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Journal of Chromatography A, 1213 (2008) 239–244

Contents lists available at ScienceDirect

Journal of Chromatography A

journa l homepage: www.e lsev ier .com/ locate /chroma

hort communication

evelopment of solid-phase microextraction followed by gashromatography–mass spectrometry for rapid analysis ofolatile organic chemicals in mainstream cigarette smoke

ing Ye ∗

epartment of Chemistry, Shangrao Normal University, Shangrao 334001, Province of Jiangxi, China

r t i c l e i n f o

rticle history:eceived 24 June 2008eceived in revised form 9 October 2008ccepted 14 October 2008vailable online 21 October 2008

a b s t r a c t

In this work, a novel, simple and efficient method based on solid-phase microextraction (SPME) fol-lowed by gas chromatography–mass spectrometry (GC–MS) was developed to the analysis of volatileorganic chemicals (VOCs) in mainstream cigarette smoke (MCS). Using a simple home-made smokingmachine device, extraction and concentration of VOCs in MCS were performed by SPME fiber, and theVOCs adsorbed on fiber were desorbed, and analyzed by GC–MS. The extraction fiber types and the des-

eywords:olatile organic chemicalsainstream cigarette smoke

olid-phase microextractionas chromatography–mass spectrometry

orption conditions were studied, and the method precision was also investigated. After the investigation,the optimal fiber was divinylbenzene/carboxen/polydemethylsiloxane (DVB/CAR/PDMS), and the optimaldesorption condition was 250 ◦C for 3 min. The method precision was from 2% to 11%. Finally, the pro-posed method was tested by its application of the analysis of VOCs in MCS from 10 brands of cigarettesand one reference cigarette. A total of 70 volatile compounds were identified by the proposed method.The experimental results showed that the proposed method was a simple, rapid, reliable, and solvent-free

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. Introduction

Cigarette smoke, an aerosol composed of gases and hetero-eneous particles, is formed when tobacco is burned during themoking of cigarettes. Depending on the position where cigarettemoke is collected, cigarette smoke is classified into two classes:idestream and mainstream. Sidestream cigarette smoke refers tohe smoke emanating from the smoldering cigarette tip betweenuffs. Mainstream cigarette smoke (MCS) is emitted at the mouth-iece of a cigarette and inhaled by the smoker. More than 30,000ompounds were identified in MCS [1–4], the vast majority of whichre considered to be very toxic or carcinogenic [5,6]. MCS is tradi-ionally divided into two major phases: the total particulate matternd gas phase. Apart from the bulk gases, nitrogen, oxygen, andarbon oxides, cigarette smoke gas phase also consists of volatilerganic compounds (VOCs), nitrogen oxides and ammonia, etc. Dur-ng the past decades, the importance of gas-phase constituents,

specially the VOCs, on the cytotoxic and carcinogenic potential ofigarette smoke has been clearly demonstrated in several cellularnd animal systems [7–10].

∗ Fax: +86 793 8150645.E-mail address: sryq6333@163.com.

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021-9673/$ – see front matter © 2008 Elsevier B.V. All rights reserved.oi:10.1016/j.chroma.2008.10.063

n of VOCs in MCS.© 2008 Elsevier B.V. All rights reserved.

Due to the complexity of cigarette smoke in MCS, many attemptsave been made to separate and identify its constituents [11].ost methods used in the analysis of cigarette smoke focus onrelatively small number of target analytes [12–17]. Few stud-

es on characterization of VOCs in MCS have been published.18–20].

The chemicals in MCS were required to be collected and under-one further sample preparation, prior to GC–MS or HPLC. Manyechniques such as solvent-filled impinger trains [21,22], adsor-ent materials [23–25], cold traps [26,27], and direct injection ofhe gas sample [28,29] were developed for this purpose. Recently,olid-phase microextraction (SPME), a simple, rapid, solvent-freeample extraction and simultaneous concentration technique waseveloped. In the past years, the use of SPME followed by GC–MSas acquired increasingly importance in food analysis [30,31], drugnalysis [32–34], environmental analysis [35–37] and traditionalhinese medicinal analysis [38–40]. In tobacco research, SPMEechnique has been applied to the analysis of various additives41–43], phenolic compounds in cigarette smoke condensate [44],OCs in tobacco and MCS [45,18], various alkaloids present in

obacco [46], and free-base nicotine associated with the particulatehase portion of mainstream cigarette smoke [17].

