Polycyclic Aromatic Hydrocarbons (PAHs) in Wildfire Smoke Accumulate on Indoor Materials and Create Postsmoke Event Exposure Pathways.

Wildfire smoke contains PAHs that, after infiltrating indoors, accumulate on indoor materials through particle deposition and partitioning from air. We report the magnitude and persistence of select surface associated PAHs on three common indoor materials: glass, cotton, and mechanical air filter media. Materials were loaded with PAHs through both spiking with standards and exposure to a wildfire smoke proxy. Loaded materials were aged indoors over ∼4 months to determine PAH persistence. For materials spiked with standards, total PAH decay rates were 0.010 ± 0.002, 0.025 ± 0.005, and 0.051 ± 0.009 day-1, for mechanical air filter media, glass, and cotton, respectively. PAH decay on smoke-exposed samples is consistent with that predicated by decay constants from spiked materials. Decay curves of smoke loaded samples show that PAH surface concentrations are elevated above background for ∼40 days after the smoke clears. Cleaning processes efficiently remove PAHs, with reductions of 71% and 62% after cleaning smoke-exposed glass with ethanol and a commercial cleaner, respectively. Laundering smoke-exposed cotton in a washing machine and heated drying removed 48% of PAHs. An exposure assessment indicates that both inhalation and dermal PAH exposure pathways may be relevant following wildfire smoke events.

Characterization of Volatile Organic Compound Emissions and CO2 Uptake from Eco-roof Plants.

Vegetation plays an important role in biosphere-atmosphere exchange, including emission of biogenic volatile organic compounds (BVOCs) that influence the formation of secondary pollutants. Gaps exist in our knowledge of BVOC emissions from succulent plants, which are often selected for urban greening on building roofs and walls. In this study, we characterize the CO2 uptake and BVOC emission of eight succulents and one moss using proton transfer reaction - time of flight - mass spectrometry in controlled laboratory experiments. CO2 uptake ranged 0 to 0.16 µmol [g DW (leaf dry weight)]-1 s-1 and net BVOC emission ranges -0.10 to 3.11 µg [g DW]-1 h-1. Specific BVOCs emitted or removed varied across plants studied; methanol was the dominant BVOC emitted, and acetaldehyde had the largest removal. Isoprene and monoterpene emissions of studied plants were generally low compared to other urban trees and shrubs, ranging 0 to 0.092 µg [g DW]-1 h-1 and 0 to 0.44 µg [g DW]-1 h-1, respectively. Calculated ozone formation potentials (OFP) of the succulents and moss range 4×10-7 - 4×10-4 g O3 [g DW]-1 d-1. Results of this study can inform selection of plants used in urban greening. For example, on a per leaf mass basis, Phedimus takesimensis and Crassula ovata have OFP lower than many plants presently classified as low OFP and may be promising candidates for greening in urban areas with ozone exceedances.

Per-Person and Whole-Building VOC Emission Factors in an Occupied School with Gas-Phase Air Cleaning.

Using real-time measurements of CO2 and volatile organic compounds (VOCs) in the air handler of an occupied middle school, we quantified source strengths for 249 VOCs and apportioned the source to the building, occupants and their activities, outdoor air, or recirculation air. For VOCs quantified in this study, there is a source to the outdoors of 8.6 ± 1.8 g/h in building exhaust air, of which 5.9 ± 1.7 g/h can be attributed to indoor sources (the building and occupants and their activities). The corresponding whole-building area emission factor from indoor sources is 1020 ± 300 µg/(m2 h), including reactive VOCs like isoprene and monoterpenes (33 ± 5.1 and 29 ± 5.7 µg/(m2 h), respectively). Per-person emission factors are calculated for compounds associated with occupants and their activities, e.g., monoterpenes are emitted at a rate of 280 ± 80 µg/(person h). The air handler included carbon scrubbing, reducing supply air concentrations of 125 compounds by 38 ± 19% (mean ± std. dev.) with a net removal of 2.4 ± 0.4 g/h of organic compounds from the building. This carbon scrubber reduces steady-state indoor concentrations of organics by 65 µg/m3 and the contribution of indoor sources of VOCs to the outdoor environment by ∼40%. These data inform the design and operation of buildings to reduce human exposure to VOCs inside buildings. These data indicate the potential for gas-phase air cleaning to improve both indoor air quality and reduce VOC emissions from buildings to the outdoor environment.

