Gas-phase organics in environmental tobacco smoke: 2. Exposure-relevant emission factors and indirect exposures from habitual smoking

Sorption of emitted gas-phase organic compounds onto material surfaces affects environmental tobacco smoke (ETS) composition and exposures indoors. We have introduced a new metric, the exposure relevant emission factor (EREF) that accounts for sorptive uptake and reemission to give the mass of individual ETS constituents available for exposure over a day in which smoking occurs. This paper describes month-long experiments to investigate sorption effects on EREFs and potential ETS exposures under habitual smoking conditions. Cigarettes were smoked in a 50-m³ furnished room over a 3-h period 6–7 days per week, with continuous ventilation at 0.3, 0.6, or 2.1 h⁻¹. Organic gas concentrations were measured every few days over 4-h “smoking”, 10-h “post-smoking” and 10-h “background” periods. Concentration patterns of volatile ETS components including 1,3-butadiene, benzene and acrolein were similar to those calculated for a theoretical non-sorbing tracer, indicating limited sorption. Concentrations of ETS tracers, e.g. 3-ethenylpyridine (3-EP) and nicotine, and lower volatility toxic air contaminants including phenol, cresols, and naphthalene increased as experiments progressed, indicating mass accumulation on surfaces and higher desorption rates. Daily patterns stabilized after week 2, yielding a steady daily cycle of ETS concentrations associated with habitual smoking. EREFs for sorbing compounds were higher under steady cycle versus single-day smoking conditions by 50% for 3-EP, and by 2–3 times for nicotine, phenol, cresols, naphthalene, and methylnaphthalenes. Our results provide relevant information about potential indirect exposures from residual ETS (non-smoker enters room shortly after smoker finishes) and from reemission, and their importance relative to direct exposures (non-smoker present during smoking). Under the conditions examined, indirect exposures accounted for a larger fraction of total potential exposures for sorbing versus non-sorbing compounds, and at lower versus higher ventilation rates. Increasing ventilation can reduce indirect exposures to very low levels for non-sorbing ETS components, but indirect routes accounted for 50% of potential nicotine exposures during non-smoking periods at all ventilation rates.     

Nicotine as a Marker for Environmental Tobacco Smoke: Implications of Sorption on Indoor Surface Materials

ABSTRACT

Recently developed models and data describing the interactions of gas-phase semi-volatile organic compounds with indoor surfaces are employed to examine the effects of sorption on nicotine's suitability as an environmental tobacco smoke (ETS) marker. Using parameters from our studies of nicotine sorption on carpet, painted wallboard, and stainless steel and previously published data on ETS particle deposition, the dynamic behavior of nicotine was modeled in two different indoor environments: a house and a stainless steel chamber. The results show that apparently contradictory observations of nicotine's behavior in indoor air can be understood by considering the effects of sorption under different experimental conditions. In indoor environments in which smoking has occurred regularly for an extended period, the sorbed mass of nicotine is very large relative to the mass emitted by a single cigarette. The importance of nicotine adsorption relative to ventilation as a gas-phase removal mechanism is reduced. Where smoking occurs less regularly or the indoor surfaces are cleaned prior to smoking (as in a laboratory chamber), nicotine deposition is more significant. Nicotine concentrations closely track the levels of other ETS constituents in environments with habitual smoking if the data are averaged over a period significantly longer than the period between cigarette combustion episodes. However, nicotine is not a suitable tracer for predicting ETS exposures at fine time scales or in settings where smoking occurs infrequently and irregularly.     

