Quan`fying “Third-‐Hand” Tobacco Polycyclic Aroma`c Hydrocarbons

Quan%fying “Third-­‐Hand” Tobacco Polycyclic Aroma%c Hydrocarbons Residue Using Dermal Swipes and GC-­‐MS Tyler Fleming, Sarang Amin, Chris Anderson, and Jeffrey Ashley Ph.D. Ins;tute for Tex;le and Apparel Product Safety, Philadelphia University, Philadelphia, PA 19144 RESULTS ABSTRACT Concentra%on (ng) 150 SMOKERS NONSMOKERS 100 • 
• 
• 
107.69 215.44 31.98 29.90 44.87 78.08 17.87 10.48 7.80 9.57 13.31 17.04 11.50 9.53 11.73 16 12.45 13.29 37.79 12.84 ** e ]fluor
anthe
n
Significant Alpha = .50 Significant Group (ng) Par%cipant Total PAHs 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 13.07 9.50 21.61 19.43 24.49 14.42 39.61 8.49 6.41 5.99 6.96 7.02 6.07 5.34 10.32 33 6.68 (ng) Table 2. Percent of Sidestream PAHs Adsorped on to a Hand per CigareQe Benz
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** B
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[k]flu
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yrene
[1,2,3
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Ideno
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Diben
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Afluo
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PAH Alpha = .10 PAH ** * Significant at 90% Confidence Interval ** Significant at 95% Confidence Interval * 1-­‐m
-­‐100 * A
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ne hena
* P
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Diben
Fluor
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* A
* Ac
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1* (8 cigareTes) 2 3 4 5 6 7 8 9 10 11 12 13 14 15 17 Average Smokers Average Nonsmokers P VALUE 0.0286 50 • 
• 
Total PAHs n = 10 dermal swipes per par%cipant Total dermal swipes = 160 n = 10 cigareQes* per par%cipant Total cigareQes = 168 SMOKERS 200 -­‐50 Par%cipant Group 250 METHODS AND MATERIALS Figure 1. Results of GC-­‐MS: Average PAH per Sample 300 INTRODUCTION Polycyclic aroma;c hydrocarbons (PAHs) are a suite of carcinogenic, organic compounds released into the environment by the incomplete combus;on of carbon-­‐containing materials, including oil, wood, or coal (Department of Health, 2000). Studies over past decades have concluded that PAHs are present in mainstream and sidestream smoke at levels as high as 0.1 -­‐ 0.25 ng/cigareTe or 3 -­‐ 29 ng/m3 respec;vely (Menzie et al, 1992). Third-­‐hand smoke is defined as the residues adsorbed onto surfaces like tex;les and skin from burning tobacco products. Third hand smoke has received some recent aTen;on in popular press including ar;cles in the New York Times and on Good Moring America. However, its has not be toughly evaluated as a poten;al source of PAHs and poten;al toxicity. A 2004 Study concluded that limi;ng smoking to outdoors contaminated indoor secngs 5 -­‐ 7 ;mes more than not smoking at all (MaT et al, 2004). This indicated that third-­‐hand smoke is a possible vector for carcinogen exposure, especially to high-­‐risk individuals. Infants, for example, ingest 0.05 – 0.25 grams of dust per day, including any PAHs that have adsorbed onto carpet or clothing material (MaT et al, 2004). To date, there exist no published values for PAH concentra%ons in third hand tobacco residue. Therefore the purpose of this study was to assess the concentra%on of PAHs that adsorb to the hand of a cigareQe smoker and determine if the levels of PAHs are a significant source of contaminant exposure. Table 1. Total PAHs per CigareQe/Dermal Swipe NONSMOKERS Polycyclic aroma;c hydrocarbons (PAHs) are a suite of poten;ally carcinogenic organic compounds generated during the incomplete combus;on of carbon-­‐containing material