Teflon bag chambers have long been used for investigating atmospheric chemical processes, including secondary organic aerosol formation. The wall-loss process of gas-phase species in Teflon bag chambers has typically been investigated at around room temperature. Recent laboratory studies started employing Teflon bag chambers at sub-273 K conditions for simulating wintertime and upper-tropospheric environments. However, temperature dependence in vapor-wall-loss processes of semi-volatile organic compounds (SVOCs) in a Teflon bag chamber has not been well investigated. In this study, we experimentally investigated wall-loss processes of C14–C19 n-alkanes in a 1 m3 Teflon bag for the temperature range of 262 to 298 K. Enhanced wall losses of the tested n-alkanes were observed following the decrease in temperature. For instance, 65 %​​​​​​​ of C14 n-alkane was lost to the wall 15 h after injection at room temperature, while the corresponding value was 95 % at 262 K. The experimental data were analyzed using a two-layer kinetic model, which considers both absorption of gas-phase species to the surface layer of the Teflon wall and diffusion to the inner layer. The experimental data demonstrated that absorption of gas-phase species by the surface layer was enhanced at lower temperatures. The temperature dependence in absorption was well accounted for using the equilibrium-dissolution model of organic compounds to the Teflon surface by considering reduced saturation vapor pressure at lower temperatures. On the contrary, diffusion of n-alkanes from the surface to the inner layer slowed down at reduced temperatures. Mechanistic studies on these processes will need to be conducted in the future to quantitatively predict the influence of temperature-dependent wall-loss processes of SVOCs on laboratory experimental results.

Human occupants themselves constitute an important source of volatile organic compounds (VOCs) in indoor environments through breath and dermal emissions. In order to quantify VOC emissions from occupants under real-world settings, previous indoor observational studies often determined emission factors (i.e., average emission rates per person). However, the values obtained across these studies exhibited large variability, and the causes of this variability still need to be understood. Herein we report 10-day real-time VOC measurements in a university student office, using a proton transfer reaction-quadrupole interface-time-of-flight mass spectrometer. A method was developed to identify VOCs of primary human origin and to quantify the corresponding emission factors, accounting for the dynamically changing occupancy level and ventilation rate in the assessed office. We found that the emission factors of many dermally emitted VOCs strongly increased as the ozone concentration increased from <3 to 10–15 ppb. These VOCs include geranyl acetone, 6-methyl-5-hepten-2-one (6-MHO), and C10-C12 saturated aldehydes, which align with characteristic first-generation ozonolysis products of skin oil. The strongest increase occurred for 6-MHO, from 113 to 337 μg/h/p. In comparison, acetone and isoprene, which are primarily emitted from human breath, varied little with the ozone level. In light of this finding, we conducted an integrated analysis of emission factors reported in the literature for two frequently reported species, namely, 6-MHO and decanal. Ozone concentration alone can explain 94–97% of the variation in their emission factors across previous studies, and the best-estimated ozone dependence obtained using the literature data is consistent with those obtained in the current study. These results suggest that the ozone concentration is a key factor regulating emission factors of many dermally emitted VOCs in real indoor environments, which has to be considered when reporting or using the emission factors.

Organic aerosol particles are oxidized by atmospheric oxidants. These particles are occasionally internally mixed with solid materials such as soot and inorganic crystals. However, potential impacts of the particles' mixing states on chemical reactivity have rarely been investigated. This study investigated the influence of the existence of crystalline ammonium sulfate on chemical reactivity of oleic acid particles with ozone for the temperature range of −20°C to +35°C using an aerosol flow tube reactor. The chemical compositions of the resulting particles were monitored using online instruments for deriving the reactive uptake coefficients (γ) of ozone by oleic acid. The values of γ were not significantly influenced by the existence of ammonium sulfate when the temperature of the reactor was higher than the melting point of oleic acid (∼13°C). The values of γ were unmeasurably small for the lower temperature range when oleic acid particles were internally mixed with crystalline ammonium sulfate. No significant change in γ was observed for the temperature range down to −13°C when the inorganic salt was absent, likely due to the formation of supercooled liquid. The difference in chemical reactivity can be explained by the occurrence of heterogeneous nucleation induced by inorganic seed.

