hydrocarbons (C6C12) and its potential applications
Chenchen Fang, Yongqiang Xiong , Qianyong Liang, Yun Li, Pingan Peng
State Key Laboratory of Organic Geochemistry (SKLOG), Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, PR China

a r t i c l e

i n f o

Article history:
Received 23 August 2010
Received in revised form 19 January 2011
Accepted 24 January 2011
Available online 31 January 2011

a b s t r a c t
In this study, headspace single-drop microextraction (HS-SDME) coupled with gas chromatographyame ionization detection (GC-FID) was tested to determine C6C12 light hydrocarbons (LHs) in petroleum and aqueous samples. Several signicant experimental parameters, such as drop solvent type, drop
volume, sample solution ionic strength, agitation speed and extraction time were optimized. Under optimum extraction conditions, specically, a 1.5 ll microdrop of n-hexadecane, 30 min extraction of a 5 ml
aqueous sample placed in a 10 ml vial, and stirring at 1000 rpm at room temperature, the reproducibility
and accuracy of this method were found to be satisfactory. Two examples using this method indicated
that HS-SDME is a simple, efcient and promising technique for the determination of volatile C6C12
LHs in complex matrices.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
C6C12 light hydrocarbons (LHs) are abundant components of
crude oils, especially in light oils or condensates. Various LH parameters have been established for identifying source and type of petroleum, evaluating their thermal maturity and making petroleum
correlations (Halpern, 1995; Thompson, 1979, 1983; Ten Haven,
1996; Obermajer et al., 2000). The quantitative analysis of C6C12
LHs involves a broad range of samples, which include natural gases,
condensates, crude oils, soils and various aqueous samples. Due to
compositional complexity of petroleum and possible matrix effects,
sample pretreatment is necessary to determine the C6C12 LHs in
some samples, especially for soils and aqueous samples.
For oil and condensate samples, because the C6C12 LH fraction
is liquid at room temperature, direct headspace sampling is not
feasible. Thus, direct injection of whole oil is frequently used to
introduce analytes into the GC inlet (e.g. George et al., 2002). However, because petroleum is a complex mixture unlike natural gas,
the direct injection will unavoidably contaminate the inlet system
of the instrument, degrade column performance and introduce
interferencing compounds. As for the dilution of whole oil sample,
addition of diluent such as n-pentane or n-hexane will also cause
interference to some extent (Whiticar and Snowdon, 1999). For
solid or aqueous samples, extraction and concentration of target
analytes is necessary prior to analysis, especially for low concentration samples. Liquidliquid extraction (LLE) is the most common method used to extract analytes from aqueous solutions.
However, conventional LLE is not only time consuming, labor
Corresponding author. Tel.: +86 20 85290744; fax: +86 20 85290706.
E-mail address: xiongyq@gig.ac.cn (Y. Xiong).
0146-6380/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.orggeochem.2011.01.009

intensive and requires large amounts of toxic and environmentally

hazardous organic solvents, but also can cause losses of volatile
components. Therefore, other analytical techniques should be
tested as potential methods to extract LHs in oils and other
matrices.
Recently, the development of fast, simple and solvent-free sample preparation methods has become an important trend in
chemical analysis (Psillakis and Kalogerakis, 2003). The headspace
solid-phase microextraction (HS-SPME), as a rapid, simple and solvent-free extraction technique, has been used to analyze gasoline
range hydrocarbons in oils (Harris et al., 1997) and seabed sediments (Abrams et al., 2009). The HS-SPME method, compared to
traditional LLE, limits loss of LHs during the sampling procedure
since it incorporates extraction, concentration and injection into
a single step, which, in turn, makes it more time efcient. Additionally, headspace sampling eliminates interference from the complex
sample matrix. However, there are still some drawbacks to this
method, including ber fragility, expensive device requirements,
limited ber choice, short life (each ber can be used for only
50100 analyses) and carry over between analyses.
Liquid phase microextraction (LPME) was developed as another
rapid, simple, inexpensive and environmentally friendly extraction
technique (Jeannot and Cantwell, 1996, 1997; Psillakis and Kalogerakis, 2001). Single-drop microextraction (SDME) is the simplest
operational mode of the LPME technique, in which the whole
extraction procedure is performed only with a microsyringe. A
drop of solvent is utilized as the collection phase, replacing the
coated ber in HS-SPME. The analytes are extracted by the microdrop of organic solvent (about 13 ll) suspended from the tip of a
microsyringe needle and either exposed to the headspace of a stirred sample solution (HS-SDME) (Theis et al., 2001) or immersed

