Reports a simple extraction method for the simultaneous measurement of nicotine and menthol. Says this method is used to study the effects of air dilution on puff-by-puff deliveries of nicotine and menthol. Finds increased air dilution enriches the nicotine content of tar more than menthol and this procedure is useful for analyzing cigarette filler.
- Shoffner, R.A.
- Ireland, Mary Sue (Lor, Product Composition Chemist, 1965)
- Minneme, H. J.
- Schultz, Frederick J., Ph.D. (VP of Lorillard, Inc. '89-95)
- Tucker, Charles. L., Jr. (Lor, Product Development Manager, 1979-1983)
- Elasticity and Product Control
- FTC machine testing and ratings
Design changes to achieve altered FTC smoke machine tar and nicotine ratings, with or without measured changes in human intake.
- Low-yield cigarettes
Modification of low yield products to assure that adequate levels of nicotine delivery are maintained, and effects of yield changes on toxicity and dependence.
- Nicotine transport, transfer, and uptake
Design changes which alter nicotine delivery or effect how the product causes and maintains dependence, including transfer of nicotine from tobacco to smoke, and uptake into the body.
- Use of additives
Modification of tobacco products through use of additives and measuring effects on dependence, behavior, and toxicity.
- Menthol delivery (Smoke menthol, menthol yield)
- Per puff delivery
Per puff tar, per puff nicotine, and per puff CO
- Puff parameters
- Total particulate matter (TPM or Tar)
- Smoke Constituent
- Total particulate matter
- Design Component
- Air dilution
- Perforated tipping paper
- Pressure drop (PD, Resistance to draw (RTD), Flow rate or Draft)
- Tipping paper
- Named Organization
- Hewlett Packard
- Lorillard Tobacco Co. (American cigarette manufacturer)
American cigarette manufacturer; makes Kent, MaxSatin, Newport, Old Gold, Style, and True cigarettes.
- Binary organic solvent system
- Cambridge filter pad
- Direct extraction
- Filtrona 12-port smoking machine
- Gas chromatography
- Carlton (ATC)
- Doral (RJR)
- Golden Lights
- Kool (BW (1933-2003)/RJR (2003-present))
First Menthol cigarette line, released in 1933. Premium priced brand.
- Merit (PM)
- Newport (Lorillard)
- Salem (RJR)
- True (Lor)
- Menthol (Additives)
- Puff Count (Measures)
- Smoke Delivery/Transport (Measures)
- Smoke Nicotine (Measures)
- Test/Smoke Machine (Testing)
- Ventilation (Design)
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Accession number 1521
Lorillard Research Center
A STUDY OF' THEI PUFF-EY-PUFF' D'ELIVERY OF MENTHOL,
ANDNIOOTINE'~ ][N CIGARETTE SMOKE'AND~THE EFFECTS
OF AIR D'ILUTIOlri' ON DELIVERY
Submitted by: Rose A. Shoffner
Report number: pate: la/23/80
Summary or Aimstract:.
A simple extraction method for the simultaneous analysis
: of menthol and nicotine has been developed. The method has been
used to study the puff-by-puff delivery of menthol and nicotine
.from several of our menthol brands along with dther low tar
competitive brands. Experimental cigarettes were developed'in
.order to study the effect of air dilution on the yield reduction,
"of tar, menthol and nicotine. It has been found that by in-
creasing air dilution, the general effect is to enrich the
nicotine content of tar more than the menthol content. Thee
procedure also has applications for the analysis of tobacco
filler for menthol and cigarettes for both menthol and1triacetin.
