Bedroom Concentrations and Emissions of Volatile Organic Compounds during Sleep.

Because humans spend about one-third of their time asleep in their bedrooms and are themselves emission sources of volatile organic compounds (VOCs), it is important to specifically characterize the composition of the bedroom air that they experience during sleep. This work uses real-time indoor and outdoor measurements of volatile organic compounds (VOCs) to examine concentration enhancements in bedroom air during sleep and to calculate VOC emission rates associated with sleeping occupants. Gaseous VOCs were measured with proton-transfer reaction time-of-flight mass spectrometry during a multiweek residential monitoring campaign under normal occupancy conditions. Results indicate high emissions of nearly 100 VOCs and other species in the bedroom during sleeping periods as compared to the levels in other rooms of the same residence. Air change rates for the bedroom and, correspondingly, emission rates of sleeping-associated VOCs were determined for two bounding conditions: (1) air exchange between the bedroom and outdoors only and (2) air exchange between the bedroom and other indoor spaces only (as represented by measurements in the kitchen). VOCs from skin oil oxidation and personal care products were present, revealing that many emission pathways can be important occupant-associated emission factors affecting bedroom air composition in addition to direct emissions from building materials and furnishings.

Characterizing PM2.5 Emissions and Temporal Evolution of Organic Composition from Incense Burning in a California Residence.

The chemical composition of incense-generated organic aerosol in residential indoor air has received limited attention in Western literature. In this study, we conducted incense burning experiments in a single-family California residence during vacancy. We report the chemical composition of organic fine particulate matter (PM2.5), associated emission factors (EFs), and gas-particle phase partitioning for indoor semivolatile organic compounds (SVOCs). Speciated organic PM2.5 measurements were made using two-dimensional gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC×GC-HR-ToF-MS) and semivolatile thermal desorption aerosol gas chromatography (SV-TAG). Organic PM2.5 EFs ranged from 7 to 31 mg g-1 for burned incense and were largely comprised of polar and oxygenated species, with high abundance of biomass-burning tracers such as levoglucosan. Differences in PM2.5 EFs and chemical profiles were observed in relation to the type of incense burned. Nine indoor SVOCs considered to originate from sources other than incense combustion were enhanced during incense events. Time-resolved concentrations of these SVOCs correlated well with PM2.5 mass (R2 > 0.75), suggesting that low-volatility SVOCs such as bis(2-ethylhexyl)phthalate and butyl benzyl phthalate partitioned to incense-generated PM2.5. Both direct emissions and enhanced partitioning of low-volatility indoor SVOCs to incense-generated PM2.5 can influence inhalation exposures during and after indoor incense use.

Assessing residential PM2.5 concentrations and infiltration factors with high spatiotemporal resolution using crowdsourced sensors.

Building conditions, outdoor climate, and human behavior influence residential concentrations of fine particulate matter (PM2.5). To study PM2.5 spatiotemporal variability in residences, we acquired paired indoor and outdoor PM2.5 measurements at 3,977 residences across the United States totaling >10,000 monitor-years of time-resolved data (10-min resolution) from the PurpleAir network. Time-series analysis and statistical modeling apportioned residential PM2.5 concentrations to outdoor sources (median residential contribution = 52% of total, coefficient of variation = 69%), episodic indoor emission events such as cooking (28%, CV = 210%) and persistent indoor sources (20%, CV = 112%). Residences in the temperate marine climate zone experienced higher infiltration factors, consistent with expectations for more time with open windows in milder climates. Likewise, for all climate zones, infiltration factors were highest in summer and lowest in winter, decreasing by approximately half in most climate zones. Large outdoor-indoor temperature differences were associated with lower infiltration factors, suggesting particle losses from active filtration occurred during heating and cooling. Absolute contributions from both outdoor and indoor sources increased during wildfire events. Infiltration factors decreased during periods of high outdoor PM2.5, such as during wildfires, reducing potential exposures from outdoor-origin particles but increasing potential exposures to indoor-origin particles. Time-of-day analysis reveals that episodic emission events are most frequent during mealtimes as well as on holidays (Thanksgiving and Christmas), indicating that cooking-related activities are a strong episodic emission source of indoor PM2.5 in monitored residences.