ETS levels in hospitality environments satisfying ASHRAE standard 62-1989: “ventilation for acceptable indoor air quality”

Prior to this study, indoor air constituent levels and ventilation rates of hospitality environments had not been measured simultaneously. This investigation measured indoor Environmental Tobacco Smoke-related (ETS-related) constituent levels in two restaurants, a billiard hall and a casino. The objective of this study was to characterize ETS-related constituent levels inside hospitality environments when the ventilation rates satisfy the requirements of the ASHRAE 62-1989 Ventilation Standard. The ventilation rate of each selected hospitality environment was measured and adjusted. The study advanced only if the requirements of the ASHRAE 62-1989 Ventilation Standard – the pertinent standard of the American Society of Heating, Refrigeration and Air Conditioning Engineers – were satisfied. The supply rates of outdoor air and occupant density were measured intermittently to assure that the ventilation rate of each facility satisfied the standard under occupied conditions. Six ETS-related constituents were measured: respirable suspended particulate (RSP) matter, fluorescent particulate matter (FPM, an estimate of the ETS particle concentrations), ultraviolet particulate matter (UVPM, a second estimate of the ETS particle concentrations), solanesol, nicotine and 3-ethenylpyridine (3-EP). ETS-related constituent levels in smoking sections, non-smoking sections and outdoors were sampled daily for eight consecutive days at each hospitality environment. This study found that the difference between the concentrations of ETS-related constituents in indoor smoking and non-smoking sections was statistically significant. Differences between indoor non-smoking sections and outdoor ETS-related constituent levels were identified but were not statistically significant. Similarly, differences between weekday and weekend evenings were identified but were not statistically significant. The difference between indoor smoking sections and outdoors was statistically significant. Most importantly, ETS-related constituent concentrations measured indoors did not exceed existing occupational standards. It was concluded that if the measured ventilation rates of the sampled facilities satisfied the ASHRAE 62-1989 Ventilation Standard requirements, the corresponding ETS-related constituents were measured at concentrations below known harmful levels as specified by the American Conference of Governmental Industrial Hygiene (ACGIH).     

Composition and emissions of VOCs in main- and side-stream smoke of research cigarettes

It is well known that mainstream (MS) and sidestream (SS) cigarette smoke contains a vast number of chemical substances. Previous studies have emphasized SS smoke rather than MS smoke to which smokers are exposed, and most have used chamber tests that have several disadvantages such as wall losses. Emissions from standard research cigarettes have been measured, but relatively few constituents have been reported, and only the 1R4F (low nicotine) cigarette type has been tested. This study provides a comprehensive characterization of total, MS and SS smoke emissions for the 1R5F (ultra low nicotine), 2R4F (low nicotine), and 1R3F (standard nicotine) research cigarettes research cigarettes, including emission factors for a number of toxic compounds (e.g., benzene) and tobacco smoke tracers (e.g., 2,5-dimethyl furan). Emissions of volatile organic compounds (VOCs) and particulate matter (PM) are quantified using a dynamic dilution emission measurement system that is shown to produce accurate, rapid and reproducible results for over 30 VOCs and PM. SS and MS emissions were accurately apportioned based on a mass balance of total emissions. As expected, SS emissions greatly exceeded MS emissions. The ultra low nicotine cigarette had lower emissions of most VOCs compared to low and standard nicotine cigarettes, which had similar emissions. Across the three types of cigarettes, emissions of benzene (296–535 μg cig⁻¹), toluene (541–1003 μg cig⁻¹), styrene (90–162 μg cig⁻¹), 2-dimethyl furan (71–244 μg cig⁻¹), naphthalene (15–18 μg cig⁻¹) and other VOCs were generally comparable to or somewhat higher than literature estimates using chamber tests.     

Characterization of organic compounds and molecular tracers from biomass burning smoke in South China I: Broad-leaf trees and shrubs

Biomass burning smoke constituents are worthy of concern due to its influence on climate and human health. The organic constituents and distributions of molecular tracers emitted from burning smoke of six natural vegetations including monsoon evergreen broad-leaf trees and shrubs in South China were determined in this study. The gas and particle samples were collected and analyzed by gas chromatography–mass spectrometry. The major organic components in these smoke samples are methoxyphenols from lignin and saccharides from cellulose. Polycyclic aromatic hydrocarbons (PAHs) are also present as minor constituents. Furanose, pyranose and their dianhydrides are the first reported in the biomass burning smoke. Some unique biomarkers were detected in this study which may be useful as specific tracers. The corresponding tracer/OC ratios are used as indicators for the two types of biomass burning. U/R (1.06–1.72) in the smoke samples may be used as parameters to distinguish broad-leaf trees and shrubs from fossil fuel. Other useful diagnostic ratios such as methylphenanthrene to phenanthrene (MPhe/Phe), phenanthrene to phenanthrene plus anthracene (Phe/(Phe + Ant)) and fluoranthene to fluoranthene plus pyrene (Flu/(Flu + Pyr)) and octadecenoic acid/OC are also identified in this study. These results are useful in efforts to better understand the emission characterization of biomass burning in South China and the contribution of regional biomass burning to global climate change.     