In this work, we designed a simple smoking machine (Fig. 1)or the extraction and concentration of VOCs in MCS by SPMEechnique. The adsorbed VOCs on SPME fiber were analyzed and

240 Q. Ye / J. Chromatogr. A 12

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dentified by GC–MS. The experimental conditions and methodalidation were studied. The proposed method was successfullypplied to the analysis of VOCs in MCS from 10 brands of cigarettesnd one reference cigarette.

. Experimental

.1. Materials and SPME fibers

The following 10 brands of cigarette and one reference cigaretteere analyzed: brand A (a), brand B (b), brand C (c), brand D (d),rand E (e), brand F (f), brand G (g), brand H (h), brand I (i), brand J (j),R4F (k). All the cigarettes were purchased from Shanghai Tobaccoonopoly store and were conditioned at 60 ± 2% relative humidity

nd 22 ± 1 ◦C for 48 h prior to use. Reference cigarette (2R4F) wasbtained from Tobacco company (Jiangxi, China).

The SPME fibers including 65 �m polydimethylsiloxane/ivinylbenzene (PDMS/DVB), 65 �m carbowax/divinylbenzeneCW/DVB), 30 �m divinylbenzene/carboxen/polydimethylsiloxaneDVB/CAR/PDMS) and 85 �m polyacrylate (PA) were purchasedrom Supelco (Bellefonte, USA).

.2. The sampling technique

The cigarette samples were smoked to 3 mm distance to the filterip by simple smoking machine (Fig. 1). The home-made smoking

achine constituents of four parts, namely constant current con-tant voltage source controlling the puff condition, micro-pump,hree-way glass tube with a volume of 35 mL, and solid-phase

icroextraction instrument, respectively. The smoking conditionsere as follows: 1 puff/min, 2 s puff duration, and 35 mL puff

olume. SPME was carried out during the course of smoking.he extracted analytes on the fibers were desorbed in the GCnjector in splitless mode at 250 ◦C for 3 min, and analyzed byC–MS.

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13 (2008) 239–244

.3. GC–MS analysis

An HP 6890 GC system, coupled with a HP MD5973 quadrupoleass spectrometer was used. The extracted compounds were sepa-

ated on an HP-5MS capillary column (30 m × 0.25 mm I.D., 0.25 �mlm). Desorption of the SPME fibers was performed in splitlessode for 3 min. The column oven temperature was programmed

o rise from an initial temperature of 40 ◦C for 3 min, followed byfirst ramp to 200 ◦C at 10 ◦C/min, and a second ramp to 280 ◦C

t 15 ◦C/min, and 280 ◦C was maintained for 5 min. The injec-ion temperature and ion source temperature were 250 ◦C and30 ◦C, respectively. Helium was used as the carrier gas with a flowate of 1.0 mL/min. The ionizing energy was 70 eV. All data werebtained by collecting the full-scan mass spectra within the scanange of 40–450 amu. The compounds were identified using theIST (National Institute of Standards and Technology) mass spectra

ibrary (http://www.nist.gov) by the ChemStation Software.

.4. Investigation of the fiber coating

At first, SPME fiber coating was studied. Four different fibersf CW–DVB, PDMS–DVB, PA and DVB–CAR–PDMS were used forhe extraction of mainstream smoke components. Next, the SPMEonditions for desorption were tested. The desorption tempera-ure (220 ◦C, 250 ◦C and 280 ◦C) and the desorption time (1 min,min, 3 min and 4 min) were simultaneously investigated, using

he optimal SPME fiber.

.5. Precision of the proposed method

The method precision was studied by four replicate analyses ofhe VOCs in MCS by SPME–GC–MS. The precision was expressed byelative standard deviation (RSD) values of the peak areas of theOCs.

.6. Analysis of VOCs in MCS from different brands of cigarettesy the proposed method

The cigarette samples were smoked by the home-made smokingachine (Fig. 1), and the VOCs in MCS were extracted using theVB–CAR–PDMS fiber simultaneously. The extracted analytes on

he fibers were analyzed by GC–MS.

. Results and discussion

As we know, the importance of VOCs in MCS on the cytotoxic andarcinogenic potential of cigarette smoke has been clearly demon-trated in several cellular and animal systems [7–10]. The analysisnd identification of VOCs in MCS are very important and interest-ng. GC–MS is the powerful tool for the separation and identificationf VOCs in MCS. Prior to GC–MS, collection, extraction and concen-ration of VOCs in MCS should be done. As always, the VOCs in vaporhase and particulate phase were collected, using tedlar brandVF bags, and glass fiber Cambridge filter pads, respectively. Then,he collected VOCs in PVF bags and Cambridge filter pads wereespectively headspace extracted and concentrated by using SPMEechnique. Finally, the VOCs on fiber was desorbed and analyzed byC–MS [18]. In the proposed method, a novel sampling technique

Fig. 1) was proposed for collection, extraction and concentration

f VOCs in MCS. The extraction and concentration of VOCs in wholemoking (including vapor phase and particulate), were performedy directly exposing the SPME fiber to the whole smoke. This leadso the short sample preparation time (about 12 min). In addition,he proposed device is simple, cheap and effective for sampling of

Q. Ye / J. Chromatogr. A 1213 (2008) 239–244 241

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ig. 2. Influence of the investigated fibers on the SPME of VOCs in MCS with brandcigarette.

