Talanta 146 (2016) 417–422

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Talanta
journal homepage: www.elsevier.com/locate/talanta

Direct determination of acrylamide in potato chips by using headspace

solid-phase microextraction coupled with gas chromatography-flame
ionization detection
Ali Reza Ghiasvand n, Somayeh Hajipour
Department of Chemistry, Lorestan University, Khoramabad, Iran

art ic l e i nf o a b s t r a c t

Article history: Acrylamide is a potentially toxic and carcinogenic substance present in many high-consumption foods.
Received 22 June 2015 Recently, this matter has been placed in category of “reasonably anticipated to be a human carcinogen”
Received in revised form by National Toxicology Program (NTP). Therefore, simple and cost-effective determination of acrylamide
3 September 2015
in food samples has attracted intense interest. The most reported techniques for this purpose are GC–MS
Accepted 4 September 2015
Available online 7 September 2015
and LC–MS, which are very expensive and available in few laboratories. In this research, for the first time,
a rapid, easy and low-cost method is introduced for sensitive and precise determination of acrylamide in
Keywords: foodstuffs, using gas chromatography-flame ionization detection (GC-FID) system after its direct trapping
Acrylamide in the upper atmosphere of samples by headspace solid-phase microextraction (HS-SPME). The effects of
Fried foods
main experimental variables were studied and the optimized parameters were obtained as the type of
Headspace solid-phase microextraction
fiber, carboxen/divinylbenzene/polydimethylsiloxane (CAR/DVB/PDMS); extraction time, 30 min; ex-
GC-FID
traction temperature, 60 °C; moisture content, 10 mL water per 1 g of sample; desorption time, 2 min; and
desorption temperature, 230 °C. The linear calibration graph was obtained in the range of 0.77–
50 mg g
1, with regression coefficient of 0.998. The detection and quantification limits of the proposed
method were 0.22 and 0.77 mg g
1, respectively. The recoveries, for different food samples, were 79.6–
95.7%. The repeatability of measurements, expressed as relative standard deviation (RSD), were found to
be 4.1–8.0% (n ¼9). The proposed HS-SPME-GC-FID method was successfully carried out for quantifying
of trace levels of acrylamide in some processed food products (chips and French fries), sold in open local
markets.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction Maillard browning reaction, which is an interaction between the

amino group of asparagine free amino acid and the carbonyl
On April 24, 2002, researchers at Swedish National Food Ad- groups of reducing sugars such as glucose and fructose, at higher
ministration and a scientific group at Stockholm University jointly temperatures and low moisture contents [6–9]. The alternative
published data and comments on disturbances caused by high mechanisms include reactions of other amino acids such as ala-
concentrations of acrylamide in various foodstuffs, particularly in nine, arginine, aspartic acid, cysteine, glutamine, methionine,
fried, roasted and baked starchy foods [1,2]. Acrylamide threonine, and valine with other sugars such as galactose, lactose,
(Scheme 1) is an odorless white crystalline solid with a molecular and sucrose [10]. The foods rich in these precursors are mainly
weight of 71.08 and melting point of 84.5 70.3 °C. It has a low derived from plant sources including potatoes and cereals (e.g.,
vapor pressure (0.005 mmHg at 25 °C) and a high boiling point barley, rice and wheat). The processed foods with high levels of
acrylamide like French fries, potato chips, crisp bread as well as
(136 °C at 3.3 kPa/25 mmHg) [3]. Its solubility in polar and non-
various baked products and cereal formulations show a wide range
polar organic solvents varies considerably, but its solubility in
of acrylamide level, different in category and brand of food. The
water is extremely high [4]. Acrylamide has been classified as a
amounts of precursors and their variations in processing condi-
“probable human carcinogen” (Group 2A) by the International
tions may explain the variable levels of acrylamide [11,12].
Agency for Research on Cancer (IARC) [5]. Over the last years, various methods have been developed for
Acrylamide formation in foods is mainly attributed to the the determination of acrylamide in the heat-treated carbohydrate-
rich foods [13,14]. UE 8316 procedure, established by US En-
n
Corresponding author. Fax: þ 98 66 33120610 12. vironmental Protection Agency (EPA), utilizes high-performance
E-mail address: [email protected] (A.R. Ghiasvand). liquid chromatography (HPLC) coupled to ultraviolet–visible (UV)