Cooking methods and kitchen ventilation availability, usage, perceived performance and potential in Canadian homes.

BACKGROUND: Cooking is a substantial contributor to air pollutant exposures in many residences. Effective use of kitchen ventilation can mitigate exposure; however, information on its availability, usage, and potential to increase its use across the population has been limited. OBJECTIVE: This study aimed to obtain nationally representative information on cooking methods, kitchen ventilation availability and usage, and the potential for education to increase effective usage. METHODS: An online survey was sent to a representative sample of Canadian homes to collect data on cooking methods, the presence and use of mechanical kitchen ventilation devices, perceived device performance, and willingness to implement mitigation strategies. Responses were weighted to match key demographic factors and analyzed using non-parametric statistics. RESULTS: Among the 4500 respondents, 90% had mechanical ventilation devices over the cooktop (66% of which were vented to the outside), and 30% reported regularly using their devices. Devices were used most often for deep-frying, followed by stir-frying, sautéing or pan-frying, indoor grilling, boiling or steaming. Almost half reported rarely or never using their ventilation devices during baking or oven self-cleaning. Only 10% were fully satisfied with their devices. More frequent use was associated with the device being vented to the outdoors, having more than two speed settings, quiet operation if only one speed, covering over half of the cooktop, and higher perceived effectiveness. After being informed of the benefits of kitchen ventilation, 64% indicated they would consider using their devices more often, preferentially using back burners with ventilation, and/or using higher ventilation device settings when needed. IMPACT: This study provides population-representative data on the most used cooking methods, kitchen ventilation availability and usage, and influencing factors in Canadian homes. Such data are needed for exposure assessments and evaluating the potential to mitigate cooking-related pollutant exposures via more effective use of kitchen ventilation. The data can be reasonably extrapolated to the United States, given the similarities in residential construction practices and cultural norms between the two countries.

Control of airborne infectious disease in buildings: Evidence and research priorities.

The evolution of SARS-CoV-2 virus has resulted in variants likely to be more readily transmitted through respiratory aerosols, underscoring the increased potential for indoor environmental controls to mitigate risk. Use of tight-fitting face masks to trap infectious aerosol in exhaled breath and reduce inhalation exposure to contaminated air is of critical importance for disease control. Administrative controls including the regulation of occupancy and interpersonal spacing are also important, while presenting social and economic challenges. Indoor engineering controls including ventilation, exhaust, air flow control, filtration, and disinfection by germicidal ultraviolet irradiation can reduce reliance on stringent occupancy restrictions. However, the effects of controls-individually and in combination-on reducing infectious aerosol transfer indoors remain to be clearly characterized to the extent needed to support widespread implementation by building operators. We review aerobiologic and epidemiologic evidence of indoor environmental controls against transmission and present a quantitative aerosol transfer scenario illustrating relative differences in exposure at close-interactive, room, and building scales. We identify an overarching need for investment to implement building controls and evaluate their effectiveness on infection in well-characterized and real-world settings, supported by specific, methodological advances. Improved understanding of engineering control effectiveness guides implementation at scale while considering occupant comfort, operational challenges, and energy costs.

Measured influence of overhead HVAC on exposure to airborne contaminants from simulated speaking in a meeting and a classroom.

Tracer gas experiments were conducted in a 158 m3 room with overhead supply diffusers to study dispersion of contaminants from simulated speaking in physically distanced meeting and classroom configurations. The room was contained within a 237 m3 cell with open plenum return to the HVAC system. Heated manikins at desks and a researcher operating the tracer release apparatus presented 8-9 thermal plumes. Experiments were conducted under conditions of no forced air and neutral, cooled, or heated air supplied at 980-1100 cmh, and with/out 20% outdoor air. CO2 was released at the head of one manikin in each experiment to simulate small (<5 µm diameter) respiratory aerosols. The metric of exposure relative to perfectly mixed (ERM) is introduced to quantify impacts, based on measurements at manikin heads and at three heights in the center and corners of the room. Chilled or neutral supply air provided good mixing with ERMs close to one. Thermal stratification during heating produced higher ERMs at most manikins: 25% were ≥2.5 and the highest were >5× perfectly mixed conditions. Operation of two within-zone air cleaners together moving ≥400 cmh vertically in the room provided enough mixing to mitigate elevated exposure variations.

