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Analysis of Volatile Organic Compounds in Mainstream Cigarette Smoke

  • TRS Consulting56 LLC

Abstract and Figures

Mainstream cigarette smoke is a complex aerosol containing more than 4400 chemicals. The proliferation of new brands has necessitated development of faster and more reliable methods capable of analyzing a wide range of compounds in cigarette smoke. Although the International Agency for Research on Cancer has classified whole cigarette smoke as a human carcinogen, many of the individual chemicals are themselves highly biologically active as carcinogens, teratogens, or have implications for cardiovascular disease. Among these chemicals are many volatile organic compounds (VOCs), e.g., benzene, ethylbenzene, and styrene. To analyze VOCs in mainstream cigarette smoke, we developed a novel headspace collection technique using polyvinylfluoride bags for sample collection followed by cannula transfer to evacuated standard 20-mL auto sampler vials. Coupling collection of the vapor-phase cigarette smoke with automated analysis by solid-phase microextraction and gas chromatography/mass spectrometry enabled us to routinely quantify selected VOCs in mainstream cigarette smoke. This technique has similar reproducibility to previous cold trap and impinger collection methods with significantly higher sample throughput and virtually no solvent waste. In this report we demonstrate the method's analytical capabilities by quantitatively analyzing 13 selected VOCs in mainstream cigarette smoke from top-selling domestic brands.
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Analysis of Volatile Organic
Compounds in Mainstream Cigarette
Emergency Response and Air Toxicants Branch, Division of
Laboratory Sciences, National Center for Environmental
Health, Centers for Disease Control and Prevention
Mainstream cigarette smoke is a complex aerosol
containing more than 4400 chemicals. The proliferation of
new brands has necessitated development of faster
and more reliable methods capable of analyzing a wide
range of compounds in cigarette smoke. Although the
International Agency for Research on Cancer has classified
whole cigarette smoke as a human carcinogen, many of
the individual chemicals are themselves highly biologically
active as carcinogens, teratogens, or have implications
for cardiovascular disease. Among these chemicals are
many volatile organic compounds (VOCs), e.g., benzene,
ethylbenzene, and styrene. To analyze VOCs in mainstream
cigarette smoke, we developed a novel headspace
collection technique using polyvinylfluoride bags for sample
collection followed by cannula transfer to evacuated
standard 20-mL auto sampler vials. Coupling collection of
the vapor-phase cigarette smoke with automated analysis
by solid-phase microextraction and gas chromatography/
mass spectrometry enabled us to routinely quantify selected
VOCs in mainstream cigarette smoke. This technique has
similar reproducibility to previous cold trap and impinger
collection methods with significantly higher sample
throughput and virtually no solvent waste. In this report
we demonstrate the method’s analytical capabilities
by quantitatively analyzing 13 selected VOCs in mainstream
cigarette smoke from top-selling domestic brands.
Cigarette smoking remains the leading preventable cause of
premature death in the United States (1). From 1995 to 1999,
an estimated 440 000 deaths were attributed each year to
cigarette smoking (1). Although nicotine is the main chemical
component of tobacco smoke that keeps people using the
product (2), many of the other compounds in mainstream
cigarette smoke are associated with cancer, birth defects, or
heart disease (3). The combustion of cigarette tobacco filler
during cigarette smoking creates an aerosol containing
numerous chemical compounds (4,5). Among the thousands
of reported chemicals generated during smoking are several
specific classes of hazardous compounds that merit concern
(3,4,6-10). The International Agency for Research on Cancer
(IARC) groups individual chemicals and chemical mixtures
according to their carcinogenicity toward humans. Cigarette
smoke contains numerous compounds classified by IARC as
known, probable, and possibly carcinogenic. Although whole
cigarette smoke as a mixture has been classified as a human
carcinogen (11), many of the individual volatile organic
compounds (VOCs) present in whole smoke, such as benzene
(12), ethylbenzene (13), and styrene (14), are known or
potential human carcinogens. Although VOCs comprise only
a small fraction (by weight) of mainstream cigarette smoke
(3), smoking is a primary exposure source for many toxic
volatile compounds, and this fraction has been proposed as
the most hazardous fraction of mainstream smoke (15). For
example, cigarette smoking accounts for nearly half of all
Americans’ exposure to benzene, a known human carcinogen
Several cigarette design factors influence the delivery and
composition of mainstream cigarette smoke. Because ciga-
rette yields are determined by machine smoking, design
differences that reduce machine yields may not reduce a
smoker’s exposure. Filter ventilation reduces machine gen-
erated mainstream smoke yields but smokers often com-
pensate by blocking the vent holes, taking larger puffs, or
puffing more frequently (17). Similarly, changes to static burn
rates, tobacco filler composition and weight, and different
filter materials can result in a reduction in machine yields.
Smokers who compensate in an effort to obtain the desired
level of nicotine defeat these design features and obtain a
much different exposure than estimated by standardized
machine smoking measurements. An accurate assessment
of cigarette design changes and their impact on mainstream
smoke yields are required to help accurately estimate the
health impact these changes may have.
Earlier studies of VOCs in mainstream cigarette smoke
were accomplished by using a variety of techniques for both
collection and analysis. Previous researchers employed
collection techniques such as solvent-filled impinger trains
(18,19), adsorbent materials (20-22), cold traps (23,24),
and direct injection of the gas sample (25,26) to isolate the
wide range of chemicals in cigarette smoke. Although these
methods exhibited good reproducibility, the possibility of
sample breakthrough, tedious cleanup steps, generation of
solvent waste, and long sample-preparation times often
limited their utility. Factors such as impinger solvent volumes,
evaporation, reactivity, breakthrough, and perturbation of
the machine puff also potentially contribute to increased
variability in any analytical technique. Minimizing the
influence of such variables improves accuracy and precision.
We present a method for analyzing VOCs in mainstream
cigarette smoke that allows for high-throughput analysis at
a relatively low cost using commercially available materials
and equipment. Key features of this method include the
appropriate selection of internal standards, inert poly-
vinylfluoride (PVF) bags for vapor-phase collection, cannula
transfer of smoke to an evacuated headspace vial, and
subsequent automated solid-phase microextraction (SPME)
and gas chromatography/mass spectrometry (GC/MS). Other
advantages include minimal use of solvents, virtually no
sample preparation or cleanup required, and no sample
carryover. Method validation is discussed along with the
analysis of ketones and arenes in 41 cigarette varieties that
provide a representative sampling of domestic cigarettes
spanning the current range of nicotine deliveries. We also
examine the delivery of VOCs as a function of selected
cigarette design features and their delivery relative to nicotine
* Corresponding author phone: (770) 488-7292; fax: (770) 488-
0181; e-mail:
Environ. Sci. Technol.
10.1021/es060609l Not subject to U.S. Copyright. Publ. 2007 Am. Chem. Soc. VOL. 41, NO. 4, 2007 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 91297
Published on Web 01/11/2007
Materials and Methods
Materials. All target compounds were purchased from Aldrich
Chemical Co. (Milwaukee, WI). Methanol was purchased from
Tedia Company Inc. (Fairfield, OH). The ultrahigh purity gas
helium was obtained from AirGas, Inc. (Atlanta, GA). Glass
fiber Cambridge filter pads (CFP), 44 mm, were purchased
from Whatman (Maidstone, England). Tedlar brand PVF bags,
carboxen-polydimethylsiloxane (carboxen-PDMS) SPME
fibers, and Mininert septum caps were purchased from
Supelco (Bellefonte, PA). All chemicals and solvents were
used without further purification.
Internal Standards. An internal standard (IS) stock
solution was prepared by adding 1 mL each of the perdeutero
compounds acetone-d6, benzene-d6, styrene-d8, tetrahydro-
furan-d8, toluene-d8, and p-xylene-d10 and diluting to 10 mL
with methanol. Working solutions of 1:100 and 1:1000
dilutions, in methanol, were prepared monthly as ISs for the
vapor and particulate phases respectively. These ISs were
stored in airtight amber vials with Mininert septum caps and
removed with a Hamilton (gas-tight) syringe as needed. A
10-µL aliquot of IS was added to each sample before analysis.
Preparation of Standard Curves. We made a calibration
stock solution by the addition of neat standards to methanol.
The amount of each analyte added to the stock calibration
mixture was recorded to the nearest 0.01 mg and diluted
with methanol to a final volume of 10 mL. Serial dilutions
of the calibration stock solution generated appropriate
concentration ranges for each analyte (Table 1). These
solutions were analyzed to prepare calibration curves for all
13 analytes in both the vapor and particulate phases. For the
vapor phase, for which PVF bags were used to collect the
smoke sample, calibration curves were generated by injection
of a standard solution and IS into an empty bag and filled
with 11 puffs of 35 mL from the smoking machine. The bag
was then removed from the smoking machine and treated
as a sample. Similarly, calibration curves for the particulate
phase collected on the CFP were prepared by the addition
of the standard solution and IS to a blank 20-mL headspace
vial and treated as samples. All calibration curves were linear
with R2values exceeding 0.99. Calibration curves were
prepared weekly and used for all analytical runs using the
associated IS.
