Brick kiln pollution and its impact on health: A systematic review and meta-analysis.

Brick kiln emissions adversely affect air pollution and the health of workers and individuals living near the kilns; however, evidence of their impacts remains limited. We conducted a systematic review of brick kiln pollution (emissions, source contributions and personal exposures) and its effects on health. We extracted articles from electronic databases and through manual citation searching. We estimated pooled, sample-size-weighted means and standard deviations for personal exposures by job type; computed mean emission factors and pollutant concentrations by brick kiln design; and meta-analyzed differences in means or proportions for health outcomes between brick kiln workers and controls or for participants living near or far away from kilns. We identified 104 studies; 74 were conducted in South Asia. The most evaluated pollutants were particulate matter (PM; n=48), sulfur dioxide (SO2; n=24) and carbon monoxide (CO; n=22), and the most evaluated health outcomes were respiratory health (n=34) and musculoskeletal disorders (n=9). PM and CO emissions were higher among traditional than improved brick kilns. Mean respirable silica exposures were only measured in 4 (4%) studies and were as high as 620 µg/m3, exceeding the NIOSH recommended exposure limit by a factor of over 12. Brick kiln workers had consistently worse lung function, more respiratory symptoms, more musculoskeletal complaints, and more inflammation when compared to unexposed participants across studies; however, most studies had a small sample size and did not fully describe methods used for sampling or data collection. On average, brick kiln workers had worse health outcomes when compared to unexposed controls but study quality supporting the evidence was low. Few studies reported silica concentrations or personal exposures, but the few that did suggest that exposures are high. Further research is needed to better understand the relationship between brick kiln pollution and health among workers, and to evaluate exposure mitigation strategies.

Assessing the Oxidative Potential of Outdoor PM2.5 in Wintertime Fairbanks, Alaska.

The oxidative potential (OP) of outdoor PM2.5 in wintertime Fairbanks, Alaska, is investigated and compared to those in wintertime Atlanta and Los Angeles. Approximately 40 filter samples collected in January-February 2022 at a Fairbanks residential site were analyzed for OP utilizing dithiothreitol-depletion (OPDTT) and hydroxyl-generation (OPOH) assays. The study-average PM2.5 mass concentration was 12.8 µg/m3, with a 1 h average maximum of 89.0 µg/m3. Regression analysis, correlations with source tracers, and contrast between cold and warmer events indicated that OPDTT was mainly sensitive to copper, elemental carbon, and organic aerosol from residential wood burning, and OPOH to iron and organic aerosol from vehicles. Despite low photochemically-driven oxidation rates, the water-soluble fraction of OPDTT was unusually high at 77%, mainly from wood burning emissions. In contrast to other locations, the Fairbanks average PM2.5 mass concentration was higher than Atlanta and Los Angeles, whereas OPDTT in Fairbanks and Atlanta were similar, and Los Angeles had the highest OPDTT and OPOH. Site differences were observed in OP when normalized by both the volume of air sampled and the particle mass concentration, corresponding to exposure and the intrinsic health-related properties of PM2.5, respectively. The sensitivity of OP assays to specific aerosol components and sources can provide insights beyond the PM2.5 mass concentration when assessing air quality.

Indoor-Outdoor Oxidative Potential of PM2.5 in Wintertime Fairbanks, Alaska: Impact of Air Infiltration and Indoor Activities.

The indoor air quality of a residential home during winter in Fairbanks, Alaska, was investigated and contrasted with outdoor levels. Twenty-four-hour average indoor and outdoor filter samples were collected from January 17 to February 25, 2022, in a residential area with high outdoor PM2.5 concentrations. The oxidative potential of PM2.5 was determined using the dithiothreitol-depletion assay (OPDTT). For the unoccupied house, the background indoor-to-outdoor (I/O) ratio of mass-normalized OP (OPmDTT), a measure of the intrinsic health-relevant properties of the aerosol, was less than 1 (0.53 ± 0.37), implying a loss of aerosol toxicity as air was transported indoors. This may result from transport and volatility losses driven by the large gradients in temperature (average outdoor temperature of -19°C/average indoor temperature of 21 °C) or relative humidity (average outdoor RH of 78%/average indoor RH of 11%), or both. Various indoor activities, including pellet stove use, simple cooking experiments, incense burning, and mixtures of these activities, were conducted. The experiments produced PM2.5 with a highly variable OPmDTT. PM2.5 from cooking emissions had the lowest OP values, while pellet stove PM2.5 had the highest. Correlations between volume-normalized OPDTT (OPvDTT), relevant to exposure, and indoor PM2.5 mass concentration during experiments were much lower compared to those in outdoor environments. This suggests that mass concentration alone can be a poor indicator of possible adverse effects of various indoor emissions. These findings highlight the importance of considering both the quantity of particles and sources (chemical composition), as health metrics for indoor air quality.