The genetic architecture of sexual dimorphism in the moss Ceratodon purpureus.

A central problem in evolutionary biology is to identify the forces that maintain genetic variation for fitness in natural populations. Sexual antagonism, in which selection favours different variants in males and females, can slow the transit of a polymorphism through a population or can actively maintain fitness variation. The amount of sexually antagonistic variation to be expected depends in part on the genetic architecture of sexual dimorphism, about which we know relatively little. Here, we used a multivariate quantitative genetic approach to examine the genetic architecture of sexual dimorphism in a scent-based fertilization syndrome of the moss Ceratodon purpureus. We found sexual dimorphism in numerous traits, consistent with a history of sexually antagonistic selection. The cross-sex genetic correlations (rmf) were generally heterogeneous with many values indistinguishable from zero, which typically suggests that genetic constraints do not limit the response to sexually antagonistic selection. However, we detected no differentiation between the female- and male-specific trait (co)variance matrices (Gf and Gm, respectively), meaning the evolution of sexual dimorphism may be constrained. The cross-sex cross-trait covariance matrix B contained both symmetric and asymmetric elements, indicating that the response to sexually antagonistic or sexually concordant selection, and the constraint to sexual dimorphism, are highly dependent on the traits experiencing selection. The patterns of genetic variances and covariances among these fitness components is consistent with partly sex-specific genetic architectures having evolved in order to partially resolve multivariate genetic constraints (i.e. sexual conflict), enabling the sexes to evolve towards their sex-specific multivariate trait optima.

Impact of Cognitive Tasks on CO2 and Isoprene Emissions from Humans.

The human body emits a wide range of chemicals, including CO2 and isoprene. To examine the impact of cognitive tasks on human emission rates of CO2 and isoprene, we conducted an across-subject, counterbalanced study in a controlled chamber involving 16 adults. The chamber replicated an office environment. In groups of four, participants engaged in 30 min each of cognitive tasks (stressed activity) and watching nature documentaries (relaxed activity). Measured biomarkers indicated higher stress levels were achieved during the stressed activity. Per-person CO2 emission rates were greater for stressed than relaxed activity (30.3 ± 2.1 vs 27.0 ± 1.7 g/h/p, p = 0.0044, mean ± standard deviation). Isoprene emission rates were also elevated under stressed versus relaxed activity (154 ± 25 µg/h/p vs 116 ± 20 µg/h/p, p = 0.041). The chamber temperature was held constant at 26.2 ± 0.49 °C; incidental variation in temperature did not explain the variance in emission rates. Isoprene emission rates increased linearly with salivary α-amylase levels (r2 = 0.6, p = 0.02). These results imply the possibility of considering cognitive tasks when determining building ventilation rates. They also present the possibility of monitoring indicators of cognitive tasks of occupants through measurement of air quality.

High-Efficiency Air Cleaning Reduces Indoor Traffic-Related Air Pollution and Alters Indoor Air Chemistry in a Near-Roadway School.