C. Fang et al. / Organic Geochemistry 42 (2011) 316322

into the stirred aqueous sample (direct SDME) (He and Lee, 1997;
Wang et al., 1998). The extract is then directly injected into a gas
chromatography system for analysis. HS-SDME is suitable for the
extraction of volatile and semi-volatile organic compounds and allows avoidance of the interference of complex sample matrices.
Additionally, HS-SDME has several advantages over HS-SPME. For
example, it does not need any special apparatus. A wide variety
of solvents and trapping agents can be chosen as a microdrop to
meet different needs. Moreover, unlike the bers of SPME, drops
of SPME can be renewed for each extraction. Therefore, this extraction technique has been widely applied in various elds and involved in a broad range of sample types, including human serum,
pharmaceutical preparations, vegetables, engine oils, degradation
products of asphaltenes as well as various water samples
(Przyjazny and Kokosa, 2002; Kokosa and Przyjazny, 2003;
Shariati-Feizabadi et al., 2003; Bahramifar et al., 2004; Lambropoulou and Albanis, 2004; Yamini et al., 2004; Shahdousti et al., 2007;
Li et al., 2010).
To date, few papers on the application of HS-SDME technique in
petroleum geochemistry have been published (Li et al., 2010). The
purpose of this study is to research the applications of HS-SDME
technique in the extraction of C6C12 light hydrocarbons (LHs)
from petroleum and petroleum-related aqueous samples by optimizing its extraction conditions.
During the drilling process, mud is usually pumped down the
well to keep the drill bit cool, facilitate the movement of cuttings
to the surface and prevent clogging and friction (Haworth et al.,
1985). The drilling mud often carries drill cuttings and formation
uids and gases to the surface. Monitoring the levels and nature
of these gases and uids is important as this can provide information about the formation and uid characteristics of the borehole.
Mud gas logging (MGL) technique, has been routinely used in
petroleum exploration and production (Haworth et al., 1985;
Whittaker, 1991). More recently, stable isotope analysis was combined with the MGL into a new technique called Mud Gas Isotope
Logging (MGIL) (Ellis et al., 2003, 2007). However, both MGL and
MGIL are used to analyze only gas components of drilling mud.
The analysis of C6C12 LHs in drilling mud can provide a supplement for understanding type, origin and evolution of deep seated
uids. Both low concentration of LHs and compositional complexity of matrices hinder the determination of the C6C12 LHs in
drilling mud by using conventional methods. Therefore, the drilling
mud sample was employed in this study to test the practicability of
HS-SDME technique in a relatively complex aqueous phase.

2. Materials and methods

2.1. Reagents and chemicals
n-Hexane (n-C6, 99%), n-heptane (n-C7, HPLC grade, 99+%), n-octane (n-C8, 98+%), n-nonane (n-C9, 99%), n-decane (n-C10, 99%),
n-undecane (n-C11, 99%), n-dodecane (n-C12, 99+%), benzene (99%),
ethylbenzene (99%), o-xylene (99%), methylcyclohexane (MCH,
99%), n-hexadecane (n-C16, 99%), o-xylene-d10 (98+%) and n-octane-d18 (n-C8D18, 99%) were all purchased from Alfar Aesar China
(Tianjin) Co., Ltd. Methanol (ACS, HPLC) was obtained from Burdick
& Jackson. Toluene (99%) and sodium chloride were obtained from
Qianhui Chemicals and Glassware Co., Ltd. (Guangzhou, China). All
other reagents in this study were of analytical grade. The water used
in the experiment was pure water from an ultrapure water purication system and was re-boiled and cooled to room temperature prior
to use.
A mixed stock solution was prepared by dissolving n-C6,
benzene, n-C7, MCH, toluene, n-C8, ethylbenzene, o-xylene, n-C9,
n-C10, n-C11, and n-C12 in methanol, with the corresponding