Particulate organic compounds emitted from experimental wildland fires in a Mediterranean ecosystem

Fine (PM_2.5) and coarse (PM_2.5–10) smoke particles from controlled biomass burnings of a shrub-dominated forest in Lousã Mountain, Portugal, enabled the quantification by chromatographic techniques of several molecular tracers for the combustion of Mediterranean forest ecosystems, which could be conducive to source apportionment studies. The major organic components in the smoke samples were pyrolysates of vegetation cuticles, mainly comprising steradienes and sterol derivatives, carbohydrates from the breakdown of cellulose, aliphatic lipids from vegetation waxes and methoxyphenols from the lignin thermal degradation. Most of these compounds are chiefly found in fine particles. Polycyclic aromatic hydrocarbons (PAH) were also present as minor constituents. Anhydrosugar and PAH molecular diagnostic ratios were applied as source assignment tools. Some biomarkers are reported for the first time in biomass burning smoke.     

Particulate matter emissions of different brands of mentholated cigarettes

Inhaling particulate matter (PM) in environmental tobacco smoke (ETS) endangers the health of nonsmokers. Menthol, an additive in cigarettes, attenuates respiratory irritation of tobacco smoke. It reduces perceptibility of smoke and therefore passive smokers may inhale ETS unnoticed. To investigate a possible effect of menthol on PM concentrations (PM₁₀, PM_2.5, and PM₁), ETS of four mentholated cigarette brands (Elixyr Menthol, Winston Menthol, Reyno Classic, and Pall Mall Menthol Blast) with varying menthol content was analyzed. ETS was generated in a standardized way using an automatic environmental tobacco smoke emitter (AETSE), followed by laser aerosol spectrometry. This analysis shows that the tested cigarette brands, despite having different menthol concentrations, do not show differences with regard to PM emissions, with the exception of Reyno Classic, which shows an increased emission, although the menthol level ranged in the midfield. More than 90% of the emitted particles had a size smaller than or equal to 1 µm. Regardless of the menthol level, the count median diameter (CMD) and the mass median diameter (MMD) were found to be 0.3 µm and 0.5 µm, respectively. These results point out that there is no effect of menthol on PM emission and that other additives might influence the increased PM emission of Reyno Classic.

Implications: Particulate matter (PM) in ETS endangers the health of nonsmokers and smokers. This study considers the effect of menthol, an additive in cigarettes, on PM emissions. Does menthol increase the amount of PM? Due to the exposure to secondhand smoke nearly 900,000 people die each year worldwide. The aim of the study is to measure the particle concentration (L^?1), mass concentration (µg m^?3), and dust mass fractions shown as PM₁₀, PM_2.5, and PM₁ of five different cigarette brands, including four with different menthol concentrations and one menthol-free reference cigarette, in a well-established standardized system.     

VOC concentrations measured in personal samples and residential indoor,outdoor and workplace microenvironments in EXPOLIS-Helsinki,Finland

