Tobacco Documents Online

D~stribution : Dr. H. J. Minnemeyer Dr. F. J. Schultz Dr. A. M. lhrig Library Ms. M. S. Ireland Accession number 988 VAPOR PHASE REMOVAL AND NICOTINE AUGMENTATION WITH ALL AIR DILUTrON CIGARETTES Submitted by:. M. A. Skladanowski Report numbar: Date:April 4, 1977 Summary ,or Abstract: A 6mg total air dilution cigarette, without a cellulose acetate filter plug, gave the following removal efficiencies: Nicotine 43% Corrected Part, Mat. 66% Carbon Monoxide 82% Nitrogen Oxide 73% Aerolein 79% Acetonitrile 62% Isoprene 67% Hydrogen Cyanide 86% Acetone 67% Furan 76% 2-Methyl Methyl ethyl ketone 71% Toluene 47~ The nicotine to tar ratio was increased 64%. The alkalinity of smoke was increasod 1.1 pH units to levels equivalent to 0.2% ammonia addition to the tobacco. These cigarettes could be considered useful for low gas phase cigarettes with tar levels from 6 to 12 mg. c) o Z r'n Z Z 0 © Z ITRIAL EXHIBIT 10,102

The object of the nicotine augmentation project was to "develop a flavorful cigarette delivering a level of nicotine higher than could be obtained by.conventional cigarette con- struction. This goal is almost an absolute necessity for brands delivering less than 8 mg of tar".(1) Several approaches to the problem other than the addition of nicotine to tobacco were studied such as the (a) treatment of tobahco with ammonia, (b) decrease of the tar from non-tobacco materials such as casings, menthol and plasticizer, and (C) air dilution. (i) This report is concerned with the study of air dilution as an alternative to the addition of nicotine for low tar cigarettes with enhanced nicotine. Two major disadvantages of adding free nicotine to tobacco is its harsh taste and its toxicity. In a recent patent for the addition of nicotine to tobacco smoking mixtures (2), the addition of nicotine as a free base was found to give the smoke an undesirable chokiness. The addition of volatile acids along with the free nicotine eliminated the chokiness. Free nicotine is very toxic to man when breathed, swallowed or absorbed b7 the skin. A study by Tong and Heck indicated that as little as 0.35 ml Of nicotine in the free base form could be fatal when absorbed through the skin (3). The use of nicotine in a manufacturing situation would require confinement of the nicotine and constant mOnitoring of the nicotine levels applied to the tobacco and in the working atmosphere. At the present time Lorillard makes two cigarettes with c~mbined air dilution and cellulose acetate filtering systems. The nicotine to tar ratios in the smoke of both cigarettes is great~.r than the ratios in the respective controls. Norman (4.) has shown that air dilution alone increases the nicotine to tar ratio even more than the combined system. The exact mechanism by which air dilution increases the nicotine to tar ratio in smoke is not agreed upon. Both Norman and Miller (4,5) have proposed that the higher ratios are caused by the modified thermal profile of the burning cone, making it more like the profile in the free burning state. It seems reasonable that the nature of the. cone may be changed by air dilution since less air passes through the cone on each puff. Whatever the mechanism, air dilution does tend to increase the nicotine to tar ratio in the smoke as com- pared to the control. It also changes the relative amounts of other smoke components, such as phenol, hydrogen cyanide, menthol, aldehydes and carbon monoxide (4). For example, menthol, a desirable flavor, is removed less efficiently ~ than the total tar. ~'~ In this study cigarettes with only air dilution for .:p removing undesirable smoke components were prepared from "~ materials easily obtained in the laboratory. The analyses ~ of the smoke showed that nicotine to tar ratios were increased slightly and va~or phase components, such as carbon monoxide, 0 m z m 0 0 0