317

concentrations of each component being 306, 362, 280, 292, 348,

288, 350, 366, 298, 288, 580, and 554 lg/ml, respectively. The
stock solution was stored at 4 C and diluted with boiled water
for use in the working solutions. An extraction solvent containing
an appropriate concentration of n-C8D18 as an internal standard
(IS) was used as the extractant for HS-SDME.
2.2. Samples
A crude oil from the Well Hade 23 in the Tarim Basin, China was
used to examine the applicability of the HS-SDME method for samples containing high concentration of LHs.
During the drilling operation, rock cuttings that circulated to
the surface were collected and placed in 946 ml cans at regular
intervals from the mud pit. The cuttings were then covered with
water, leaving one-third of the can empty. Next, the can was
sealed, allowing gases contained in the cuttings to be liberated into
the headspace. Finally, the collected headspace cans were transported to the laboratory for analysis. A batch of such headspace
cans was collected from a drilling well in the South China Sea.
2.3. HS-SDME procedure
Fifty microliters of the diluted stock solution or sample were
spiked into a 10 ml glass vial with 5 ml of water, a magnetic stir
bar and an aluminum cap seal containing a PTFE-faced silicone
septum. The vial was then placed on a magnetic stirrer (Jiangsu
Guohua, China). A 10 ll microsyringe (SGE Analytical Science, Australia) was used as both the extraction and injection syringe. After
a certain volume of extraction solvent containing 472 lg/ml nC8D18 as the internal standard was drawn into the microsyringe,
the syringe needle was inserted through the rubber septum of
the sample vial until its tip was about 0.5 cm above the surface
of the working or sample solution. The micro syringe was xed
above the extraction vial by a metal clamp during the extraction.
The syringe plunger was then carefully and slowly depressed until
the micro drop of extraction solvent was suspended at the needle
tip. After the extraction, the micro drop was retracted back into the
needle carefully and slowly and directly injected into the gas chromatography system for analysis.
2.4. Gas chromatography (GC)
GC analyses were performed on an Agilent 7890 GC instrument
equipped with a split/splitless injector, an HP-PONA fused silica
capillary column (50 m  0.20 mm  0.50 lm), and a ame ionization detector (FID). Temperatures for both injection and detection
were set at 300 C. Nitrogen (P99.999%) was used as the carrier
gas at a ow rate of 1.0 ml/min. The injection was operated in
the split mode (100:1 for oils, 30:1 for drilling mud samples).
The GC oven temperature was initially held for 5 min at 35 C, then
programmed to 50 C at a rate of 1.5 C/min and nally programmed at 8 C/min to 300 C, which was held for 5 min. Quantication of C6C12 LHs was performed by the integration of the peak
areas. The response factors of LHs relative to the internal standard
(n-C8D18) were calculated based on the peak area ratios of each
C6C12 hydrocarbon to the internal standard.
3. Results and discussion
3.1. Optimization of HS-SDME conditions
For HS-SDME, the critical factors that affect extraction efciency
include solvent type, drop volume, sample ionic strength, agitation
speed and extraction time (Kokosa and Przyjazny, 2003).

