Gcms and Hplc Methods

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Journal of Chromatography A, 1141 (2007) 9097

Gas chromatography/mass spectrometry versus liquidchromatography/fluorescence detection in the analysis

of phenols in mainstream cigarette smoke

Serban C. Moldoveanu , Melissa Kiser

R.J. Reynolds Tobacco Co., 950 Reynolds Boulevard, Winston-Salem, NC 27105, USA

Received 19 October 2006; received in revised form 28 November 2006; accepted 29 November 2006

Available online 19 December 2006

Abstract

A newgas chromatographic/massspectrometric(GC/MS)technique for the analysis of hydroxybenzenes (phenols)in mainstream cigarettesmoke

has been developed. The technique allows the measurement of 24 individual compounds, and the sum of a few other alkyl-dihydroxybenzenes.

A critical evaluation is done for the new technique and for an established high-performance liquid chromatographic (HPLC) technique reported

in the literature for the analysis of hydroxybenzenes in cigarette smoke, which uses fluorescence detection. Compared with the HPLC procedure,

the new technique has similar accuracy, precision, and robustness. However, the GC/MS procedure allows for a larger number of phenols to be

analyzed simultaneously, and eliminates any potential interference that may appear in the HPLC method. Using the GC/MS analysis, it was found

that besides the main phenols typically measured in mainstream cigarette smoke such as phenol, catechol, hydroquinone, and cresols, many other

phenols that are present at lower levels can be quantitated in mainstream cigarette smoke.

2006 Elsevier B.V. All rights reserved.

Keywords: Phenols; Hydroxybenzenes; HPLC; GC/MS; Mainstream cigarette smoke

1. Introduction

Hydroxybenzenes (phenols) are present in cigarette smoke

and contribute to cigarette sensory properties [1]. Also, some

phenols are considered toxic compounds [2] and their pres-

ence in smoke has been related to environmental and health

issues. Thus, the analysis of phenols in smoke has been the

subject of several studies, some reported in peer reviewed liter-

ature [310]. Outside the tobacco industry, numerous published

reports describe phenol analysis, which has been commonly per-

formed on samples such as water [1118], food [1921], plant

materials (fruits, vegetables) [22], pharmaceuticals [23,24], etc.

Phenols can be analyzed by both high-performance liquid chro-

matographic (HPLC) and gas chromatography (GC). The HPLC

analysis can be done with UV detection [25,26] or fluores-

cence detection [3,23,27]. Several advantages of fluorescence

versus UV detection are described in the literature, the sensi-

Corresponding author. Tel.: +1 336 741 7948; fax: +1 336 728 9112.

E-mail address: [email protected] (S.C. Moldoveanu).

tivity and selectivity of fluorescence detection being in general

better than that of UV detection [23]. The analysis of phenols by

GC or gas chromatography/mass spectrometry (GC/MS) is usu-

ally done after derivatization [7,10,24,28,29]. Other analytical

techniques for phenols determination are also reported such as

micellar electrokinetic chromatography [30]. The phenols typi-

cally analyzed in cigarette smoke by the HPLC method include

1,4-dihydroxybenzene (hydroquinone), 1,2-dihydroxybenzene

(catechol), 1,3-dihydroxybenzene (resorcinol), hydroxyben-

zene (phenol), 4-methyl + 3-methyl-hydroxybenzene (p- + m-

cresol), and 2-methylhydroxybenzene (o-cresol). Although

2-methoxyphenol (guaiacol) is not usually analyzed by HPLC

this compound can be easily measured by this technique.

