Environ. Sci. Technol. 2010, 44, 8289–8294
Assessment of Environmental Tobacco Smoke Contamination in Public Premises: Significance of 2,5-Dimethylfuran as an Effective Marker MONICA ALONSO, ANNA GODAYOL, ´ , AND ENRIQUETA ANTICO JUAN M. SANCHEZ* Chemistry Department, University of Girona, Campus Montilivi s/n, 17071-Girona, Spain
Received May 13, 2010. Revised manuscript received September 9, 2010. Accepted September 10, 2010.
Contamination by environmental tobacco smoke (ETS) on premises where smoking is permitted is evaluated. Although all target VOCs evaluated show significant differences between smoking and nonsmoking indoors, the results obtained indicate that 2,5-dimethylfuran is the most appropriate and effective marker of ETS contamination given that this compound is only detected in environments where people have smoked and so the detection of this compound cannot be attributed to other contamination sources such as traffic. Moreover, the air levels of this compound due to coffee aroma are below the detection limits for this methodology. A preliminary study is performed to evaluate whether 2,5-dimethylfuran, a smoking breath biomarker, can be detected in passive smokers working in smoking environments. The compound was continuously detected in the breath of nonsmoking employees after being in direct contact with ETS for just a few hours. The Tedlar gas sampling bags had 5% loss of 2,5-dimethylfuran after 3 h of storage, which we took as the maximum recommended period for air sample storage.
1. Introduction Environmental tobacco smoke (ETS) is the smoke generated in indoor environments by cigarettes, which can be inhaled by a passive smoker (1–3). It is a complex mixture of gases and particles that has been classified as a group A carcinogen (1). The gaseous phase includes hundreds of volatile organic compounds (VOCs), some of which are individually classified as carcinogenic (3). The composition of ETS, or secondhand smoke, arises from two different sources of tobacco smoke: (i) mainstream smoke, which is generated during puffdrawing from the burning tip of the tobacco, and (ii) sidestream smoke, which is a combination of the smoke emitted into air during burning of a tobacco product between puffs, the smoke escaping into the surrounding air during puffs, and the compounds of smoke that diffuse through cigarette paper (4). Smoking has been banned or severely restricted in many nonresidential buildings in several countries, but significant contamination still occurs in many residences and on other premises (e.g., hospitality industry), which are not subject * Corresponding author phone: +34 972418276; fax: +34 972418150; e-mail:
[email protected]. 10.1021/es1016075
2010 American Chemical Society
Published on Web 10/04/2010
to smoking restrictions. In cases such as these, ETS is usually the main indoor contaminant source of VOCs and it is therefore not necessary to be a smoker to be exposed to the harmful effects of tobacco smoke. To further investigate this question, it is necessary to evaluate the levels of ETS exposure and find appropriate ETS markers. The suitability of nicotine, the most widely evaluated marker of ETS exposure, has been questioned due to its low volatility and high adsorption rate by indoor surfaces, its tendency to be reemitted even in the absence of active smoking, its short half-life in the body fluids, its intersubject variability, and the likelihood of it not being an active agent causing adverse effects (1, 5–7). Moreover, tobacco smoke is not the unique source of nicotine (8). Another common marker is 3-ethenylpyridine (3-EP), a pyrolysis product of nicotine. It is more volatile than nicotine, correlates well with other components of tobacco smoke (5, 9–12), and is less adsorbed by surfaces than nicotine (11). However, it has been reported that an increase in 3-EP concentration is not lineally correlated to ETS increase (13). Other compounds commonly evaluated are VOCs such as benzene, toluene, xylenes, phenol, limonene, and naphthalene (7, 12, 14–18). The existence of many different sources other than tobacco smoke for all these compounds has limited their efficiency as appropriate markers for ETS. Recently 2,5-dimethylfuran has also been postulated as a possible ETS marker (12, 14–16) and for two reasons is considered an effective marker of smoking contamination in indoor environments. First, preliminary studies (14, 15) indicated that 2,5-dimethylfuran may satisfy all the requirements for an ETS marker, and second, it has been found to be a highly selective breath biomarker of active smoking (19). The aim of this study was to evaluate a large cohort of air samples by measuring the levels of different VOCs commonly found in the gas-phase of ETS and to demonstrate that 2,5dimethylfuran is an appropriate marker to confirm contamination by ETS. Moreover, preliminary attempts are performed to demonstrate that 2,5-dimethylfuran can also be detected in the breath of passive smokers working on premises where smoking is permitted.