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C. Fang et al. / Organic Geochemistry 42 (2011) 316322

Firstly, the stability of the drop during extraction is fundamental to the choice of extraction solvent. The boiling point of solvent
must be high enough to avoid evaporation, but it must be compatible with GC analysis. To select an appropriate solvent, 1-butanol,
1-octanol, chloroform and n-hexadecane were tested as extractants. Results showed that n-hexadecane was the most suitable
extraction solvent because of its relatively low volatility, no interfering peaks, good afnity with the C6C12 LHs, and good separation of its GC peak from those of the C6C12 LHs. Fig. 1 shows a
typical chromatogram after HS-SDME extraction of C6C12 LHs
using n-hexadecane as the extraction solvent.
Previous studies have indicated that the drop volume inuences
the amount of extracted analytes and that the extraction efciency
is enhanced with an increase in drop volume (Shariati-Feizabadi
et al., 2003; Bahramifar et al., 2004). However, larger drops are difcult to manipulate and a large injection volume will lead to bad
separation in the chromatography analysis. Therefore, a microdrop
volume of 13 ll is usually used (Lambropoulou and Albanis,
2004; Yamini et al., 2004; Bahramifar et al., 2004). In this work, different drop volumes of n-hexadecane (1.0, 1.5, 2.0, and 2.5 ll) were
used to examine the extraction efciency of HS-SDME. In addition
to difculties in maintaining the stability of suspended microdrops
during the extraction, peak tailing and bad separation were observed in the chromatogram when the microdrop volume was
more than 2 ll. Hence, a 1.5 ll microdrop was selected in succeeding experiments.
Other HS-SDME conditions, such as ionic strength, agitation
speed and extraction time, were optimized according to the relative peak areas of each compound obtained from twelve experiments conducted under different conditions. The extraction
conditions of these experiments are listed in Table 1. Twelve parallel working solutions at concentrations of 3.06 lg/ml (n-hexane), 3.62 lg/ml (benzene), 2.80 lg/ml (n-heptane), 2.92 lg/ml
(methylcyclohexane), 3.48 lg/ml (toluene), 2.88 lg/ml (n-octane),
3.50 lg/ml (ethylbenzene), 3.66 lg/ml (o-xylene), 2.98 lg/ml (nnonane), 2.88 lg/ml (n-decane), 5.80 lg/ml (n-undecane) and
5.54 lg/ml (n-dodecane) in water were used in this optimization
procedure. Fig. 2 shows the relative peak areas of each C6C12
LHs per microliter injection volume under different experimental
conditions. The results of experiments 13 demonstrate that ionic
strength has varying effects on the extraction of different types of
hydrocarbons. The 30% (w/v) NaCl concentration is favorable for
the extraction of aromatic hydrocarbons, while 15% (w/v) NaCl
is good for C9C12 alkanes, and 0% NaCl is good for C6C8 alkanes.

Table 1
Extraction conditions of HS-SDME.
Experiment

NaCl (W/V) (%)

Stirring speed (rpm)

Extraction time (min)

1
2
3
4
5
6
7
8
9
10
11
12

0
15
30
30
30
30
0
0
15
15
30
30

1000
1000
1000
750
500
250
1000
1000
1000
1000
1000
1000

20
20
20
20
20
20
30
40
30
40
30
40

Experiments 36 indicate that the extraction efciencies of C6C12

LHs all decrease with decreasing stirring speeds. As for extraction
time, it depends on ionic strength and analytes (Fig. 2). For instance, experiments 1, 7 and 8 show that longer extraction time
has little impact on extraction efciencies for all concentrations
of NaCl. Increases in ionic strength can obviously improve the
extraction efciencies of LHs, especially for C9C12 n-alkanes.
However, more time is required to reach the equilibrium of
extraction (experiments 2, 9 and 10). Experiments 3, 11 and 12 reveal that the optimum extraction time is 30 min under the 30%
(w/v) NaCl concentration. Although the relative peak areas of each
C6C12 measured under the tenth and eleventh experimental conditions are large, their reproducibilities under the two experimental conditions are bad. Furthermore, since the main LHs used for
geochemical indicators fall in the range of C6C8 alkanes, no addition of NaCl is selected in this study. Consequently, the condition
in the seventh experiment is selected as optimal, i.e., 1.5 ll of nhexadecane, 1000 rpm stirring rate, 30 min extraction time and
0% NaCl concentration for the determination of LHs in the following work.
3.2. Evaluation of HS-SDME
Validation procedures of the HS-SDME method for quantitative
analysis of C6C12 LHs were performed under the optimized conditions described in Section 3.1. The working solutions for the calibration study were prepared by spiking boiled pure water with
the stock solution over concentration ranges of 10.51836, 6.70
2172, 1.411680, 1.471752, 1.752088, 1.451728, 1.762100,