Thirty target volatile organic compounds (VOC) were analyzed in personal 48-h exposure samples and residential indoor, residential outdoor and workplace indoor microenvironment samples as a component of EXPOLIS-Helsinki, Finland. Geometric mean residential indoor concentrations were higher than geometric mean residential outdoor concentrations for all target compounds except hexane, which was detected in 40% of residential outdoor samples and 11% of residential indoor samples, respectively. Geometric mean residential indoor concentrations were significantly higher than personal exposure concentrations, which in turn were significantly higher than workplace concentrations for compounds that had strong residential indoor sources (d-limonene, alpha pinene, 3-carene, hexanal, 2-methyl-1-propanol and 1-butanol). 40% of participants in EXPOLIS-Helsinki reported personal exposure to environmental tobacco smoke (ETS). Participants in Helsinki that were exposed to ETS at any time during the 48-h sampling period had significantly higher personal exposures to benzene, toluene, styrene, m,p-xylene, o-xylene, ethylbenzene and trimethylbenzene. Geometric mean ETS-free workplace concentrations were higher than ETS-free personal exposure concentrations for styrene, hexane and cyclohexane. Geometric mean personal exposures of participants not exposed to ETS were approximately equivalent to time weighted ETS-free indoor and workplace concentrations, except for octanal and compounds associated with traffic, which showed higher geometric mean personal exposure concentrations than any microenvironment (o-xylene, ethylbenzene,benzene, undecane, nonane, decane, m,p-xylene, and trimethylbenzene). Considerable differences in personal exposure concentrations and residential levels of compounds with mainly indoor sources suggested differences in product types or the frequency of product use between Helsinki, Germany and the United States.     

Wood smoke as a source of particle-phase organic compounds in residential areas

The objective of this study was to investigate the organic composition of wood smoke emissions and ambient air samples in order to determine the wood smoke contribution to the ambient air pollution in the residential areas. From November 2005 to March 2006 particle-phase PM₁₀ samples were collected in the residential town Dettenhausen surrounded by forests near Stuttgart in southern Germany. Samples collected on pre-baked glass fibre filters were extracted using toluene with ultrasonic bath and analysed by gas chromatography mass spectrometry (GC-MS). 21 polycyclic aromatic hydrocarbons (PAH) including 16 USEPA priority pollutants, different organic wood smoke tracers, primarily 21 species of syringol and guaiacol derivatives, levoglucosan and its isomers mannosan, galactosan and dehydroabietic acid were detected and quantified in this study. The concentrations of these compounds were compared with the fingerprints of emissions from hardwood and softwood combustion carried out in test facilities at Universitaet Stuttgart and field investigations at a wood stove during real operation in Dettenhausen. It was observed that the combustion derived PAH was detected in higher concentrations than other PAH in the ambient air PM₁₀ samples. Syringol and its derivatives were found in large amounts in hardwood burning but were not detected in softwood burning emissions. On the other hand, guaiacol and its derivatives were found in both softwood and hardwood burning emissions, but the concentrations were higher in the softwood smoke compared to hardwood smoke. So, these compounds can be used as typical tracer compounds for the different types of wood burning emissions. In ambient air samples both syringol and guaiacol derivatives were found which indicates the wood combustion contribution to the PM load in such residential areas. Levoglucosan was detected in high concentrations in all ambient PM₁₀ samples. A source apportionment modelling, Positive Matrix Factorization (PMF) was implemented to quantify the wood smoke contribution to the ambient PM₁₀ bound organic compounds in the residential area.     

Assessment of environmental tobacco smoke and respirable suspended particle exposures for nonsmokers in Basel by personal monitoring

One hundred and ninety-six randomly selected nonsmoking subjects collected air samples close to their breathing zone by wearing personal monitors for 24 h. The study was centred in Basel, Switzerland, and comprised housewives in one group, primarily for assessing exposures in the home, and office workers in a second group to assess the contribution of the workplace to overall exposure. Samples collected were analysed for respirable suspended particles (RSP), nicotine, 3-ethenylpyridine and environmental tobacco smoke (ETS) particles by using ultraviolet absorbance, fluorescence and solanesol measurements. Saliva cotinine analyses were also undertaken to confirm the nonsmoking status of the subjects. Based upon median 24 h time weighted average concentrations, office workers who live and work with smokers were exposed to 39 μg m^-3 RSP, 6.6 μg m^-3 ETS particles and 0.90 μg m^-3 nicotine. Housewives living with smokers were exposed to median concentrations of 34 μg m^-3 RSP, 1.4 μg m^-3 ETS particles and 0.60 μg m^-3 nicotine. Workplaces where smoking occurred were estimated, on average, to contribute between 34 and 46% to annual exposure of ETS particles and nicotine. Based upon 90th percentile values the most highly exposed housewives, those living with smokers, would potentially inhale 18 cigarette equivalents per year whilst the most highly exposed office workers, both living and working with smokers, might inhale 61 cigarette equivalents. The rate at which subjects misreported their nonsmoking status varied between 9.7 and 12.2%.     