Smoking Conditions. Prior to smoking, cigarette filter
ventilation levels were measured with a QTM-5 (Cerulean,
Milton Keynes, UK). For 24 h before smoking, cigarettes were
conditioned in an environmental chamber (Parameter
Generation Control, Inc, Black Mountain, NC) that was
maintained, as specified in ISO 3402:1999, at a temperature
of 22 °C and 60% relative humidity. Cigarettes were smoked
according to the conditions detailed in ISO 3308:2000 (35
mL puff of 2 s duration every 60 s) on an automated linear
16-port ASM 500 smoking machine (Cerulean, Milton Keynes,
UK) to a butt length of either filter +8 mm or filter overwrap
+3 mm, whichever was greater.
VOC Collection-Vapor Phase. The vapor-phase portion
of mainstream cigarette smoke was collected in individual
1-L PVF bags attached directly to the exhaust ports of the
ASM 500 puffing engines. To reduce background and sample
carryover, the smoking machine was programmed to com-
plete 30 blank puffs per port before attachment of the PVF
bags. Background levels of all analytes were measured on a
per port basis and corrections, if needed, were applied to all
results for that day’s analytical runs. Prior to smoking, 10 µL
of the 1:100 IS solution was added to each 1-L PVF bag. After
smoking, the PVF bags were closed and immediately removed
from the smoking machine. A portion of the smoke sample,
collected in the PVF bag, was subsequently transferred to an
evacuated 20-mL headspace vial (Microliter Corporation,
Atlanta, GA) by a 27 gauge cannula. Vials, containing the
analytical samples were subsequently loaded onto a LEAP
Combi-Pal auto sampler (LEAP Technologies, Carrboro, NC)
equipped with SPME sampling for analysis by GC/MS.
VOC Collection-Particulate Phase. The particulate phase
of the mainstream cigarette smoke was collected on a
standard 44-mm CFP. After smoking, the CFP was removed
from the holder and placed in a 20-mL headspace vial and
spiked with 10 µL of the 1:1000 IS solution. The sample was
then loaded on a LEAP Combi-Pal autosampler and analyzed
by automated SPME/GC/MS.
VOC Analysis. VOCs were quantitatively analyzed using
an Agilent 6890 gas chromatograph coupled to an Agilent
5973 mass spectrometer. The sample was incubated at 30 °C
for 2 min before the vial was sampled for 30 s with a 75-µm
carboxen-PDMS SPME fiber. Analytes were then desorbed
from the fiber at 260 °C in a heated inlet and focused onto
an Agilent DB-624 capillary column (30.0 m ×320 µm×1.80
µm). Helium flow was maintained in constant flow mode at
an average linear velocity of 46 cm/sec. For the analysis of
vapor-phase samples, the GC oven, equipped with liquid
nitrogen cryo cooling, was programmed to start at -20 °C,
hold for 2 min, and ramp to 200 °Cat8°C/min, for a total
run time of 29.50 min. The GC analysis of the particulate
phase samples differed in that the oven started at 40 °C, was
held constant for 2 min, and then ramped to 230 °Cat6
°C/min, for a total run time of 35 min. Both methods used
a transfer line temperature of 255 °C and source and
quadrupole temperatures of 230 °C and 150 °C, respectively.
Data were acquired in full-scan mode over 30-200 amu.
Cigarettes for Testing. We selected premium and value
cigarette brands, ranging from full-flavor to ultralight,
including both mentholated and non-mentholated varieties,
from the top four domestic cigarette producers for analysis.
The cigarettes were purchased at commercial retail outlets
in the Atlanta metropolitan area or were provided by the
Massachusetts Department of Public Health. The 1R4F and
2R4F research cigarettes were purchased from the University
of Kentucky Tobacco and Health Research Institute (Lex-
ington, KY). All cigarettes were stored in their original
packaging at -70 °C until being conditioned prior to analysis.
Quality Control Materials. The 2R4F research cigarette
was used as a quality control (QC) material. QC cigarettes
were smoked daily and analyzed with all runs performed
that day. All 13 analytes measured in the smoke of the 2R4F
cigarettes were characterized to determine the mean and
the 95th and 99th confidence intervals for each analyte
studied. Acceptance criteria for QC and blank samples
followed the criteria prescribed by Taylor (27).
TABLE 1. Linear Calibration Range, Calculated Limits of
Detection (LOD), and Correlation Coefficients (R2) for the
Vapor-Phase Portion of Mainstream Cigarette Smoke
linear range
benzene 0.86-344 0.09 0.9999
-xylene 0.086-34.4 0.01 0.9991
acetone 2.78-1110 2.16 0.9986
-xylene 0.091-36.4 0.02 0.9998
2,3-butanedione 0.98-394 0.76 0.9999
2-pentanone 0.080-32.2 0.22 0.9994
toluene 0.84-338 0.21 1.0000
styrene 0.091-36.2 0.28 0.9995
ethylbenzene 0.089-35.4 0.10 0.9996
3-ethyltoluene 0.045-18.2 0.09 1.0000
3-euten-2-one 0.85-340 0.15 0.9999
3-pentanone 0.081-32.2 0.24 0.9989
2-butanone 0.79-316 0.81 0.9994
Results and Discussion
Calibration, detection, and quantification of the 13 analytes
were straightforward. The linear quantification range, LOD,
and linear regression coefficients were more than adequate
to provide quantitative data for the analytes studied (Table
1). The LODs for these analytes, calculated as three times the
standard deviation extrapolated to zero concentration (27),
ranged from 0.01 µg to 2.12 µg per cigarette. Although not
needed for this study, switching to single ion monitoring
rather than a full spectral scan should improve LODs. The
results for each analyte in this study are presented on a per-
cigarette basis which simplifies data analysis and provides
for direct cigarette-to-cigarette comparisons.
Accurate quantification of the chemicals in mainstream
cigarette smoke dictates the analysis of both the particulate
and vapor phases. We accomplished this by parallel analysis
of the particulate matter located on the CFP and the vapor-
phase sample. Because of the highly volatile nature of the
analytes selected for this study, we found the fraction in the
particulate phase to be extremely low. Quantification of the
13 analytes in the particulate- and vapor-phase samples for
the 2R4F research cigarettes confirmed that these analytes
resided mainly in the vapor phase. In fact, the levels of 12
of the 13 analytes on the CFP had values below the method
limit of detection (LOD). The only measurable analyte in the
particulate phase, 2,3-butanedione, represented less than
2% of the measured vapor sample. Because of the nearly
complete gas-phase partitioning, we only report levels
measured in the vapor phase for the remainder of the
Because of the potential for sample loss and the reactivity
of selected analytes in this study, the choice of an appropriate
IS was important. Isotopically labeled ISs for each analyte
was not practical because of the large number and wide
concentration ranges of the chemicals in cigarette smoke.
Limiting the number of ISs simplifies sample preparation
times and increases SPME sensitivity. Also, the use of a limited
number of ISs can greatly reduce the cost per analysis.
Therefore, we selected six perdeutero ISs for quantification
of VOCs in mainstream cigarette smoke. Carbonyl com-
pounds were quantified using either acetone-d6or THF-d8
and aromatic compounds using benzene-d6, toluene-d8,
FIGURE 1. Vapor-phase sample stability as a function of time.
FIGURE 2. A typical vapor-phase full scan chromatogram for the 2R4F research cigarette. Compounds quantified in this study are labeled.
For clarity, signal before 7 min and after 21 min are not shown.
TABLE 2. Analyte Yields (in Micrograms Per Cigarette),
Standard Deviation (σ), and Percent Relative Standard
Deviation (%RSD) for the 2R4F Kentucky Research Cigarette
over a 6 Month Period (N)100)
analyte average σ%RSD
benzene 44.1 5.1 11.7
toluene 57.4 5.8 10.2
styrene 2.2 0.4 17.0
-xylene 1.7 0.3 14.8
xylene 9.9 1.3 13.6
3-ethylbenzene 4.4 0.6 13.3
3-ethyltoluene 1.6 0.6 37.1
acetone 366.9 64.2 17.5
3-buten-2-one 45.7 7.5 16.3
2,3-butanedione 89.3 13.1 14.7
2-butanone 86.3 11.8 13.7
2-pentanone 12.8 2.4 18.6
3-pentanone 6.1 1.3 20.8
TABLE 3. Vapor-phase Mainstream Cigarette Smoke Yields of
Previously Reported Volatile Organic Compounds from a
Kentucky 1R4F Research Cigarette. Literature Reported Values
Included for Comparison. Values Are Shown (Standard
Deviation (n)5)
previously Reported
Results (µg/cig)
benzene 41 (445
toluene 60 (7 68,
styrene 2.9 (0.6 2.1,
xylenes 12.9 (1.9 10.6
acetone 340 (41 284,
From ref
From ref
From ref
From ref
From ref
p-xylene-d10, or styrene-d8. Appropriate pairing of IS to
analyte was determined by a similarity in vapor pressure,
structure, and as was the case for styrene, reactivity, to achieve
optimal linear response.