Ms. M. S. Ireland
Dr. H. J. Minnemeyer
Dr. F. J. Schultz
Mr. O. L. Tucker
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A review of the literature shows comparatively few methods
reported for the determination of menthol in cigarette smoke
condensate.©ur currentmetho~d of menthol analysis1 isusedito
determine menthol levels on the tobacco filler. Mitchell, Barbee
and Irby reported a method for the determination of'rnenthol in
smoke 2 which involved vaporiaation~from a Cambridge filter into
a cold trap. Another vapor chromatographic method'3' was reported
by Lyerly. A simple direct extraction method 4 has been reported
by Ctarran for determining menthol in filters and on tobacco. A
method similar to the one described by Curran wgs used by Parks
or ng menthol in smoke puff
The method described in this report is based on the simul-
taneous extraction of menthol and nicotine using a binary organic
solvent system. This report also g,ives information on the puff-
by-puffana~lysis of several of our menthol brands, competiitive
.brands, and experimental cigarettes. The~ experimental cigarettes
were developed~in order to study the effects of different air
filtration systems on the delivery of menthol and nicotine.
1. Filtrona 12-port smoking machine
. Hewlett-Packard 583'0-A Gas Chiromatograph equipped,
with flame ionization detector and'CC terminal, or
. GC'column - 61 x 1/8" s:tainless steel, 10% ' Carbowax
20M on Anakrom ABS 80/90 mesh.
. Cambridge filter pads and holders
. Sample vials with rubber stoppers
. 15 ml calibrated dispenser
5. 10, ul syringe
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Extraction solution - 4:1 ratio of Trichlorotrifluoro-
ethane (Freon 113) to isopropanol
Internal standard solution - anethole (,= 2 mg/ml)' in
. Freon~ 113
Menthol - 0'.3'60' mg/ml in~ Freon 113
Nicotine - 1.154 mg/ml in Freon 113
. GC'Calibration Solution:.
3 ml menthol standard
2' mi nicotine standard
1 ml internal standard
6 ml Freon 113
3' mil Isopropanol
1. Sample Preparation - Menthol cigarettes were conditioned'
in packs overnight at 750 + 2oF and 60% + 2%relative
humidity. They were sorted according,too pressure
drop, percent air dilution and'weight then smoked im-
Smoking - Cambridge filter pads and holders were weighed
, before and after smoking in order to determine wet tar.
Cigarettes were smoked on a puff-by-puff basis using
40.1cigarettes. The first cigarette was placed inithe
,first port and lighted as the machine took a puff. The
cigarette was then moved to the second port and another
cigarette placed'inithe first port. On the second cycle,
the cigarette in the first port was lighted and then
moved to the second port after the cigarette there
was moved'to the third port. This process was repeated
until all forty' cigarettes were smoked. Cigarettes
were smoked toia standard butt length of tipping paper
plus.3 mm. Puff counts were takeniand'averaged,
3. Extraction - Cambridge filter pads were removed from
the holders and placed in the sample vials containing
1 ml of the internal standard toawhichiwasadd'ed 15 mil
of'the extraction solution,. The bottles were stoppered
and shaken horizontally on a mechanical shaker for 30
minutes. The solutions were then injectedlinto the GC'.
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4. Gas Chromatog;raphic Conditions - GC oven conditions
and'iprogram conditions are shownlin Figure 1.
Recovery of Menthol - Recovery of menthol from Cambridge
filter pads was checkediby smoking five nonmentholated
cigarettes on each pad and then adding 1 ml of the menthol
stock solution to the pads. The pads were then placed in,
sample vials,, stopperediand allowed to sit 30 minutes
before extracting., Results shown in Table 1 indicate
a recovery of 100%.
Recovery of Nicotine - Recovery of nicotine from Cambridge
fi]lter pads was checked by smoking,five low tar/nicotine
cigarettes on each pad and thenadiding 1 m,l of the nicotine
stock solutions to the pads. The pads were then placed in
sample vials, stoppered and allowed'to:sit 30 minutes before
extracting. Results are shown in Table 2.