were reduced to very low levels. Air dilution also increased the alkalinity of the mainstream smoke to levels equivalent to adding 0.2% ammonia to the tobacco (16). EXPERIMENTAL: The samples of total air dilution cigarettes were prepared from either True 85 or Kent 85 cigarettes. The filters were removed before the cigarettes were selected by weight. The selected cigarettes were then modified as described in the following sections. A control was prepared for each of the samples. Tar and nicotine in the smoke was determined by the Lorillard smoking laboratory. The vapor phase analyses and smoke alkalinity were determined by Winston Barnes. (17) Sample AD66-109 True 85 - The filter end is basically a hollow cylinder with air vents in the cylinder wall midway between the tobacco column and the end near the smoker a. The plastic tip and cellulose acetate filter were removed from forty True Blue 85 cigarettes (11.6 mg tar). b. The plug wrap paper from the inside of the filter tube was removed. C. The True plastic mouthpiece was placed in the tip of the cigarette near the smoker's mouth. d. Three holes 0.6 mm diameter were added to the True air dilution holes. Samples ADT0-8 and AD70-55 True 85 - The filter is basically a hollo~ cylinder with a mouthpiece which restricts the passage of smoke to the smoker. Soma mouthpieces were made so that a portion of the smoke passed undiluted to the smaker. Air vents were located midway along the tipping paper (19,20). The plastic mouthpieces, ceflulose acetate plugs and plug wraps were removed from True 85 production cigarettes (5 mg). 2. A 0.4 mm drill bit was used to make holes in the bottoms o~ 6.4 mm diameter gas chromatography column caps. Two patterns for the holes were made, one with nine hoses and one with eight holes. 3. Pieces of True plastic rod 2.0 cm long were cut and three rectangular holes 0 4 cm by 0.5 cm were cut equidistantly in the outer wall between the supporting spines, and 0.5 cm from the ends. 4. The modified True plastic sections and column caps were inserted into the filterless True 85 cigarettes. The Caps were secured with tipping paper glue. 5. Additional holes 0.6 mm in diameter were put in the tipping paper Where the True air vents are located. m z z m > 0

- 3- Sample AD70-40 Kent 85 - The filter end of the cigarette had a hollow tube for the filter with a mouthpiece which restricted the passage of smoke and provided for an acceptable pressure drop. The air vents were located in the top of the tobacco column where the tipping paper and cigarette paper overlap. i. The cellulose acetate plugs were removed from Kent 85 production cigarettes. A. 0.4 mm drill bit was used to make eight holes in the bottom of 6.4 mm diameter gas chromatography column caps. The column caps were inserted into the filterless Kent 85 cigarettes and secured with tipping paper glue. 4. Vent holes 0.6 mm in diameter were placed where the tipping paper and cigarette paper overlap. RESULTS : Air dilution alone, without a cellulose acetate filter, increased the nicotine to tar ratio in the smoke and the number of puffs per cigarette as shown in Table 1 (18). By simply removing the cellulose acetate filter and adding air vents, a True 85 cigarette with i1.5 mg tar and 0.6 mg nicotine was modified to deliver 13 mg tar and 1 mg nicotine. The nicotine to tar ratio in the smoke of modified cigarette AD66-109 True 85 was 52% greater than in the control. The pressure drop of these cigarettes was low. An adequate pressure drop could be obtained in total air dilution cigarettes by inserting a mouthpiece which restricted the passage of smoke, The mouthpieces for samples prepared in the labo- ratory were made from gas chromatography column caps. Holes were drilled in the end of the cap. For the mass production of total air dilution cigarettes a mouthpiece such as that shown in Figure l, which could be made by an extrusion pro- cess, might be preferred. The air vents and smoke passages through the mouthpiece were adjusted in sample AD70-55 True 85 so that 6 mg of tar and 0.6 mg of nicotine were delivered per cigarette. The data from the analyses of the vapor phase and particulate phase are shown in Table 2. A comparison of the smoke from AD70-55 True 85 and the control gave the following results: 1. Nicotine to tar ratio increased 64% 2. Alkalinity increased i.i pH units. 3. Carbon monoxide reduced 82%. 4. Nitrogen oxide reduced 73%. 5. Acrolein reduced 79%. 6. Acetonitrile reduced 62%. 7. Isoprene reduced 67%. 8. Hydrogen cyanide reduced 86%. 9. Acetone reduced 67%.