Sample stability was of great concern because of numerous
reactive compounds associated with mainstream cigarette
smoke. Previous reports have indicated problems with sample
stability over time (24,26). To examine sample stability, a
2R4F cigarette was smoked and aliquots of the vapor phase
were transferred by cannula into 10 individual headspace
vials. These vials were sequentially sampled and analyzed
over the following 20 h. During this time, a steady decrease
in the raw area counts was observed for all analytes. Although
both analyte and IS ion counts decreased over time, change
in the analyte relative response ratio was less than 15% for
all analytes over a 20-hr period (Figure 1). Therefore, to
minimize temporal variability, all samples were analyzed
within 20 h of collection.
Concentration of the sample on the SPME fiber, coupled
with the relatively high abundances of the chosen analytes
in mainstream cigarette smoke, provided sufficient sensitivity
to allow full-scan mass spectral detection. Using full-scan
data acquisition provided quantitative analysis of the analytes
while retaining spectral information for qualitative analysis
of additional smoke constituents. The total ion chromatogram
for a 2R4F research cigarette (Figure 2) demonstrates the
good separation, high signal response, and adequate run
time for all 13 analytes. Given the chemical complexity of
smoke and the large number of chemicals readily identified
in the vapor phase, this method could be readily expanded
to analyze additional, volatile, cigarette smoke constituents.
Method reproducibility was assessed by evaluating the
results generated over a 6 month period for all 13 analytes
when a 2R4F cigarette was machine smoked. During that
time more than 100 analytical determinations were made
for the mainstream smoke of 2R4F cigarettes. The average
deliveries and standard deviations for the analytes studied
were determined from these data (Table 2). The calculated
relative standard deviation for all 13 compounds was, on
average, 16.9% for the 2R4F cigarette. Day-to-day variability
in this method can be attributed both to the variability in the
analytical process and sample-to-sample variability among
the 2R4F cigarettes.
The recent replacement of the 1R4F reference cigarette
with the 2R4F research cigarette made delivery comparisons
with other researchers tenuous. To make meaningful com-
parisons, we also analyzed some of the older 1R4F cigarettes.
However, of the 13 analytes reported here, only values for
TABLE 4. Delivery of Aromatic Volatile Organic Compounds in Mainstream Cigarette Smoke of 41 U.S. Brandsa
full flavored brands % vent benzene toluene styrene
-xylene Et-benzene 3-Et-toluene
Basic 0 49.8 (5.9 69.0 (9.6 4.3 (0.4 2.4 (0.1 13.1 (1.2 6.1 (0.7 2.3 (0.3
Camel (M) 0 52.9 (3.6 74.6 (5.8 5.0 (0.6 2.7 (0.3 15.0 (1.3 6.9 (0.6 2.8 (0.7
Newport (M) 0 50.7 (2.5 72.3 (3.7 4.3 (0.0 2.4 (0.0 13.2 (0.4 6.3 (0.3 2.2 (0.6
Salem (M) 0 56.8 (6.9 81.2 (12.7 5.3 (1.1 2.9 (0.5 16.0 (2.8 7.5 (1.2 2.9 (0.9
Camel Jade (M) 1 57.1 (3.5 82.4 (3.7 5.4 (0.4 3.0 (0.3 16.4 (1.4 7.8 (0.7 2.7 (1.1
Kool (M) 1 50.5 (4.5 73.1 (3.1 4.2 (0.2 2.3 (0.2 13.4 (0.9 6.2 (0.3 1.8 (0.4
GPC 5 56.4 (0.7 75.0 (2.8 4.7 (0.2 2.6 (0.1 14.4 (0.8 6.9 (0.3 2.4 (0.0
Marlboro 12 46.8 (0.5 67.0 (3.6 3.9 (0.3 2.2 (0.1 12.8 (0.4 5.6 (0.2 2.3 (0.3
Benson & Hedges 13 50.7 (2.4 73.8 (6.4 3.8 (0.9 2.4 (0.4 14.1 (2.2 6.1 (0.9 2.4 (0.8
Camel 15 56.6 (0.9 76.1 (2.0 4.8 (0.1 2.7 (0.1 14.7 (0.6 6.7 (0.2 2.6 (0.2
Marlboro (M) 16 42.8 (3.3 62.4 (6.2 3.2 (0.2 1.9 (0.2 11.1 (1.0 5.1 (0.4 1.6 (0.3
Kent 20 38.3 (2.1 57.2 (5.8 3.0 (0.4 1.7 (0.1 9.8 (0.3 4.6 (0.7 1.3 (0.9
Doral 22 50.0 (7.4 66.0 (12.0 4.6 (0.7 2.7 (0.4 14.6 (1.5 6.3 (0.6 2.9 (0.7
Winston 23 51.5 (1.5 68.9 (1.7 4.1 (0.3 2.4 (0.1 13.7 (0.1 6.1 (0.2 2.2 (0.1
medium or mild brands
GPC 12 43.8 (3.6 57.9 (8.5 3.1 (0.2 1.7 (0.1 9.7 (0.9 4.8 (0.3 1.3 (0.2
Marlboro (M) 13 43.9 (3.1 62.0 (5.2 3.0 (0.4 1.9 (0.2 10.8 (0.9 5.2 (0.5 1.5 (0.2
Newport (M) 20 42.2 (4.2 58.5 (6.1 3.2 (0.5 1.8 (0.2 10.0 (1.3 4.7 (0.6 1.7 (0.3
Marlboro 22 41.9 (4.3 57.6 (7.5 3.0 (0.3 1.9 (0.1 11.0 (0.9 4.9 (0.5 1.6 (0.2
light brands
Basic 15 42.0 (0.7 55.1 (1.4 2.9 (0.2 1.8 (0.1 10.1 (0.3 4.7 (0.1 1.6 (0.4
GPC 21 38.2 (3.5 50.3 (4.3 2.5 (0.4 1.5 (0.2 8.5 (1.0 4.1 (0.5 1.4 (0.3
Marlboro 22 40.4 (3.0 55.4 (6.5 2.7 (0.1 1.8 (0.2 10.4 (1.2 4.6 (0.5 1.8 (0.3
Newport (M) 23 31.6 (3.1 43.2 (5.4 1.8 (0.4 1.2 (0.1 6.8 (0.9 3.3 (0.5 0.9 (0.2
Camel Jade (M) 24 42.8 (3.8 60.3 (4.7 3.4 (0.3 1.9 (0.2 10.9 (1.1 5.3 (0.5 1.6 (0.4
Camel (M) 25 39.6 (3.9 57.1 (9.3 2.8 (0.6 1.6 (0.3 9.7 (1.8 4.8 (1.0 1.1 (0.6
Marlboro (M) 25 37.0 (5.9 51.3 (9.4 2.3 (0.3 1.4 (0.3 8.6 (1.7 4.1 (0.6 0.9 (0.5
Doral 26 38.2 (5.8 53.4 (6.9 2.9 (0.6 1.8 (0.3 10.0 (1.4 4.4 (0.7 1.8 (0.2
Camel 30 39.4 (3.5 52.6 (6.6 2.6 (0.3 1.6 (0.2 9.0 (1.1 4.2 (0.5 1.4 (0.3
Winston 30 44.5 (3.4 57.2 (5.7 2.9 (0.4 1.9 (0.2 10.4 (1.4 4.8 (0.5 1.5 (0.2
Misty 49 30.7 (2.6 39.9 (3.3 1.8 (0.3 1.2 (0.1 6.9 (0.8 3.2 (0.3 0.9 (0.1
Misty (M) 50 25.4 (1.5 32.3 (1.9 1.2 (0.3 0.8 (0.1 4.8 (0.5 2.2 (0.2 0.5 (0.0
ultralight brands
Basic 32 25.6 (5.0 32.0 (6.7 1.4 (0.5 1.0 (0.3 5.6 (1.7 2.7 (0.7 0.7 (0.4
Marlboro 47 25.5 (2.8 33.6 (4.8 1.4 (0.3 1.0 (0.2 5.9 (1.1 2.7 (0.3 0.8 (0.4
GPC 49 26.7 (3.5 34.5 (4.0 1.9 (0.3 1.2 (0.2 6.5 (1.0 3.0 (0.4 1.1 (0.4
Camel 52 29.3 (1.1 39.7 (2.5 2.1 (0.3 1.4 (0.1 7.6 (0.6 3.4 (0.3 1.3 (0.4
Marlboro (M) 53 27.3 (2.6 33.3 (3.3 1.2 (0.3 1.0 (0.1 5.8 (0.5 2.7 (0.3 0.7 (0.1
Winston 55 26.6 (0.2 31.7 (1.8 1.5 (0.3 1.1 (0.1 6.2 (0.4 2.8 (0.3 0.9 (0.1
Doral 61 19.7 (1.9 27.7 (2.9 1.2 (0.2 1.0 (0.0 5.7 (0.3 2.5 (0.2 0.8 (0.2
Misty (M) 67 15.7 (1.3 21.0 (3.1 0.7 (0.2 0.7 (0.1 4.0 (0.8 1.7 (0.2 0.4 (0.3
True 68 15.0 (1.1 18.8 (2.1 0.9 (0.3 0.6 (0.1 3.7 (0.3 1.7 (0.2 0.5 (0.0
Carlton 77 6.3 (0.6 7.3 (0.7 0.3 (0.1 0.3 (0.1 1.9 (0.3 1.0 (0.1 0.2 (0.1
Carlton (M) 78 3.7 (0.9 4.5 (1.3 0.3 (0.3 0.2 (0.1 1.5 (0.4 0.8 (0.2 0.0 (0.0
All analytes are expressed as micrograms per cigarette along with the corresponding standard deviation, (M) denotes a mentholated brand.