Fig. 1. Typical gas chromatogram of C6C12 light hydrocarbons extracted from the working solution by HS-SDME method using n-hexadecane as an extraction solvent. 1 = nhexane (130 lg/l), 2 = benzene (154 lg/l), 3 = n-heptane (119 lg/l), 4 = methylcyclohexane (124 lg/l), 5 = toluene (148 lg/l), 6 = n-octane-d18 (IS, 472 lg/ml), 7 = n-octane
(123 lg/l), 8 = ethylbenzene (149 lg/l), 9 = o-xylene (156 lg/l), 10 = n-nonane (127 lg/l), 11 = n-decane (123 lg/l), 12 = n-undecane (247 lg/l), 13 = n-dodecane (236 lg/l).

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C. Fang et al. / Organic Geochemistry 42 (2011) 316322

Peak Area

4500
4000

n-C6

3500

Benzene
n-C7
MCH

3000

Toluene

2500

n-C8 -d 18
n- C8
EB
o-Xylene

2000
1500
1000

n- C9
n- C10

500

n- C11

10

11

12

n- C12

Experiments
Fig. 2. Peak areas of C6C12 light hydrocarbons per microliter using the HS-SDME method under different extraction conditions at concentrations of each compound as
n-hexane (3.06 lg/ml), benzene (3.62 lg/ml), n-heptane (2.80 lg/ml), methylcyclohexane (2.92 lg/ml), toluene (3.48 lg/ml), n-octane-d18 (0.48 lg/ml), n-octane (2.88 lg/
ml), ethylbenzene (3.50 lg/ml), o-xylene (3.66 lg/ml), n-nonane (2.98 lg/ml), n-decane (2.88 lg/ml), n-undecane (5.80 lg/ml) and n-dodecane (5.54 lg/ml) in the
water.

1.842196, 1.501788, 2.381728, 4.793480 and 4.573324 lg/l

in the water for n-hexane, benzene, n-heptane, methylcyclohexane, toluene, n-octane, ethylbenzene, o-xylene, n-nonane, n-decane, n-undecane and n-dodecane, respectively. The calibration
curves were constructed using ratios of peak area of each C6C12
LHs to the internal standard (ACn/AIS) versus the corresponding
concentration ratios (CCn/CIS). Linearity was evaluated according
to the correlation coefcients of the regression equations of the
calibration curves. The calculated calibration curves showed good
linearity for all C6C12 LHs, with the correlation coefcients (R2)
ranging from 0.9953 to 0.9999 (Table 2).
Reproducibility of the method was examined by extracting ve
parallel working solutions at the concentrations of 158 lg/l (nhexane), 187 lg/l (benzene), 144 lg/l (n-heptane), 150 lg/l (methylcyclohexane), 179 lg/l (toluene), 148 lg/l (n-octane), 180 lg/l
(ethylbenzene), 189 lg/l (o-xylene), 154 lg/l (n-nonane), 148 lg/l
(n-decane), 299 lg/l (n-undecane) and 285 lg/l (n-dodecane) in
water under optimized experimental conditions. As shown in
Table 2, relative standard deviations (RSD, %) vary between 3.8%
and 6.1%, indicating that the reproducibility of this extraction
method is satisfactory.
HS-SDME is a non-exhaustive extraction technique. However,
the large decrease of the acceptor to donor phase ratio permits
large enrichment factors (Pena-Pereira et al., 2009), as was shown
in this work. The concentration enrichment (E) is calculated by the
following equation for each analyte:

Ei

C i;a
C i;s

where Ei is the concentration enrichment of the compound i. The

terms Ci,a and Ci,s are the concentrations of i originally present in
the sample and the concentration of the compound nally collected
in the acceptor solution, respectively. The calculated enrichment
factors range from 200 to 4095 for C6C12 LHs from 5 ml water
(Table 2). Detection limits between 0.264.33 lg/l (Table 2) were
calculated according to the signal that differed 10 times from the
blank average signal.
3.3. Applications
For high concentration oils, the sample need be diluted with
methanol prior to HS-SDME. Approximately 40 ll of the oil sample
from the Tarim Basin was added to a 4 ml glass vial and weighed.
The vial was then lled with a certain volume of methanol, tightly
capped and extracted ultrasonically for 10 min. Three replicate
extractions were performed on the methanol solution by using
the optimized extraction conditions of HS-SDME. In this case, the
matrix effect of crude oil must be negligible, because the dilution
factor is close to 10,000. To check the performance of the HS-SDME
method, a direct injection of the whole oil was conducted. Fig. 3
shows the distribution of C6C12 LHs in the crude oil achieved by
the HS-SDME method and the direct injection method. Compared

Table 2
Quantitative results of HS-SDME.
Analyte

Equation

R2

Linear range (lg/l)

RSD (%, n = 5)

LOD (lg/l)

Enrichment factor

n-C6
Benzene
n-C7
MCH
Toluene
n-C8
Ethylbenzene
o-Xylene
n-C9
n-C10
n-C11
n-C12

y = 1197.6x + 0.0962
y = 474.71x + 0.0027
y = 2922.7x + 0.0433
y = 3457.6x + 0.0468
y = 1467.9x + 0.0092
y = 5290.6x + 0.0658
y = 3222.1x + 0.0158
y = 5909.8x + 0.0299
y = 7258.3x + 0.0299
y = 8041.8x + 0.0651
y = 7080.1x + 0.0644
y = 5078.3x + 0.165

0.9989
0.9997
0.9993
0.9991
0.9997
0.9997
0.9997
0.9999
0.9999
0.9999
0.9995
0.9953

10.51836
6.702172
1.411680
1.471752
1.752088
1.451728
1.762100
1.842196
1.501788
2.381728
4.793480
4.573324

6.1
4.1
5.9
5.8
4.1
5.2
4.2
3.8
5.6
3.9
4.8
3.8

1.71
4.33
0.70
0.60
1.40
0.39
0.64
0.35
0.28
0.26
0.29
0.41

535
200
1378
1557
685
2698
1546
3662
3662
4095
3321
2209

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C. Fang et al. / Organic Geochemistry 42 (2011) 316322

Fig. 3. Gas chromatograms of the C6C12 light hydrocarbons extracted from the Tarim Basin oil by using: (a) the HS-SDME method and (b) the direct injection method. 1 = nhexane, 2 = benzene, 3 = n-heptane, 4 = methylcyclohexane, 5 = toluene, 6 = n-octane-d18 (IS), 7 = n-octane, 8 = ethylbenzene, 9 = o-xylene, 10 = n-nonane, 11 = n-decane,
12 = n-undecane, 13 = n-dodecane.

with the LH distribution from the direct GC injection (Fig. 3b), the
concentrations of n-hexane, benzene and C10C12 n-alkanes are
low when analyzed by HS-SDME (Fig. 3a). This may be explained
by relatively higher or lower boiling points for these compounds,
such that a higher boiling point does not favor the volatilization
of C10C12 n-alkanes from the donor phase, while a lower boiling
point allows n-hexane and benzene to escape easily from the
acceptor solution. This kind of effect from the HS-SDME method
could be corrected by calibration curves. In addition, the result of
three replicated analyses shows that the HS-SDME technique has
a good reproducibility, RSD (%) being less than 5% for most target
compounds.
The drilling mud was taken as an example of a low concentration and aqueous phase in this study. Headspace gas analyses of
the drilling mud samples from a well in the South China Sea
showed several intervals with relatively higher concentrations in