2. Experimental Section 2.1. Chemicals. All reagents were reagent grade (purity g99.0%) and obtained from Sigma-Aldrich (Steinheim, Germany). Stocks were prepared in cleaned 10 L Tedlar gassampling bags (SKC, Eighty Four, PA) filled with nitrogen 5.0 (99.9990% purity, purified for hydrocarbons, oxygen, and water vapor) by injecting 1-2 µL of individual components. Calibration standards were prepared by taking a fixed volume of the stock gas with a gastight syringe and diluting to 10 L with purified nitrogen in a clean Tedlar bag. Stocks and standards were freshly prepared for each calibration. The stability of the target compounds in the Tedlar bags was evaluated for the period used for storage. 2.2. Study Site. The field study was carried out on 56 different premises (37 cafe´s and 19 restaurants) located in two different cities of the province of Girona (northeastern Spain). Premises were selected from different, widely separated areas with various potential sources of pollution due to traffic. Samples were obtained between September 2009 and March 2010. Smoking was permitted on 41 premises (33 cafe´s and 8 restaurants) and forbidden on the other 15 (4 cafe´s and 11 restaurants). 2.3. Sampling. Indoor sampling was performed at the center of each establishment at a height equivalent to the distance where a seated person would normally breath (∼1.5 VOL. 44, NO. 21, 2010 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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m). Outdoor samples were taken outside the premises at the same time as indoor samples at a distance of about 5 m from the main door. Temperature and relative humidity (RH) were also measured. Additional data (e.g., number of smokers, number of employees, smoking habit of the employees, and extraction) were registered for each sampling location. Preliminary analyses showed that greater contamination is usually found during the mornings for the type of premises evaluated, so samples were always obtained between 9 and 12 a.m. Approximately 1 L of air samples was taken with a 1 L gastight syringe (SGE JUMBO syringe, SGE Europe, UK) in approximately 30 s. The sample was then introduced and stored until analysis in a cleaned Tedlar bag. No losses from the syringes were detected. 750 mL of the sample was analyzed with a microtrap coupled to a GC-MS system (19, 20). Each sampling bag was cleaned with purified nitrogen several times before samples were collected. The last portion of nitrogen used in the cleaning process was analyzed, and no detectable background levels of the target compounds were found. Each bag was used for a maximum of five samples to avoid cross-contamination. The measurements were carried out between Monday and Friday during working hours. Breath samples from nonsmoking employees were collected at 1.5 h intervals during a regular working day. Approximately 1 L of end-expired (∼alveolar) breath sample was obtained for each participant in a Tedlar gas-sampling bag and 750 mL was analyzed no more than 30 min after collection. A detailed description of the methodology used for breath sampling and analysis can be found in ref 19. 2.4. Analysis of VOCs. For the analysis of air and breath samples, an in-house capillary thermal desorption device connected to a GC (Focus GC, Thermo Scientific, Waltham, MA) with MS detection (DSQ II, Thermo Scientific) was used (20). Component separation was achieved by the use of a ZB-5 ms column (30 m length, 0.25 mm i.d., 0.25 µm film thickness) (Phenomenex, Torrance, CA). The oven temperature program was 40 °C held for 2 min, then ramped at 10 °C · min-1 to 270 °C and held for 2 min. The MS analyses were carried out in full-scan mode (scan range 40-200 amu). Electron impact ionization was applied at 70 eV. Purified helium carrier gas was used, with a constant inlet pressure of 31 kPa. The acquisition of chromatographic data was performed by means of Xcalibur software (v. 1.4, Thermo Electron). Method detection limits (for a sample volume of 750 mL) were 0.02 µg · m-3 for benzene, 2,5-dimethylfuran, and toluene and 0.05 µg · m-3 for ethylbenzene, m-, p-, o-xylene, styrene, benzaldehyde, and 2-ethyltoluene. Quantification limits were 0.1 µg · m-3 for benzene and 2,5dimethylfuran, 0.2 µg · m-3 for toluene, ethylbenzene, m-, p-, and o-xylene, and 0.3 µg · m-3 for styrene, benzaldehyde and 2-ethyltoluene (expressed as the concentration of the lowest calibration point used). 