Indoor air quality in new and renovated low-income apartments with mechanical ventilation and natural gas cooking in California.

This paper presents pollutant concentrations and performance data for code-required mechanical ventilation equipment in 23 low-income apartments at 4 properties constructed or renovated 2013-2017. All apartments had natural gas cooking burners. Occupants pledged to not use windows for ventilation during the study but several did. Measured airflows of range hoods and bathroom exhaust fans were lower than product specifications. Only eight apartments operationally met all ventilation code requirements. Pollutants measured over one week in each apartment included time-resolved fine particulate matter (PM2.5 ), nitrogen dioxide (NO2 ), formaldehyde and carbon dioxide (CO2 ) and time-integrated formaldehyde, NO2 and nitrogen oxides (NOX ). Compared to a recent study of California houses with code-compliant ventilation, apartments were smaller, had fewer occupants, higher densities, and higher mechanical ventilation rates. Mean PM2.5 , formaldehyde, NO2 , and CO2 were 7.7 µg/m3 , 14.1, 18.8, and 741 ppm in apartments; these are 4% lower, 25% lower, 165% higher, and 18% higher compared to houses with similar cooking frequency. Four apartments had weekly PM2.5 above the California annual outdoor standard of 12 µg/m3 and also discrete days above the World Health Organization 24-hour guideline of 25 µg/m3 . Two apartments had weekly NO2 above the California annual outdoor standard of 30 ppb.

Factors Impacting Range Hood Use in California Houses and Low-Income Apartments.

Venting range hoods can control indoor air pollutants emitted during residential cooktop and oven cooking. To quantify their potential benefits, it is important to know how frequently and under what conditions range hoods are operated during cooking. We analyzed data from 54 single family houses and 17 low-income apartments in California in which cooking activities, range hood use, and fine particulate matter (PM2.5) were monitored for one week per home. Range hoods were used for 36% of cooking events in houses and 28% in apartments. The frequency of hood use increased with cooking frequency across homes. In both houses and apartments, the likelihood of hood use during a cooking event increased with the duration of cooktop burner use, but not with the duration of oven use. Actual hood use rates were higher in the homes of participants who self-reported more frequent use in a pre-study survey, but actual use was far lower than self-reported frequency. Residents in single family houses used range hoods more often when cooking caused a discernible increase in PM2.5. In apartments, residents used their range hood more often only when high concentrations of PM2.5 were generated during cooking.

Wildfire Smoke Adjustment Factors for Low-Cost and Professional PM2.5 Monitors with Optical Sensors.

Air quality monitors using low-cost optical PM2.5 sensors can track the dispersion of wildfire smoke; but quantitative hazard assessment requires a smoke-specific adjustment factor (AF). This study determined AFs for three professional-grade devices and four monitors with low-cost sensors based on measurements inside a well-ventilated lab impacted by the 2018 Camp Fire in California (USA). Using the Thermo TEOM-FDMS as reference, AFs of professional monitors were 0.85 for Grimm mini wide-range aerosol spectrometer, 0.25 for TSI DustTrak, and 0.53 for Thermo pDR1500; AFs for low-cost monitors were 0.59 for AirVisual Pro, 0.48 for PurpleAir Indoor, 0.46 for Air Quality Egg, and 0.60 for eLichens Indoor Air Quality Pro Station. We also compared public data from 53 PurpleAir PA-II monitors to 12 nearby regulatory monitoring stations impacted by Camp Fire smoke and devices near stations impacted by the Carr and Mendocino Complex Fires in California and the Pole Creek Fire in Utah. Camp Fire AFs varied by day and location, with median (interquartile) of 0.48 (0.44-0.53). Adjusted PA-II 4-h average data were generally within ±20% of PM2.5 reported by the monitoring stations. Adjustment improved the accuracy of Air Quality Index (AQI) hazard level reporting, e.g., from 14% to 84% correct in Sacramento during the Camp Fire.

Performance of a CO2 sorbent for indoor air cleaning applications: Effects of environmental conditions, sorbent aging, and adsorption of co-occurring formaldehyde.