C2C5 gaseous hydrocarbons, inferring the presence of oil or gas

layers. A mud sample from one of these intervals was selected to
determine the C6C12 LHs using the optimized HS-SDME technique. Firstly, 5 ml of liquid from the drilling mud was transferred
into a 10 ml glass vial equipped with a magnetic stir bar. Then, the
other procedures were the same as above. Fig. 4 shows the gas
chromatogram obtained from the drilling mud. Abundant C6C12
LHs were found in the drill mud sample, indicating that this interval may be an oil layer.
Although the uptake of the C6C12 LHs using HS-SDME may be
affected by the complex mud matrix, the percent recovery determination of surrogates added to the matrix can give some indication of
the degree of the matrix effect. Alternatively, the dilution with organic free pure water for the oil based mud sample with high concentration hydrocarbons will minimize the matrix effect. Therefore,
further study will be needed for real geological applications.

C. Fang et al. / Organic Geochemistry 42 (2011) 316322

321

Fig. 4. Gas chromatogram of C6C12 light hydrocarbons extracted from the drilling mud sample. 1 = n-hexane, 2 = 2,4-dimethylpentane (24DMP), 3 = benzene (Ben),
4 = cyclohexane (CH), 5 = n-heptane, 6 = methylcyclohexane (MCH), 7 = toluene (Tol), 8 = n-octane-d18 (IS), 9 = n-octane, 10 = ethylbenzene (EB), 11 = m + p-xylene, 12 = oxylene-d10 (IS), 13 = o-xylene, 14 = n-nonane, 15 = 1,2,4-trimethylbenzene (124TMB), 16 = n-decane, 17 = n-undecane, 18 = naphthalene (Na), 19 = n-dodecane, 20 = 2,2dimethylpentane (22DMP), 21 = 2,2,3-trimethylbutane (223TMB), 22 = 3,3-dimethylpentane (33DMP), 23 = 2-methylhexane (2MH), 24 = 2,3-dimethylpentane (23DMP),
25 = 1,1-dimethylcyclopentane (11DMCP), 26 = 3-methylhexane (3MH), 27 = cis 1,3-dimethylcyclopentane (c13DMCP), 28 = trans 1,3-dimethylcyclopentane (t13DMCP),
29 = 3-ethylpentane (3EP), 30 = trans 1,2-dimethylcyclopentane (t12DMCP), 31 = ethylcyclopentane (ECP).

4. Conclusions

Acknowledgements

In this work, the HS-SDME method was optimized for the

extraction of C6C12 LHs from the aqueous phase. n-Hexadecane
was found to be a suitable extraction solvent. Extraction conditions were optimized and 1.5 ll extraction solvent, 1000 rpm stirring rate, 30 min extraction time and no NaCl were selected.
Under the optimized extraction conditions, calibration curves
with good linearity and reproducibility were obtained, with the
correlation coefcients ranging between 0.9953 and 0.9997, and
RSD (%) values ranging from 3.8% to 6.1% (n = 5). The enrichment
factors for C6C12 LHs ranged from 2004095. Based on the
advantages of HS-SDME method, i.e., less organic solvent and
time consumption, no sample carry over, simple operation and
high enrichment, we believe that it is an alternative method for
the extraction of volatile C6C12 LHs in complex matrices. Two
examples using this method indicated that the HS-SDME can be
used for the determination of the C6C12 LHs in petroleum and
drilling muds. In addition, combined with ultrasonic extraction
(methanol as an extraction solvent), it can also be easily expanded to the determination of C6C12 LHs in solid samples, such
as soils. Therefore, HS-SDME is a simple, efcient and promising
technique for the determination of volatile C6C12 LHs in complex
matrices.

This work was nancially supported by the Chinese Academy of

Sciences (Grant No. KZCX2-YW-JC103) and the National Natural
Science Foundation of China (Grant No. 40972096). This is contribution No. IS-1287 from GIGCAS. We thank Mark Obermajer,
Simon C. George and two anonymous reviewers for their constructive comments.

Associate EditorSimon George

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