OCs in MCS. In the work, at first, sampling conditions and methodrecision were investigated.

.1. Optimization of the SPME fiber and desorption conditions

The choice of an appropriate coating is necessary for the SPMEethod. The extraction efficiency depends on the molecular mass

nd the polarity of the analytes. Four commercially available SPMEber coatings, with different polarity and inner structure, as men-ioned above were tested for the efficiency of SPME extraction ofOCs in MCS. Brand D cigarette was used to optimize the SPMEonditions. The five compounds of p-xylene, styrene, limonene, tri-cetin, nicotine in MCS, were used for the determination of theptimal fiber coating. Fig. 2 shows the effect of fiber coating on theeak areas of the five main compounds. As seen from Fig. 2, theest extraction efficiency was obtained by using DVB/CAR/PDMSber. Hence, the DVB/CAR/PDMS was regarded as the optimal fiberoating, and used in the work.

Next, the desorption temperature (220 ◦C, 250 ◦C and 280 ◦C)nd the desorption time (1 min, 2 min, 3 min and 4 min) weretudied. Fig. 3 shows the effect of desorption temperature and des-rption time on peak area sum of the five compounds (p-xylene,tyrene, limonene, triacetin, nicotine) in MCS. As seen from Fig. 3,he desorption reached balance at 250 ◦C for 3 min

.2. Precision of SPME–GC–MS

To obtain the method precision, four replicate analyses of VOCsn MCS (brand D, Production time: December, 2007) were per-ormed by SPME–GC–MS at the optimum conditions. The RSD

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Fig. 4. The total ion chromatogram of VOCs in MC

Fig. 3. The SPME conditions for desorption.

alues were calculated by their peak areas, and the obtainedSD values is from 1.3% to 10.9% Also, we used different brandigarettes (brand B, brand C, brand E, brand F) cigarettes, andhe same brand cigarettes with different production time (brand, Production time: December, 2007 and June, 2008) to investi-ate the method precision, the similar results (about 2–11%) wasbtained. This shows that the method has an acceptance preci-ion.

.3. Analysis of VOCs in MCS in different brands of cigarettes byhe proposed method

The proposed method was applied to the analysis of VOCsn MCS from different brands of cigarettes. The total ion chro-

atogram of VOCs in a cigarette mainstream smoke is shownn Fig. 4. The analytical results are shown in Table 1 . A totalf 70 volatile compounds were identified in MCS. As seenrom Table 1, different VOCs were detected in the differentrand of cigarette, and the common 38 compounds were pre-ented in all brands of cigarettes, which mainly include benzene,oluene, 2,5-dimethyl furan, ethylbenzene, p-xylene, styrene, 1-thyl-3-methyl benzene, 3-ethenyl pyridine, 1-ethenyl-3-methyl

enzene, 1,2-diethyl benzene, limonene, cyclopropyl benzene,

ndene, 1-undecene,1-methyl-4-(1-methylethenyl) benzene, 2-ethylindene, 1-butynyl benzene, 1-dodecene, naphthalene,

riacetin, nicotine, etc.

S by SPME–GC–MS with brand D cigarette.

242Q

.Ye/J.Chrom

atogr.A1213

(2008)239–244

Table 1Identification of volatile organic chemicals from mainstream cigarette smoke in 10 brands of cigarettes and one reference cigarette.

