Volatile organic chemicals are produced from reactions of ozone with squalene in human skin oil. Both primary and secondary reaction products, i.e., 6-methyl-5-hepten-2-one (6-MHO) and 4-oxopentanal (4-OPA), have been reported in indoor occupied spaces. However, the abundance of these products indoors is a function of many variables, including the amount of ozone and occupants present as well as indoor removal processes. In this study, we develop a time-dependent kinetic model describing the behavior of ozone/squalene reaction products indoors, including the reaction process and physical adsorption process of products on indoor surfaces. The key parameters in the model were obtained by fitting time-resolved concentrations of 6-MHO, 4-OPA, and ozone in a university classroom on 1 day with multiple class sessions. The model predictions were subsequently tested against observations from four additional measurement days in the same classroom. Model predictions and experimental data agreed well (R² = 0.87-0.92) for all test days, including ∼7 class sessions covering a range of occupants (10-70) and ozone concentrations (0.09-32 ppb), demonstrating the effectiveness of the model. Accounting for surface uptake of 6-MHO and 4-OPA significantly improved model predictions (R² = 0.52-0.76 without surface uptake), reflecting the importance of including surface interactions to quantitatively represent product behavior in indoor environments.

Research on the sources of indoor airborne chemicals has traditionally focused on outdoor air, building materials, furnishings, and activities such as smoking, cooking, and cleaning. Relatively little research has examined the direct role of occupant emissions, even though this source clearly contributes to indoor volatile organic compounds (VOCs) and influences indoor chemistry. In this work, we quantify occupant-related gaseous VOC emissions in a university classroom using a proton-transfer-reaction time-of-flight mass spectrometer. Time-resolved concentrations of VOCs in room air and supply air were measured continuously during occupied and unoccupied periods. The emission factor for each human-emitted VOC was determined by dividing the occupant-associated source rate by the corresponding occupancy. Among the most abundant species detected were compounds associated with personal care products. Also prominent were human metabolic emissions, such as isoprene, methanol, acetone, and acetic acid. Additional sources included human skin oil oxidation by ozone, producing compounds such as 4-oxopentanal (4-OPA) and 6-methyl-5-hepten-2-one (6-MHO). By mass, human-emitted VOCs were the dominant source (57%) during occupied periods in a well-ventilated classroom, with ventilation supply air the second most important (35%), and indoor nonoccupant emissions the least (8%). The total occupant-associated VOC emission factor was 6.3 mg h^-1 per person.

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.

Direct human emissions are known to contribute volatile organic compounds (VOCs) to indoor air via various mechanisms. However, few measurements that determine the emissions of a full suite of occupant-associated VOCs are available. We measured occupant-related VOC emissions from engineering students in a classroom using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS). The dominant compound emitted was a cyclic volatile methylsiloxane (cVMS), decamethylcyclopentasiloxane (D5), which is a major inactive ingredient in some personal care products such as antiperspirants. D5 was found to contribute ∼30% of the total indoor VOC mass concentration as measured by the PTR-TOF-MS. Octamethylcyclotetrasiloxane (D4) and dodecamethylcyclohexasiloxane (D6) were detected at abundances that were 1-2 orders of magnitude lower. The per-person emission rate of these three cVMS declined monotonically from morning into the afternoon, consistent with expectations for emissions from daily morning application of personal care products.

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.

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.

We present direct indoor measurements of the nitrate radical (NO3) and dinitrogen pentoxide (N2O5) produced from combustion cooking emissions in a residential kitchen. When the indoor ozone (O3) concentration was low (∼4 ppbv), nitric oxide (NO) emitted from gas stove combustion suppressed NO3 formation. However, at moderate O3 levels (∼40 ppbv), measured NO3 concentrations reached 3-4 pptv, and the indoor NO3 reactivity loss rate coefficient reached 0.8 s-1. A box model of known chemistry agrees with the reactivity estimate and shows that moderate O3 levels led to a nitrate radical production rate of 7 ppbv h-1. These indoor NO3 production rates and reactivities are much higher than those typically found outdoors. We conclude that at low O3 levels indoor combustion suppresses nitrate radical chemistry, but when sufficient O3 enters residences from outdoors or is emitted directly from indoor sources, gas stove combustion emissions promote indoor NO3 chemistry.

Background

Microbes can grow in indoor environments if moisture is available, and we need an improved understanding of how this growth contributes to emissions of microbial volatile organic compounds (mVOCs). The goal of this study was to measure how moisture levels, building material type, collection site, and microbial species composition impact microbial growth and emissions of mVOCs. We subjected two common building materials, drywall, and carpet, to treatments with varying moisture availability and measured microbial communities and mVOC emissions.

Results

Fungal growth occurred in samples at >75% equilibrium relative humidity (ERH) for carpet with dust and >85% ERH for inoculated painted drywall. In addition to incubated relative humidity level, dust sample collection site (adonis p=0.001) and material type (drywall, carpet, adonis p=0.001) drove fungal and bacterial species composition. Increased relative humidity was associated with decreased microbial species diversity in samples of carpet with dust (adonis p= 0.005). Abundant volatile organic compounds (VOCs) that accounted for >1% emissions were likely released from building materials and the dust itself. However, certain mVOCs were associated with microbial growth from carpet with dust such as C₁₀H₁₆H⁺ (monoterpenes) and C₂H₆SH⁺ (dimethyl sulfide and ethanethiol). CO₂ production from samples of carpet with dust at 95% ERH averaged 5.92 mg hr^-1 kg^-1, while the average for carpet without dust at 95% ERH was 2.55 mg hr^-1 kg^-1.

Conclusion

Microbial growth and mVOC emissions occur at lower relative humidity in carpet and floor dust compared to drywall, which has important implications for human exposure. Even under elevated relative humidity conditions, the VOC emissions profile is dominated by non-microbial VOCs, although potential mVOCs may dominate odor production. Video Abstract.

Accurately modeled biogenic volatile organic compound (BVOC) emissions are an essential input to atmospheric chemistry simulations of ozone and particle formation. BVOC emission models rely on basal emission factor (BEF) distribution maps based on emission measurements and vegetation land-cover data but these critical input components of the models as well as model simulations lack validation by regional scale measurements. We directly assess isoprene emission-factor distribution databases for BVOC emission models by deriving BEFs from direct airborne eddy covariance (AEC) fluxes (Misztal et al., 2014) scaled to the surface and normalized by the activity factor of the Guenther et al. (2006) algorithm. The available airborne BEF data from approx. 10000km of flight tracks over California were averaged spatially over 48 defined ecological zones called ecoregions. Consistently, BEFs used by three different emission models were averaged over the same ecoregions for quantitative evaluation. Ecoregion-averaged BEFs from the most current land cover used by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) v.2.1 resulted in the best agreement among the tested land covers and agreed within 10% with BEFs inferred from measurement. However, the correlation was sensitive to a few discrepancies (either overestimation or underestimation) in those ecoregions where land-cover BEFs are less accurate or less representative for the flight track. The two other land covers demonstrated similar agreement (within 30% of measurements) for total average BEF across all tested ecoregions but there were a larger number of specific ecoregions that had poor agreement with the observations. Independently, we performed evaluation of the new California Air Resources Board (CARB) hybrid model by directly comparing its simulated isoprene area emissions averaged for the same flight times and flux footprints as actual measured area emissions. The model simulation and the observed surface area emissions agreed on average within 20%. We show that the choice of model land-cover input data has the most critical influence on model-measurement agreement and the uncertainty in meteorology inputs has a lesser impact at scales relevant to regional air quality modeling.