Precision of the Method - Precision of the method for nicotine
was.checked by smoking 24 samples (5 cigarettes/pad). one-
half of these samples was analyzed for nicotine by the method
described above and the other half by our smoking; lab's GC
standard procedure for nicotine. TabSe.3' shows the statistical
comparisons of the data collected. No statisticall difference
was found in precision of the two methods at a 95% confidence
Figure 2 shows a typical chromatographic separation of'
a sample. Menthol is eluted at 2.2'minutes, followediby
the!internal standard, anethole, at 4.6 minutes and nicotine
at 5.5 minutes. The small peak that elutes after nicotine
was identified using,GC/FT-IR and GC/MS as neophiytadiene.
In order tolkeep this peak from interfering with nicotine,
it was necessary to run the program isothermally at 170u.
1. Menthol - preliminary results of menthol analysis
appeared to be low when compared with results found in the
literature. 3' Several experiments were run to determine why
these results were low. After running!analysis on!freshly
opened packs of Triumph Menthol and comparing those results
with, previous ones, it was hypothesized that menthol levels
could be dropping due:to time spent in the conditioning room
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in opened trays. This hypothesis was checked'by analyzing
Triumph Menthol-cigarettes that had been placed in the con-
ditioning, chamber and allowed to~ sit open for six days.,
Results shown in Table 4 indicated that there was a loss of
menthol during the conditioning period. In order to over-
come this problem, the procedure was changed so that samples
were conditioned in unopened packs and opened immediately
before smoking. Figures 31 and 4 show the puff-by-puff
delivery of menthol for our brands and competitive brands,
respectively. The total amount of menthol delivexed/cigarette
for our brands ranged from 301 pg for Newport Lig,ht -to 152 _
pg for Triumph. -The competitive brands gave slightly lower
deliveries than our average. Table 5I shows the calculated
values for percent delivery of menthol per puff basedionn
2. Nicotine - puff-by-puff analysis of nicotine for our
brands and'competitive brands is shown in Figiures 5 and 6,
respectively. Salem Light 85's delivered the highest
total amount of nicotine at 938'Ug followed by Newport.
Light 85's at 760 jng,. The nicotine results foundiby using
this procedure were within the range reported by our smoking
lab. The percent delivery of nicotine per puff is shown
in Table 6.,
Air Dilution Versus Delivery
Experimental cigarettes were developed in order to study
e t+he effocts off' air dilution on the delivery of menthol
andlnicotine. The cigarettes were made using the same
blend and filter construction with the only difference
being the number of lines of'perforations in the tipping
paper. Cigarettes were selected'so that the air d'ilution.
.values ranged from 0-50%. Figure 7 shows the comparative
rates at which~ menthol and nicotine are reduced in~ the smoke
condensate as a function of increasing air dilution., When
looking at the total amount delivered, we found that the
amount of nicotine present in smoke drops faster with in-
creasing air dilution than that of menthol. Figures 8 and 9
show the puff-by-puffdeliveryof menthol and nicotine,,
respectively. Table 7 shows the comparative differences on
the experimental cigarettes and the percent yield reductions
for tar, menthol, andlnicotine. These values are shown
graphically iniFigure 10'as percent yield reduction vs. per-
cent air d'ilution,. As expected, the yield reduction for 0
tar approaches the 1:1 ratio line when comparedito air O'
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toiair dilution. On aipercent reduction basis, menthol
is reduced more than nicotine. Therefore, increasing
air dilution enriches the nicotine content of tar more
than the menthol content.
Experiments are being conducted'in order to:determine
the applications of this method to include the analyses of
tobacco filler for menthol and cigarettes for both menthol
and triacetin. Production samples are being analyzed froin
the same groups oif samples takenifor analysis by our Quality
Control lab. Preliminary results indicate that this method
may be acceptable but no definite conclusions can be drawn
until data have been analyzed for comparison of the two
1 Wagner J. R. and Thaggard, N. A.,, "An Automated Method
for the Gas Chromatographic Determination of Nicotine in
Smoke°', TobaccoiScience, 18', 63-66 (1974) .
Mitchell, B. C'..,, Barbee E. P., and Irby, R. M., "The
Chromatographic Determination of Menthol in Cigarettes
and Cigarette Smoke" , Tobacco Science, 7, 6'4'-70 (1963), .