No. Retention time (min) Compounds MW Peak area (107)

A B C D E F G H I J K

1 3.13 Benzene 78 0.73 1.02 0.53 0.56 0.57 0.35 0.42 0.48 0.77 0.57 0.392 4.56 Pyridine 79 ND 0.72 ND 0.62 ND ND ND ND ND ND 0.483 4.94 Toluene 92 1.20 2.07 0.92 1.35 1.08 0.68 0.96 1.18 1.49 1.20 0.814 6.01 2-Methyl pyridine 93 ND 0.78 ND 0.50 ND ND ND ND ND ND 0.675 6.33 2,5-Dimethyl furan 96 4.05 0.72 3.23 0.75 1.39 1.72 1.70 1.00 1.12 0.81 3.056 6.92 Ethylbenzene 106 0.62 0.75 0.55 0.60 0.57 0.31 0.62 1.25 0.84 0.60 0.547 6.95 3-Methyl Pyridine 93 1.27 2.28 0.99 1.02 ND ND ND ND 0.51 0.62 0.218 7.08 p-Xylene 106 2.18 2.90 1.65 2.11 2.15 1.21 2.87 1.66 2.21 1.64 1.059 7.45 2-Cyclopenten,1,4-dione 96 0.83 ND 0.80 ND ND ND ND ND ND ND ND

10 7.53 Styrene 104 1.64 3.25 1.57 2.13 1.80 0.74 2.08 2.21 2.03 1.65 2.0511 7.87 2-Methyl-2-cyclopenten-1-one 96 1.54 0.80 1.16 0.62 0.76 0.65 0.69 0.62 0.57 0.57 0.5112 7.96 5,5-Dimethyl-1,3-hexadiene 110 ND ND 0.50 ND ND ND ND ND ND ND ND13 8.48 1,2-Dimethyl cyclopenten 110 0.38 0.47 0.37 ND ND ND ND ND ND ND ND14 8.76 Propyl benzene 120 ND 0.67 ND ND ND ND ND ND 0.43 ND ND15 8.82 1,5-Dimethyl 1,5-cyclooctadiene, 136 0.88 0.90 0.72 0.58 0.60 0.37 0.78 0.61 0.71 0.59 0.5616 8.92 1-Ethyl-3-methyl benzene 120 1.92 2.53 2.33 1.91 1.69 0.44 2.42 1.10 2.17 1.80 1.0517 8.98 5-Methyl 2-furancarboxaldehyde 110 2.24 ND 2.30 ND 0.72 1.08 0.62 ND 0.74 0.42 ND18 9.04 3-Ethenyl Pyridine 105 2.52 2.28 2.69 1.76 1.78 1.17 2.30 1.58 2.20 1.88 1.8119 9.26 1-Ethyl-2-methyl benzene 120 0.50 0.73 0.59 0.47 0.48 0.16 0.57 0.47 0.60 0.46 0.3320 9.30 �-Methylstyrene 118 0.62 0.80 0.66 0.66 0.52 0.20 0.78 0.58 0.64 0.54 0.5521 9.35 2,3-Dimethyl- 2-cyclopenten-1-one 110 ND ND ND ND ND ND 0.78 0.73 ND ND ND22 9.40 1-Decene 140 1.36 1.18 1.30 0.98 0.83 0.54 1.06 1.00 1.04 0.93 1.1423 9.45 Cis-2,6-dimethyl- 2,6-octadiene 138 1.00 1.08 0.77 0.78 0.65 0.48 0.92 0.71 0.77 0.62 0.3424 9.52 3-Methyl bicyclo[4,2,0] 1,3,5-octatriene 118 2.62 2.91 2.59 2.54 2.18 1.26 2.89 2.51 2.32 1.85 1.1625 9.60 1-Ethenyl-3-methyl benzene 118 2.80 2.60 2.67 2.24 2.02 1.33 2.65 2.17 2.06 1.72 1.9826 9.70 3-Carene 136 ND ND ND ND ND ND 0.55 ND ND ND ND27 9.86 2,5,6-Trimethyl 1,3,6-heptatriene 136 1.27 1.28 1.06 1.11 0.95 0.54 1.32 1.02 1.00 0.83 0.3628 10.00 1-Methyl-4-(1-methylethyl) Cyclohexene 138 1.48 1.27 1.23 1.09 1.16 0.72 1.47 1.26 1.10 0.82 0.6729 10.06 1,2-Diethyl benzene 134 1.86 1.64 1.78 1.53 1.56 0.91 2.03 1.74 1.57 1.11 1.0230 10.14 Limonene 136 11.30 10.29 9.39 9.26 8.47 5.68 11.15 9.36 8.52 7.38 6.1131 10.30 Cyclopropyl benzene 118 0.77 0.60 0.79 0.48 0.51 0.32 0.67 0.50 0.51 0.34 0.2832 10.35 2,3-Dimethyl- 2-cyclopenten-1-one 110 1.06 ND 1.00 ND 0.43 0.34 ND 0.41 0.49 0.37 ND33 10.43 3,7-Dimethyl- 1,3,6-octatriene 136 1.20 0.92 1.02 0.91 0.77 0.44 0.86 0.78 0.81 0.60 0.6634 10.47 Indene 116 1.78 1.42 2.00 1.26 1.12 0.90 1.56 1.17 1.15 0.91 0.9835 10.64 1,3-Diethyl benzene 134 1.54 0.70 1.16 0.61 ND ND 1.50 1.18 0.75 ND ND36 10.75 2,3-4-Trimethyl -2-cyclopenten-1-one 124 ND ND 0.62 ND ND ND ND ND ND ND ND37 11.00 2,3-Epoxycarane 152 1.38 ND 1.56 0.95 0.88 ND 1.23 0.96 ND ND ND38 11.06 Methyl[1-methylethenyl] benzene 132 0.96 0.62 0.92 0.66 0.55 ND 0.85 0.57 0.56 ND ND39 11.12 1-Undecene 154 1.63 1.52 1.63 1.52 1.19 0.69 1.71 1.28 1.26 1.05 1.2240 11.18 1-Methyl-4-(1-methylethenyl) benzene 132 2.22 1.37 2.10 1.54 1.48 1.05 2.23 1.58 1.45 1.06 1.8841 11.56 1,3,8-p-menthatriene 134 1.68 0.78 1.65 0.96 0.88 0.72 1.39 0.87 0.82 0.65 1.0042 11.77 2,6-Dimethyl- 2,4,6-octatriene 136 1.62 1.04 1.39 1.26 1.06 0.66 1.52 1.09 1.00 0.78 0.7543 11.99 3,4-Dimethyl- 2,4,6-octatriene 136 1.18 0.58 1.07 0.78 0.64 0.47 1.12 0.67 0.63 0.42 0.8844 12.03 2-Butenyl benzene 132 1.30 ND 1.28 ND ND ND ND ND ND ND ND45 12.21 2-Methylindene 130 3.06 1.59 3.06 1.87 1.50 1.31 2.30 1.50 1.48 1.24 1.2646 12.30 1-Butynyl benzene 130 2.79 1.10 2.83 0.65 1.08 1.00 2.35 0.73 1.06 0.85 0.8247 12.49 2-[5-Methylfaryl] -methanethiol 142 1.23 ND 1.09 0.49 0.80 0.75 0.83 0.60 0.60 ND 0.4548 12.62 3-Methyl-2-butenyl benzene 146 0.70 ND 1.59 ND ND ND ND ND ND ND ND49 12.69 1-Dodecene 168 1.64 1.03 1.53 1.41 0.86 0.61 1.52 0.81 0.85 0.65 0.5650 12.80 Naphthalene 128 2.60 0.90 2.50 1.28 0.95 1.05 1.77 0.96 0.94 0.67 0.7751 13.11 2-[Hydroxyphenyl] buta-1,3-diene 146 0.94 ND 0.94 ND ND ND 0.44 ND ND ND ND52 13.22 2-Ethyl 1h-benzimidazole 146 1.27 ND 1.19 ND ND ND ND ND ND ND ND