Schools in proximity to roadways expose students to traffic-related air pollution (TRAP). We investigate impacts of air-cleaning on indoor TRAP levels and indoor chemistry in a renovated school adjacent an interstate highway. We monitor air pollutants pre- and post-renovation and quantify efficiency of particle (MERV8 and 16 filters) and gas (functionalized activated carbon) air-cleaning. Time-resolved measurements show air-cleaning systems are effective, with in situ particle removal efficiency >94% across 10 nm to 10 µm. Activated carbon removed BTEX and NO2 with variability in removal efficiency. Over eight months of monitoring, NO2 removal efficiency was 96% initially and decreased to 61%; and BTEX removal efficiency was >80% or increased to >80%. Air-cleaning reduced indoor TRAP to below or near urban background. Air-cleaning systems suppressed indoor chemistry by reducing indoor levels of oxidants (NO2, O3) and reactive organics of indoor origin. When the air cleaning system was inactive, our data show that indoor SOA formation within the school was elevated. Loss rates of NO2 and O3 through the air-cleaning system were ∼1.5-2.4 h-1 and ∼2.3 h-1, respectively. Air-cleaning was 83% and 69% efficient, respectively, in removing monoterpenes and isoprene. By suppressing precursors, scaling calculations show air-cleaning prevented ∼3.4 mg/h of indoor SOA formation due to indoor ozone-monoterpene chemistry. For comparison, we estimate that filtration removed ∼130 mg/h of PM0.01-0.3.

Measuring the Building Envelope Penetration Factor for Ambient Nitrogen Oxides.

Much of human exposure to nitrogen oxides (NOx) of ambient origin occurs indoors. Reactions with materials inside building envelopes are expected to influence the amount of ambient NOx that infiltrates indoors. However, envelope penetration factors for ambient NOx constituents have never been measured. Here, we develop and apply methods to measure the penetration factor and indoor loss rates for ambient NOx constituents using time-resolved measurements in an unoccupied apartment unit. Multiple test methods and parameter estimation approaches were tested, including natural and artificial indoor NOx elevation with and without accounting for indoor oxidation reactions. Twelve of 16 tests yielded successful estimates of penetration factors and indoor loss rates. The penetration factor for NO was confirmed to be ∼1 and the mean (±s.d.) NO2 penetration factor was 0.72 ± 0.06 with a mean relative uncertainty of ∼15%. The mean (±s.d.) indoor NO2 loss rate was 0.27 ± 0.12 h-1, ranging 0.06-0.47 h-1, with strong correlations with indoor relative and absolute humidity. Indoor NO loss rates were strongly correlated with the estimated ozone concentration in infiltrating air. Results suggest that envelope penetration factors and loss rates for NOx constituents can be reasonably estimated across a wide range of conditions using these approaches.

Modeling ozone removal to indoor materials, including the effects of porosity, pore diameter, and thickness.

We develop an ozone transport and reaction model to determine reaction probabilities and assess the importance of physical properties such as porosity, pore diameter, and material thickness on reactive uptake of ozone to five materials. The one-dimensional model accounts for molecular diffusion from bulk air to the air-material interface, reaction at the interface, and diffusive transport and reaction through material pore volumes. Material-ozone reaction probabilities that account for internal transport and internal pore area, γ(ipa), are determined by a minimization of residuals between predicted and experimentally derived ozone concentrations. Values of γ(ipa) are generally less than effective reaction probabilities (γ(eff)) determined previously, likely because of the inclusion of diffusion into substrates and reaction with internal surface area (rather than the use of the horizontally projected external material areas). Estimates of γ(ipa) average 1 × 10(-7), 2 × 10(-7), 4 × 10(-5), 2 × 10(-5), and 4 × 10(-7) for two types of cellulose paper, pervious pavement, Portland cement concrete, and an activated carbon cloth, respectively. The transport and reaction model developed here accounts for observed differences in ozone removal to varying thicknesses of the cellulose paper, and estimates a near constant γ(ipa) as material thickness increases from 0.02 to 0.16 cm.

Impact of physical properties on ozone removal by several porous materials.