4 i0. 2-methyl furan reduced 76%. ii. Methyl ethyl ketone reduced 71%. 12. Toluene reduced 47%. The 6 mg total air dilution cigarette exhibited better gas phase removal than a True 85 cigarette by the following percentages: 1. Carbon monoxide reduced 44%. 2. Nitrogen oxide reduced 40%. 3. Acrolein reduced 83%. 4. Hydrogen cyanide reduced 13%. Since cellulose acetate is ineffective for removing gas phase components, it was the 60% air dilution in the True 85 which produced the gas phase removals shown in Table 2. The effec- tiveness of total air dilution for removing gas phase compo- nents also.compared favorably with charcoal as shown in Table 2. Air dilution was less effective than charcoal for removing isoprene, acetone or toluene, however air dilution was more effective for removing carbon monoxide, nitrogen oxide, hydrogen cyanide and acrolein. The characteristic taste imparted to smoke by charcoal, which has been considered undesirable, was not noticed in the air dilution cigarettes (20). At the present time the amounts of vapor phase com- ponents in smoke are not generally published, however recent articles in the Readers Digest on the gas phase (21,22) may arouse public interest. Carbon monoxide has been implicated as a factor in heart disease (23). Acetaldehyde, acro~ein, aoetonitrile and hydrogen cyanide have been shown to be ciliastatic agents (24). Nitrogen Oxides have been shown to be associated with chronic bronchitis and emphysema (22). The tar and nicotine in the mainstream smoke of total air dilution cigarettes could be adjusted by modifying the size of the air vents or the smoke passageways as shown in Table 3. (20). A nicotine to tar ratio of 0.i0 was the highest that was obtained with the True 85 tobacco b~lend.~ As shown in Table 5, increasing the nicotine tO tar ratio in the tobacco increased the ratio in the smoke, however the percent removals were unchanged. When the tar level of an all air dilution cigarette was lower than 6 mg, problems with pressure drop, too little flavor and difficulty in lighting the cigarette made the samples unacceptable. Sample ADT0-40 Kent 85 was prepared with the air vents located at the top of the tobacco column Where the tipping paper and cigarette paper overlap. As compared to the con- trol data, the nicotine to tar ratios in the smoke of the sample were increased 53% (.078) and the number of puffs was increased 19% (9.4 puffs per cigarette) as shown in Table 4. These results were similar to those with the air vents in the tipping paper. If a mouthpiece such as that in Figure 3 was used in place of the cap,. this

design may be more practical than previous samples prepared in the laboratory. No attempt has been made to work on the taste of all air dilution cigarettes however some evaluations have been favorable (2). Total air dilution cigarettes with ~ mg of tar or greater have plenty of taste and a satisfying amount of smoke per puff. Sample AD70-55 True 85 was considered "out of balance" by one member of the expert panel. This may be due to the high pH and nicotine content of the smoke. SUMMARY : Nicotine to tar ratios of 0.1 were achieved using the True 85 tobacco rod in a total air dilution 6 mg cigarette. The ratio for a True 85 cigarette, July 8, 1976, was'0.085 (26). The gas phase study of the all air dilution cigarette also showed significant removals of gas phase components. The carbon monoxide concentration was reduced to half of that in a True 85 cigarette. Acrolein, a component, which has been designated as a ciliostatic agent by several workers, was reduced almost six times that in the True 85 cigarette. The hydrogen cyanide was similar to that in the True 85 cigarette. Overall the total air dilution system for "filter" cigarettes appears to be a good way to reduce the undesirable components in tobacco smoke. The alkalinity of the smoke was also increased by the a11 air dilution system and some reports indicated that higher smoke pH increases the physiological effectiveness of nicotine. The alkalinity was similar to that achieved by adding 0.2% ammonium hydroxide to the True 85 blend; From the work to date it does not appear that the total air dilution system would be useful for the production of a 2 mg tar cigarette. At tar levels below 6 mg the problems of wisping undesirable pressure drops and difficulty in llgh~ing the cigarette occurred. The use of ali air dilution systems may be useful in low gas phase cigarettes with tar levels of 6 to 12 mg. Although all air dilution cigarettes are not commercially available, the idea is not a new one. Examples of proposed filtering devices for tobacco smoke which utilize air dilu- ~ tion of the smoke as the sole mechanism for removal are ~ found in the patent literature. Several patents ~ere issued ~ to A. P. Miller. (6-9) Basically Miller's filters are ~ hollow chambers for mixing incoming smoke and air, and ~ orifices through which the smoke air mixture must pass to ~ reach the smoker. In 1961 a patent was granted for the idea of locating the air vents in the filter paper of cigarettes rather than in the cigarette paper (i0). A patent for a cigar m m 0 © ©