2.5. Data Analysis. Statistical analysis was performed using SPSS for Windows version 15.0. For calculations of statistical significance, two-sided testing was used and p < 0.05 was considered as significant. The Shapiro-Wilk test was used to determine whether the samples came from normally distributed populations. Non-normal distributions were found for the majority of subgroups evaluated. Normally distributed populations were found in some subgroups evaluated for specific compounds. Therefore, nonparametric statistics was used in subsequent analyses to compare the values obtained between different groups. The Mann-Whitney test was used to compare the values found between smoking, nonsmoking indoors, and outdoors. The Spearman correlation was used to determine the correlations between the levels of compounds. 8290
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FIGURE 1. Normalized concentrations for benzene and 2,5-dimethylfuran stored in a Tedlar bag over different storage times. Concentration values were normalized to their initial concentration in the bag. Vertical bars show the standard deviation obtained for the three bags evaluated.
3. Results and Discussion 3.1. Storage Capability of Tedlar Bags. Tedlar sampling bags are a popular container for collecting gas samples. It has been demonstrated, however, that the levels of some VOCs decrease with storage time because of diffusion through the bag or adsorption into the inner bag walls or valve fittings. Beauchamp et al. (21) found that a storage time of 10 h offers “adequate sampling authenticity replication”. We have evaluated the stability of some VOCs commonly determined for ETS contamination for a storage period up to 48 h at room temperature (20 ( 2 °C). Acetone, chloroform, and dichloromethane gave anomalous results. Similar results have been described with acetone (21), and it was found to be due to diffusion interferences from higher levels of this compound in the ambient air than inside the bags. These results led us to eliminate these three compounds from the target list of VOCs. Benzene, toluene, ethylbenzene, and xylenes showed either no losses or losses less than 5% during the first 24 h and slightly larger losses (1 for the VOCs evaluated when smoking and nonsmoking environments were mixed in indoor air calculations (values ranged from 1.8 to 38). Significantly higher I/O ratios were obtained when smoking indoors was compared to outdoors (values ranged from 2.4 to 75). The most significant results were obtained for 2,5-dimethylfuran, which gave the largest ratio when data containing smoking indoors were compared to outdoors (I/O ratio ) 75). In the case of nonsmoking indoors, the results showed I/O ratios of around 1 (only styrene and ethyltoluene yielded a ratio of 2.0). An interesting finding was that 2,5-dimethylfuran, which has rarely been analyzed, was not detected in nonsmoking indoors nor outdoors. Indoor air load by BTEX compounds in nonsmoking indoors mainly originated from outdoors, principally from traffic pollution. However, I/O ratios were significantly higher for smoking indoor environments, which confirms that ETS is the most significant source of contamination in these environments. 3.3. Effect of the Type of Smoking Environment. It has been demonstrated that there are differences in the levels of nicotine detected in smoking premises, depending on the
restaurants (n ) 8)
compound
median
range
median
range
