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.

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.

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.

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.