Indoor pollution of manmade semivolatile organic compounds (SVOCs) such as phthalates are a growing threat to human health. Herein we summarize the dust-phase phthalate concentrations in Chinese residences reported from 2011 to 2021 and simulate corresponding airborne concentrations based on equilibrium models. The simulation considers seasonal and regional variations in indoor temperature and PM2.5 concentration, in contrast to the common practice of using constant values. Results show that variations in these two environmental factors lead to up to ten- and six-fold variations in the monthly median gas- and particle-phase concentrations of phthalates, respectively, in residences in individual climate zones. For higher-vapor-pressure species di-n-butyl phthalate and di-isobutyl phthalate, the resultant seasonal and regional variations in aggregate non-diet intake can reach six- and three-fold, respectively. These results have important implications on exposure assessment of SVOCs and epidemiological evaluation of their health effects.

Ozone reactions on human body surfaces produce volatile organic compounds (VOCs) that influence indoor air quality. However, the dependence of VOC emissions on the ozone concentration has received limited attention. In this study, we conducted 36 sets of single-person chamber experiments with three volunteers exposed to ozone concentrations ranging from 0 to 32 ppb. Emission fluxes from human body surfaces were measured for 11 targeted skin-oil oxidation products. For the majority of these products, the emission fluxes linearly correlated with ozone concentration, indicating a constant surface yield (moles of VOC emitted per mole of ozone deposited). However, for the second-generation oxidation product 4-oxopentanal, a higher surface yield was observed at higher ozone concentrations. Furthermore, many VOCs have substantial emissions in the absence of ozone. Overall, these results suggest that the complex surface reactions and mass transfer processes involved in ozone-dependent VOC emissions from the human body can be represented using a simplified parametrization based on surface yield and baseline emission flux. Values of these two parameters were quantified for targeted products and estimated for other semiquantified VOC signals, facilitating the inclusion of ozone/skin oil chemistry in indoor air quality models and providing new insights on skin oil chemistry.

Semivolatile organic compounds (SVOCs) represent an important class of indoor pollutants. The partitioning of SVOCs between airborne particles and the adjacent air influences human exposure and uptake. Presently, little direct experimental evidence exists about the influence of indoor particle pollution on the gas–particle phase partitioning of indoor SVOCs. In this study, we present time-resolved gas- and particle-phase distribution data for indoor SVOCs in a normally occupied residence using semivolatile thermal desorption aerosol gas chromatography. Although SVOCs in indoor air are found mostly in the gas phase, we show that indoor particles from cooking, candle use, and outdoor particle infiltration strongly affect the gas–particle phase distribution of specific indoor SVOCs. From gas- and particle-phase measurements of SVOCs spanning a range of chemical functionalities (alkanes, alcohols, alkanoic acids, and phthalates) and volatilities (vapor pressures from 10–13 to 10–4 atm), we find that the chemical composition of the airborne particles influences the partitioning of individual SVOC species. During candle burning, the enhanced partitioning of gas-phase SVOCs to indoor particles not only affects the particle composition but also enhances surface off-gassing, thereby increasing the total airborne concentration of specific SVOCs, including diethylhexyl phthalate.

Coatings often cover two-thirds of the surfaces in indoor environments and represent important sources of indoor volatile organic compounds (VOCs). Temperature is known to affect VOC emission rates from coatings, yet inter-species difference in the temperature dependence still needs to be understood. Based on time-resolved VOC measurements in an indoor air campaign conducted in residences in Beijing, China, we identified dibasic ester (DBE), a solvent mixture often used in coatings, and found that the concentration ratios of DBE components exhibited strong temperature dependence in an apartment when the indoor temperature declined stepwise over a multiweek period. To interpret the observational results, we developed a simplified mechanistic model relating the temperature dependence of VOC emission rates from coated surfaces to the temperature dependence of the diffusion coefficient of the emitted VOCs in the coating layer and further to a predicable molecular property of the emitted VOCs, molar volumes at 0 K, based on the free-volume theory. This correlation was quantitatively verified using the DBE data as well as using the data of alkanes, another set of VOCs that might be emitted from coatings, observed in two apartments in the same campaign. Given that indoor temperature varies considerably over seasons and across regions, the correlation proposed herein may help better predict indoor VOC emissions from coatings.