Indoor air cleaning systems that incorporate CO2 sorbent materials enable HVAC load shifting and efficiency improvements. This study developed a bench-scale experimental system to evaluate the performance of a sorbent under controlled operation conditions. A thermostatic holder containing 3.15 g sorbent was connected to a manifold that delivered CO2 -enriched air at a known temperature and relative humidity (RH). The air stream was also enriched with 0.8-2.1 ppm formaldehyde. The CO2 concentration was monitored in real-time upstream and downstream of the sorbent, and integrated formaldehyde samples were collected at different times using DNPH-coated silica cartridges. Sorbent regeneration was carried out by circulating clean air in countercurrent. Almost 200 loading/regeneration cycles were performed in the span of 17 months, from which 104 were carried out at reference test conditions defined by loading with air at 25°C, 38% RH, and 1000 ppm CO2 , and regenerating with air at 80°C, 3% RH and 400 ppm CO2 . The working capacity decreased slightly from 43-44 mg CO2 per g sorbent to 39-40 mg per g over the 17 months. The capacity increased with lower loading temperature (in the range 15-35°C) and higher regeneration temperature, between 40 and 80°C. The CO2 capacity was not sensitive to the moisture content in the range 6-9 g/m3 , and decreased slightly when dry air was used. Loading isothermal breakthrough curves were fitted to three simple adsorption models, verifying that pseudo-first-order kinetics appropriately describes the adsorption process. The model predicted that equilibrium capacities decreased with increasing temperature from 15 to 35°C, while adsorption rate constants slightly increased. The formaldehyde adsorption efficiency was 80%-99% in different cycles, corresponding to an average capacity of 86 ± 36 µg/g. Formaldehyde was not quantitatively released during regeneration, but its accumulation on the sorbent did not affect CO2 adsorption.

Indoor air quality in California homes with code-required mechanical ventilation.

Data were collected in 70 detached houses built in 2011-2017 in compliance with the mechanical ventilation requirements of California's building energy efficiency standards. Each home was monitored for a 1-week period with windows closed and the central mechanical ventilation system operating. Pollutant measurements included time-resolved fine particulate matter (PM2.5 ) indoors and outdoors and formaldehyde and carbon dioxide (CO2 ) indoors. Time-integrated measurements were made for formaldehyde, NO2 , and nitrogen oxides (NOX ) indoors and outdoors. Operation of the cooktop, range hood, and other exhaust fans was continuously recorded during the monitoring period. Onetime diagnostic measurements included mechanical airflows and envelope and duct system air leakage. All homes met or were very close to meeting the ventilation requirements. On average, the dwelling unit ventilation fan moved 50% more airflow than the minimum requirement. Pollutant concentrations were similar to or lower than those reported in a 2006-2007 study of California new homes built in 2002-2005. Mean and median indoor concentrations were lower by 44% and 38% for formaldehyde and 44% and 54% for PM2.5 . Ventilation fans were operating in only 26% of homes when first visited, and the control switches in many homes did not have informative labels as required by building standards.

Pollutant exposures from natural gas cooking burners: a simulation-based assessment for Southern California.

BACKGROUND: Residential natural gas cooking burners (NGCBs) can emit substantial quantities of pollutants, and they are typically used without venting range hoods. OBJECTIVE: We quantified pollutant concentrations and occupant exposures resulting from NGCB use in California homes. METHODS: A mass-balance model was applied to estimate time-dependent pollutant concentrations throughout homes in Southern California and the exposure concentrations experienced by individual occupants. We estimated nitrogen dioxide (NO2), carbon monoxide (CO), and formaldehyde (HCHO) concentrations for 1 week each in summer and winter for a representative sample of Southern California homes. The model simulated pollutant emissions from NGCBs as well as NO2 and CO entry from outdoors, dilution throughout the home, and removal by ventilation and deposition. Residence characteristics and outdoor concentrations of NO2 and CO were obtained from available databases. We inferred ventilation rates, occupancy patterns, and burner use from household characteristics. We also explored proximity to the burner(s) and the benefits of using venting range hoods. Replicate model executions using independently generated sets of stochastic variable values yielded estimated pollutant concentration distributions with geometric means varying by <10%. RESULTS: The simulation model estimated that-in homes using NGCBs without coincident use of venting range hoods-62%, 9%, and 53% of occupants are routinely exposed to NO2, CO, and HCHO levels that exceed acute health-based standards and guidelines. NGCB use increased the sample median of the highest simulated 1-hr indoor concentrations by 100, 3,000, and 20 ppb for NO2, CO, and HCHO, respectively. CONCLUSIONS: Reducing pollutant exposures from NGCBs should be a public health priority. Simulation results suggest that regular use of even moderately effective venting range hoods would dramatically reduce the percentage of homes in which concentrations exceed health-based standards.