Besides the six (seven, if 2-methoxyphenol is added) phenols

typically analyzed by HPLC/fluorescence, a number of other

phenols are present in cigarette smoke [31]. They are not listed

as biologically active agents [2] and their levels are relatively

low. Nevertheless, their presence in smoke may contribute to

the properties of smoke, and a full chemical characterization of

cigarette smoke should include them. However, the analysis of

these additional phenols by HPLC/fluorescence raises a selec-

0021-9673/$ see front matter 2006 Elsevier B.V. All rights reserved.

doi:10.1016/j.chroma.2006.11.100
mailto:[email protected]://localhost/var/www/apps/conversion/tmp/scratch_2/dx.doi.org/10.1016/j.chroma.2006.11.100http://localhost/var/www/apps/conversion/tmp/scratch_2/dx.doi.org/10.1016/j.chroma.2006.11.100mailto:[email protected]


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S.C. Moldoveanu, M. Kiser / J. Chromatogr. A 1141 (2007) 9097 91

tivity problem, since the separation of some of these phenols

may be difficult by HPLC. Also, their positive identification

without a mass spectrum can be questionable. For this reason, a

GC/MS technique for phenol analysis in cigarette mainstream

smoke has been developed and is described in this study. The

application of the HPLC/fluorescence analysis and of GC/MS

analysis on the same samples allows a good comparison of

advantages and disadvantages of both techniques.

2. Experimental

2.1. Smoke collection

Smoke collection was done with a Borgwaldt RM20 CSR

smoking machine, tuned for conditions similar to those recom-

mended by US Federal Trade Commission (FTC) [32]. That

consisted of 35 mL puff volume, each puff taken every 2 s, with

60 s puff interval, the cigarettes being smoked to 3 mm distance

to the filter overwrap. Other smoking regimes [3336] can also

be utilized depending on the purpose of the analysis. Five differ-entcigarettes were used in thestudy. This included two Kentucky

references cigarettes indicated as 1R5F and 2R4F (University of

Kentucky, Kentucky Tobacco Research & Development Center,

KY, USA) and three commercial cigarettes. The description of

these cigarettes is given in Table 1.

Smoke from five cigarettes was collected in each run on a

92 mm Cambridge pad. The results previously reported in the

literature [3] indicate that phenols are effectively collected from

mainstream smoke by this procedure. A chromatographic stan-

dard consisting of 100L solution containing 250g/mL of

4-chlorophenol was added to the pad. The pad was extracted on

a mechanical shaker for 30 min with 25 mL water containing 1%acetic acid and 0.1% ascorbic acid (both from Aldrich/Sigma,

Milwaukee, WI, USA). The solution extract was used as is,

after filtration through 0.45m pore size polyvinilydene flu-

oride (PVDF) filters, for the HPLC analysis. The solutions can

be kept in a freezer for at least 1 week without affecting the

phenols content. For the GC/MS analysis a sample prepara-

tion using solid-phase extraction (SPE) was necessary before

the chromatographic step.

2.2. HPLC/fluorescence detection analytical procedure

The analysis by HPLC/fluorescence followed a procedure

described in the literature [3]. One difference in the present work

was the use of a fixed amount of extracting solution (25 mL)

Fig. 1. HPLC/fluorescence chromatogram obtained for the main phenols in

mainstream smoke of a 2R4F Kentucky reference cigarette.

instead of adjusting this volume to obtain a solution contain-

ing approximately 1 mg/mL of total particulate matter (TPM).

The ascorbic acid in the present method was added to prevent

any potential oxidation of the phenols. Also, a chromatographic

standard (further described) was used in the present work. Theinstrumentation used for the HPLC analysis consisted of two

Waters 510 pumps, a 717plus Waters autosampler and a 474

Waters scanning fluorescence detector (Waters, Milford, MA,

USA). The separation was achieved on a Beckman Ultrasphere

ODS column 15 cm4.6mmI.D.,5m particle size (Beckman

Coulter, Fullerton, CA, USA). The separation took place under

gradient conditions using two solutions, one being water with

1% acetic acid (sol. A) and the other acetonitrile with 1% acetic

acid (sol. B). The acetic acid is necessary for improving the sta-

bility of phenols fluorescence [3]. The initial solution contained

4% sol. B (and it is not pure water) in order to avoid the outgas-

ing commonly seen when mixing pure water and acetonitrile.The flow rate was 1.4 mL/min. The composition of the mobile

phase was changed (linear) to reach 31% sol. B at 10.5 min and

100% sol. B at 15.5 min. Sol. B was flown through the column

for another 4.5 min and then the conditions were restored to the

initial mobile phase composition. Multiple injections were done

every 27 min. Thefluorescencewas measured initially at 304 nm

ex and 338 nmem. The conditions were changed to 274 nmexand 298 nm em after 3.5 min, and to 232 nm ex and 310 nm

em after 13.2 min. The data acquisition was performed for

20 min. Theinjection volume was8L. A typical chromatogram

obtained in these conditions for the mainstream smoke of the

2R4F Kentucky reference cigarette is shown in Fig. 1.