http://dx.doi.org/10.1016/j.talanta.2015.09.004
0039-9140/& 2015 Elsevier B.V. All rights reserved.
418 A.R. Ghiasvand, S. Hajipour / Talanta 146 (2016) 417–422

and effective sample preparation technique which uses a fused-

silica or metal fiber, coated on the outside with an appropriate
stationary phase. The analytes are directly transported from the
sample matrix, or indirectly from the headspace, to the fiber's
coating and the trapped analytes are then thermally desorbed into
the GC injector [38]. It is interesting to note that, there is only one
report about the measurement of acrylamide using GC-FID. In this
research, Pedersen et al. developed a Soxhlet extraction method
coupled to GC-FID for the quantification of acrylamide from potato
chips [30]. In this way, a defatted potato chips sample was con-
tinuously extracted by methanol for 10 days. A constant con-
Scheme 1. Acrylamide (prop-2-enamide). centration of acrylamide in the extract was appeared after about
7 days. However, the application of such a time-consuming and
detection (at 195 nm) with the limit of detection (LOD) of tedious method showed a detection limit of 14500 μg kg
1, using
10 μg L
1, in aqueous matrices [15]. In addition, gas chromato- GC–MS and GC-FID by standard addition procedure.
graphy-electron capture detection (GC-ECD) based on the bromi- The aforesaid descriptions clarify that the need for fast, simple,
nation of acrylamide double bound, was used in aqueous matrices low-cost, and effective methods for the extraction and determi-
and resulted in an LOD of 0.032 mg L
1 [16]. In UE 8032a method, nation of acrylamide is an undeniable fact. Accordingly, this re-
acrylamide was analyzed by liquid chromatography (LC) in com- search tries to develop an easy, fast and inexpensive technique for
bination with pulsed amperometric detection (LC-PAD) and the the effective extraction and quantification of acrylamide in food
LOD was 1.4 mg kg
1[17]. In another report, liquid chromato- samples using headspace solid-phase microextraction (HS-SPME)
graphy–tandem mass spectrometry (LC–MS/MS) with the LOD of coupled to GC-FID. Therefore, an HS-SPME-GC-FID method for the
13 mg kg
1 was used to determine acrylamide in food samples headspace sampling and determination of acrylamide, released
[18]. The content of acrylamide was also determined, after deri- from the heated potato chips and French fries samples, was de-
vatization in aqueous samples, by using GC–MS in the selected ion veloped, optimized, and validated. A commercial SPME fiber with
monitoring (SIM) mode with the LOD of 0.9 mg kg
1 [19]. A solid- carboxen/divinylbenzene/polydimethylsiloxane (CAR/DVB/PDMS)
phase extraction ultra-performance liquid chromatography (SPE- coating was used to extract trace acrylamide from the headspace
UPLC) strategy with UV detection at 202 nm, for batch determi- of solid matrices followed by GC-FID measurement, without de-
nation of acrylamide in mainstream cigarette smoke, was released rivatization and without any sample preparation step. The effec-
in 2009 [20]. In this method, LOD was found to be 10 ng mL
1. tive parameters on the extraction and determination of acrylamide
Pedreschi et al. used near infrared interactance and visual re- were evaluated and optimized for the proposed HS-SPME-GC-FID
flectance imaging to analyze the content of acrylamide in potato method, using a model solid matrix. Then, the optimized HS-
chips [21]. HPLC-MS method with the LOD of 5 mg kg
1 was used SPME-GC-FID strategy was evaluated to quantify acrylamide in