Performance assessment of U.S. residential cooking exhaust hoods.

This study assessed the performance of seven new residential cooking exhaust hoods representing common U.S. designs. Laboratory tests were conducted to determine fan curves relating airflow to duct static pressure, sound levels, and exhaust gas capture efficiency for front and back cooktop burners and the oven. Airflow rate sensitivity to duct flow resistance was higher for axial fan devices than for centrifugal fan devices. Pollutant capture efficiency (CE) ranged from <15% to >98%, varying across hoods and with airflow and burner position for each hood. CE was higher for back burners relative to front burners, presumably because most hoods covered only part of the front burners. Open hoods had higher CE than those with grease screen and metal-covered bottoms. The device with the highest CE--exceeding 80% for oven and front burners--had a large, open hood that covered most of the front burners. The airflow rate for this hood surpassed the industry-recommended level of 118 L·s(-1) (250 cfm) and produced sound levels too high for normal conversation. For hoods meeting the sound and fan efficacy criteria for Energy Star, CE was <30% for front and oven burners.

A method to estimate the chronic health impact of air pollutants in U.S. residences.

BACKGROUND: Indoor air pollutants (IAPs) cause multiple health impacts. Prioritizing mitigation options that differentially affect individual pollutants and comparing IAPs with other environmental health hazards require a common metric of harm. OBJECTIVES: Our objective was to demonstrate a methodology to quantify and compare health impacts from IAPs. The methodology is needed to assess population health impacts of large-scale initiatives-including energy efficiency upgrades and ventilation standards-that affect indoor air quality (IAQ). METHODS: Available disease incidence and disease impact models for specific pollutant-disease combinations were synthesized with data on measured concentrations to estimate the chronic heath impact, in disability-adjusted life-years (DALYs) lost, due to inhalation of a subset of IAPs in U.S. residences. Model results were compared with independent estimates of DALYs lost due to disease. RESULTS: Particulate matter ≤ 2.5 µm in aerodynamic diameter (PM2.5), acrolein, and formaldehyde accounted for the vast majority of DALY losses caused by IAPs considered in this analysis, with impacts on par or greater than estimates for secondhand tobacco smoke and radon. Confidence intervals of DALYs lost derived from epidemiology-based response functions are tighter than those derived from toxicology-based, interspecies extrapolations. Statistics on disease incidence in the United States indicate that the upper-bound confidence interval for aggregate IAP harm is implausibly high. CONCLUSIONS: The approach demonstrated in this study may be used to assess regional and national initiatives that affect IAQ at the population level. Cumulative health impacts from inhalation in U.S. residences of the IAPs assessed in this study are estimated at 400-1,100 DALYs lost annually per 100,000 persons.

Thirdhand tobacco smoke: emerging evidence and arguments for a multidisciplinary research agenda.

BACKGROUND: There is broad consensus regarding the health impact of tobacco use and secondhand smoke exposure, yet considerable ambiguity exists about the nature and consequences of thirdhand smoke (THS). OBJECTIVES: We introduce definitions of THS and THS exposure and review recent findings about constituents, indoor sorption-desorption dynamics, and transformations of THS; distribution and persistence of THS in residential settings; implications for pathways of exposure; potential clinical significance and health effects; and behavioral and policy issues that affect and are affected by THS. DISCUSSION: Physical and chemical transformations of tobacco smoke pollutants take place over time scales ranging from seconds to months and include the creation of secondary pollutants that in some cases are more toxic (e.g., tobacco-specific nitrosamines). THS persists in real-world residential settings in the air, dust, and surfaces and is associated with elevated levels of nicotine on hands and cotinine in urine of nonsmokers residing in homes previously occupied by smokers. Much still needs to be learned about the chemistry, exposure, toxicology, health risks, and policy implications of THS. CONCLUSION: The existing evidence on THS provides strong support for pursuing a programmatic research agenda to close gaps in our current understanding of the chemistry, exposure, toxicology, and health effects of THS, as well as its behavioral, economic, and sociocultural considerations and consequences. Such a research agenda is necessary to illuminate the role of THS in existing and future tobacco control efforts to decrease smoking initiation and smoking levels, to increase cessation attempts and sustained cessation, and to reduce the cumulative effects of tobacco use on morbidity and mortality.