Volatile methyl siloxanes (VMS) are ubiquitous in indoor environments due to their use in personal care products. This paper builds on previous work identifying sources of VMS by synthesizing time-resolved proton-transfer reaction time-of-flight mass spectrometer VMS concentration measurements from four multiweek indoor air campaigns to elucidate emission sources and removal processes. Temporal patterns of VMS emissions display both continuous and episodic behavior, with the relative importance varying among species. We find that the cyclic siloxane D5 is consistently the most abundant VMS species, mainly attributable to personal care product use. Two other cyclic siloxanes, D3 and D4, are emitted from oven and personal care product use, with continuous sources also apparent. Two linear siloxanes, L4 and L5, are also emitted from personal care product use, with apparent additional continuous sources. We report measurements for three other organosilicon compounds found in personal care products. The primary air removal pathway of the species examined in this paper is ventilation to the outdoors, which has implications for atmospheric chemistry. The net removal rate is slower for linear siloxanes, which persist for days indoors after episodic release events. This work highlights the diversity in sources of organosilicon species and their persistence indoors.

Abstract We performed a cross-sectional survey of 2143 female students in a university in Tianjin, China regarding perceived air quality (PAQ) and sick building syndrome (SBS) symptoms in the student dormitory. The prevalence of general, mucosal, and skin symptoms was 22.1%, 21.9%, and 26.3%, respectively. The three most prevalent PAQ complaints were ?dry air? (48.9% often), ?stuffy odor? (18.2%), and ?other unpleasant odors? (5.1%), and they were significant risk factors for 11?12 out of 12 SBS symptoms (adjusted odds ratios [AOR]: 1.6?5.8). Survey data of 1471 undergraduates, whose dorms were of uniform layout and furnishing, were used to further investigate the influences of occupancy level and occupant behaviors on PAQ and SBS symptoms. Frequent use of air freshener/perfume was a significant risk factor for ?dry air,? less frequent room cleaning and higher occupancy density were significant risk factors for ?stuffy odor,? and less natural ventilation was a significant risk factor for both ?stuffy odor? and ?pungent odor.? These factors were also significantly associated with some SBS symptoms. In particular, the use of air freshener/perfume exhibited a significant dose?response pattern with ?fatigue? (sometimes: AOR 1.3; often: AOR 2.0) and with ?irritated, stuffy, or runny nose? (sometimes: AOR 1.6; often: AOR 2.2).

More than 8 million people fly on commercial aircraft each day with approximately 5% having a pre-existing respiratory disease. Thus it is necessary to provide high air quality in aircraft to protect public health. Volatile organic compounds (VOCs) present in aircraft cabins are suspected to contribute to the reported complaints. We investigated concentrations of VOCs, air temperature, relative humidity, and CO2 concentrations in a total of 46 flights, including 26 Chinese domestic flights and 20 international flights. We focused on the data from the cruising phase without meal serving in which the air supply and air recirculation were steady. A total of 284 passengers (i.e., 101 on international flights and 183 on Chinese domestic flights) were invited to participate in questionnaire surveys in this phase. We performed a linear mixed model analysis by controlling for potential confounders (age, gender, smoke habits, and history of allergy) to study associations between VOCs exposures and passengers' complaints. Xylene was significantly associated with irritations of the eyes, nose, and throat on both international and domestic flights, with antilog beta values from 1.12 to 1.28 (p < 0.05). The association of some aldehydes (i.e., nonanal, decanal, and heptanal), which are potential oxidation products with ozone, with passengers' sensory irritations was also significant, especially during international flights (antilog beta values: 1.19–1.22). It indicates that VOCs, especially xylene and aldehydes, in aircraft cabins may influence the perceived indoor air quality and complaints among passengers.