- 6- or cigarette holder With air vents was also granted in 1962 (11). The use of air dilution in cigarettes has created the problem of providing vents which war% reproducible and uniform. Generally porous and perforated papers are used to achieve the desired air dilution. A patent for a valve along the cigarette seams was granted. It was claimed that the valve gave reproducible air vents and could be constructed with axisting machines and paper. The valves eliminated the need for special porous papers, the porosity of which ie difficult to control. Grassi's patent (13) also was concerned with better ways to make air vents in cigarette paper. Recently a patent was granted to Norman (14) for a filter design which provided a mixing chamber for the air and smoke plus a restrictor to regulate the pressure drop of the cigarette. A csntral smoke passageway was provided for the smoke. Data was reported for the amounts of nicotine, tar, hydrogen cyanide, water and other vapors in the main- stream smoke as the size of the air vents and smoke passage- way was varied. The nicotine to tar ratio for the control was 0.057 and in one of the patented filters the ratio was 0.082, a 44% increase. The hydrogen cyanide concentration in the control was 26.7 ug/puff whereas one particular design had only 5.6 ug/puff. Optimum designs for the particular emoke composition desired could be selected from Norman's data. Summers (15) attempted to solve the problem of decreasing air dilution from the first to the last puff. A piston devise which was slowly moved with each draw thus uncovering r~re available air vents increased the air dilution in the last puffs. 0 rn 0

Figure 1. Sketch of air dilution filter proposed by Tom Larson - Extruded solid plastic mouthpiece with ridges along the outer walls.

Table I. Smoke analyses for Sample AD66-I09 True 85a all air dilution cigarette. The control had filter removed and holes taped. AD66-109 Weight g/Fig 0,895 Pressure Drop mm/cig 29.0 Dry Part. Mat. mg/cig 14.0 Nicotine mg/cig 0,96 Corrected Part. Mat. mg/cig 13.1 Puff Count 8.6 Percent Nicotine Removal 18 Percent CPM Removal 46 Nicotine/CPM 0.073 a. Diagram showing AD66-I09 True 85 (old True) Cont____rol True 85 4/76 0.866 .989 70.2 115.7 25.511.4 1.170.67 24.3I0 • 8 7.2 7.7 - 45,8~ - 56.1% 0.048 0.062 O "T1 Z r- Z cn O --t

b Table 2. Results of the smoke analyses of sample AD70-55 - True 85 all air dilution cigarette AD70-55 Control True 85(5mg) Pressure Drop mm/cig 97.2 67.7 Dry Part. Mat. mg/cig 7.0 4.4 Nicotine mg/cig 0~62 0.35 Corrected Part. Mat. mg/cig 6.4 4.1 Puff Count6.9 6.3 Nicotine/CPM .097 .085 Oxygen mg/cig 54,8 24.0 41,9 Nitrogen mg/cig 198.2 139.2 169.9 Carbon Monoxide mg/cig 2.2 12.5 3.9 Carbon Dioxide mg/cig 15.2 42.4 18.2 pH of Smoke 7.09 . ~.98 - Hydrogen Cyanide ~g/cig 27 187 31 Nitrogen Oxide ug/cig 48 181 79 Isoprene ~g/cig 107.8 326.7 Acetaldehyde Ug/clg141.8 720.9 Acetone ~/cig 99.8 301.3 Acrcle£n ~g/cig 6.8 32.7 41~1 2-Methyl Furan ~g/cig 13.8 56,4 Methyl Ethyl Ketone ~.g/cig 48.3 163.8 Benzene ~g/cig 27.3 72.D Acetonitrile ~g/cig55.4 145.1 Toluene ug/cig 60.1 114.3 a. Art Ihrig calculated gas phase for charcoal filter with a control similar to the True 85 (5 mg controll. b. Diagram showing AD-70-55 True 85 (new True) Charcoala ~ilter,, 60 190 4O 120 50 10 15 35 20 50 35 Z