VOC source identification from personal and residential indoor,outdoor and workplace microenvironment samples in EXPOLIS-Helsinki,Finland

Principal component analyses (varimax rotation) were used to identify common sources of 30 target volatile organic compounds (VOCs) in residential outdoor, residential indoor and workplace microenvironment and personal 48-h exposure samples, as a component of the EXPOLIS-Helsinki study. Variability in VOC concentrations in residential outdoor microenvironments was dominated by compounds associated with long-range transport of pollutants, followed by traffic emissions, emissions from trees and product emissions. Variability in VOC concentrations in environmental tobacco smoke (ETS) free residential indoor environments was dominated by compounds associated with indoor cleaning products, followed by compounds associated with traffic emissions, long-range transport of pollutants and product emissions. Median indoor/outdoor ratios for compounds typically associated with traffic emissions and long-range transport of pollutants exceeded 1, in some cases quite considerably, indicating substantial indoor source contributions. Changes in the median indoor/outdoor ratios during different seasons reflected different seasonal ventilation patterns as increased ventilation led to dilution of those VOC compounds in the indoor environment that had indoor sources. Variability in workplace VOC concentrations was dominated by compounds associated with traffic emissions followed by product emissions, long-range transport and air fresheners. Variability in VOC concentrations in ETS free personal exposure samples was dominated by compounds associated with traffic emissions, followed by long-range transport, cleaning products and product emissions. VOC sources in personal exposure samples reflected the times spent in different microenvironments, and personal exposure samples were not adequately represented by any one microenvironment, demonstrating the need for personal exposure sampling.     

A review of biomarker compounds as source indicators and tracers for air pollution

An overview of the application of organic geochemistry to the analysis of organic matter on aerosol particles is presented here. This organic matter is analyzed as solvent extractable bitumen/ lipids by gas chromatography-mass spectrometry. The organic geochemical approach assesses the origin, the environmental history and the nature of secondary products of organic matter by using the data derived from specific molecular analyses. Evaluations of production and fluxes, with cross-correlations can thus be made by the application of the same separation and analytical procedures to samples from point source emissions and the ambient atmosphere. This will be illustrated here with typical examples from the ambient atmosphere (aerosol particles) and from emissions of biomass burning (smoke). Organic matter in aerosols is derived from two major sources and is admixed depending on the geographic relief of the air shed. These sources are biogenic detritus (e.g., plant wax, microbes, etc.) and anthropogenic particle emissions (e.g., oils, soot, synthetics, etc.). Both biogenic detritus and some of the anthropogenic particle emissions contain organic materials which have unique and distinguishable compound distribution patterns (C₁₄-C₄₀). Microbial and vascular plant lipids are the dominant biogenic residues and petroleum hydrocarbons, with lesser amounts of the pyrogenic polynuclear aromatic hydrocarbons (PAH) and synthetics (e.g., chlorinated compounds), are the major anthropogenic residues. Biomass combustion is another important primary source of particles injected into the global atmosphere. It contributes many trace substances which are reactants in atmospheric chemistry and soot paniculate matter with adsorbed biomarker compounds, most of which are unknown chemical structures. The injection of natural product organic compounds into smoke occurs primarily by direct volatilization/steam stripping and by thermal alteration based on combustion temperature. Although the molecular composition of organic matter in smoke particles is highly variable, the molecular tracers are generally still source specific. Retene has been utilized as a tracer for conifer smoke in urban aerosols, but is not always detectable. Dehydroabietic acid is generally more concentrated in the atmosphere from the same emission sources. Degradation products from biopolymers (e.g., levoglucosan from cellulose) are also excellent tracers. An overview of the biomarker compositions of biomass smoke types is presented here. Defining additional tracers of thermally-altered and directly-emitted natural products in smoke aids the assessment of the organic matter type and input from biomass combustion to aerosols. The precursor to product approach of compound characterization by organic geochemistry can be applied successfully to provide tracers for studying the chemistry and dispersion of ambient aerosols and smoke plumes. Presented at the 6th FECS Conference on Chemistry and the Environment, Atmospheric Chemistry and Air Pollution, August 26–28, 1998, Copenhagen.     