acetone (8,26), benzene (22-24,26,28), styrene (23,24),
toluene (23,24,28), and total xylenes (24) were reported in
previous studies for the 1R4F research cigarette. Quantified
values for the deliveries of these five analytes in 1R4F cigarette
smoke were comparable to previously reported values (Table
3). These previous methods used a variety of smoke collection
techniques, including the use of solvent filled cold traps as
well as directly sampling the cigarette vapor phase or smoke,
which differed from the PVF bag technique used in the current
study. The agreement with previous work helps to support
the validity of our reported results. Additionally, the measured
values of all 13 analytes for the 1R4F research cigarette are
comparable to the newer 2R4F research cigarette (Tables 4
and 5) and should provide a useful future reference.
Brand and manufacturer differences among top-selling
domestic cigarettes were investigated for the analytes in this
study. Delivery data, along with filter ventilation are reported
in Tables 4 and 5. When separated into groups on the basis
of their FTC mainstream smoke delivery designations (full-
flavor, medium, light, or ultralight), no statistical differences
(p<0.05) existed between the individual VOC smoke
concentrations in the 41 commercial brands examined from
the four major domestic manufacturers for brands grouped
together according to comparable delivery. Further statistical
analysis of analyte delivery for all 41 cigarette brands showed
that filter ventilation was the main cigarette design parameter
influencing delivery of the 13 analytes. For example, benzene
delivery, when analyzed as a function of filter ventilation
(Figure 3), showed a good linear relation for all 41 brands,
as did the other 12 VOCs analyzed in this study. In
comparison, physical characteristics such as filler mass and
filter length were much poorer predictors of the overall
mainstream smoke delivery of these analytes.
One limitation of the current study is the smoking
parameters were based on standardized machine smoking
methods, which do not accurately estimate smoke deliveries
for modern cigarettes (29). Kozlowski et al. (17) have shown
that smokers of low delivery cigarettes may compensate to
obtain sufficient nicotine by blocking the vent holes or by
taking more frequent, larger, and deeper puffs. Such com-
pensation behavior would result in much higher deliveries
of all constituents in cigarette smoke. If the present results
are normalized to the reported nicotine delivery of the
cigarette, all cigarettes studied had, within standard deviation,
nearly identical deliveries of all 13 analytes (Figure 4). Work
is under way in our laboratories to define the relationship
between the amount of nicotine delivered under a wide range
of smoking conditions and the resultant potential exposure
to these and other VOCs in mainstream cigarette smoke.
TABLE 5. Delivery of Volatile Organic Ketones in Mainstream Cigarette Smoke of 41 U.S. Brandsa
full flavored brands % vent acetone 2,3-butanedione 2-pentanone 2-butanone 3-pentanone 3-buten-2-one
Basic 0 401.4 (43.5 105.4 (3.5 15.1 (0.4 95.5 (6.4 6.6 (0.4 60.7 (2.7
Camel (M) 0 511.7 (34.7 128.1 (9.0 21.4 (2.2 126.2 (9.5 9.7 (0.9 78.2 (8.6
Newport (M) 0 488.7 (6.0 115.1 (8.7 18.8 (2.6 116.8 (7.5 8.5 (1.0 74.4 (3.5
Salem (M) 0 534.2 (47.3 128.0 (15.7 21.2 (2.9 127.9 (13.8 9.8 (1.2 81.5 (8.7
Camel Jade (M) 1 541.4 (39.6 124.9 (12.5 21.2 (3.2 129.5 (13.5 10.3 (1.8 80.1 (8.7
Kool (M) 1 494.0 (81.9 107.2 (30.6 16.8 (4.9 107.7 (24.3 8.3 (2.3 79.1 (18.8
GPC 5 477.8 (25.8 115.5 (3.9 18.2 (0.5 114.7 (4.4 8.1 (0.4 79.3 (6.0
Marlboro 12 402.7 (11.7 101.3 (15.0 15.1 (2.5 94.8 (9.1 6.7 (0.9 64.0 (9.8
Benson & Hedges 13 438.1 (27.0 100.4 (10.6 15.9 (2.3 101.2 (8.8 7.4 (1.5 64.6 (5.8
Camel 15 470.7 (10.0 122.2 (5.0 18.6 (1.6 115.4 (5.3 8.5 (1.5 73.5 (5.5
Marlboro (M) 16 376.9 (31.4 106.3 (9.5 14.8 (1.4 92.1 (7.0 6.7 (0.7 53.5 (5.8
Kent 20 376.0 (51.3 95.0 (6.2 12.0 (3.0 83.3 (2.1 5.3 (1.6 49.2 (2.9
Doral 22 472.5 (97.0 145.0 (71.0 22.5 (8.5 129.6 (46.3 9.7 (3.0 94.8 (47.5
Winston 23 433.3 (36.2 119.6 (10.3 16.5 (2.9 104.3 (12.7 6.9 (1.4 68.7 (6.4
medium or mild brands
GPC 12 356.1 (21.4 82.4 (9.9 10.9 (0.8 77.6 (1.6 4.7 (0.3 50.5 (6.4
Marlboro (M) 13 358.6 (31.3 88.6 (13.6 12.8 (1.8 83.9 (9.4 5.6 (0.4 47.7 (9.3
Newport (M) 20 375.3 (31.0 94.1 (12.9 14.5 (3.2 91.2 (13.8 6.8 (1.3 55.5 (7.7
Marlboro 22 332.2 (35.5 79.8 (2.3 12.2 (0.7 78.5 (6.2 5.3 (0.4 53.2 (3.8
light brands
Basic 15 336.9 (3.2 84.0 (5.7 12.3 (0.9 79.4 (2.2 5.4 (0.4 50.6 (1.5
GPC 21 304.7 (17.7 75.8 (8.6 10.7 (1.9 70.5 (8.4 4.7 (0.7 44.8 (6.2
Marlboro 22 321.2 (20.9 75.0 (6.7 12.0 (1.4 76.1 (5.7 5.2 (0.7 50.1 (2.3
Newport (M) 23 301.6 (28.8 73.5 (4.1 10.2 (0.9 68.0 (4.9 4.6 (0.3 41.2 (1.2
Camel Jade (M) 24 353.2 (27.8 88.9 (5.1 13.1 (0.4 84.8 (4.1 6.4 (0.3 50.1 (3.2
Camel (M) 25 353.4 (59.8 78.7 (3.9 10.7 (0.5 76.9 (8.5 4.6 (0.9 44.9 (4.9
Marlboro (M) 25 313.0 (20.3 76.8 (2.8 9.9 (1.8 69.6 (7.0 4.3 (0.8 40.5 (2.7
Doral 26 294.5 (34.7 73.7 (6.8 10.2 (0.6 67.5 (6.3 4.5 (0.5 42.4 (3.9
Camel 30 299.6 (28.6 72.6 (2.5 9.8 (1.0 68.0 (3.1 4.7 (0.8 42.3 (3.4
Winston 30 350.1 (21.0 88.3 (3.0 12.1 (0.6 81.7 (4.1 5.2 (0.6 52.2 (2.5
Misty 49 255.5 (17.9 68.0 (1.2 8.9 (0.4 59.3 (3.0 3.7 (0.3 38.8 (1.4
Misty (M) 50 232.6 (21.3 64.7 (18.8 7.5 (2.4 52.1 (9.8 3.6 (1.2 38.3 (14.8
ultralight brands
Basic 32 194.0 (21.4 48.8 (6.8 6.0 (1.4 43.1 (6.6 2.7 (0.5 25.4 (4.3
Marlboro 47 202.3 (25.1 48.0 (5.3 6.8 (1.3 45.5 (6.6 3.0 (0.5 30.5 (5.3
GPC 49 213.6 (24.2 56.7 (8.4 7.1 (1.4 50.0 (7.3 3.3 (0.7 29.2 (5.5
Camel 52 228.8 (12.7 57.3 (2.0 7.6 (0.8 52.3 (1.7 3.6 (0.5 31.1 (2.4
Marlboro (M) 53 197.4 (15.9 44.3 (3.7 6.1 (0.4 43.7 (2.6 2.6 (0.3 27.9 (3.6
Winston 55 195.2 (5.8 49.5 (2.1 5.7 (0.2 42.7 (1.4 2.5 (0.1 26.2 (0.2
Doral 61 156.1 (13.8 36.5 (0.7 4.8 (0.4 34.0 (1.6 2.1 (0.2 20.1 (2.4
Misty (M) 67 139.9 (6.2 36.4 (3.4 3.9 (0.6 29.7 (2.4 1.7 (0.3 17.7 (1.0
True 68 122.2 (9.0 32.6 (2.4 3.3 (0.2 26.3 (1.6 1.5 (0.1 15.2 (0.6
Carlton 77 55.2 (4.7 15.1 (1.9 1.4 (0.1 11.7 (1.0 0.6 (0.0 7.5 (1.0
Carlton (M) 78 45.6 (10.6 12.7 (2.0 1.1 (0.2 10.0 (1.8 0.5 (0.0 5.5 (0.9
All analytes are expressed as micrograms per cigarette along with the corresponding standard deviation, (M) denotes a mentholated brand.