to determine acrylamide in some types of bread [22]. In 2014, the potato chips and French fries samples provided by local super-
enzyme-linked immunosorbent assay (ELISA) procedure was used markets and fast-food restaurants.
to determine acrylamide in fried foods with the LOD of 5 ng mL
1
[23]. A deep literature review showed that various other techni-
ques have also been used for quantification of trace amounts of 2. Experimental
acrylamide in food samples include adsorption stripping voltam-
metry (ASV) [24], fluorescence detection (FLD) [25], derivatization 2.1. Materials and solutions
with trifluoroacetic anhydride (TFAA) followed by GC-ECD [26]
and GC-ion trap mass spectrometry (GC-IT-MS) determination Acrylamide (purity 499.9%, electrophoresis grade, catalog no:
[27]. 1.10784) was purchased from Merck chemical company (Darm-
Among the aforementioned techniques for the determination stadt, Germany) and used without further purification. Analytical-
of acrylamide, GC–MS and LC–MS–MS appeared to be the most grade acetonitrile was also supplied by Merck. Acrylamide stock
widely used methods [13,28,29]. Although, these instruments solution (1000 mg L
1) was prepared by dissolving 0.1000 g of it
show proper precision and accuracy for the quantification of ac- in acetonitrile and diluted to 100 mL in a volumetric flask. The
rylamide, they are highly expensive, and the issue of the main- working standard solutions, for obtaining linear calibration graph
tenance and management of them is mostly a major problem, for and using throughout the optimization process, were prepared by
many ordinary laboratories. On the other hand, people today have further dilution of the stock solution to the concentration se-
a keen interest in fried fast foods and many food quality control quences over the range of 5–100 mg L
1. All stock and working
laboratories are required to use simple and low-cost techniques to standards were stored at 4 °C until analysis.
determine acrylamide. Thus, in this article, we use a rapid and
less-expensive method (GC-FID) for the determination of acryla- 2.2. Instrumentation
mide in foodstuffs for the first time.
Acrylamide is extracted from food samples using various SPME manual fiber holder and 30/50-μm CAR/DVB/PDMS, 65-
methods including Soxhlet [30], liquid–liquid extraction (LLE) μm carbowax/divinylbenzene (CW/DVB), 85-μm polyacrylate (PA),
[31,32], sonication [33], dispersion [34], and solid-phase extraction and 100-μm polydimethylsiloxane (PDMS) commercial fibers were
(SPE) [35,36]. However, these conventional extraction methods obtained from Supelco Company (Bellefonte, PA, USA). Prior to the
show significant disadvantages of beeing time-consuming and the first usage, the fibers were conditioned according to the manu-
high amounts of organic solvents required. Furthermore, using facturer’s recommended procedures. The extractions were per-
large volumes of organic solvents usually interferes with the trace formed in 10-mL sample vials with crimp caps and PTFE-coated
analysis of acrylamide through chromatographic or electro- silicone septa (Supelco). An A3229 Unicam ProGC gas chromato-
chemical techniques. To overcome the drawbacks of conventional graph (USA), equipped with a BP20 polar capillary column (poly-
extraction methods, solid-phase microextraction (SPME) was de- ethylene glycol, 30 m  0.25 mm  0.25 μm) from SGE Company
veloped in 1990 [37]. SPME, as a solvent-free method, is a reliable and a flame ionization detector (FID), was employed for the
 A.R. Ghiasvand, S. Hajipour / Talanta 146 (2016) 417–422 419