such as tobacco. Though PAH concentra;ons have been widely studied in first and second hand smoke, there is a paucity of data sets characterizing levels in ‘third hand’ smoke. The purpose of this study was to quan;fy the levels of various PAHs in tobacco smoke residue, or third hand smoke, and assess whether these concentra;ons are significant as a vector for exposure to nonsmokers, especially children. To quan;fy PAH levels within third hand smoke, test subjects’ hands used to hold the cigareTe were cleaned before and swabbed aUer smoking with solvent-­‐saturated coTon gauze. PAHs were subsequently Soxhlet extracted with hexane. Hand swipes were analyzed for 20 PAHs using gas chromatography mass spectrometry (GC-­‐MS). Smokers’ bodies had significantly higher PAH levels than non-­‐smokers. For example, aUer only one cigareTe smoked under ambient condi;ons, total PAHs were as high as 200 ng/hand for smokers compared to <40 ng/hand for nonsmokers. PAH residues on smokers’ bodies (and apparel) may represent a poten;al source of third hand smoke exposure to nonsmokers, par;cularly children, and indoor environments. Residue Level of CigareQe (ng per cigareQe) Mass of PAH in Percent Sidestream Smoke Adsorp%on
¢¢
(ng per cigareQe)¢ 0.72 2684.00 0.03 Acenaphthylene Mean recovery (%) of PAH surrogate was 67.2 ± 33.5% 1.74 960.00 0.18 Acenaphthene 0.63 1429.00 0.04 Fluorene There were significant differences in the level of PAH contamina;on between smokers (avg. = 37.79 ng per cigareTe) and nonsmokers 7.05 2818.00 0.25 Phenanthrene (avg. = 12.84 ng) (Table 1). 9.68 755.00 1.28 Anthracene 0.52 699.00 0.07 17 PAHs were found to be significant at 90% confidence including (Figure 1): Fluoranthene 3.36 528.00 0.64 Pyrene •  Acenapththylene, Acenaphthene, Fluorene, Phenanthrene, Anthracene, 1-­‐Methylphenanthrene, Fluoranthene, Pyrene, BenzoAFluorene, BenzoBFluorene, 0.61 44.70 1.37 Benzo[g,h,i]perylene Benzo[g,h,i,]perylene, Dibenzo[a,h+a,c]anthracene, Ideno[1,2,3-­‐cd]anthracene, Perylene, Benzo[a]pyrene, Benzo[e]pyrene and Benzo[k]fluoranthene. 1.49 41.70 3.57 Ideno[1,2,3-­‐cd]perylene 11 PAHs of the above 12 PAHs were found to be significant at 95% confidence including (Figure 1): 1.44 23.60 6.12 Perylene •  Fluorene, Fluoranthene, BenzoAFluorene, BenzoBFluorene, Benzo[g,h,i,]perylene, Dibenzo[a,h+a,c]anthracene, Ideno[1,2,3-­‐cd]anthracene, Perylene, 2.12 91.70 2.32 Benzo[a]pyrene Benzo[a]pyrene, Benzo[e]pyrene and Benzo[k]fluoranthene. 1.14 94.90 1.20 Benzo[e]pyrene The percentage of sidestream smoke which was adsorbed onto the hand (becoming third hand smoke residue) ranged from 0.03% to ¢Second-­‐hand smoke data from sidestream tobacco study in 2008 (Moir et al). ¢¢Percent of residue adsorbed onto hand from second-­‐hand smoke. 6.12% for significant PAHs (Table 2). * PAH Significant at 90% CI For the 11 PAHs significant at 95% confidence interval the third hand residue of a cigar was 3.6 to 329 ;mes that of a single cigareTe ** PAH Significant at 95% CI (Table 3). SAMPLE COLLECTION Table 3. CigareQe Cigar Equivalency INSTRUMENTAL ANALYSIS Smoker’s hands washed prior to each cigareTe One cigareTe smoked as per the smoker’s usual smoking habits with the cigareTe held in one hand for en;re smoke Hand holding cigareTe cleaned with an isopropanol soaked coTon ball (photograph 1) PAH** (Significant at 95% CI) Fluorene Fluoranthene BenzoAFluorene BenzoBFluorene 0.63 0.52 0.33 0.34 CigareQe (ng per cigareQe) 220.77 171.74 1.93 6.00 Cigar (ng per cigar) 329.15 5.85 17.44 Cigar/CigareQe PAH Ra%o 352.20 Samples extracted with hexane using Soxhlet extrac;on (Perylene-­‐d12 as surrogate) Samples were “cleaned-­‐up” using bench top solid-­‐liquid chromatography with alumina as the