benzene 2,5-dimethylfuran toluene ethylbenzene m-, p-xylene o-xylene styrene benzaldehyde 2-ethyltoluene
3.11 0.88 7.11 1.43 3.55 1.36 1.56 1.41 1.13
11.4 9.3 65.3 10.3 38.0 9.4 11.2 15.6 6.6
1.77 0.58 4.05 1.55 2.27 1.25 1.21 0.52 0.96
2.3 1.3 6.0 0.9 2.1 3.2 0.6 1.9 0.7
type of environment (9, 25). From the 41 smoking premises evaluated, 33 (80.5%) were classified as cafe´s/bars and eight (19.5%) as restaurants. Statistical analyses only showed significant differences between the two type of premises for styrene. It is important to note that the number of samples for the subgroup of restaurants was small and that a larger cohort would be more appropriate. Two trends can be identified from the results (Table 2): (i) the variability (range columns) in the values found in cafe´s was larger than in restaurants, and (ii) median values were commonly higher in cafe´s. The statistical evaluation of the differences between central tendency values between cafe´s and restaurants showed that either the median (p ) 0.019) or the mean values (p ) 0.011) for cafe´s were significantly higher than for restaurants (one-sided testing). It seems clear from these results that ETS exposure in cafe´s/bars tends to be more significant than in restaurants and that there is a large variability in their contamination levels. The level of exposure in restaurants, however, is smaller and is more stable and constant. 3.4. Seasonal Variations on Smoking Premises. It has been found that there are seasonal variations in indoor VOC levels, obtaining increased levels in the cold than in the warm seasons (26). The evolution of indoor air quality in smoking premises (n ) 41) during two different periods was evaluated (Table 3). A first group of samples (n ) 21, 51.2%) was obtained between September and mid-October 2009 (mild/warm weather: outdoor temperature at sampling time of 23.9 ( 1.6 °C). The second group of samples (n ) 20, 48.8%) was obtained between mid-January and March 2010 (cold weather: outdoor temperature of 12.3 ( 1.8 °C). Statistical comparison of the values obtained between the two sampling periods showed significant differences for the indoor temperature, indoor RH, and benzene, 2,5dimethylfuran, toluene, m-, p-, o-xylene, styrene, and benVOL. 44, NO. 21, 2010 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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TABLE 3. Seasonal Differences in the Statistical Parameters of the VOCs Analyzed in Smoking Indoors (n = 41)a fall (n ) 21)
benzene 2,5-dimethylfuran toluene ethylbenzene m-, p-xylene o-xylene styrene benzaldehyde 2-ethyltoluene a
winter (n ) 20)
mean
median
max
min
SD
mean
median
max
min
SD
1.65 0.54 5.67 1.94 2.56 1.39 1.28 0.83 1.12
1.39 0.44 3.63 1.54 2.15 1.19 1.24 0.53 1.14
5.49 1.40 22.51 7.95 6.78 4.10 1.73 2.53 1.73
0.42 ndb 1.80 1.01 0.73 0.34 1.10 0.43 0.47
1.11 0.39 4.69 1.51 1.42 0.80 1.60 0.63 0.27
5.79 2.49 19.29 2.77 8.87 2.48 4.05 7.61 1.50
5.71 1.27 14.53 2.12 6.68 2.04 3.17 8.72 0.98
11.86 9.26 67.12 10.85 38.68 9.71 12.32 15.59 6.97
1.75 0.44 2.38 0.54 1.74 0.71 0.83 ndb 0.34
3.04 2.47 17.79 2.41 8.65 2.01 2.95 5.94 1.58
Concentration values are expressed in µg · m-3.
b
Not detected (a value of 0.0 was used for statistical analysis).
TABLE 4. Spearman Correlation Coefficients for Air Pollutant Levels Measured Indoors (n = 56)
1. temperature 2. RH 3. benzene 4. 2,5-dimethylfuran 5. toluene 6. ethylbenzene 7. m-, p-xylene 8. o-xylene 9. styrene 10. benzaldehyde 11. 2-ethyltoluene a
1
2
3
4
5
6
7
8
9
10
11
1.000 0.262 -0.587a -0.503a -0.292a 0.015 -0.420a -0.201 -0.471a -0.392a 0.050
1.000 -0.079 -0.100 0.192 0.317a 0.090 0.307a -0.032 0.070 0.216
1.000 0.857a 0.793a 0.452a 0.757a 0.479a 0.799a 0.672a 0.156
1.000 0.683a 0.452a 0.642a 0.445a 0.768a 0.573a 0.258
1.000 0.794a 0.837a 0.742a 0.754a 0.521a 0.354a
1.000 0.703a 0.755a 0.534a 0.242 0.572a
1.000 0.856a 0.812a 0.494a 0.463a
1.000 0.679a 0.311a 0.442a
1.000 0.570a 0.394a
1.000 -0.042
1.000
Significant (p < 0.05).