separation and determination of acrylamide. Nitrogen (99.999%) 70

was used as the carrier gas, with a constant flow rate of
60
2.3 mL min
1. The optimized temperature program to be applied
in the GC-FID was as follows: It was started from 45 °C by 2 min 50
hold time, and then raised to 150 °C by the rate of 10 °C min
1.

Peak Area
The temperature of the detector and injector was held at 200 and 40
230 °C, respectively. Under these conditions, acrylamide was
30
eluted at a retention time of 4.038 min.
20
2.3. Preparation of model solid matrix
10
For more realistic evaluation and optimization of the experi-
0
mental conditions in HS-SPME experiments, it is recommended to PDMS PA CW/DVB CAR/PDMS/DVB
use a real sample matrix without analytes, especially for solid
Fig. 1. Comparison of different commercial fibers for extraction of acrylamide from
samples [39]. Therefore, 100 g of raw and non-heated potato was the potato model matrix (error bars represent SD for three replicate experiments).
cut using an electric slicing machine and the resulted slices were
rinsed in distilled water to remove starch from their surface. Then, is similar to that of acrylamide.
potato slices were dried by using a household fruit-dryer (Fuma
Star fruit-dryer, model FU-731) at 45 °C for 20 h and homogenized
3.2. Optimization of extraction temperature
by means of a Kenwood kitchen blender (Kenwood, model BL 530,
UK). This sample was considered as the blank (control) or model
Headspace sampling is the most effective and interference-free
solid sample matrix, for using throughout the optimization
mode of SPME, which extracts analytes from the sample without
experiments.
the contact of fiber with the matrix [41]. On the other hand, re-
leasing low volatile analytes from their native matrix into the
2.4. Preparation of real sample
headspace and subsequent collecting volatiles onto microextrac-
tion phase are two main challenges in HS-SPME are especially in
Potato chips samples were purchased from local supermarkets
complicated solid matrices. The most effective solution to release
and French fries were prepared from fast-food restaurants in
analytes from their matrix is thermal desorption with several
Khoramabad (Lorestan Province in west of Iran). The samples were
advantages, such as providing enough kinetic energy, reinforcing
homogenized by using the kitchen blender and stored in clean
molecules to escape from their matrix, enhancing the mass
vials at room temperature.
transfer to pass through the matrix, and increasing their con-
centration in the headspace by increasing their vapor pressure.
2.5. HS-SPME sampling of acrylamide
However, due to the exothermic character of adsorption, increas-
ing temperature of the sample can conversely decrease the trap-
The SPME fiber was fitted into a manual holder and located into
ping of analytes onto the fiber’s coating. Indeed, temperature has a
the headspace above the sample for the extraction of acrylamide
bilateral effect. It increases the extraction efficiency by increasing
(30 min at 60 °C). The fiber was then withdrawn into the needle
the concentration in the headspace, but decreases the tendency of
and immediately injected into GC-FID system. Desorption of the
adsorbed analytes onto the coating. Therefore, in the temperature
analyte was performed at 230 °C for 2 min. Acrylamide was de-
termined in triplicate by using a GC-FID system. profile of any HS-SPME sampling, there is usually an ascending
part and following that a descending region, with an optimum
temperature between them [42]. In this study, the effect of ex-
3. Results and discussion traction temperature on the amounts of analytes trapped on the
fiber's coating was evaluated by exposing the fiber to the sample
The extraction efficiency of SPME experiments may be affected headspace for 30 min at different temperatures. As shown in Fig. 2,
by the sorbent type, extraction method, extraction temperature, the extraction amount of acrylamide reaches to its maximum at
desorption temperature and time, sample matrix, and some other 60 °C. Thus, 60 °C was chosen as the optimum extraction tem-
variables according to the characteristics of method, detection perature. The extraction temperature profile of the proposed HS-
system, and sample matrix [19,40]. Different types of coatings SPME method is in accordance with the aforesaid descriptions. It
provide different absorption/adsorption properties for different
90
kinds of analytes. The choice of an appropriate coating is crucial
for the SPME method. Therefore, to obtain the highest efficiency
for the extraction and quantification of acrylamide using the 80
proposed HS-SPME-GC-FID strategy, type of fiber's coating, ex-
Peak Area

traction temperature and time, moisture content of sample, des-

70
orption time, and desorption temperature were evaluated as the
important effective experimental factors.
60
3.1. Effect of fiber's coating type