For the quantitation of phenols, calibration curves were

generated using a series of four standards. The standards

Table 1

Description of Kentucky reference and commercial cigarettes

Descriptor 1R5F Kentucky ref. 2R4F Kentucky ref. 16.2 mg tar 10.6 mg tar 5.0 mg tar

FTC tar (mg/cig) 1.7 8.9 16.2 10.6 5.0

Cigarette length (mm) 84 84 83 83 83

Filter length (mm) 32 27 21 27 27

Filter ventilation (%) 72 28 23 32 54

Blend type American American American American American

Nicotine (mg/cig) 0.16 0.75 1.31 0.92 0.5

CO (mg/cig) 3 12.0 13.9 10.7 7.4


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Table 3

List of standards of phenols, their retention times, and m/z values used for the

detection/quantitation

No. Compound Retention

time (min)

m/z

1 Phenol 6.88 166

2 o-Cresol 8.57 180

3 m-Cresol 8.76 1804 p-Cresol 9.08 180

5 2-Ethylphenol 10.28 194

6 2,5-Dimethylphenol 10.70 194



9 2-Methoxyphenol 11.28 196

10 4-Ethylphenol 11.59 194

11 (I.S.) 4-Chlorophenol 11.71 185






17 Catechol (1,2-dihydroxybenzene) 13.88 254

18 Resorcinol (1,3-dihydroxybenzene) 16.05 254

19 4-Methylcatechol 16.27 268

20 Hydroquinone (1,4-dihydroxybenzene) 16.73 254

21 3-Methylcatechol 16.71 268

22 3-Methylresorcinol 18.19 268

23 2-Methylresorcinol+ methylhydroquinone 18.66 268

24 4-Ethylresorcinol 19.90 282

25 2,5-Dimethylresorcinol 20.18 282

the ions (m/z) used for the measurement of TMS derivatives.

The standards solution was processed through the SPE similar

to a smoke extract (2 mL added on the cartridge). The individ-

ual concentrations in the standards solution varied between 2.0and 2.5g/mL. The SIM chromatogram for an extract of smoke

from a 2R4F cigarette generated the chromatogram shown in

Fig. 3.

In addition to the dimethyl- and/or ethyl-dihydroxybenzenes

(C2-dihydroxybenzenes) for which standards were available,

several other peaks in the chromatogram shown in Fig. 3, eluting

between 20.5 and 22.5 min were identified based only on their

spectrum as C2- or C3-dihydroxybenzenes (C3 indicating any

alkyl with three carbon atoms). Because of the similarity of the

spectra of these compounds, the exact position of the substitu-

Fig. 3. SIM chromatogram of the phenols from the smoke of a 2R4F cigarette.

Peak identification based on retention times given in Table 3.

tion on the benzene ring was not possible (no standards were

obtained for these compounds).

The quantitation of phenols by the GC/MS technique was

also done with calibration curves. The calibration curves for

hydroquinone, catechol, resorcinol, phenol, p-cresol, m-cresol,

o-cresol, and guaiacol were generated with the same series of

four standards used for the calibration of HPLC method. Curves

representing quantity versus peak areas normalized by the area

of the internal standard (4-chlorophenol) were generated. The

curves were linear and theR2 values for the dependence were all

above 0.993. For the other phenols only three point calibrations

were generated (phenols from Aldrich/Sigma, Milwaukee, WI,

USA).

3. Results and discussion

Several aspects of the two analytical techniques for phenols

analysis, the HPLC and the GC/MS, were investigated with the

purpose of their comparison. These aspects included selectiv-

ity, accuracy, precision, limit of detection and of quantitation,recovery, and robustness. A comparison of advantages and dis-

advantages of the two techniques was possible following the

description of these parameters.