Models of reactive uptake of ozone in indoor environments generally describe materials through aerial (horizontal) projections of surface area, a potentially limiting assumption for porous materials. We investigated the effect of changing porosity/pore size, material thickness, and chamber fluid mechanic conditions on the reactive uptake of ozone to five materials: two cellulose filter papers, two cementitious materials, and an activated carbon cloth. Results include (1) material porosity and pore size distributions, (2) effective diffusion coefficients for ozone in materials, and (3) material-ozone deposition velocities and reaction probabilities. At small length scales (0.02-0.16 cm) increasing thickness caused increases in estimated reaction probabilities from 1 × 10(-6) to 5 × 10(-6) for one type of filter paper and from 1 × 10(-6) to 1 × 10(-5) for a second type of filter paper, an effect not observed for materials tested at larger thicknesses. For high porosity materials, increasing chamber transport-limited deposition velocities resulted in increases in reaction probabilities by factors of 1.4-2.0. The impact of physical properties and transport effects on values of the Thiele modulus, ranging across all materials from 0.03 to 13, is discussed in terms of the challenges in estimating reaction probabilities to porous materials in scenarios relevant to indoor environments.

Indoor air pollution in developing countries: research and implementation needs for improvements in global public health.

Exposure to indoor air pollution (IAP) from the burning of solid fuels for cooking, heating, and lighting accounts for a significant portion of the global burden of death and disease, and disproportionately affects women and children in developing regions. Clean cookstove campaigns recently received more attention and investment, but their successes might hinge on greater integration of the public health community with a variety of other disciplines. To help guide public health research in alleviating this important global environmental health burden, we synthesized previous research on IAP in developing countries, summarized successes and challenges of previous cookstove implementation programs, and provided key research and implementation needs from structured discussions at a recent symposium.

Measurement of Polycyclic Aromatic Hydrocarbons (PAHs) on Indoor Materials: Method Development.

Wildfire smoke penetrates indoors, and polycyclic aromatic hydrocarbons (PAHs) in smoke may accumulate on indoor materials. We developed two approaches for measuring PAHs on common indoor materials: (1) solvent-soaked wiping of solid materials (glass and drywall) and (2) direct extraction of porous/fleecy materials (mechanical air filter media and cotton sheets). Samples are extracted by sonication in dichloromethane and analyzed with gas chromatography-mass spectrometry. Extraction recoveries range from 50-83% for surrogate standards and for PAHs recovered from direct application to isopropanol-soaked wipes, in line with prior studies. We evaluate our methods with a total recovery metric, defined as the sampling and extraction recovery of PAHs from a test material spiked with known PAH mass. Total recovery is higher for "heavy" PAHs (HPAHs, 4 or more aromatic rings) than for "light" PAHs (LPAHs, 2-3 aromatic rings). For glass, the total recovery range is 44-77% for HPAHs and 0-30% for LPAHs. Total recoveries from painted drywall are <20% for all PAHs tested. For filter media and cotton, total recoveries of HPAHs are 37-67 and 19-57%, respectively. These data show acceptable HPAH total recovery on glass, cotton, and filter media; total recovery of LPAHs may be unacceptably low for indoor materials using methods developed here. Our data also indicate that extraction recovery of surrogate standards may overestimate the total recovery of PAHs from glass using solvent wipe sampling. The developed method enables future studies of accumulation of PAHs indoors, including potential longer-term exposure derived from contaminated indoor surfaces.

A novel VOC breath tracer method to evaluate indoor respiratory exposures in the near- and far-fields; implications for the spread of respiratory viruses.