Use of trade names is for identification only and does not
imply endorsement by the Centers for Disease Control and
Prevention or by the U.S. Department of Health and Human
Services. The findings and conclusions in this report are those
of the author(s) and do not necessarily represent the views
of the Centers for Disease Control and Prevention.
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FIGURE 3. The relation between filter ventilation and the level of
benzene in the vapor phase of mainstream cigarette smoke for top
selling domestic cigarettes. Each data point is the result of at least
three measurements and error bars representing the standard
deviation are included. A linear regression of the points in provided
for reference.
FIGURE 4. Average selected analyte deliveries normalized to Federal
Trade Commission (FTC) nicotine values. Errors bars are at one
standard deviation.
... 0.002 0.04 Jeffery et al., 2018) 0.009 ) Benzo[k]fluoranthene 0.02 (Moriwaki et al., 2009;Ding et al., 2006b) 0 . 0 7 Gao et al., 2015;Hearn et al., 2018;Ho et al., 2010;Ho et al., 2011;Jeffery et al., 2018;Shi et al., 2015;Toriba et al., 2014;Vu et al., 2015;Wang et al., 2015a;Zhang et al., 2015;Grimmer et al., 1987) 0.08 Toriba et al., 2014;Mottier et al., 2010) Benzo[b + k]fluoranthene 0.15 (Dobaradaran et al., 2020;Dobaradaran et al., 2019a) 0.15 0.11 Benzo[b]fluoranthene 0.009 (Moriwaki et al., 2009;Demirci, 2014;Demirci & Alver, 2013) 0.06 Gao et al., 2015;Gmeiner et al., 1997;Hearn et al., 2018;Ho et al., 2010;Ho et al., 2011;Jeffery et al., 2018;Samara et al., 2021;Shi et al., 2015;Toriba et al., 2014;Vu et al., 2015;Wang et al., 2015a;Zhang et al., 2015;Ding et al., 2006b) 0.04 Toriba et al., 2014) Benzo 5.68 Bi et al., 2005;Gao et al., 2015;Gmeiner et al., 1997;Hearn et al., 2018;Ho et al., 2010;Ho et al., 2011;Yershova et al., 2016;Zha et al., 2002;Li et al., 2003;Samara et al., 2021;Shi et al., 2015;Toriba et al., 2014;Vu et al., 2015;Wang et al., 2015a;Zhang et al., 2015) 0.57 Toriba et al., 2014;Lee et al., 2011) Acephenanthrylene 8.06 ) Benzene 0.16 (Dobaradaran et al., 2021a) 63.75 Moir et al., 2008;Counts et al., 2005b;Bi et al., 2005;Chen et al., 2008;Charles et al., 2007;Brunnemann et al., 1989;Jiang et al., 2013;Marcilla et al., 2012;Mola et al., 2008;Polzin et al., 2007;Polzin et al., 2008) 361.49 (Gori & Mantel, 1991;Moir et al., 2008;Charles et al., 2007;Brunnemann et al., 1989) Toluene 0.64 (Dobaradaran et al., 2021a) 1 6 1 . ...
... (Gori & Mantel, 1991;Moir et al., 2008;Charles et al., 2007;Brunnemann et al., 1989) Toluene 0.64 (Dobaradaran et al., 2021a) 1 6 1 . 4 6 Moir et al., 2008;Counts et al., 2005b;Bi et al., 2005;Charles et al., 2007;Brunnemann et al., 1989;Jiang et al., 2013;Marcilla et al., 2012;Mola et al., 2008;Polzin et al., 2007;Seeman et al., 2002) 471.51 (Gori & Mantel, 1991;Moir et al., 2008;Brunnemann et al., 1989) o-Xylene 0.13 (Dobaradaran et al., 2021a) 15.09 Charles et al., 2007;Polzin et al., 2007) 85.99 (continued on next page) concentrations of aromatic amines ranged from 0.00001 (tolidine) to 0.16 μg/cig (aniline) in MS and 0.01 (2-aminonaphthalene) to 3 μg/cig (2-Toluidine) in SS. Among these compounds, 4-aminobiphenyl has been studied more compared to other aromatic amines (Table 4). ...
... (Gori & Mantel, 1991;Moir et al., 2008;Charles et al., 2007;Brunnemann et al., 1989) Toluene 0.64 (Dobaradaran et al., 2021a) 1 6 1 . 4 6 Moir et al., 2008;Counts et al., 2005b;Bi et al., 2005;Charles et al., 2007;Brunnemann et al., 1989;Jiang et al., 2013;Marcilla et al., 2012;Mola et al., 2008;Polzin et al., 2007;Seeman et al., 2002) 471.51 (Gori & Mantel, 1991;Moir et al., 2008;Brunnemann et al., 1989) o-Xylene 0.13 (Dobaradaran et al., 2021a) 15.09 Charles et al., 2007;Polzin et al., 2007) 85.99 (continued on next page) concentrations of aromatic amines ranged from 0.00001 (tolidine) to 0.16 μg/cig (aniline) in MS and 0.01 (2-aminonaphthalene) to 3 μg/cig (2-Toluidine) in SS. Among these compounds, 4-aminobiphenyl has been studied more compared to other aromatic amines (Table 4). ...
The commercially sold cigarettes contain more than 7000 chemicals., and their combustion produces potential toxicants in mainstream smoke (MS), sidestream smoke (SS), secondhand smoke (SHS), thirdhand smoke (THS), and discarded cigarette butts (CBs). We conducted a systematic review of published literature to compare the toxicants produced in each of these phases of tobacco combustion (MS, SS, and CBs). The initial search included 12,301 articles, but after screening and final restrictions considering the aims of this review, 159 published studies were selected for inclusion. Additionally, SHS and THS are briefly discussed here. Overall, polycyclic aromatic hydrocarbons (PAHs) and other aromatic hydrocarbons have been represented in more studies than other compounds. However, metals and nitrosamines were detected in higher concentrations than other components in SS. The concentrations of most PAHs and other aromatic hydrocarbons in MS and SS are higher compared to concentrations found in CBs. Also, the concentrations of all the studied carbonyl compounds, aldehydes and ketones in SS and MS were higher than in CBs. The mean levels of alcohols and phenols in SS were higher than those reported for both MS and CBs. Tobacco toxicants are inhaled by smokers and transmitted to the environment through SS, SHS, THS, and discarded CBs. However, further studies are necessary to assess adverse effects of toxicants found in CBs and THS not only on human health, but also on the environment and ecosystems. The results of this review provide updated information on the chemical contents of MS, SS, SHS, THS, and CBs. It adds to the growing understanding that smoking creates major health problems for smokers and passive smokers, but also that it generates environmental hazards with consequences to the ecosystems and human health through discarded CBs, SHS, and THS exposure.
... According to the classification of The International Agency for Research on Cancer (IARC), a cigarette sap contains many compounds that are carcinogenic [13]- [17]. The content of cigarette smoke includes TVOC which is a volatile organic compound consisting of benzene, ethylbenzene, and styrene and formaldehyde [13]. ...
... According to the classification of The International Agency for Research on Cancer (IARC), a cigarette sap contains many compounds that are carcinogenic [13]- [17]. The content of cigarette smoke includes TVOC which is a volatile organic compound consisting of benzene, ethylbenzene, and styrene and formaldehyde [13]. ...