Formation of carcinogens indoors by surface-mediated reactions of nicotine with nitrous acid, leading to potential thirdhand smoke hazards.

This study shows that residual nicotine from tobacco smoke sorbed to indoor surfaces reacts with ambient nitrous acid (HONO) to form carcinogenic tobacco-specific nitrosamines (TSNAs). Substantial levels of TSNAs were measured on surfaces inside a smoker's vehicle. Laboratory experiments using cellulose as a model indoor material yielded a > 10-fold increase of surface-bound TSNAs when sorbed secondhand smoke was exposed to 60 ppbv HONO for 3 hours. In both cases we identified 1-(N-methyl-N-nitrosamino)-1-(3-pyridinyl)-4-butanal, a TSNA absent in freshly emitted tobacco smoke, as the major product. The potent carcinogens 4-(methylnitrosamino)-1-(3-pyridinyl)-1-butanone and N-nitroso nornicotine were also detected. Time-course measurements revealed fast TSNA formation, with up to 0.4% conversion of nicotine. Given the rapid sorption and persistence of high levels of nicotine on indoor surfaces-including clothing and human skin-this recently identified process represents an unappreciated health hazard through dermal exposure, dust inhalation, and ingestion. These findings raise concerns about exposures to the tobacco smoke residue that has been recently dubbed "thirdhand smoke." Our work highlights the importance of reactions at indoor interfaces, particularly those involving amines and NO(x)/HONO cycling, with potential health impacts.

Ozone levels in passenger cabins of commercial aircraft on North American and transoceanic routes.

Ozone levels in airplane cabins, and factors that influence them, were studied on northern hemisphere commercial passenger flights on domestic U.S., transatlantic, and transpacific routes. Real-time data from 76 flights were collected in 2006--2007 with a battery-powered UV photometric monitor. Sample mean ozone level, peak-hour ozone level, and flight-integrated ozone exposures were highly variable across domestic segments (N = 68), with ranges of < 1.5 to 146 parts per billion by volume (ppbv), 3--275 ppbv, and < 1.5 to 488 ppbv-hour, respectively. On planes equipped with ozone catalysts, the mean peak-hour ozone level (4.7 ppbv, N = 22)was substantially lower than on planes not equipped with catalysts (47 ppbv, N = 46). Peak-hour ozone levels on eight transoceanic flight segments, all on planes equipped with ozone catalysts, were in the range < 1.5 to 65 [corrected] ppbv. Seasonal variation on domestic routes without converters is reasonably modeled by a sinusoidal curve that predicts peak-hour levels to be approximately 70 ppbv higher in Feb--March than in Aug--Sept The temporal trend is broadly consistent with expectations, given the seasonal cycle in tropopause height. Episodically elevated (>100 ppbv) ozone levels on domestic flights were associated with winter-spring storms that are linked to enhanced exchange between the lower stratosphere and the upper troposphere.

Indoor secondary pollutants from household product emissions in the presence of ozone: A bench-scale chamber study.

Ozone-driven chemistry is a source of indoor secondary pollutants of potential health concern. This study investigates secondary air pollutants formed from reactions between constituents of household products and ozone. Gas-phase product emissions were introduced along with ozone at constant rates into a 198-L Teflon-lined reaction chamber. Gas-phase concentrations of reactive terpenoids and oxidation products were measured. Formaldehyde was a predominant oxidation byproduct for the three studied products, with yields for most conditions of 20-30% with respect to ozone consumed. Acetaldehyde, acetone, glycolaldehyde, formic acid, and acetic acid were each also detected for two or three of the products. Immediately upon mixing of reactants, a scanning mobility particle sizer detected particle nucleation events that were followed by a significant degree of secondary particle growth. The production of secondary gaseous pollutants and particles depended primarily on the ozone level and was influenced by other parameters such as the air-exchange rate. Hydroxyl radical concentrations in the range 0.04-200 x 10(5) molecules cm(-3) were determined by an indirect method. OH concentrations were observed to vary strongly with residual ozone level in the chamber, which was in the range 1-25 ppb, as is consistent with expectations from a simplified kinetic model. In a separate chamber study, we exposed the dry residue of two products to ozone and observed the formation of gas-phase and particle-phase secondary oxidation products.