zaldehyde levels. No significant differences were obtained for ethylbenzene and 2-ethyltoluene. The warm weather during the fall resulted in no significant differences between outdoor (23.9 ( 1.6 °C) and indoor (24.7 ( 0.8 °C) temperatures and between outdoor (51.9 ( 5.0%) and indoor (55.8 ( 5.4%) RH at sampling times. This can be accounted for by the fact that no air-conditioning/heater systems were running inside the premises and main doors and windows were left open during working hours. In the winter season the cold weather resulted in significant differences between outdoor (12.3 ( 1.8 °C) and indoor (20.5 ( 0.4 °C) temperatures and between outdoor (57.1 ( 9.7%) and indoor (44.3 ( 6.1) RH at sampling time. During this period, heater systems were running and doors and windows remained closed. Indoor temperature and indoor RH values were significantly higher in the samples obtained during the warm season. Temporal variations in indoor air VOC levels have been associated principally with the air change rate and seasonal variation in indoor air temperature and/or humidity (26). Although not a specific target of our study, the results we obtained fit well with the hypothesis that air change/ extraction has the largest effect on the level of VOCs measured. Correlation coefficients obtained (Table 4) show that RH did not correlate significantly with most of the VOCs. Temperature showed a significant, although weak, negative correlation with most VOCs (except for ethylbenzene and 2-ethyltoluene). These results agree with other studies that found increased levels of VOCs during periods of cold weather (26) but confirm that indoor temperature and RH did not greatly affect the VOCs measured, which agrees with previous results by Xie et al. (15). After examining the air change/extraction systems used on the premises studied, it was found that all premises evaluated had standard air-conditioning units with low or no air exchange capacity. So, the stronger effect on air change rates was attributed to open doors and windows. Given this, 8292
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the higher air exchange during the fall (i.e., warm outdoor temperatures meant that doors and windows were often left open during working hours) explains the fact than lower levels of VOCs were detected in indoor environments during this period. 3.5. Daily Evolution of Indoor Air Contamination in Smoking Environments. One of the great advantages of the methodology used in the present study is that it makes it possible to evaluate contamination at different moment during the day. Figure 3 shows the diurnal variations in VOC concentrations on two different smoking premises. Indoor temperature was constant during working hours (21.0 ( 0.5 °C for Figure 3a and 20.5 ( 0.2 °C for Figure 3b). Outdoor temperatures ranged from 10.2 to 15.2 °C during the sampling period. Maximum concentration levels were higher in the regular cafe´ (11.9, 9.3, 50.0, and 9.7 µg · m-3 for benzene, 2,5dimethylfuran, toluene, and o-xylene, respectively) than in the cafe´-restaurant (9.2, 5.6, 21.2, and 4.0 µg · m-3 respectively). It can be seen that the cafe´/restaurant (Figure 3a) yielded the maximum contamination levels during the morning (when it only played the role of a cafe´/bar and had the greatest number of smokers). A significant decrease was observed at lunchtime, when it is common to stop smoking. There was a slight recovery in the levels of VOCs after lunch, when customers drink an after-lunch coffee and return to their smoking habits. The low level of patronage of this establishment in the afternoons resulted in significantly lower levels for all VOCs during this period. Diurnal variations were different for a regular cafe´ (Figure 3b). The profile obtained is like a sawtooth wave. A maximum peak is obtained at regular Spanish coffee-break hours (10-11 a.m.), followed by a decrease over the morning until minimum levels were reached at lunchtime (when the premise was practically empty). A new peak was reached during the period when coffee was taken after meals. The low air exchange capacity of this premise led to some windows