3.1. Methods selectivity

The selectivity of the HPLC procedure was difficult to ver-

ify, since no sample was available containing the same matrix

but without phenols. However, potential interferences from the

matrix are not likely for the phenols found in relatively high

levels in smoke. The extraction with water of smoke conden-

sate eliminates many compounds that are not water soluble, andthe fluorescence of phenols is selective. The separation of p-

cresol from m-cresol was not achieved, and the results for the

two compounds were given as their sum. Some changes in the

elution gradient that modified the retention times of the analytes,

as well as the use of a longer column (Ultrasphere ODS 5 m,

4.6 mm25 cm) did not change peak areas for the analytes for

samples generated from a 2R4F Kentucky reference cigarette

as well as those from the analyzed commercial cigarettes. This

basically indicated that the measured peaks are pure.

Selectivity was enhanced for the GC/MS procedure com-

pared to the HPLC. The SPE processing of the sample provided

besides concentration and solvent change, a cleanup step. The

availability of the mass spectra for identification and the use ofselected ions for quantitation also increased the method selec-

tivity. This allowed the separation of cresols (m- and p-cresol

were not separated using the HPLC procedure) and the peaks

of other hydroxybenzenes that were not analyzed by HPLC

were very well separated in the GC/MS method (see Fig. 2).

Only 2-methylresorcinol and methylhydroquinone had identi-

cal retention times and very similar mass spectra and were not

separated in the conditions described in this study.

A potential interference in the measurement of hydro-

quinone for both GC/MS and HPLC procedures may occur if

p-benzoquinone is present. This substance is reduced to hydro-

quinone in the presence of ascorbic acid. In order to prove that


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94 S.C. Moldoveanu, M. Kiser / J. Chromatogr. A 1141 (2007) 9097

Table 4

Comparison for the results of phenols from 2R4F cigarette obtained by the HPLC procedure using solution for pad extraction with and without 0.1% of ascorbic acid

Compound Average g/cig. HPLC

with ascorbic acid

RSD % Average g/cig. HPLC

without ascorbic acid

RSD % Difference %

Phenol 9.21 2.3 9.19 3.5 0.22

o-Cresol 2.34 6.1 2.14 2.8 8.93

m +p-Cresol 6.95 4.6 6.77 4.7 2.62

Catechol 35.60 1.9 35.81 3.8 0.59Hydroquinone 28.80 4.9 28.71 3.8 0.31

Resorcinol 0.84 10.6 0.79 8.9 6.13

Guaiacol 1.61 4.0 1.52 4.5 5.75

Table 5

Comparison with literature data for the results obtained using the HPLC and the GC/MS procedures for the phenols from 2R4F and from 1R5F cigarettes

2R4F 1R5F

Compound Average

g/cig.

HPLC

RSD %

HPLC

Average

g/cig.

GC/MS

RSD %

GC/MS

Ref. [38]

g/cig.

Average

g/cig.

HPLC

RSD %

HPLC

Average

g/cig.

GC/MS

RSD %

GC/MS

Ref. [10]

g/cig.

Phenol 9.21 2.3 7.49 4.5 7.32 1.18 8.6 0.76 3.5 0.9

o-Cresol 2.34 6.1 2.45 2.6 1.89 0.47 13.1 0.35 0.8 0.2m +p-Cresol 6.95 4.6 6.22 2.7 5.84 0.74 4.6 0.62 2.4 0.3