Effect of ozone on nicotine desorption from model surfaces: evidence for heterogeneous chemistry.

Assessment of secondhand tobacco smoke exposure using nicotine as a tracer or biomarker is affected by sorption of the alkaloid to indoor surfaces and by its long-term re-emission into the gas phase. However, surface chemical interactions of nicotine have not been sufficiently characterized. Here, the reaction of ozone with nicotine sorbed to Teflon and cotton surfaces was investigated in an environmental chamber by monitoring nicotine desorption over a week following equilibration in dry or humid air (approximately 0% or 65-70% RH, respectively). The Teflon and cotton surfaces had N2-BET surface areas of 0.19 and 1.17 m2 g(-1), and water mass uptakes (at 70% RH) of 0 and 7.1% respectively. Compared with dry air baseline levels in the absence of O3, gas-phase nicotine concentrations decreased by 2 orders of magnitude for Teflon after 50 h at 20-45 ppb O3, and by a factor of 10 for cotton after 100 h with 13-15 ppb O3. The ratios of pseudo first-order rate constants for surface reaction (r) to long-term desorption (k) were r/k = 3.5 and 2.0 for Teflon and cotton surfaces, respectively. These results show that surface oxidation was competitive with desorption. Hence, oxidative losses could significantly reduce long-term re-emissions of nicotine from indoor surfaces. Formaldehyde, N-methylformamide, nicotinaldehyde, and cotinine were identified as oxidation products, indicating that the pyrrolidinic N was the site of electrophilic attack by O3. The presence of water vapor had no effect on the nicotine-O3 reaction on Teflon surfaces. By contrast, nicotine desorption from cotton in humid air was unaffected by the presence of ozone. These observations are consistent with complete inhibition of ozone-nicotine surface reactions in an aqueous surface film present in cotton but not in Teflon surfaces.

Indoor sorption of surrogates for sarin and related nerve agents.

Sorption rate parameters were determined for three organophosphorus (OP) compounds [dimethyl methylphosphonate (DMMP), diethyl ethylphosphonate (DEEP), and triethyl phosphate (TEP)] as surrogates for the G-type nerve agents sarin (GB), soman (GD), and tabun (GA). OP surrogates were injected and vaporized with additional volatile organic compounds into a 50 m3 chamber finished with painted wallboard. Experiments were conducted at two furnishing levels: (i) chamber containing only hard surfaces including a desk, a bookcase, tables, and chairs and (ii) with the addition of plush materials including carpet with cushion, draperies, and upholstered furniture. Each furnishing level was studied with aged and new painted wallboard. Gas-phase concentrations were measured during sealed chamber adsorb and desorb phases and then fit to three mathematical variations of a previously proposed sorption model having a surface sink and allowing for an embedded sink. A four-parameter model allowing unequal transport rates between surface and embedded sinks provided excellent fits for all conditions. To evaluate the potential effect of sorption, this model was incorporated into an indoor air quality simulation model to predict indoor concentrations of a G-type agent and a nonsorbing agent for hypothetical outdoor releases with shelter-in-place (SIP) response. Sorption was simulated using a range of parameters obtained experimentally. Simulations considered outdoor Gaussian plumes of 1- and 5-h duration and infiltration rates of 0.1, 0.3, and 0.9 h(-1). Indoor toxic loads (TL) for a 10-h SIP were calculated as integral C2 dt for a G-type agent. For the 5-h plume, sheltering reduced TLs for the nonsorbing agent to approximately 10-65% of outdoor levels. Analogous TLs for a G-type agent were 2-31% or 0.3-12% of outdoor levels assuming slow or moderate sorption. The relative effect of sorption was more pronounced for the longer plume and higher infiltration rates.