Largely limited by measurement technique, dynamics of semivolatile organic compounds (SVOCs) in the indoor air is not well understood. This study reports time-resolved measurements of airborne concentration of di-2-ethylhexyl phthalate (DEHP) in an office, using semivolatile thermal desorption aerosol gas chromatography (SV-TAG). The measurements were conducted in two separate periods during the summer-to-fall transition in 2020, each for more than 10 days. The indoor gas-plus-particle DEHP concentration varied by more than one order of magnitude in each observation period, and the temporal pattern exhibited possible influences of the indoor temperature, particle mass concentration, and outdoor DEHP concentrations. Further analysis focusing on window-closed conditions (i.e., with less outdoor contribution) reveals that the DEHP dynamics was primarily driven by variations in the indoor temperature (R2 = 0.85) during the first, warmer period (24–29 °C), and by variations in the particle mass concentration (R2 = 0.83) during the subsequent cooler period (20–23 °C). The unexpected transition of the key driving factor with change of the temperature was qualitatively justified by a simplified mechanistic model. Moreover, the particle fraction of DEHP was measured during the latter, cooler period, and it exhibited strong dependence on particle concentration, which can be fitted assuming gas-particle equilibrium partitioning, with a best-fit apparent partitioning coefficient of 0.053 ± 0.006 m3/$μ$g at 20 ± 1 °C. Overall, these results improve our understanding of real-world SVOC dynamics.

Many manmade organic air pollutants are semivolatile and primarily used and exposed indoors. It remains unclear how indoor environmental parameters affect indoor air dynamics of semivolatile organic compounds (SVOCs) in real-world indoor conditions, which directly relates to human exposure. By making time-resolved SVOC measurements over multiple weeks in an office, we characterized the indoor air dynamics of six representative SVOCs which were mainly present in the gas phase and of indoor origins, and investigated the effects of the temperature and ventilation rate. The six species include di-isobutyl phthalate and di-n-butyl phthalate, as well as two n-alkanes and two siloxanes. Airborne concentrations of all six SVOCs responded strongly and quickly to changes in the indoor temperature. The temperature dependence of individual species can be well fitted in the form of the van't Hoff equation, and explained 65–86% of the observed variation in the logarithm-transformed concentrations. In contrast, increasing the ventilation rate by a factor of 3–5 for hours at a constant temperature had no discernible influence on the SVOC concentrations. Further kinetic modeling analysis suggests that the observed fast temperature response and indiscernible ventilation effect are both associated with SVOC sorption onto indoor surfaces, which dramatically slows the response of SVOC concentration to changes in the ventilation rate and speeds up the response to changes in the temperature. These results highlight the importance of sorption reservoirs on regulating indoor SVOC dynamics and also have important implications for controlling and assessing indoor air exposure to SVOCs.

Abstract We present OH observations made in Amazonas, Brazil during the Green Ocean Amazon campaign (GoAmazon2014/5) from February to March of 2014. The average diurnal variation of OH peaked with a midday (10:00?15:00) average of 1.0 ? 106 (±0.6 ? 106) molecules cm?3. This was substantially lower than previously reported in other tropical forest photochemical environments (2?5 ? 106 molecules cm?3) while the simulated OH reactivity was lower. The observational data set was used to constrain a box model to examine how well current photochemical reaction mechanisms can simulate observed OH. We used one near-explicit mechanism (MCM v3.3.1) and four condensed mechanisms (i.e., RACM2, MOZART-T1, CB05, CB6r2) to simulate OH. A total of 14 days of analysis shows that all five chemical mechanisms were able to explain the measured OH within instrumental uncertainty of 40% during the campaign in the Amazonian rainforest environment. Future studies are required using more reliable NOx and VOC measurements to further investigate discrepancies in our understanding of the radical chemistry in the tropical rainforest.

Time spent in residences substantially contributes to human exposure to volatile organic compounds (VOCs). Such exposures have been difficult to study deeply, in part because VOC concentrations and indoor occupancy vary rapidly. Using a fast-response online mass spectrometer, we report time-resolved exposures from multi-season sampling of more than 200 VOCs in two California residences. Chemical-specific source apportionment revealed that time-averaged exposures for most VOCs were mainly attributable to continuous indoor emissions from buildings and their static contents. Also contributing to exposures were occupant-related activities, such as cooking, and outdoor-to-indoor transport. Health risk assessments are possible for a subset of observed VOCs. Acrolein, acetaldehyde, and acrylic acid concentrations were above chronic advisory health guidelines, whereas exposures for other assessable species were typically well below the guideline levels. Studied residences were built in the mid-20th century, indicating that VOC emissions even from older buildings and their contents can substantially contribute to occupant exposures.