Overview of the Alaskan Layered Pollution and Chemical Analysis (ALPACA) Field Experiment.

The Alaskan Layered Pollution And Chemical Analysis (ALPACA) field experiment was a collaborative study designed to improve understanding of pollution sources and chemical processes during winter (cold climate and low-photochemical activity), to investigate indoor pollution, and to study dispersion of pollution as affected by frequent temperature inversions. A number of the research goals were motivated by questions raised by residents of Fairbanks, Alaska, where the study was held. This paper describes the measurement strategies and the conditions encountered during the January and February 2022 field experiment, and reports early examples of how the measurements addressed research goals, particularly those of interest to the residents. Outdoor air measurements showed high concentrations of particulate matter and pollutant gases including volatile organic carbon species. During pollution events, low winds and extremely stable atmospheric conditions trapped pollution below 73 m, an extremely shallow vertical scale. Tethered-balloon-based measurements intercepted plumes aloft, which were associated with power plant point sources through transport modeling. Because cold climate residents spend much of their time indoors, the study included an indoor air quality component, where measurements were made inside and outside a house to study infiltration and indoor sources. In the absence of indoor activities such as cooking and/or heating with a pellet stove, indoor particulate matter concentrations were lower than outdoors; however, cooking and pellet stove burns often caused higher indoor particulate matter concentrations than outdoors. The mass-normalized particulate matter oxidative potential, a health-relevant property measured here by the reactivity with dithiothreiol, of indoor particles varied by source, with cooking particles having less oxidative potential per mass than pellet stove particles.

Model Framework for Predicting Semivolatile Organic Material Emissions Indoors from Organic Aerosol Measurements: Applications to HOMEChem Stir-Frying.

Cooking activities emit myriad low-volatility, semivolatile, and highly volatile organic compounds that together form particles that can accumulate to large indoor concentrations. Absorptive partitioning thermodynamics governs the particle-phase organic aerosol concentration mainly via temperature and sorbing mass impacts. Cooking activities can increase the organic sorbing mass by 1-2 orders of magnitude, increasing particle-phase concentrations and affecting emission rate calculations. Although recent studies have begun to probe the volatility characteristics of indoor cooking particles, parametrizations of cooking particle mass emissions have largely neglected these thermodynamic considerations. Here, we present an improved thermodynamics-based model framework for estimating condensable organic material emission rates from a time series of observed concentrations, given that adequate measurements or assumptions can be made about the volatility of the emitted species. We demonstrate the performance of this methodology by applying data from stir-frying experiments performed during the House Observations of Microbial and Environmental Chemistry (HOMEChem) campaign to a two-zone box model representing the UTest House. Preliminary estimates of organic mass emitted on a per-stir-fry basis for three types of organic aerosol factors are presented. Our analysis highlights that using traditional nonvolatile particle models and emission characterizations for some organic aerosol emitting activities can incorrectly attribute concentration changes to emissions rather than thermodynamic effects.

Characterizing metals in particulate pollution in communities at the fenceline of heavy industry: combining mobile monitoring and size-resolved filter measurements.

Exposures to metals from industrial emissions can pose important health risks. The Chester-Trainer-Marcus Hook area of southeastern Pennsylvania is home to multiple petrochemical plants, a refinery, and a waste incinerator, most abutting socio-economically disadvantaged residential communities. Existing information on fenceline community exposures is based on monitoring data with low temporal and spatial resolution and EPA models that incorporate industry self-reporting. During a 3 week sampling campaign in September 2021, size-resolved particulate matter (PM) metals concentrations were obtained at a fixed site in Chester and on-line mobile aerosol measurements were conducted around Chester-Trainer-Marcus Hook. Fixed-site arsenic, lead, antimony, cobalt, and manganese concentrations in total PM were higher (p < 0.001) than EPA model estimates, and arsenic, lead, and cadmium were predominantly observed in fine PM (<2.5 µm), the PM fraction which can penetrate deeply into the lungs. Hazard index analysis suggests adverse effects are not expected from exposures at the observed levels; however, additional chemical exposures, PM size fraction, and non-chemical stressors should be considered in future studies for accurate assessment of risk. Fixed-site MOUDI and nearby mobile aerosol measurements were moderately correlated (r ≥ 0.5) for aluminum, potassium and selenium. Source apportionment analyses suggested the presence of four major emissions sources (sea salt, mineral dust, general combustion, and non-exhaust vehicle emissions) in the study area. Elevated levels of combustion-related elements of health concern (e.g., arsenic, cadmium, antimony, and vanadium) were observed near the waste incinerator and other industrial facilities by mobile monitoring, as well as in residential-zoned areas in Chester. These results suggest potential co-exposures to harmful atmospheric metal/metalloids in communities surrounding the Chester-Trainer-Marcus Hook industrial area at levels that may exceed previous estimates from EPA modeling.