Lyerly, L: A., "Direct Vapor Chromatographic Determination
of Menthol, Propylene Glycol, Nicotine and Triacetin in
Cigarette Smoke'"', Tobacco. Science, 11, 49-.51 (1967).
C'urrani,, J. G., "Delivery of Menthol from Cigarettes
Containing Either a Mentholated Filter or Mentholated
Tobacco"', Tobacco Science, 16,, 40-42' (1972).
Parks, R. Mi., "'Menthol in Smoke II"',, Lorillard Research
Report, Accessi:oniNbi. 445 (;19.73).
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TABLE 1 - RECOVERY OF' MENTHOL
Sample % Recovery
1 9'9 . 2.
4 _ 100.6
6 100'. 3
& 100. 0'.
. TABLE 2' - RECOVERY OF NICOTINE
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Std., Dev. 0. 0'599
Std. Error of Mean 0.0173
Coeff. of Variatzon 4.3.889~
TABLE 3 - PRECISION OF' TH'EI METHOD
TABLE'4 - LOSS OF MENTHOL DURING CONDITIONING
Triumph - 5 cig/pad -
Triumph - 5 cig/pad
6 days opened in, cond', chamber
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True Green 85
True Green 100
Golden Light 10!.0~
Newport Light 85
Golden Light 85
Salem Light 85
Kool Super Light
TABLE' 5 - MENTHOL DELIVERY
D'TL ~. WT. OF' MENT .
, 3' .
, 5'~ .
69 5.09 ' . 0 9' .,2 2 .26. . 28 .40 5 '. .541
52 3.3'6 .29' .82 1.11 1. 2' 1 1.4'2 1.,51 1.62
34 4.04 .30 .79~ 91 1.01 1.27 1.40' 1.78
56 1.96 .105 .18' . 3!9'. .53 .56 .68' .9'6
36 3'.19 ~ .61 1. 0'2' 1.2'1 1.30 1.55 1.7'0 2.05
42 3'.12 . 2'9, . 83 ' 1.06' 1.1~7 1.2'4. 1.,44
18' 2'.62. .,46
1.3'6 1.22' I 1. 5.4. 1.73
30 3'.83' .32 .8'3' 1.02 1.01 1.32 1.47 1.80'
49 3'.. 34 .13 .38I .49 .53' .71 .83 1.20
8'0. 8.9'0 .,02. . 0.6 .11 .13'. .210 .25
56 3'. 4 5 .22. .59. .76 . 7 3' 1.0'1 1.17 1.16
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TABLE 6 - NICOTINE'DELIVERY
$, T., OF NIC. -
IR ' ON TOBACCQ ' % DELIVERY/PUFF
BRAND' IL. (mg/Cig. y 1 2' 3 4 5 6 7 8
, ~~- .
~ 17.2 1 . ~0~6~ .12' ~ .15
~ .17 ! .25~~
~ .32' .~3'6
True~ Green 85 ~152 ' ]12'.16~~ .17' .~4!2' .53 .58 ~ .69'
I .~75~' ~ .78 ' -
True Green 100 34 14.84 .2'4 .46 .54 .55 ' .66 , .T6 .912 I -
Golden Light 100' 56 17.60, I .08 .14, .26 .30 .35 .41 .46 .54
Newport Light 85 '3I6 14.,85
~ . 34! . 59. .,69 . 72 . 88 .92 1. 0'0 -
Golden Light 8~~5~
Salem Light 85 18' 13'.93' .34 I .63 .80 I.71 .,97' 1.04 1.0'9. 1.~16
Merit 85 30 10.91 ' .28 '' .,5'8 . 72'. . 68' .92 . 98 .94 -
bCool ' Super Light
13.96 .14 . 27 .36 . 39' .51 I. 57' .66
;Carlton 85 8'.0 I 9.76 .04 .08' .12 .14 .2'.1 .24 - -
'~ .44 4~4