Volatile organic compounds (VOCs) emitted from building and furnishing materials represent a major concern of indoor air quality, in particular in new buildings. We carried out multiweek nontargeted VOC measurements in 10 new apartments in Beijing, China, using online chemical ionization mass spectrometry. Dimethyl esters of succinic, glutaric, and adipic acids, which are rarely known for their presence in indoor air, were identified in three apartments. The identification was confirmed using authentic standards and by gas chromatography/mass spectrometry analysis. Despite varying concentrations, the three compounds exhibited largely consistent ratios across the three apartments and throughout the observation periods. The observed ratios resemble chemical composition of dibasic esters (DBE), which are a solvent mixture of the three compounds and have been used in the coating industry. A field “sniffing” experiment further confirms DBE emissions from the coatings of some wooden furniture in at least one apartment. The average airborne DBE concentrations in the three apartments were 41, 5, and 4 $μ$g/m3, respectively, exceeding the screening level of 1 $μ$g/m3 recommended by the Michigan Department of Environmental Quality, United States. In the context of fast-growing DBE usage, the current results suggest that DBE might be emerging indoor air pollutants and merit further investigation.

Experimental estimates of residential intake fractions for indoor volatile organic compound (VOC) releases are scarce. We evaluated individual intake fractions (iFi, mass inhaled by an individual per unit mass emitted) using approximately five months of time-resolved VOC measurements acquired at two residences. First, we directly estimated iFi using inert tracer gases that were released at fixed rates. Tracer gas iFi values were generally consistent between occupants and comparable across seasons. Furthermore, iFi for sources released on different floors of a residence were statistically indistinguishable, suggesting that source location within the living space was not strongly influential. Emissions from living space sources (iFi ∼ 0.3% = 3000 ppm) contributed to occupant exposures at rates 2–4 times higher than crawl space sources (iFi ∼ 1000 ppm) and greater than 40 times higher than attic sources (iFi < ∼70 ppm). Second, we indirectly estimated iFi for 251 VOCs using net emission rates estimated by indoor–outdoor material balance. Although emission patterns varied between compounds, all VOC-specific iFi estimates were clustered near the values of the living space tracer gases. These experimental observations substantiate the theoretical expectation that iFi values are largely independent of analyte characteristics, a useful simplification for exposure assessments.

Squalene can react with indoor ozone to generate a series of volatile and semi-volatile organic compounds, some of which may be skin or respiratory irritants, causing adverse health effects. Better understanding of the ozone/squalene reaction and product transport characteristics is thus important. In this study, we developed a physical–chemical coupling model to describe the behavior of ozone/squalene reaction products, that is, 6-methyl-5-hepten-2-one (6-MHO) and 4-oxopentanal (4-OPA) in the gas phase and skin, by considering the chemical reaction and physical transport processes (external convection, internal diffusion, and surface uptake). Experiments without intervention were performed in a single-family house in California utilizing time- and space-resolved measurements. The key parameters in the model were extracted from 5 day data and then used to predict the behaviors in some other days. Predictions from the present model can reproduce the concentration profiles of the three compounds (ozone, 6-MHO, and 4-OPA) well (R2 = 0.82–0.89), indicating high accuracy of the model. Exposure analysis shows that the total amount of 6-MHO and 4-OPA entering the blood capillaries in 4 days can reach 14.6 and 30.1 $μ$g, respectively. The contribution of different sinks to ozone removal in the tested realistic indoor environment was also analyzed.