Q. Ye / J. Chromatogr. A 12

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13 (2008) 239–244 243

.4. Comparison of peak area of VOCs in MCS from differentrands of cigarettes

Among the identified analytes, 11 compounds were selectedresenting high toxicity or abundance in smoke: benzene, toluene,thylbenzene, p-xylene, styrene, 3-ethylpyridine, limonene,ndene, naphthalene, triacetin and nicotine [18,19]. As seen fromable 1, limonene is shown as having the greatest peak arean all brands tested. As we know, limonene mainly is from thedditive spice in the cigarette, This suggests that limonene is theain compounds in the additive spices. Brand B cigarette had

he highest values for benzene, toluene, p-xylene, styrene; brandcigarette had the highest values for limonene, naphthalene,

riacetin and nicotine; brand C cigarette had the highest valuesor 3-ethylpyridine and indene. Brand F cigarette had lowestalues for benzene, toluene, ethylbenzene, p-xylene, styrene,-ethylpyridine, limonene, indene; brand J cigarette had lowestalues for naphthalene. The results showed that the compoundsnd their amounts of VOCs in MCS are very different for differentrands of cigarettes, respectively. This indicated that the VOCs inCS are related to the quality of cigarettes.

. Conclusions

In the study, we successfully developed SPME–GC–MS for theetermination of VOCs in MCS, and 70 compounds were identified

n MCS by the proposed method. It has been shown that collection,xtraction, and concentration of volatile organic chemicals in MCSan be performed in a single step, using the proposed method. Theime of the whole sample preparation was less than 12 min. Thexperimental results demonstrated that the proposed method is aimple, rapid, reliable, and solvent-free technique for the determi-ation of VOCs in MCS.

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