Catechol 35.60 1.9 35.88 1.8 37.90 6.42 8.2 6.90 3.8 7.4

Hydroquinone 28.80 4.9 32.74 5.7 32.40 6.58 8.2 6.30 3.4 4.9

Resorcinol 0.84 10.6 1.27 7.9 0.91 0.24 23.5 0.51 4.5 0.6

Guaiacol 1.61 4.0 1.42 3.2 Not available 0.37 13.6 0.20 6.1 Not available

the addition of 0.1% ascorbic acid in the extraction solution

of phenols does not affect the results regarding hydroquinone

(or other phenols), the analysis for the 2R4F cigarette was

done by the same procedure as previously described without

the addition of ascorbic acid in the Cambridge pad extract-

ing solution [3]. The results are shown for triplicate samples

with each chromatographic runs performed twice (total of six

data points) in Table 4 for the HPLC method only. The agree-

ment between the data is very good. Further comparison of the

accuracy of the results obtained with the present procedure for

2R4F and 1R5F Kentucky reference cigarettes with the litera-

ture data also proved to be very good. This indicates that the

equilibrium quinone/hydroquinone is strongly displaced toward

hydroquinone in mainstream cigarette smoke.

3.2. Methods accuracy

The results obtained for 2R4F and 1R5F Kentucky refer-

ence cigarettes were compared with the data from the literature[10,35] ([3] shows data only for 1R4F Kentucky reference

cigarette). Only results for seven common phenols in cigarette

smoke were available for comparison. The results are given in

Table 5. For this comparison, triplicates of each sample were

smoked and processed, followed by chromatographic runs per-

formed twice for each sample (total of six data points). The

results from Table 5 show good agreement between the HPLC

results, the GC/MS results, and also the results published in lit-

erature ([38] provides data from a collaborative study between

six laboratories). Larger discrepancies were noticed only in the

results for resorcinol, which is present in cigarette smoke at

lower levels compared to the other phenols shown in Table 5.

This indicates that both the HPLC and the GC/MS procedure

have good accuracy.

3.3. Precision, limit of detection and of quantitation

The RSD values given in Table 5 show that both the HPLCandGC/MS procedures havegood precision. Forthe HPLC anal-

ysis of the 1R5F cigarette the RSD values were higher than

those obtained by the GC/MS procedure. The fluorescence sig-

nal for the 1R5F samples was relatively low compared to the

noise, which may explain the increased RSD values. However, a

lower volume of solution used to extract the Cambridge pads can

increase the concentration of phenols in the analyzed solution

and, therefore can possibly improve the repeatability of the tech-

nique. Calculated as 3SD (where SD is the standard deviation

for a sample with low levels of phenols), the limit of detection

(LOD) obtained from Table 5 is given in Table 6. The limits

of detection given in Table 6 can be considerably improved if

certain changes are performed in the sample processing. For the

Table 6

Limit of detection calculated as 3SD, where SD is the standard deviation for

a low sample

Compound LOD g/cig. HPLC LOD g/cig. GC/MS

Phenol 0.30 0.08

o-Cresol 0.18 0.01

m +p-Cresol 0.10 0.04

Catechol 1.58 0.79

Hydroquinone 1.62 0.64

Resorcinol 0.17 0.07

Guaiacol 0.15 0.04


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Table 7

Other phenols detected in the mainstream cigarette smoke of 2R4F and 1R5F cigarettes

No. Compound Average 2R4F g/cig. RSD % 2R4F Average 1R5F g/cig. RSD % 1R5F

1 m-Cresol 1.76 2.26 0.15 0.49

2 p-Cresol 4.46 2.68 0.47 2.41

3 2-Ethylphenol 0.57 2.40 0.17 1.10

4 2,5-Dimethylphenol 0.57 1.44 0.14 4.15

5 3,5-Dimethylphenol 0.62 2.28 0.16 11.906 2,4-Dimethylphenol 1.09 1.16 0.26 3.35