Various fiber coatings such as PDMS, PA, CW/DVB, and CAR/ 50

DVB/PDMS fibers were examined for the extraction of acrylamide 25 30 35 40 45 50 55 60 65

by using the HS-SPME-GC-FID method. The results revealed that Extraction temperature (°C)
the CAR/DVB/PDMS fiber was the best for the acrylamide extrac- Fig. 2. Effect of extraction temperature on the extraction efficiency of acrylamide
tion (Fig. 1). This preference is attributed to the polarity of acry- using the proposed HS-SPME-GC-FID method (conditions: fiber, CAR/PDMS/DVB;
lamide. The CAR/DVB/PDMS fiber is a polar coating, and its polarity extraction time, 30 min).
420 A.R. Ghiasvand, S. Hajipour / Talanta 146 (2016) 417–422

70
100

60 80

Peak Area
Peak Area

60
50
40

40
20

30 0
5 15 25 35 45 55 0 2 4 6 8 10 12

Extraction time (min) Water added to sample (µL/g)

Fig. 3. Effect of extraction time on the extraction efficiency of the HS-SPME Fig. 4. Changes trend of extraction efficiency of acrylamide vs. addition of different
strategy used to extract acrylamide (conditions: fiber, CAR/PDMS/DVB; extraction volumes of water to sample matrix (conditions: fiber, CAR/PDMS/DVB; extraction
temperature, 60 °C). temperature, 60 °C; extraction time, 30 min).

140
increases with temperature (ascending part) to 60 °C (maximum
130
temperature) and decreases after that (descending region).
120

Peak Area
3.3. Optimization of extraction time
110

In the next step, the extraction time profile of the HS-SPME 100
procedure was established by plotting the amount of the extracted
acrylamide against time. As show the results, the extracted 90

amount of acrylamide increases with passing the time to 30 min

80
(Fig. 3). Longer times would be anticipated to have no serious ef- 1 2 3 4 5 6 7 8 9 10
fect on the extraction efficiency. However, the extraction efficiency
Desorption time (min)
decreases with a gentle slope after 30 min. These observations
may be due to the sorption of the likely interfering substances in Fig. 5. Influence of fiber's retaining time in GC injector on the amount of desorbed
acrylamide (conditions: fiber, CAR/PDMS/DVB; extraction temperature, 60 °C; ex-
the sample matrix. These interfering compounds may compete
traction time, 30 min; water added to sample, 10 mL g
1).
with the analyte in longer times. Therefore, 30 min was chosen as
the optimal extraction time. 3.6. Study of the effect of desorption temperature

3.4. Study of the amount of water added to sample matrix In addition to desorption time, desorption temperature is an-
other important factor which should be optimized for the com-
There are usually many unknown variables that may affect the plete release of analytes from the SPME fiber into the GC injector.
attachment of an analyte to its native matrix in solid samples, To obtain the best desorption condition, different temperatures
especially foods and plants [39]. Therefore, routine extraction over the range of 150–250 °C, were applied in 2 min as desorption
strategies are not usually able to completely release analytes from
time. The results revealed that the chromatographic peak area of
their matrix. In addition to thermal desorption, another effective
acrylamide increases with temperature up to 230 °C and then re-
way is the use of modifier. Water is a suitable modifier, which
mains relatively constant (Fig. 6). Therefore, 230 °C was chosen as
strongly adsorbed on the active sites of sample matrix competi-
the suitable desorption temperature for the complete elution of
tively and releases analyte molecules, especially in matrices
acrylamide through its extraction and determination using the
formed along with biological processes. In this research, different
amounts of water were added to the sample for more effective proposed HS-SPME-GC-FID method.
release of acrylamide from the potato matrix. It is obvious from
160
the results that the extraction efficiency increases with the spike
of water to 10 mL g
1 and then starts decreasing (Fig. 4). Any de-
crease in the extraction efficiency may be due to creating a high 140
water vapor pressure in the headspace, which can compensate for
Peak Area

the analyte trapping on the SPME fiber or the probable analyte

120
leakage from the extraction vial [42].