FIGURE 3. Normalized diurnal variation of selected VOCs on two smoking premises: (a) a cafe´ serving meals at lunchtime and (b) a cafe´/bar not serving meals. Concentration values were normalized to the highest concentration detected (see the text for values). being opened because the level of contamination was considerable at that time (benzene levels reached a value of 12 µg · m-3) and this fact resulted in a drop in the levels of all VOCs. Once the windows were closed, all VOCs increased again. 3.6. 2,5-Dimethylfuran as a Marker for ETS and Passive Smoking. The results obtained in the present study show that 2,5-dimethylfuran is the only evaluated VOC that can act as a robust and qualitative marker of smoking contamination in indoor environments. On no occasion was this compound detected in outdoor environments, ruling out any association with traffic emissions, and it was only detected in one nonsmoking indoor environment as opposed to 39 of the smoking indoor environments evaluated (95.1%). It has been reported that 2,5-dimethylfuran can be released by roasted coffee beans (27). However, we failed to detect the compound when analyzing room air in areas surrounding coffee machines and grinding devices in several nonsmoking premises. This confirms that the detection of this compound on smoking premises can be attributed to ETS contamination. Two of the employees working on smoking premises were nonsmokers and agreed to participate in a preliminary test to analyze their breath at 1.5 h intervals during a working day (five samples/day for each volunteer). Measurements were made at the beginning of the spring season on a day with mild weather (Toutdoor ranged from 16.9 to 20.3 °C). Breath samples obtained during the first three working hours did not show the presence of 2,5-dimethylfuran. After being in contact with ETS for more than 3 h, 2,5-dimethylfuran was detected in consecutive breath samples spread over a 4-h period. This indicates that 2,5-dimethylfuran could be used as a breath biomarker of exposure to ETS for passive smokers. These results were obtained during mild weather conditions with considerable air exchange due to doors and windows being left open on the premises during long periods. It is noteworthy that although these were adequate conditions
for cleaning the air of the premises and reducing ETS contamination, it was possible to detect the presence of the smoking breath biomarker in the breath of nonsmoker employees after a few hours of contact with ETS. It is expected that passive smoking contamination for hospitality workers could be detected at higher levels during colder weather days and/or higher ETS contamination. Further investigation will be needed to confirm this hypothesis. 3.7. Indoor Air Quality. It is interesting to note that although (i) indoor levels tend to be systematically higher than outdoor levels and (ii) people spend between 70% and 90% of their day in indoor environments (28), only ambient air (i.e., outdoor air) quality is internationally regulated (in the US, occupational exposure standards have been set, although at substantially higher levels, around 3 orders of magnitude higher, than for ambient air). Benzene is usually the most regulated compound because it is a known human carcinogen (29). Although there is no identifiable threshold below which there is no risk to human health, benzene has been regulated in Europe to an annual mean concentration not exceeding 5 µg · m-3 with a lower and upper assessment threshold set at 2 and 3.5 µg · m-3 (30); an inhalation reference concentration (RfC) of 30 µg · m-3 has been set by the US Environment Protection Agency (31). While we know that benzene is not a good marker for ETS, due to the fact that this compound can have different sources of origin, the fact that 2,5-dimethylfuran has such a close correlation with benzene in smoking environments (Table 4) suggests that benzene levels could be used as a indoor air quality marker. So, the levels regulated by the EU for outdoors have been used for performing an assessment of indoor air quality, despite the absence of regulated quality parameters for this. The results obtained indicate that 26 smoking environments (63% of smoking premises) were above the lower assessment threshold, 14 (34%) were above the upper assessment threshold, and 12 (29%) exceeded the limit value. In the case of nonsmoking environments, no samples exceeded the lower assessment threshold. For outdoor measurements, the lower assessment threshold was exceeded only in one sample (2.6 µg · m-3). None of the samples evaluated were above the guideline values given in the US regulations.
Acknowledgments This study has been financed by the MICINN (Spanish Ministry of Education and Science), project CTM2008-06847C02-02/TECNO. M. Alonso acknowledges the Spanish Ministry of Education for her research grant (AP2008-01628). We thank the employees and employers of the premises that have participated in the study for their collaboration.
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