7 4-Ethylphenol 1.43 0.98 0.28 3.56

8 2,6-Dimethylphenol 0.58 11.35 0.23 14.72

9 2,3-Dimethylphenol 1.33 1.16 0.14 3.19

11 3,4-Dimethylphenol 0.50 11.96 0.15 7.10

12 3-Methoxyphenol 0.28 9.44 0.13 4.90

13 4-Methoxyphenol 0.46 12.23 0.22 2.52

14 4-Methylcatechol 4.32 4.78 0.88 3.48

15 3-Methylcatechol 4.52 3.42 0.93 4.04

15 3-Methylresorcinol 0.83 11.06 0.30 2.00

17 2-Methylresorcinol+ methylhydroquinone 3.91 2.11 0.65 5.96

18 4-Ethylresorcinol 0.40 6.87 0.17 6.85

19 2,5-Dimethylresorcinol 1.26 7.33 0.33 7.12

20 Other C2-dihydroxybenzenes 3.97 8.10 0.49 9.10

21 Sum of C3-dihydroxybenzenes 0.63 4.33 0.27 5.97

GC/MS technique for example, the volume of the solution of

particulate phase smoke extract added to the SPE cartridge can

be increased from 2 mL to a higher volume, without resulting

in any breakthrough of the analytes. However, for the analysis

of phenols in mainstream cigarette smoke this increase was not

considered necessary. The values for the limit of quantitation

(LOQ) can be evaluated as 3LOD.

3.4. Recovery

The recovery of the HPLC procedure has been previ-

ously reported [3]. The efficiency of phenols extraction from

the cigarette smoke particulate matter (TPM) collected on a

Cambridgepad using a 1% aceticacidaqueous solution was thor-

oughly evaluated in this previously reported HPLC technique

[3]. For this reason, the dissimilarity between the extraction of

phenols from TPM or from the clean pad was not expected to

generate considerable differences. The recovery for the GC/MS

wasperformedbyaddingonaCambridgepad100L solution of

a mixture of standards containing between 500 and 625 g/mL

of individual phenols. The pad was further processed by the

procedure previously described, and the results compared to theinitial amount added. Recoveries between 93 and 105% were

obtained for all the phenols analyzed. This indicated that no

recovery problems are encountered during pad extraction and

the SPE step.

3.5. Robustness

Robustness refers to the quality of an analytical procedure

to not be influenced by small experimental modifications dur-

ing its performance. Both HPLC and the GC/MS techniques

described in this study were simple and no difficult steps were

encountered. Some attentionis required in the GC/MS procedure

during the drying of the SPE cartridge. The presence of water

in the DMF eluate, noticeable by strong heating of the sam-

ple when the reagent BSTFA is added for derivatization, leads

to lower peaks in the chromatogram and incorrect quantitation

(slight heating of thesamples still occurseven with drysamples).

However, after 1 h of drying the SPE cartridge with ambient air,

the potential problem of hydrolyzing the TMS derivatives was

eliminated.

3.6. Comparison of HPLC and GC/MS procedures

Both HPLC and GC/MS procedures give good results for the

analysis of the major phenols from cigarette mainstream smoke.

The HPLC procedure is simpler since after the pad extraction,

the solutions are directly subject to the chromatographic pro-

cess. A slightly lower precision noticed during the analysis of

the 1R5F cigarette by the HPLC method is not critical, and can

be improved by using smaller extraction volumes of the Cam-

bridge pad. The advantage of the GC/MS technique consists

mainly in the extension of the list of analytes and in the separa-

tion of m- and p-cresols. Also, the detection based on the ions

characteristic for each phenol further eliminates the chances forinterferences. Theresults for the level of other phenols present in

smoke of the 2R4F and 1R5F Kentucky reference cigarettes as

obtained by the GC/MS technique are given in Table 7. As seen

from Table 7, only the C1-dihydroxybenzenes and to a lower

extent C2-dihydroxybenzenes are present in smoke of the two

Kentucky reference cigarettes at appreciable levels compared

to those of the major phenols. Most other phenols in smoke

besides phenol, catechol, hydroquinone, and cresols are present

at lower levels, however their total sum accounts for about 25%

of total phenols in smoke. The same conclusion was obtained

from the analysis of smoke from other cigarettes. As an exam-

ple, the analysis of phenols from the mainstream smoke of three


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96 S.C. Moldoveanu, M. Kiser / J. Chromatogr. A 1141 (2007) 9097