It has been suggested that indoor exposure to ozone oxidation products contributes materially to the apparent associations between outdoor ozone concentration and morbidity and mortality. Our current understanding of indoor ozone chemistry derives mainly from studies with test surfaces under controlled conditions. Little is known about the overall impact of ozone chemistry on air composition in dynamically changing indoor residential environments. The results presented here reflect a quantitative characterization of overall indoor ozone chemistry in a normally occupied home. Findings reveal a strong influence of off-body skin lipids on indoor ozone chemistry. Being able to elucidate indoor air pollutants derived from ozone chemistry facilitates the investigation of causal links between outdoor ozone concentrations and adverse health effects.Outdoor ozone transported indoors initiates oxidative chemistry, forming volatile organic products. The influence of ozone chemistry on indoor air composition has not been directly quantified in normally occupied residences. Here, we explore indoor ozone chemistry in a house in California with two adult inhabitants. We utilize space- and time-resolved measurements of ozone and volatile organic compounds (VOCs) acquired over an 8-wk summer campaign. Despite overall low indoor ozone concentrations (mean value of 4.3 ppb) and a relatively low indoor ozone decay constant (1.3 h−1), we identified multiple VOCs exhibiting clear contributions from ozone-initiated chemistry indoors. These chemicals include 6-methyl-5-hepten-2-one (6-MHO), 4-oxopentanal (4-OPA), nonenal, and C8-C12 saturated aldehydes, which are among the commonly reported products from laboratory studies of ozone interactions with indoor surfaces and with human skin lipids. These VOCs together accounted for ≥12% molecular yield with respect to house-wide consumed ozone, with the highest net product yield for nonanal (≥3.5%), followed by 6-MHO (2.7%) and 4-OPA (2.6%). Although 6-MHO and 4-OPA are prominent ozonolysis products of skin lipids (specifically squalene), ozone reaction with the body envelopes of the two occupants in this house are insufficient to explain the observed yields. Relatedly, we observed that ozone-driven chemistry continued to produce 6-MHO and 4-OPA even after the occupants had been away from the house for 5 d. These observations provide evidence that skin lipids transferred to indoor surfaces made substantial contributions to ozone reactivity in the studied house.All study data are included in the article and supporting information.

Ambient particulate matter (PM) is often used as a proxy of personal exposure in epidemiological studies of PM-induced health effects, yet whether this proxy biases the estimates of health effects is still unknown. On the basis of a panel study in Beijing, China, we investigated the dependence of 24 h personal exposure concentration to fine particles (PM2.5) and its carbonaceous components on the corresponding 24 h ambient concentration. The associated changes in inflammatory biomarkers with personal and ambient exposure were further examined using linear mixed-effect models. At ambient PM2.5 levels of \textless25 $μ$g m–3, personal exposure to PM2.5 was often several times higher, with a median personal/ambient ratio of ∼3. The ratio declined with an increase in ambient concentration, approaching ∼1 at ambient PM2.5 levels of \textgreater75 $μ$g m–3. Similar trends were also observed for organic carbon and elemental carbon. Personal exposures were significantly associated with both respiratory and systemic inflammatory biomarkers, such as fractional exhaled nitric oxide and white blood cell count. When ambient data were used, the association with systemic inflammation weakened. Our findings imply that the use of the ambient pollutant concentration as a proxy for personal exposure may be inaccurate and could bias the estimates of PM-induced health effects.

Measurements by semivolatile thermal desorption aerosol gas chromatography (SV-TAG) were used to investigate how semivolatile organic compounds (SVOCs) partition among indoor reservoirs in (1) a manufactured test house under controlled conditions (HOMEChem campaign) and (2) a single-family residence when vacant (H2 campaign). Data for phthalate diesters and siloxanes suggest that volatility-dependent partitioning processes modulate airborne SVOC concentrations through interactions with surface-laden condensed-phase reservoirs. Airborne concentrations of SVOCs with vapor pressures in the range of C13 to C23 alkanes were observed to be correlated with indoor air temperature. Observed temperature dependencies were quantitatively similar to theoretical predictions that assumed a surface-air boundary layer with equilibrium partitioning maintained at the air-surface interface. Airborne concentrations of SVOCs with vapor pressures corresponding to C25 to C31 alkanes correlated with airborne particle mass concentration. For SVOCs with higher vapor pressures, which are expected to be predominantly gaseous, correlations with particle mass concentration were weak or nonexistent. During primary particle emission events, enhanced gas-phase emissions from condensed-phase reservoirs partitioned to airborne particles, contributing substantially to organic particulate matter. An emission event related to oven-usage was inferred to deposit siloxanes in condensed-phase reservoirs throughout the house, leading to the possibility of reemission during subsequent periods with high particle loading.