Secondary organic aerosol formation from ozone-initiated reactions with nicotine and secondhand tobacco smoke

We used controlled laboratory experiments to evaluate the aerosol-forming potential of ozone reactions with nicotine and secondhand smoke. Special attention was devoted to real-time monitoring of the particle size distribution and chemical composition of SOA as they are believed to be key factors determining the toxicity of SOA. The experimental approach was based on using a vacuum ultraviolet photon ionization time-of-flight aerosol mass spectrometer (VUV-AMS), a scanning mobility particle sizer (SMPS) and off-line thermal desorption coupled to mass spectrometry (TD-GC-MS) for gas-phase byproducts analysis. Results showed that exposure of SHS to ozone induced the formation of ultrafine particles (<100 nm) that contained high molecular weight nitrogenated species (m/z 400–500), which can be due to accretion/acid–base reactions and formation of oligomers. In addition, nicotine was found to contribute significantly (with yields 4–9%) to the formation of secondary organic aerosol through reaction with ozone. The main constituents of the resulting SOA were tentatively identified and a reaction mechanism was proposed to elucidate their formation. These findings identify a new component of thirdhand smoke that is associated with the formation of ultrafine particles (UFP) through oxidative aging of secondhand smoke. The significance of this chemistry for indoor exposure and health effects is highlighted.     

Improved Titrilog Sensitivity

ABSTRACT

A method was developed to reproducibly measure environmental tobacco smoke (ETS) components generated by different cigarettes. Measurements were carried out in an unventilated, controlled environment chamber. True ETS (the aged and diluted combination of exhaled mainstream plus sidestream smoke) was generated by human smokers. To reliably quantitate components normally present at trace levels, the comparisons were carried out at elevated ETS concentrations—greater than 40 times those typically encountered in “real-world” settings.

The method was applied to four commercially available cigarettes and a cigarette prototype that primarily heats tobacco. Forty-three properties and components of the gas and particulate phases of ETS generated by the different cigarettes were measured. Good precision of measurement was obtained both within and between tests. Statistically significant differences in the concentration of ETS components were observed among the different commercial cigarettes and between the commercial and prototype cigarettes. Most ETS components from the prototype cigarette were reduced by >90% when compared to the commercial cigarettes. The method was used to determine the effect of cigarette design changes on the generation of ETS.     

Effectiveness of Smokeless Ashtrays

Abstract

Most environmental tobacco smoke (ETS) issues from the tips of smoldering cigarettes between puffs. Smokeless ashtrays are designed to reduce ETS exposure by removing particulate and/or gas-phase contaminants from this plume. This paper describes an experimental investigation of the effectiveness of four smokeless ashtrays: two commercial devices and two prototypes constructed by the authors. In the basic experimental protocol, one or more cigarettes was permitted to smolder in a room. Particulate or gas-phase pollutant concentrations were measured in the room air over time. Device effectiveness was determined by comparing pollutant concentrations with the device in use to those obtained with no control device. A lung deposition model was applied to further interpret device effectiveness for particle removal. The commercial ashtrays were found to be substantially ineffective in removing ETS particles because of the use of low-quality filter media and/or the failure to draw the smoke through the filter. A prototype ashtray using HEPA filter material achieved better than 90% particle removal efficiency. Gasphase pollutant removal was tested for only one prototype smokeless ashtray, which employed filters containing activated carbon and activated alumina. Removal efficiencies for the 18 gas-phase compounds measured (above the detection limit) were in the range of 70 to 95%.     