BACKGROUND: Several studies suggest that far-field transmission (>6 ft) explains a significant number of COVID-19 superspreading outbreaks. OBJECTIVE: Therefore, quantifying the ratio of near- and far-field exposure to emissions from a source is key to better understanding human-to-human airborne infectious disease transmission and associated risks. METHODS: In this study, we used an environmentally-controlled chamber to measure volatile organic compounds (VOCs) released from a healthy participant who consumed breath mints, which contained unique tracer compounds. Tracer measurements were made at 0.76 m (2.5 ft), 1.52 m (5 ft), 2.28 m (7.5 ft) from the participant, as well as in the exhaust plenum of the chamber. RESULTS: We observed that 0.76 m (2.5 ft) trials had ~36-44% higher concentrations than other distances during the first 20 minutes of experiments, highlighting the importance of the near-field exposure relative to the far-field before virus-laden respiratory aerosol plumes are continuously mixed into the far-field. However, for the conditions studied, the concentrations of human-sourced tracers after 20 minutes and approaching the end of the 60-minute trials at 0.76 m, 1.52 m, and 2.28 m were only ~18%, ~11%, and ~7.5% higher than volume-averaged concentrations, respectively. SIGNIFICANCE: This study suggests that for rooms with similar airflow parameters disease transmission risk is dominated by near-field exposures for shorter event durations (e.g., initial 20-25-minutes of event) whereas far-field exposures are critical throughout the entire event and are increasingly more important for longer event durations. IMPACT STATEMENT: We offer a novel methodology for studying the fate and transport of airborne bioaerosols in indoor spaces using VOCs as unique proxies for bioaerosols. We provide evidence that real-time measurement of VOCs can be applied in settings with human subjects to estimate the concentration of bioaerosol at different distances from the emitter. We also improve upon the conventional assumption that a well-mixed room exhibits instantaneous and perfect mixing by addressing spatial distances and mixing over time. We quantitatively assessed the exposure levels to breath tracers at alternate distances and provided more insights into the changes on "near-field to far-field" ratios over time. This method can be used in future to estimate the benefits of alternate environmental conditions and occupant behaviors.

Measuring the penetration of ambient ozone into residential buildings.

Much of human exposure to ambient ozone and ozone reaction byproducts occurs inside buildings. However, there are currently no experimental data on the ability of ozone to penetrate through building envelopes and into residences. This paper presents a method to determine the penetration factor for ozone in buildings, and applies it in an unoccupied test house and seven single-family residences. The mean (±SD) ozone penetration factor was measured as 0.79 ± 0.13 in the eight homes using this method, ranging from 0.62 ± 0.09 to 1.02 ± 0.15. An analysis of tests across the homes revealed that ozone penetration was significantly higher in homes with more painted wood envelope materials, homes with larger air leakage exponents from fan pressurization tests, and older homes. The test method utilizes a large calibrated fan to elevate air exchange rates and steady-state indoor ozone concentrations to levels that can be accurately measured, so there is a potential for overpredicting ozone penetration factors. However, evidence suggests that this bias is likely small in most of the homes, and, even if a bias exists, the measured ozone penetration factors were lower than the usual assumption of unity in seven of the eight tested homes.

A novel VOC breath tracer method to evaluate indoor respiratory exposures in the near- and far-fields.

Several studies suggest that far-field transmission (> 6 ft) explains the significant number of COVID-19 superspreading outbreaks. Therefore, quantitative evaluation of near- and far-field exposure to emissions from a source is key to better understanding human-to-human airborne infectious disease transmission and associated risks. In this study, we used an environmentally-controlled chamber to measure volatile organic compounds (VOCs) released from a healthy participant who consumed breath mints, which contained unique tracer compounds. Tracer measurements were made at 2.5 ft, 5 ft, 7.5 ft from the participant, as well as in the exhaust plenum of the chamber. We observed that 2.5 ft trials had substantially (~36-44%) higher concentrations than other distances during the first 20 minutes of experiments, highlighting the importance of the near-field relative to the far-field before virus-laden respiratory aerosol plumes are continuously mixed into the far-field. However, for the conditions studied, the concentrations of human-sourced tracers after 20 minutes and approaching the end of the 60-minute trials at 2.5 ft, 5 ft, and 7.5 ft were only ~18%, ~11%, and ~7.5% higher than volume-averaged concentrations, respectively. Our findings highlight the importance of far-field transmission of airborne pathogens including SARS-CoV-2, which need to be considered in public health decision making.

Measuring volatile emissions from moss gametophytes: A review of methodologies and new applications.