Full-text available
Introduction: In surgeons, electrosurgical surgical devices are gaining attention that stands out as one of the most useful and most widely used instruments. Thus, the instrument of electrical surgery is undoubtedly one of the most useful and most frequently used tools by surgeons. However, not many realize that the use of electrosurgery can produce smoke containing quite harmful gases such as TVOC gases such as benzene, nitrile, hydrocyanides and other hydrocarbons as well as Formaldehyde. Methods: This study used a Crossectional Observational research design with a control group, namely cigarette smoke, and a cauter smoke treatment group. Samples in the form of TVOC and fromaldehyde levels were taken as a result of all cigarette smoke and cauterized smoke operating at IBS Sanglah Hospital in Denpasar. Then patients from each age level will be randomized using the Online Research Randomizer ( application. Then the levels of TVOC and fromaldehyde are measured in the area of operation, and for cigarette smoke it is carried out using non-filtered cigarettes. Results: In this study, the cigarette group had an average TVOC of 9,841 mg/m3 and formaldehyde of 1,197 mg/m3. Meanwhile, the average TVOC in the electrocautery group was 6.34 mg/m3with the average formaldehyde contained in this study of 0.87 mg/m3. It was also found in the combined levels of TVOC and formaldehyde in the cigarette group of 5.51 mg/m3which was greater than the electrocauter group of 3.60 mg/m3. Conclusion: Levels of TVOC and formaldehyde in orthopedic surgical electrocauteric smoke are lower levelsthan cigarette smoke. The combined total level of electrocauteric smoke of TVOC and formaldehyde content in orthopedic surgery is lower than the combined total level of TVOC and formaldehyde content in cigarette smoke.
... Tobacco smoke is the main source of non-occupational exposure to harmful VOCs in the United States (31). Toxic and carcinogenic VOCs such as acrylonitrile and benzene (32) contribute to the risks of different tobacco-related cancers and to noncancer disease risk (33)(34)(35). ...
... PAHs in cigarette smoke have also been linked to cardiovascular disease (60), and the current findings are also consistent with similar risks of CVD between menthol and nonmenthol smokers (61). Tobacco smoke contains over thousands of chemicals, including carcinogenic and toxicants that lead to malignancy and disease, regardless of the cigarette flavor being smoked (32). The tobacco industry has historically marketed different tobacco products, especially menthol cigarettes, to Black Americans in urban communities (39). ...
Background: The United States Food and Drug Administration (FDA) announced its commitment to prohibiting menthol as a characterizing flavor in tobacco. The relationship between cigarette menthol and exposure to toxic substances in mainstream tobacco smoke is not well characterized. Methods: Data from the National Health and Nutrition Examination Survey (NHANES) 2015-2016 special sample were used to study markers of 26 Harmful and Potentially Harmful Constituents (HPHCs) in tobacco smoke. These include urine metabolites of polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs), and heavy metals in exclusive menthol (n=162) and nonmenthol (n=189) cigarette smokers. Urine metabolites of 7 PAHs, 15 VOCs and 4 heavy metal biomarkers were compared by menthol status. Multivariable analyses were conducted on creatinine-adjusted concentrations. Results: There were no significant differences in cotinine levels or in 22 of 26 HPHCs. Among the urine metabolites of PAHs, the levels of 1-hydroxyphenanthrene were about 16% lower in menthol smokers. Among the urine metabolites of VOCs, menthol cigarette smokers presented significantly lower concentrations of acrylamide, N, N-dimethylformamide and acrylonitrile. Menthol and nonmenthol smokers presented similar levels of heavy metals. Menthol did not affect the levels of cotinine and the nicotine metabolite ratio in urine. Conclusions: Menthol and nonmenthol cigarettes deliver similar levels of most HPHCs. Impact: Findings on toxicity are similar for menthol and nonmenthol cigarettes.
... Many efforts have been dedicated to identify possible tobacco smoke (TS) tracers and know the respective relationships with cultivar, cigarette preparation, breathing time profile, etc. Chemically, TS displays a complex composition. Therefore, the first investigations were focused on TS macro-components (e.g., organic and elemental carbon, NOx, volatile hydrocarbons, and tar) Eatough et al. 1990;Nelson et al. 1997Nelson et al. , 1998Baek and Jenkins 2004;Bi et al. 2005;Polzin et al. 2007; Moir et al. 2008;Pandey and Kim 2010;Uchiyama et al. 2018). Hundreds of micro-components have been identified in TS, including metals, alkanes, carbonyls, polycyclic aromatic hydrocarbons, aza-heterocyclics, and organic acids and bases (Schmeltz and Hoffmann 1977;Eatough et al. 1989;Leaderer and Hammond 1991;Rogge et al. 1994;Gundel et al. 1995;Singer et al. 2002;Ding et al. 2006;Charles et al. 2008;Lauterbach et al. 2010;Gao et al. 2015;Whitehead et al. 2015;Edwards et al. 2017;Ishizaki and Kataoka 2019). ...
... Various authors have explored the occurrence in TS of 2methyl (iso), 3-methyl (anteiso), and linear (n) long-chain alkanes, overall within the C 28 -C 34 range, with the prevalence of odd iso and even anteiso homologs Kavouras et al. 1998;Bi et al. 2005;Polzin et al. 2007;Uchiyama et al. 2018). This molecular signature accompanies the saw-tooth fingerprint of long-chainn alkanes [>C 24 ], typical of natural emissions and biomass exhausts. ...
Full-text available
Tobacco smoke (TS) is the source of a number of toxicants affecting the atmosphere and poses a threat to smokers and the whole community. Chemical, physical, and toxicological features of smoking products (vapors as well as mainstream, side stream, and third-hand smoke) have been investigated extensively. Special attention is paid to organic compounds (individually or in combination giving rise to peculiar molecular fingerprints), potentially able to act as “chemical signature” of TS. In this regard, the percent distribution of long-chainnormal, iso, and anteiso alkanes was ascertained as typical of TS. Nevertheless, until now no indexes have been identified as suitable for assessing the global TS contribution to environmental pollution, e.g., the TS percentage in carbonaceous aerosol and in deposited dusts, the only exception consisting in the use of nicotelline as tracer. This paper describes the results of an extensive study aimed at chemically characterizing the nonpolar lipid fraction associated to suspended particulates (PMs) and deposition dusts (DDs) collected at indoor and outdoor locations. Based on the iso, anteiso, and normal C29–C34 alkane profile in the samples as well in tobacco smoke- and no-TS-related emissions (literature data), various parameters describing the distribution of compounds were investigated. Finally, a cumulative variable was identified as the tobacco smoke impact index (TS%) suitable for estimating the TS percentage occurring in the particulate matter. The TS% rates were plotted vs. the exceedance of normal C31 alkane with respect to the average of C29 and C33 homologs, which results higher in TS than in most other emissions, revealing a link in the case of suspended particulates but not of deposited dusts. According to back analysis carried out on all particulate matter sets, it was found that traces of TS affect even remote areas, while inside the smokers’ homes the contributions of TS to PM could account for up to ~61% and ~10%, respectively, in PM and DD. This confirms the need of valuing the health risk posed by TS to humans, by means of tools easy to apply in extensive investigations.
... Another study utilized a smoking machine to evaluate potentially inhaled smoke from 41 different types of cigarettes, GC/MS for analysis with ISO parameters, and reported a measured range of 12.7-145 µg diacetyl/cigarette [63]. NIOSH also reported that electronic cigarette liquids often contain diacetyl [64,65]. ...
In the last two decades scrutiny of several retrospective occupational studies on performed by NIOSH in the early 2000’s on ambient indoor air exposures to the flavoring chemical diacetyl and more complex butter flavoring formulations has led to a reported association between diacetyl and severe irreversible lung disease, primarily bronchiolitis obliterans. A group of laboratory rodent studies, performed primarily by associated researchers, followed in the next two decades with the intent to determine a plausible physiological mechanism for bronchiole scarring applicable to the human respiratory tract. Recently, a renewed interest in diacetyl as a flavoring constituent of vaping liquids and marijuana and inhalation exposures has emerged. This paper reviews the universe of published literature to date in relation to whether diacetyl or butter flavors containing diacetyl causes occupational or environmental lung disease, more specifically BO (i.e., general causation) and whether specific levels of inhaled diacetyl or butter flavors containing diacetyl are associated with chronic lung disease. The review included numerous journal articles, government reports, etc. Based upon the evidence, while the literature reflects a statistical association between both diacetyl and butter flavoring diacetyl mixtures and lung disease, there is sufficient evidence to conclude that general causation between exposure to diacetyl concentrations measured in the ambient air environments studied to date and chronic lung disease does not exist.