sta;onary phase and hexane as the mobile phase (photograph 2) This process repeated 9 more ;mes (total of 10 cigareTes per par;cipant) Fluoranthene-­‐d10 added as internal standard Nonsmoker’s hands cleaned and swabbed using a soaked coTon ball and repeated to collect 10 coTon balls per par;cipant 20 individual PAHs quan;fied by gas chromatography-­‐mass spectrometry using a five point calibra;on curve Photograph 1 (LeU): Hand Swiping Photograph 2 (Right): Alumina Columns Benzo[g,h,i]perylene Dibenzo[a,h+c,c]anthracene 0.61 0.78 4.09 3.62 6.67 4.61 Ideno[1,2,3-­‐cd]perylene 1.49 11.71 7.86 Discussion • Smoking cigareTes significantly increases the PAH residue on smokers’ hands by approximately 3 ;mes (Figure 1 and Table 1). The nonsmokers in this study represent the ambient PAH contamina;on that is absorbed from the environment by all individuals and serves as the control. • The large range of variability in third hand smoke residue was expected in this study (Figure 1). This study tried to be as realis;c as possible so the smokers were not asked to change their smoking habits. Therefore things like hand size, dura;on of smoking, environmental condi;ons such as wind and temperature, and if the smoker took long deep drags or fewer drags as sidestream smoke has been shown to have higher levels of PAHs then mainstream smoke (Menzie et al, 1992). • Between 0.03 and 6.12% of sidestream PAHs may be adsorbed onto a smoker’s hand (Table 2). We can speculate that a similar propor;on of third hand residue remains aUer the dissipa;on of second hand smoke across the smoker’s body or throughout a room. • An interes;ng side study involved the comparison of the PAH levels in a single cigar to cigareTes (Table 3). The cigar was smoked for 20 minutes consuming approximately 25% of the cigar’s length. Therefore the numbers tabulated in Table 3 could be quadrupled to es;mate the absolute difference in PAH concentra;on between a cigar and cigareTe. The difference in levels observed is not solely due to the differences in smoking ;me for a cigareTe (approximately 6-­‐7 minutes for a cigareTe versus greater than 20 minutes for a cigar). • The ra;o in Table 3 can be read as the number of cigareTes that would need to be smoked simultaneously to reach the contamina;on produced by a quarter of a cigar Perylene 1.44 10.30 7.13 Benzo[a]pyrene 2.12 44.99 21.17 Benzo[e]pyrene Benzo[k]fluoranthene 1.14 0.90 4.11 6.44 3.60 7.17 CONCLUSION This study demonstrated that the level of PAH residue is significantly increased aUer smoking a cigareTe. This validates the exposure concerns of nonsmokers and children to ‘third hand’ residue. Tangents from this study include assessing indoor environments such as automobiles and ‘third hand’ adsorp;on onto tex;les. To fully understand the health risk posed future studies will need to address the degree and to which adsorbed PAHs are re-­‐released back into the environment. REFERENCES Department of Health and Family Services. (2000). Environmental Health Resources. Division of Public Health. Retrieved March 30, 2011, from hTp://dhfs.wisconsin.gov/eh MaT, G., Quintana, P., Larson, S., Hovell, M., Bernert, J., Song, S., et al. (2004). Households contaminated by environmental tobacco smoke: sources of infant exposure. Tobacco Control, 13, 29-­‐37. Menzie, C., Potocki, B., Santodonato, J. (1992). Exposure to carcinogenic PAHs in the environment. Environmental Science Technology, 26, 1278-­‐1282. Moir, D., Rickert, W., Levasseur, G., Larose, Y., Maertens, R., White, P., Desjardins, S. (2008). A comparison of mainstream and sidestream marijuana and tobacco cigareTe smoke produced under two machine smoking condi;ons. Chemical Research in Toxicology, 21, 494-­‐502.