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.

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.

Aromatic organosulfates are identified and quantified in fine particulate matter (PM_2.5) from Lahore, Pakistan, Godavari, Nepal, and Pasadena, California. To support detection and quantification, authentic standards of phenyl sulfate, benzyl sulfate, 3-and 4-methylphenyl sulfate and 2-, 3-, and 4-methylbenzyl sulfate were synthesized. Authentic standards and aerosol samples were analyzed by ultra-performance liquid chromatography (UPLC) coupled to negative electrospray ionization (ESI) quadrupole time-of-flight (ToF) mass spectrometry. Benzyl sulfate was present in all three locations at concentrations ranging from 4 - 90 pg m^-3. Phenyl sulfate, methylphenyl sulfates and methylbenzyl sulfates were observed intermittently with abundances of 4 pg m^-3, 2-31 pg m^-3, 109 pg m^-3, respectively. Characteristic fragment ions of aromatic organosulfates include the sulfite radical (^•SO₃^-, m/z 80) and the sulfate radical (^•SO₄^-,m/z 96). Instrumental response factors of phenyl and benzyl sulfates varied by a factor of 4.3, indicating that structurally-similar organosulfates may have significantly different instrumental responses and highlighting the need to develop authentic standards for absolute quantitation organosulfates. In an effort to better understand the sources of aromatic organosulfates to the atmosphere, chamber experiments with the precursor toluene were conducted under conditions that form biogenic organosulfates. Aromatic organosulfates were not detected in the chamber samples, suggesting that they form through different pathways, have different precursors (e.g. naphthalene or methylnaphthalene), or are emitted from primary sources.

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.

Inhalation of particulate matter is associated with adverse health outcomes. The fluorescent portion of supermicron particulate matter has been used as a proxy for bioaerosols. The sources and emission rates of fluorescent particles in residential environments are not well-understood. Using an ultraviolet aerodynamic particle sizer (UVAPS), emissions of total and fluorescent supermicron particles from common human activities were investigated during the HOMEChem campaign, a test-house investigation of the chemistry of indoor environments. Human occupancy and activities, including cooking and mopping, were found to be considerable sources of indoor supermicron fluorescent particles, which enhanced the indoor particle concentrations by two orders of magnitude above baseline levels. The estimated total (fluorescent) mass emission rates for the activities tested were in the range of 4-30 (1-11) mg per person meal for cooking and 0.1-4.9 (0.05-4.7) mg/h for occupancy and mopping. Model calculations indicate that, once released, the dominant fate of coarse particles (2.5-10 micrometer in diameter) was deposition onto indoor surfaces, allowing for the possibility of subsequent resuspension and consequent exposures over durations much longer than the ventilation time scale. Indoor coarse particle deposition would also contribute to soiling of indoor surfaces.

An addition to the Acknowledgments of our paper is required. It is as follows: This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under Contract No. DE-AC02-05CH11231.

2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was examined in smog chambers under varied initial nitric oxide (NO) and aerosol acidity levels. Results indicate measurable SOA from MBO under low-NO conditions. Moreover, increasing aerosol acidity was found to enhance MBO SOA. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C(5)H(12)O(6)S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. Ambient fine aerosol (PM(2.5)) samples collected from the BEARPEX campaign during 2007 and 2009, as well as from the BEACHON-RoMBAS campaign during 2011, were also analyzed. The MBO-derived organosulfate characterized from laboratory-generated aerosol was observed in PM(2.5) collected from these campaigns, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Furthermore, mass concentrations of the MBO-derived organosulfate are well correlated with MBO mixing ratio, temperature, and acidity in the field campaigns. Importantly, this compound accounted for an average of 0.25% and as high as 1% of the total organic aerosol mass during BEARPEX 2009. An epoxide intermediate generated under low-NO conditions is tentatively proposed to produce MBO SOA.