A Comparative Study of Environmental Tobacco Smoke Particulate Mass Measurements in an Environmental Chamber

Particulate mass concentration measurements have been made on environmental tobacco smoke (ETS) for the purpose of assessing the relative accuracy of several measurement procedures. ETS over a range of concentrations was generated in an environmental chamber by three methods. Mass concentration was measured by a gravimetric/spectrophotometric collection procedure, piezoelectric particle mass monitors, two nephelometry-based mass monitors, and a particle counting and sizing system. Two-hour average mass concentrations were determined by each method for concentrations ranging from very low levels up to those achieved by smoking one entire cigarette in the chamber. Statistical comparisons were made among procedures employing the gravimetric filter measurement as the basis for comparison. One nephelometry-based procedure gave significantly higher and the other significantly lower values than the filter determination. In one case, a correction for the difference between the particle mass density of the calibrating aerosol and that of ETS brought the nephelometry-based procedure into reasonable agreement with the filter measurement, while for the other, the correction did not resolve the discrepancy between methods. Statistically significant differences between the responses of two supposedly identical piezoelectric mass monitors were found, as was some slight dependence of the nephelometry- based procedures on method of ETS generation. In summary, the results indicate that significant errors can be expected if the instruments studied are used “off the shelf,” even for ETS generated under controlled laboratory conditions. Caution should be employed in field measurements where numerous sources and types of particulate matter can be encountered.     

Characterization of organic aerosol in Big Bend National Park,Texas

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study was conducted in Big Bend National Park, Texas, July through October 1999. Daily PM_2.5 organic aerosol samples were collected on pre-fired quartz fiber filters. Daily concentrations were too low for detailed organic analysis by gas chromatography-mass spectrometry (GC-MS) and were grouped based on their air mass trajectories. A total of 12 composites, each containing 3–10 daily samples, were analyzed. Alkane carbon preference indices suggest primary biogenic emissions were small contributors to primary PM_2.5 organic matter (OM) during the first 3 months, while in October air masses advecting from the north and south were more strongly influenced by biogenic sources. A series of trace organic compounds previously shown to serve as particle phase tracers for various carbonaceous aerosol source types were examined. Molecular tracer species were generally at or below detection limits, except for the wood smoke tracer levoglucosan in one composite, so maximum possible source influences were calculated using the detection limit as an upper bound to the tracer concentration. Wood smoke was found not to contribute significantly to PM_2.5 OM, with contributions for most samples at <1% of the total organic particulate matter. Vehicular exhaust also appeared to make only minor contributions, with maximum possible influences calculated to be 1–4% of PM_2.5 OM. Several factors indicate that secondary organic aerosol formation was important throughout the study, and may have significantly altered the molecular composition of the aerosol during transport.     

Contributions of biogenic volatile organic compounds to the formation of secondary organic aerosols over Mt. Tai,Central East China

To better understand the contribution of biogenic volatile organic compounds to the formation of secondary organic aerosol (SOA) in high mountain regions, ambient aerosols were collected at the summit of Mt. Tai (1534 m, a.s.l.), Central East China (CEC) during the Mount Tai Experiment 2006 campaign (MTX2006) in early summer. Biogenic SOA tracers for the oxidation of isoprene, α/β-pinene, and β-caryophyllene were measured using gas chromatography/mass spectrometry. Most of the biogenic SOA tracers did not show clear diurnal variations, suggesting that they are formed during long-range atmospheric transport or over relatively long time scales. Although isoprene- and α/β-pinene-derived SOA tracers did not correlate with levoglucosan (a biomass burning tracer), β-caryophyllinic acid showed a good correlation with levoglucosan, indicating that crop residue burning may be a source for this acid. Total concentrations of isoprene oxidation products are much higher than those of α/β-pinene and β-caryophyllene oxidation products. The averaged ratio of isoprene to α/β-pinene oxidation products (R_iso/pine) was 4.9 and 6.7 for the daytime and nighttime samples, respectively. These values are among the highest in the aerosols reported in different geographical regions, which may be due to the large isoprene fluxes and relatively high levels of oxidants such as OH in CEC. Using a tracer-based method, we estimated the concentrations of secondary organic carbon (SOC) derived from isoprene, α/β-pinene, and β-caryophyllene to be 0.42–3.1 μgC m^?3 (average 1.6 μgC m^?3) during the daytime and 0.11–4.2 μgC m^?3 (1.7 μgC m^?3) during the nighttime. These values correspond to 2.9–23% (10%) and 3.2–28% (9.8%) of the total OC concentrations, in which isoprene-derived SOC accounts for 58% and 63% of total SOC during the daytime and nighttime, respectively. This study suggests that isoprene is a more significant precursor for biogenic SOA than α/β-pinene and β-caryophyllene at high altitudes in CEC.     