Submicron Aerosol Composition and Source Contribution across the Kathmandu Valley, Nepal, in Winter.

The Kathmandu valley experiences an average wintertime PM1 concentration of ∼100 µg m-3 and daily peaks over 200 µg m-3. We present ambient nonrefractory PM1 chemical composition, and concentration measured by a mini aerosol mass spectrometer (mAMS) sequentially at Dhulikhel (on the valley exterior), then urban Ratnapark, and finally suburban Lalitpur in winter 2018. At all sites, organic aerosol (OA) was the largest contributor to combined PM1 (C-PM1) (49%) and black carbon (BC) was the second largest contributor (21%). The average background C-PM1 at Dhulikhel was 48 µg m-3; the urban enhancement was 120% (58 µg m-3). BC had an average of 6.1 µg m-3 at Dhulikhel, an urban enhancement of 17.4 µg m-3. Sulfate (SO4) was 3.6 µg m-3 at Dhulikhel, then 7.5 µg m-3 at Ratnapark, and 12.0 µg m-3 at Lalitpur in the brick kiln region. Chloride (Chl) increased by 330 and 250% from Dhulikhel to Ratnapark and Lalitpur on average. Positive matrix factorization (PMF) identified seven OA sources, four primary OA sources, hydrocarbon-like (HOA), biomass burning (BBOA), trash burning (TBOA), a sulfate-containing local OA source (sLOA), and three secondary oxygenated organic aerosols (OOA). OOA was the largest fraction of OA, over 50% outside the valley and 36% within. HOA (traffic) was the most prominent primary source, contributing 21% of all OA and 44% of BC. Brick kilns were the second largest contributor to C-PM1, 12% of OA, 33% of BC, and a primary emitter of aerosol sulfate. These results, though successive, indicate the importance of multisite measurements to understand ambient particulate matter concentration heterogeneity across urban regions.

Wintertime Air Quality across the Kathmandu Valley, Nepal: Concentration, Composition, and Sources of Fine and Coarse Particulate Matter.

The Kathmandu Valley in Nepal experiences poor air quality, especially in the dry winter season. In this study, we investigated the concentration, chemical composition, and sources of fine and coarse particulate matter (PM2.5, PM10, and PM10-2.5) at three sites within or near the Kathmandu Valley during the winter of 2018 as part of the second Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE 2). Daily PM2.5 concentrations were very high throughout the study period, ranging 72-149 µg m-3 at the urban Ratnapark site in Kathmandu, 88-161 µg m-3 at the suburban Lalitpur site, and 40-74 µg m-3 at rural Dhulikhel on the eastern rim of the Kathmandu Valley. Meanwhile, PM10 ranged 194-309, 174-377, and 64-131 µg m-3, respectively. At the Ratnapark site, crustal materials from resuspended soil contributed an average of 11% of PM2.5 and 34% of PM10. PM2.5 was largely comprised of organic carbon (OC, 28-30% by mass) and elemental carbon (EC, 10-14% by mass). As determined by chemical mass balance source apportionment modeling, major PM2.5 OC sources were garbage burning (15-21%), biomass burning (10-17%), and fossil fuel (14-26%). Secondary organic aerosol (SOA) contributions from aromatic volatile organic compounds (13-23% OC) were larger than those from isoprene (0.3-0.5%), monoterpenes (0.9-1.4%), and sesquiterpenes (3.6-4.4%). Nitro-monoaromatic compounds-of interest due to their light-absorbing properties and toxicity-indicate the presence of biomass burning-derived SOA. Knowledge of primary and secondary PM sources can facilitate air quality management in this region.