... L'émission de ce gaz dans l'air ambiant via la fumée de cigarette est l'une des principales raisons pour justifier l'interdiction de fumer dans les lieux publics (Jo et al., 2004). Les COV présents dans la fumée de cigarette sont issus de la combustion incomplète des molécules organiques du tabac lors d'une bouffée (Polzin et al., 2007). Ils font partie des composés les plus toxiques retrouvés dans ces émissions (Fowles, 2003). ...
Le tabagisme est responsable de 8 millions de morts par an dans le monde. Le sevrage tabagique est actuellement la seule solution pour endiguer cette mortalité mais il est rendu difficile du fait de l’addiction à la nicotine. Depuis quelques années, de nouveaux dispositifs de délivrance de nicotine sont arrivés sur le marché : la cigarette électronique (e-cig) et le tabac chauffé. ien qu’ils soient généralement perçus comme des alternatives plus saines à la cigarette, leur impact précis sur la santé humaine reste à déterminer.Le premier objectif de cette thèse était d’analyser la composition chimique et la toxicité in vitro des émissions d’e-cig de différentes puissances (un modèle de deuxième génération et un modèle de troisième génération (Modbox) réglé à une puissance faible, Mb18W, ou forte, Mb30W) et du tabac chauffé et de les comparer à la fumée de cigarette. Nous avons pu montrer que le tabac chauffé génère beaucoup moins de composés carbonylés et de HAP que la cigarette, mais bien plus que l’e-cig, quel que soit le modèle. e manière concordante, l’exposition de cellules épithéliales bronchiques humaines (BEAS-2 ) cultivées à l’interface air-liquide aux émissions des différents dispositifs a permis de mettre en évidence que les émissions de tabac chauffé induisent une cytotoxicité réduite par rapport à la fumée de cigarette, mais bien plus élevée que les émissions d’e-cig. De plus, des expositions à 12 bouffées de tabac chauffé ou à 120 bouffées d’e-cig induisent un stress oxydant et la sécrétion de certaines cytokines pro-inflammatoires. Des effets similaires sont observés pour la fumée de cigarette mais seulement après 1 bouffée. e manière intéressante, en ce qui concerne l’e-cig, nous avons pu démontrer que la quantité de composés carbonylés émis et le stress oxydant augmentent avec la puissance du dispositif.Le deuxième objectif de mon projet doctoral consistait à évaluer sur un modèle murin la toxicité respiratoire sur le long terme des émissions d’e-cig de troisième génération. Des souris BALB/c ont été exposées exclusivement par voie nasale pendant 4 jours, 3 mois ou 6 mois aux aérosols de Mb18W ou de Mb30W, ou à la fumée de cigarette. Nos expérimentations in vivo ont montré que, d’une part, les émissions d’e-cig générées à 18 W et 30 W sont responsables de modifications épigénétiques induisant sur le long terme une hyper méthylation de l’ N et la dérégulation de certains mi RN à tous les temps d’exposition, mais que, d’autre part, seules celles générées à 30 W sont capables de provoquer des lésions oxydatives de l’ N, sans pour autant aboutir à des aberrations chromosomiques ou des mutations géniques. Les données transcriptomiques obtenues après 6 mois d’exposition aux aérosols d’e-cig ont mis en évidence la dérégulation de plusieurs voies de signalisation impliquées notamment dans la réponse inflammatoire, le stress oxydant et le métabolisme de composés carbonylés et, en particulier, des métabolites du propylène glycol. Cependant, le faible nombre de gènes impactés dans chacune de ces voies ne garantit pas que les dérégulations observées aient un réel impact biologique. Par comparaison, la fumée de cigarette a induit, dans les mêmes conditions d’exposition, la dérégulation d’un nombre plus important de voies de signalisation, notamment en lien avec l’inflammation et le métabolisme des H P, et impliquant chacune un nombre de gènes plus conséquent.Globalement, nos analyses chimiques et in vitro suggèrent que les émissions de tabac chauffé sont moins toxiques que la fumée de cigarette conventionnelle mais bien plus nocives que celles des e-cig, quelle que soit leur puissance. Par ailleurs, les expérimentations in vivo décrites dans ce travail n’ont pas permis de mettre en évidence une toxicité avérée des émissions d’e-cig sur le long terme [...]
... Currently, pre-analytical and analytical factors limit the routine application of U-B [18]. In addition, SPMA, t,t-MA, and U-B are affected by smoking habits due to the direct inhalation of significant amounts of benzene in tobacco products; these doses might be of the same magnitude as low occupational exposure [19]. Thus, urinary cotinine (U-C) analyses are necessary to evaluate the smoking habits impact on occupational exposure measurements [20]. ...
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Airborne benzene in workplaces has progressively decreased due to preventive actions and the redesigning of facility processes. Professionals who assess occupational exposure should select techniques to detect benzene levels comparable to ambient air exposure. Thus, sensitive biomarkers are needed to discriminate the effects of confounding factors, such as smoking or sorbic acid (SA). In order to identify sensitive biomarkers and to study their correlation with confounding factors, 23 oil refinery workers were enrolled in the study; their airborne benzene exposures and biomarkers were monitored. Urinary benzene (U-B), t,t-muconic acid (t,t-MA), and S-phenylmercapturic acid (SPMA) were quantified. Urinary cotinine (U-C) and t,t-sorbic acid (t,t-SA) were evaluated to flag smoking and SA intake, respectively. The benzene measured in personal inhalation sampling ranged from 0.6 to 83.5 (median 1.7) µg/m3. The concentration range of the biomarkers, U-B, t,t-MA, and SPMA, were 18–4893 ng/m3, <10–79.4 µg/g creatinine, and <0.5–3.96 µg/g creatinine, respectively. Pearson tests were carried out; the best correlations were between airborne benzene and U-B (µg/L r = 0.820, p < 0.001) and between benzene and SPMA (g/L r = 0.812, p < 0.001), followed by benzene and t,t-MA (mg/L r = 0.465, p = 0.039). From our study, U-B and SPMA result to be the most reliable biomarkers to assess the internal number of low doses of benzene exposure, thanks to their specificity and sensitivity.
Diacetyl is the simplest diketone. It occurs endogenously in humans, is a natural byproduct of bacterial fermentation and pyrolysis of organic matter, and is present naturally in a number of foods. In its pure form, diacetyl is a greenish‐yellow liquid that is moderately soluble in water and has a very strong buttery, quinone‐like, or chlorine‐like odor. It has been used as a synthetic food additive and flavoring, most notably in microwave popcorn, for its buttery and caramel or toffee notes; however, since the mid‐2000s, its use has declined in favor of substitutes. Diacetyl has also been used as a reactant or starting material in chemical and/or biochemical reactions. Exposure to the general population is ubiquitous, not just from use and consumption of flavored consumer products and foods, but also through naturally occurring diacetyl in various foodstuffs and beverages and direct or secondhand exposure to tobacco smoke. Diacetyl has low toxicity from ingestion and dermal exposure. Its respiratory toxicity potential has been thoroughly evaluated via animal studies. As with most volatile organic compounds, the most sensitive health endpoint is upper airways effects and inflammation. Findings from some epidemiological studies have suggested that, at very high concentrations, diacetyl may cause reduced lung function and even severe restrictive or obstructive lung diseases, including bronchiolitis obliterans. In addition, the weight of the evidence indicates that diacetyl is neither a teratogen, nor a carcinogen. Diacetyl's potential as a sensory irritant and respiratory sensitizer remains equivocal.
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Molecular Imprinting polymers (MIPs) are synthetic materials with pores or cavities to specifically retain a molecule of interest or analyte. Their synthesis consists of the generation of three-dimensional polymers with the specific shape, arrangement, orientation, and bonds to selectively retain a particular molecule called target. After removed the target from the binding sites, it leaves the empty cavities to be re-occupied by the analyte or a highly related compound. Although MIPs have been used in areas that require high selectivity such as chromatographic methods, sensors and contaminant removal, their use as highly selective extraction materials are the most widely used application because it exhibits low cost, easy preparation, reversible adsorption and desorption, thermal, mechanical, and chemical stability. Emerging pollutants are traces of substances that have been recently found in wastewater, river waters, and drinking water samples and represent a special concern for human and ecological health. The low concentration in which these pollutants are found in the environment and the complexity of their chemical structures make the current wastewater treatment not efficient for complete degradation, moreover, these substances are not yet regulated or controlled for their discharge in the environment. According to the literature, the use of MIPs as a highly selective adsorbent material is a promising approach for the quantification and monitoring of emerging contaminants in complex matrices. Therefore, the main objective of this work was to give an overview of the actual state-of-art of applications in adsorption by MIPs in the recovery and concentration of emerging pollutants.