Table 8

Comparison of phenol levels in three common commercial cigarettes

Cigarette

No. Compound 5.0 mg tar 10.6 mg tar 16.2 mg tar

Average g/cig. RSD % Average g/cig. RSD % Average g/cig. RSD %

1 Phenol 4.86 2.85 9.29 5.30 16.07 4.26

2 o-Cresol 1.23 0.03 2.62 4.14 3.70 4.96

3 m-Cresol 0.93 1.91 1.97 2.25 2.95 4.44

4 p-Cresol 2.12 2.69 5.02 3.25 6.97 4.69

5 2-Ethylphenol 0.31 1.60 0.70 3.97 0.75 2.85

6 2,5-Dimethylphenol 0.29 2.63 0.67 2.98 0.79 3.72

7 3,5-Dimethylphenol 0.36 9.59 0.82 2.04 1.00 3.40

8 2,4-Dimethylphenol 0.56 2.68 1.28 2.54 1.47 2.61

9 2-Methoxyphenol 0.65 4.05 1.43 2.31 2.40 2.48

10 4-Ethylphenol 0.77 3.32 1.67 1.78 2.10 3.67

11 2,6-Dimethylphenol 0.30 7.55 0.73 9.33 0.68 2.43

12 2,3-Dimethylphenol 0.54 6.29 0.84 11.34 1.62 1.32

13 3,4-Dimethylphenol 0.29 3.10 0.60 5.95 0.73 4.24

14 3-Methoxyphenol 0.15 6.42 0.36 9.53 0.33 11.61

15 4-Methoxyphenol 0.25 11.88 0.63 5.36 0.53 3.36

16 Catechol 20.00 4.61 45.20 2.48 62.35 1.58

17 Resorcinol 0.72 9.86 1.81 8.48 1.80 1.01

18 4-Methylcatechol 2.43 4.52 6.19 6.08 7.59 2.13

19 Hydroquinone 19.78 6.36 43.00 6.41 56.44 1.81

20 3-Methylcatechol 2.37 3.74 5.58 1.75 6.50 2.92

21 3-Methylresorcinol 0.46 7.94 1.16 7.57 1.19 0.58

22 2-Methylresoecinol+ methylhydroquinone 1.83 7.89 3.57 13.11 5.70 2.32

23 4-Ethylresoecinol 0.21 5.23 0.53 7.51 0.47 2.22

24 2,5-Dimethylresorcinol 0.63 7.09 1.49 9.84 1.73 3.28

25 C2-Dihydroxyphenol 1.29 10.94 2.93 11.10 4.65 2.76

26 C3-Dihydroxyphenol 0.34 12.96 0.57 4.61 0.81 1.99

Total phenols 63.69 140.68 190.29

common commercial cigarettes of different tar levels was per-formed. The cigarettes included a 5.0 mg FTC tar cigarette,

(where tar is defined as the weight of total mainstream smoke

condensate (or wet particulate matter) minus the weight of nico-

tine and water) a 10.6 mg tar and a 16.2 mg tar cigarette, with

the description given in Table 1. The results for the phenols anal-

ysis are given in Table 8. As it can be calculated from Table 8

the proportion of different phenols relative to the total amount of

phenols in smoke is notvery differentfor differentcigarettes,and

phenol, catechol, hydroquinone, and cresols account for about

75% of total phenols in smoke.

4. Conclusions

This study presents a new GC/MS analytical technique for

phenol analysis, which allows the measurement of 24 individ-

ual compounds and of the sum of certain C2-dihydroxybenzenes

and of C3-dihydroxybenzenes. The main characteristics of the

GC/MS analytical procedure are compared to those of a HPLC

technique with fluorescence detection. Both techniques pro-

vide very reliable results for the analysis of phenols. Both

methods are equally accurate for the analysis of 67 major

phenolic compounds from mainstream cigarette smoke. Using

the GC/MS procedure it was found that besides the phenols

typically analyzed in cigarette smoke some other phenols are

present, accounting together for about 25% of total phenols inmainstream smoke. However, the GC/MS method requires two

additional steps compared to the HPLC method (the SPE and the

derivatization). Also, the GC/MS equipment is typically more

expensivethan theHPLC one. Forroutine laboratoriesthe HPLC

technique is probably recommended, while the GC/MS is nec-

essary only when a detailed analysis of phenols in mainstream

cigarette smoke is desired.

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