Mosses inhabit nearly all terrestrial ecosystems and engage in important interactions with nitrogen-fixing microbes, sperm-dispersing arthropods, and other plants. It is hypothesized that these interactions could be mediated by biogenic volatile organic compounds (BVOCs). Moss BVOCs may play fundamental roles in influencing local ecologies, such as biosphere-atmosphere-hydrosphere communications, physiological and evolutionary dynamics, plant-microbe interactions, and gametophyte stress physiology. Further progress in quantifying the composition, magnitude, and variability of moss BVOC emissions, and their response to environmental drivers and metabolic requirements, is limited by methodological and analytical challenges. We review several sampling techniques with various analytical approaches and describe best practices in generating moss gametophyte BVOC measures. We emphasize the importance of characterizing the composition and magnitude of moss BVOC emissions across a variety of species to better inform and stimulate important cross-disciplinary studies. We conclude by highlighting how current methods could be employed, as well as best practices for choosing methodologies.

Emerging investigator series: primary emissions, ozone reactivity, and byproduct emissions from building insulation materials.

Building insulation materials can affect indoor air by (i) releasing primary volatile organic compounds (VOCs) from building enclosure cavities to the interior space, (ii) mitigating exposure to outdoor pollutants through reactive deposition (of oxidants, e.g., ozone) or filtration (of particles) in infiltration air, and (iii) generating secondary VOCs and other gas-phase byproducts resulting from oxidant reactions. This study reports primary VOC emission fluxes, ozone (O3) reaction probabilities (γ), and O3 reaction byproduct yields for eight common, commercially available insulation materials. Fluxes of primary VOCs from the materials, measured in a continuous flow reactor using proton transfer reaction-time of flight-mass spectrometry, ranged from 3 (polystyrene with thermal backing) to 61 (cellulose) µmol m-2 h-1 (with total VOC mass emission rates estimated to be between ∼0.3 and ∼3.3 mg m-2 h-1). Major primary VOC fluxes from cellulose were tentatively identified as compounds likely associated with cellulose chemical and thermal decomposition products. Ozone-material γ ranged from ∼1 × 10-6 to ∼30 × 10-6. Polystyrene with thermal backing and polyisocyanurate had the lowest γ, while cellulose and fiberglass had the highest. In the presence of O3, total observed volatile byproduct yields ranged from 0.25 (polystyrene) to 0.85 (recycled denim) moles of VOCs produced per mole of O3 consumed, or equivalent to secondary fluxes that range from 0.71 (polystyrene) to 10 (recycled denim) µmol m-2 h-1. Major emitted products in the presence of O3 were generally different from primary emissions and were characterized by yields of aldehydes and acetone. This work provides new data that can be used to evaluate and eventually model the impact of "hidden" materials (i.e., those present inside wall cavities) on indoor air quality. The data may also guide building enclosure material selection, especially for buildings in areas of high outdoor O3.

Indoor and outdoor particulate matter in primary school classrooms with fan-assisted natural ventilation in Singapore.

We conducted multiday continuous monitoring of indoor and outdoor particulate matter (PM) in classrooms with fan-assisted natural ventilation (NV) at five primary schools in Singapore. We monitored size-resolved number concentration of PM with diameter 0.3-10 µm at all schools and alveolar deposited surface area concentrations of PM with diameter 0.01-1.0 µm (SA0.01-1.0) at two schools. Results show that, during the monitoring period, schools closer to expressways and in the downtown area had 2-3 times higher outdoor PM0.3-1.0 number concentrations than schools located in suburban areas. Average indoor SA0.01-1.0 was 115-118 µm(2) cm(-3) during periods of occupancy and 72-87 µm(2) cm(-3) during unoccupied periods. There were close indoor and outdoor correlations for fine PM during both occupied and unoccupied periods (Pearson's r = 0.84-1.0) while the correlations for coarse PM were weak during the occupied periods (r = 0.13-0.74). Across all the schools, the size-resolved indoor/outdoor PM ratios (I/O ratios) were 0.81 to 1.58 and 0.61 to 0.95 during occupied and unoccupied periods, respectively, and average infiltration factors were 0.64 to 0.94. Average PM net emission rates, calculated during periods of occupancy in the classrooms, were lower than or in the lower range of emission rates reported in the literature. This study also reveals that indoor fine and submicron PM predominantly come from outdoor sources, while indoor sources associated with occupancy may be important for coarse PM even when the classrooms have high air exchange rates.