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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]7/28/2019 Gcms and Hplc Methods
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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
7 3,5-Dimethylphenol 11.07 194
8 2,4-Dimethylphenol 11.20 194
9 2-Methoxyphenol 11.28 196
10 4-Ethylphenol 11.59 194
11 (I.S.) 4-Chlorophenol 11.71 185
12 2,6-Dimethylphenol 11.79 194
13 2,3-Dimethylphenol 12.02 194
14 3,4-Dimethylphenol 12.32 194
15 3-Methoxyphenol 13.17 196
16 4-Methoxyphenol 13.47 196
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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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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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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