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Although humans are generally exposed to second-hand smoke (SHS), volatile organic compounds (VOCs) exposure derived from SHS and its health hazard to non-smokers are rarely investigated. Thus, we examined the effects of SHS on VOCs exposure and oxidative stress damage via a passive smoking simulation experiment in 6 children and 7 adults. To further validate the studied urinary VOC metabolites as biomarkers for passive smoking, 259 children were recruited. The levels of 8-hydroxy-2′-deoxyguanosine (8-OHdG), malonaldehyde (MDA), trans-3′-hydroxycotinine (OH-Cot) and 31 VOC metabolites in urine were determined. The results showed that the geomean concentrations of 17 VOC metabolites in urine of children were 26.5%–138% higher than those of adults after passive smoking. The levels of urinary 8-OHdG, MDA and OH-Cot increased by 24.6%, 18.8% and 600% in children, but only 1.25%, 10.3% and 116% in adults, respectively. Therefore, children are more vulnerable to SHS than adults. After exposure to SHS, the levels of 8 urinary VOC metabolites of benzene, acrylonitrile, 1-bromopropane, propylene oxide, toluene, methyl methacrylate and cyanide increased by 60.9%–538% within 23 h. These 8 VOC metabolites were also significantly associated with 8-OHdG or MDA in urine (p < 0.01). Therefore, exposure to VOCs caused by SHS increases body oxidative stress damage. OH-Cot level higher than 2.00 μg/g Cr can be used as a threshold of passive smoking. The levels of urinary s-benzylmercapturic acid (BMA) and s-phenylmercapturic acid (PMA) in children increased by 494% and 728% within 6 h after passive smoking, respectively. Population validation study indicated that BMA and PMA levels were significantly elevated in children exposed to SHS. Therefore, in addition to OH-Cot, urinary BMA and PMA are potentially useful short-term biomarkers of passive smoking. Future studies should focus on the differences in VOC metabolism and detoxification mechanisms between children and adults.
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The relative proportions of the major smoke components and N-containing components in the semi-volatile phase and the non-volatile phase from some varieties of tobacco, i.e. flue-cured, Burley and Turkish tobacco, were determined. In flue-cured tobacco smoke, 2-furfural, 5-methylfurfural, 5-hydroxymethylfurfural and other carbohydrate pyrolysates, catechols and organic acids were present in higher concentrations than in the smoke from the other tobaccos. In Burley tobacco smoke, myosmine was present in much higher concentration than in the smoke from the other tobaccos. In Turkish tobacco smoke, glycerol and β-methylvaleric acid were both present in much higher concentrations.
A method well suited to the analysis of gas phase organic compounds in ultra-low tar delivery cigarette smoke has been developed. The cigarette is smoked directly through a filter and a Tenax trap arranged in series. The components collected on Tenax are analyzed by thermal-desorption programmed-temperature gas chromatography. Components are then quantitated by the use of external standards. The smoke from high tar delivery cigarettes also can be analyzed by thermal desorption gas chromatography of portions of well mixed solid dilutions of the trapping Tenax. Deliveries of 34 gas phase components were determined for 4 ultra-low tar cigarettes having tar deliveries ranging from <0.01 to 3 mg tar/cigarette, and 24 components for 5 cigarettes delivering 7 to 45 mg tar/cigarette.
Methods for the pre-concentration of headspace volatiles for trace organic analysis by gas chromatography are reviewed, emphasizing the dynamic methods of headspace gas analysis. The theoretical basis of static and dynamic procedures in headspace gas analysis is discussed, demonstrating the necessity for the latter procedures in trace organic analysis. Experimental arrangements for the enrichment of volatiles by means of dynamic procedures on solid adsorbents are discussed with respect to their efficiency. A comparison is made of liquid and thermal desorption for the trapped analytes on solid adsorbents, for their introduction into the GC column, leading to a greater analytical potential of thermal desorption when it is feasible. The applications and physico-chemical properties of a wide range of graphitized and polymeric adsorbents are presented.
This paper presents a simple gas chromatography–mass spectrometry (GC–MS) technique for the analysis of vapor phase mainstream cigarette smoke. The analysis includes two parts: (A) separation and identification of as many as possible compounds in vapor phase smoke, and (B) quantitative analysis of a selected number of analytes. For achieving these objectives, the cigarettes are smoked using a Borgwaldt RM20/CS smoking machine using Federal Trade Commission (FTC), International Organization for Standardization (ISO), or other recommended conditions. The vapor phase smoke is separated from particulate phase smoke with a standard Cambridge pad. The vapor phase is collected in a gas bag, and then a precise volume (1 or 5 mL) is injected in a GC–MS system for separation and analysis. About 90 compounds are separated and identified in vapor phase smoke. A quantitative procedure was developed for acetaldehyde, 1,3-butadiene, acrolein, propionaldehyde, acetonitrile, acetone, isoprene, propionitrile, benzene, crotonaldehyde, hydrogen cyanide (HCN), and styrene. Using appropriate standards, most of the other compounds identified in vapor phase smoke could also be quantitated. Excellent reproducibility is obtained using this technique, the results being in good agreement with previously reported work. © 2000 John Wiley & Sons, Inc. J Micro Sep 12: 142–152, 2000
The behavioural misuse of low-yield, ventilated-filter cigarettes is evaluated in two studies. The first reports the results of interviews with 46 low-yield smokers. Fifty-two per cent admitted to having blocked the ventilation holes on these cigarettes at some time with either lips, fingers, or tape. Although only three smokers admitted blocking the holes at the present time, 41 per cent (of the 39 who were observed smoking) gave evidence (by direct observation and by inspection of characteristic stain patterns on the filter) of currently blocking the holes. Study 2 demonstrates, using a modified smoking-machine assay (a 2.4 sec., 47 ml puff, with a 44 sec. interval, vent-holes blocked), how much tar, nicotine, and CO an average smoker might derive from the lowest-yield cigarettes in the U.K., Canada, and the U.S. In comparison to standard assays, tar increases from 15- to 39-fold, nicotine from 8- to 19-fold and CO from 10- to 43-fold. Smokers should be advised of the risks of blocking the holes of ventilated-filter cigarettes and taught how to detect whether they are doing it. The construction of low-yield cigarettes that will ensure low yields to smokers requires careful attention to the behaviour of smokers.
The cigarette smoke from 26 commercial brands was drawn into a separatory funnel containing an aqueous cysteamine solution. Almost the entire smoke from a cigarette was trapped as mainstream cigarette smoke. The carbonyl compounds in the smoke were derivatized to thiazolidines and were then quantitatively analyzed by gas chromatography with nitrogen-phosphorus detection. Total carbonyl compounds recovered ranged from 2.37 to 5.14 mg/cigarette. The general decreasing order of the carbonyl compounds yielded was acetaldehyde, butanal, hexanal, propanal, acetone, octanal, 2-methylpropanal and formaldehyde. Acetaldehyde was the major aldehyde in the smoke sample from 26 brands and it made up 46–72% of the total carbonyl compounds in the sample. Amounts of formaldehyde ranged from 73.8 to 283.8 μg/cigarette. It is hypothesized that these carbonyl compounds form from lipid and wax constituents in tobacco leaves.
A cryogenic trapping method with isotope dilution gas chromatography-mass spectrometry analysis has been developed for the determination of benzene, toluene, styrene and acrylonitrile in mainstream vapor phase cigarette smoke. The method is simple, direct, and quantitative. Vapor phase samples are collected cryogenically in a series of four traps following removal of the particulate phase with a Cambridge filter pad. For all four analytes, 75-85% of the total amounts recovered were found in the initial trap and less than 1% in the final trap. Assessment of instrumental precision by multiple injections of a sample gave relative standard deviations of less than 2%. Linear calibration for all analytes over the analysis range gave an r2 value greater than 0.99 with average relative standard deviations at the mean ranging from 1.4 to 8.2%. The cigarettes analyzed include a reference cigarette (Kentucky 1R4F), a commercial ultra-low "tar" mentholated cigarette, and two cigarettes that heat but do not burn tobacco. The values determined for the four analytes in the 1R4F samples are comparable to reported values of similar cigarettes. The cigarettes which heat rather than burn tobacco yield less of all four analytes compared to the other cigarettes in the study.
An analytical procedure was developed for the analysis of 1,3-butadiene, acrolein, isoprene, benzene and toluene in the gas phase of cigarette smoke and environmental tobacco smoke (ETS) utilizing cryogenic gas chromatography-mass selective detection (GC-MSD). The MSD was operated in the selective ion monitoring (SIM) mode. The compounds of interest eluted in < 15 min. The gas phase of freshly generated mainstream smoke was introduced into the GC - MSD via a 10-port gas sampling valve on a puff-by-puff basis. This method minimizes the ageing of tobacco smoke. The levels of 1,3-butadiene in the mainstream smoke ranged from 16 to 75 µg/cigarette. The gas phase of sidestream smoke was trapped in methanol using three midget impingers at -78°C. The amount of 1,3-butadiene in the sidestream smoke ranged from 205-361 µg/cigarette. The concentration of 1,3-butadiene in ETS in a smoke-filled bar amounted to 2.7-4.5 µg/m3.