Particulate and Nicotine Sampling in Public Facilities and Offices

Abstract

The purpose of this study was to characterize and measure indoor air quality in public facilities and office buildings. The pollutants of interest were particulate matter smaller than 2.5 μm in diameter, PM-2.5, and environmental tobacco smoke (ETS). Integrated PM- 2.5 samples were taken on Teflon membrane filters using Harvard Aerosol Impactors as a pre-size selector. Filters were analyzed by gravimetric analysis. Nicotine, which was used as a marker for ETS, was collected on sodium-bisulfate-impregnated, glass-fiber filters and was analyzed by gas chromatography. Twenty-one structures were monitored in Metropolitan Boston. Measured particle concentrations ranged from 6.0 μg/m³ to about 550 μg/m³. Nicotine concentrations were as high as 26 μg/m³ in a designated smoking room. Real-time measurements were also taken using two types of nephelometers; a Handheld Aerosol Monitor (HAM) and a Miniature Real-Time Aerosol Monitor (MINIRAM). Short-term field measurements with these instruments correlated better with the integrated PM-2.5 concentrations in smoking locations than with concentrations in non-smoking areas.     

Participant-based monitoring of indoor and outdoor nitrogen dioxide,volatile organic compounds,and polycyclic aromatic hydrocarbons among MICA-Air households

The Mechanistic Indicators of Childhood Asthma (MICA) study in Detroit, Michigan introduced a participant-based approach to reduce the resource burden associated with collection of indoor and outdoor residential air sampling data. A subset of participants designated as MICA-Air conducted indoor and outdoor residential sampling of nitrogen dioxide (NO₂), volatile organic compounds (VOCs), and polycyclic aromatic hydrocarbons (PAHs). This participant-based methodology was subsequently adapted for use in the Vanguard phase of the U.S. National Children’s Study. The current paper examines residential indoor and outdoor concentrations of these pollutant species among health study participants in Detroit, Michigan.Pollutants measured under MICA-Air agreed well with other studies and continuous monitoring data collected in Detroit. For example, NO₂ and BTEX concentrations reported for other Detroit area monitoring were generally within 10–15% of indoor and outdoor concentrations measured in MICA-Air households. Outdoor NO₂ concentrations were typically higher than indoor NO₂ concentration among MICA-Air homes, with a median indoor/outdoor (I/O) ratio of 0.6 in homes that were not impacted by environmental tobacco smoke (ETS) during air sampling. Indoor concentrations generally exceeded outdoor concentrations for VOC and PAH species measured among non-ETS homes in the study. I/O ratios for BTEX species (benzene, toluene, ethylbenzene, and m/p- and o-xylene) ranged from 1.2 for benzene to 3.1 for toluene. Outdoor NO₂ concentrations were approximately 4.5 ppb higher on weekdays versus weekends. As expected, I/O ratios pollutants were generally higher for homes impacted by ETS.These findings suggest that participant-based air sampling can provide a cost-effective alternative to technician-based approaches for assessing indoor and outdoor residential air pollution in community health studies. We also introduced a technique for estimating daily concentrations at each home by weighting 2- and 7-day integrated concentrations using continuous measurements from regulatory monitoring sites. This approach may be applied to estimate short-term daily or hourly pollutant concentrations in future health studies.