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.

Anthropogenic emissions alter secondary organic aerosol (SOA) formation chemistry from naturally emitted isoprene. We use correlations of tracers and tracer ratios to provide new perspectives on sulfate, NOx, and particle acidity influencing isoprene-derived SOA in two isoprene-rich forested environments representing clean to polluted conditions—wet and dry seasons in central Amazonia and Southeastern U.S. summer. We used a semivolatile thermal desorption aerosol gas chromatograph (SV-TAG) and filter samplers to measure SOA tracers indicative of isoprene/HO2 (2-methyltetrols, C5-alkene triols, 2-methyltetrol organosulfates) and isoprene/NOx (2-methylglyceric acid, 2-methylglyceric acid organosulfate) pathways. Summed concentrations of these tracers correlated with particulate sulfate spanning three orders of magnitude, suggesting that 1 $μ$g m–3 reduction in sulfate corresponds with at least ∼0.5 $μ$g m–3 reduction in isoprene-derived SOA. We also find that isoprene/NOx pathway SOA mass primarily comprises organosulfates, ∼97% in the Amazon and ∼55% in Southeastern United States. We infer under natural conditions in high isoprene emission regions that preindustrial aerosol sulfate was almost exclusively isoprene-derived organosulfates, which are traditionally thought of as representative of an anthropogenic influence. We further report the first field observations showing that particle acidity correlates positively with 2-methylglyceric acid partitioning to the gas phase and negatively with the ratio of 2-methyltetrols to C5-alkene triols.

Phthalate esters, commonly used as plasticizers, can be found indoors in the gas phase, in airborne particulate matter, in dust, and on surfaces. The dynamic behavior of phthalates indoors is not fully understood. In this study, time-resolved measurements of airborne phthalate concentrations and associated gas-particle partitioning data were acquired in a normally occupied residence. The vapor pressure and associated gas-particle partitioning of measured phthalates influenced their airborne dynamic behavior. Concentrations of higher vapor pressure phthalates correlated well with indoor temperature, with little discernible influence from direct occupant activity. Conversely, occupant-related behaviors substantially influenced the concentrations and dynamic behavior of a lower vapor pressure compound, diethylhexyl phthalate (DEHP), mainly through production of particulate matter during cooking events. The proportion of airborne DEHP in the particle phase was experimentally observed to increase under higher particle mass concentrations and lower indoor temperatures in correspondence with theory. Experimental observations indicate that indoor surfaces of the residence are large reservoirs of phthalates. The results also indicate that two key factors influenced by human behavior—temperature and particle mass concentration—cause short-term changes in airborne phthalate concentrations.

Abstract We investigate source characteristics and emission dynamics of volatile organic compounds (VOCs) in a single-family house in California utilizing time- and space-resolved measurements. About 200 VOC signals, corresponding to more than 200 species, were measured during 8 weeks in summer and five in winter. Spatially resolved measurements, along with tracer data, reveal that VOCs in the living space were mainly emitted directly into that space, with minor contributions from the crawlspace, attic, or outdoors. Time-resolved measurements in the living space exhibited baseline levels far above outdoor levels for most VOCs; many compounds also displayed patterns of intermittent short-term enhancements (spikes) well above the indoor baseline. Compounds were categorized as ?high-baseline? or ?spike-dominated? based on indoor-to-outdoor concentration ratio and indoor mean-to-median ratio. Short-term spikes were associated with occupants and their activities, especially cooking. High-baseline compounds indicate continuous indoor emissions from building materials and furnishings. Indoor emission rates for high-baseline species, quantified with 2-hour resolution, exhibited strong temperature dependence and were affected by air-change rates. Decomposition of wooden building materials is suggested as a major source for acetic acid, formic acid, and methanol, which together accounted for \~75% of the total continuous indoor emissions of high-baseline species.

Abstract Semivolatile organic compounds (SVOCs) emitted from building materials, consumer products, and occupant activities alter the composition of air in residences where people spend most of their time. Exposures to specific SVOCs potentially pose risks to human health. However, little is known about the chemical complexity, total burden, and dynamic behavior of SVOCs in residential environments. Furthermore, little is known about the influence of human occupancy on the emissions and fates of SVOCs in residential air. Here, we present the first-ever hourly measurements of airborne SVOCs in a residence during normal occupancy. We employ state-of-the-art semivolatile thermal-desorption aerosol gas chromatography (SV-TAG). Indoor air is shown consistently to contain much higher levels of SVOCs than outdoors, in terms of both abundance and chemical complexity. Time-series data are characterized by temperature-dependent elevated background levels for a broad suite of chemicals, underlining the importance of continuous emissions from static indoor sources. Substantial increases in SVOC concentrations were associated with episodic occupant activities, especially cooking and cleaning. The number of occupants within the residence showed little influence on the total airborne SVOC concentration. Enhanced ventilation was effective in reducing SVOCs in indoor air, but only temporarily; SVOCs recovered to previous levels within hours.