100
3.5. Study of the desorption time

The time of placing fiber into the GC injector for the complete 80
release of the trapped acrylamide from the fiber's coating, i.e. 140 160 180 200 220 240
desorption time, was investigated within a range of 1–6 min. The Desorption temperature (°C)
experimental findings summarized in Fig. 5 indicate that 2 min is
Fig. 6. Effect of different desorption temperatures on the peak area of acrylamide
sufficient for the complete desorption of acrylamide from the fiber.
extracted by the proposed HS-SPME-GC-FID procedure (conditions: fiber, CAR/
Thus, this interval time (2 min) was considered as the optimal PDMS/DVB; extraction temperature, 60 °C; extraction time, 30 min; water added to
desorption time for further studies. sample, 10 mL g
1; desorption time, 2 min).
 A.R. Ghiasvand, S. Hajipour / Talanta 146 (2016) 417–422 421

Table 1 comparable as reported in Table 2.

Recovery percent for potato chips and French fries samples (without acrylamide)
spiked with 20 mg g
1 of acrylamide and determined using the proposed HS-SPME-
GC-FID method.
4. Conclusion
Sample Acrylamide determined (lg g
1) Recovery (%) RSD (%)
Despite the impressive advances in the analysis of hazardous
Potato chips 1 18.64 93.2 8.0
materials, extraction of acrylamide in food samples is still con-
Potato chips 2 16.46 82.3 5.2
Potato chips 3 15.92 79.6 4.1 ducted by using conventional extraction methods such as Soxhlet.
French fries 1 17.42 87.1 7.4 Additionally, acrylamide is mainly determined through expensive
French fries 2 19.14 95.7 6.7 and complicated techniques of GC–MS and LC–MS which are
French fries 3 17.58 87.9 5.1 rarely available in routine food's quality control laboratories [27–
29]. Due to importance of the tracing of acrylamide, existing in
many staple foods, this research tries to introduce a rapid, low-
Table 2 cost and reliable method for the accurate quantification of acry-
Concentration of acrylamide in potato chips samples obtained by the proposed HS-
lamide in foodstuffs. For this purpose, HS-SPME approach, as a
SPME-GC-FID method and a validated Soxhlet-GC–MS extraction procedure (n¼ 3).
solvent-free sample pretreatment method, was employed for the
Sample Acrylamide determined (lg g
1) by fast and efficient extraction of acrylamide from foods, with the
least preparation steps. Moreover, expensive detection systems
The proposed HS-SPME-GC-FID Soxhlet-GC–MS
such as MS were replaced by FID as a low-cost and easily available
Potato chips 1 6.157 6.2 8.56 7 5.3 detector, with reasonable sensitivity and without any derivatiza-
Potato chips 2 4.87 7 7.4 6.917 3.1 tion process. This newly developed HS-SPME-GC-FID method is
Potato chips 3 7.38 7 2.3 9.017 5.0 simple, fast, low-cost, sensitive, and requires no sample pretreat-
ment and no derivatization step. It was successfully used to extract
and determine acrylamide in potato chips and French fries sam-
3.7. Analytical performance ples. Verifying the results of the real samples showed that the
concentration of acrylamide in these kinds of potato chips is quite
The linear dynamic range (LDR), limit of detection (LOD), limit high compared to the other types, studied before. This may be due
of quantification (LOQ), and repeatability of the method were to multiple use of frying oil for economic saving, duration of frying,
characterized when the optimum conditions for the HS-SPME-GC- and different dough formulations.
FID procedure were established. The LDR was determined by ex-
tracting the spiked model samples with acrylamide over the
concentration range of 0.1–75 mg g
1 in triplicate experiments. In Acknowledgments
this way, the LDR was found to be in the range of 0.77–50 mg g
1
with the regression equation "Peak area ¼0.8778 Ac- The authors sincerely acknowledge the director and staff of
rylamide
0.1597" and the correlation coefficient "R2 ¼ 0.9977". Lorestan Environmental Protection Department for using their GC-
The LOD and LOQ, obtained as the minimum amount of the ana- FID system. They are also grateful to Dr. Fershteh Mousavi, English
lyte producing a signal-to-noise ratios of 3 and 10 (S/N ¼ 3 and 10), translator and instructor, for proofreading this article.
were found to be 0.23 and 0.77 μg g
1, respectively.

3.8. Analysis of real samples and comparison with the standard References
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