Aerosol Mass Spectral Profiles from NAMaSTE Field-Sampled South Asian Combustion Sources.

Unit mass resolution mass spectral profiles of nonrefractory submicron aerosol were retrieved from undersampled atmospheric emission sources common to South Asia using a "mini" aerosol mass spectrometer. Emission sources including wood- and dung-fueled cookstoves, agricultural residue burning, garbage burning, engine exhaust, and coal-fired brick kilns were sampled during the 2015 Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) campaign. High-resolution peak fitting estimates of the mass spectra were used to characterize ions found within each source profile and help identify mass spectral signatures unique to aerosol emissions from the investigated source types. The first aerosol mass spectral profiles of dung burning, charcoal burning, garbage burning, and brick kilns are provided in this work. The online aerosol mass spectra show that organics were generally the dominant component of the nonrefractory aerosol. However, inorganic aerosol components including ammonium and chloride were significant in dung- and charcoal-fired cookstove emissions and sulfate compounds were major components of the coal-fired brick kiln emissions. Organic mass spectra from both the charcoal burning and zigzag brick kiln were dominated by nitrogen-containing ions thought to be from the electron ionization of amines and amides contained in the emissions. The mixed garbage burning emissions profiles were dominated by plastic combustion with very low fractions of organic markers associated with biomass burning. The plastic burning emissions were associated with enhanced organic signal at mass-to-charge (m/z) 104 and m/z 166, which could be useful fragment ion indicators for garbage burning in ambient aerosol profiles. Finally, a framework for the identification of emission sources using the unit mass resolution organic mass fractions at m/z 55 (f 55), m/z 57 (f 57), and m/z 60 (f 60) is proposed in this work. Plotting the ratio of f 55 to f 57 versus f 60 is found to be effective for the identification of emissions by the fuel type and even useful in separating emissions of similar source types. Although the sample size was limited, these results give further context to the aerosol and gas-phase emission factors presented in other NAMaSTE works and provide a critical reference for future aerosol composition measurements in South Asia.

Detailed Investigation of the Contribution of Gas-Phase Air Contaminants to Exposure Risk during Indoor Activities.

Analytical capabilities in atmospheric chemistry provide new opportunities to investigate indoor air. HOMEChem was a chemically comprehensive indoor field campaign designed to investigate how common activities, such as cooking and cleaning, impacted indoor air in a test home. We combined gas-phase chemical data of all compounds, excluding those with concentrations <1 ppt, with established databases of health effect thresholds to evaluate potential risks associated with gas-phase air contaminants and indoor activities. The chemical composition of indoor air is distinct from outdoor air, with gaseous compounds present at higher levels and greater diversity─and thus greater predicted hazard quotients─indoors than outdoors. Common household activities like cooking and cleaning induce rapid changes in indoor air composition, raising levels of multiple compounds with high risk quotients. The HOMEChem data highlight how strongly human activities influence the air we breathe in the built environment, increasing the health risk associated with exposure to air contaminants.

Simulating indoor inorganic aerosols of outdoor origin with the inorganic aerosol thermodynamic equilibrium model ISORROPIA.

Outdoor aerosols can transform and have their composition altered upon transport indoors. Herein, IMAGES, a platform that simulates indoor organic aerosol with the 2-dimensional volatility basis set (2D-VBS), was extended to incorporate the inorganic aerosol thermodynamic equilibrium model, ISORROPIA. The model performance was evaluated by comparing aerosol component predictions to indoor measurements from an aerosol mass spectrometer taken during the summer and winter seasons. Since ammonia was not measured in the validation dataset, outdoor ammonia was estimated from aerosol measurements using a novel pH-based algorithm, while nitric acid was held constant. Modeled indoor ammonia sources included temperature-based occupant and surface emissions. Sensitivity to the nitric acid indoor surface deposition rate ß g , HNO 3 , g was explored by varying it in model runs, which did not affect modeled sulfate due to its non-volatile nature, though the fitting of a filter efficiency was required for good correlations of modeled sulfate with measurements in both seasons. Modeled summertime nitrate well-matched measured observations when ß g , HNO 3 , g = 2.75 h - 1 , but wintertime comparisons were poor, possibly due to missing thermodynamic processes within the heating, ventilating, and air-conditioning (HVAC) system. Ammonium was consistently overpredicted, potentially due to neglecting thirdhand smoke impacts observed in the field campaign, as well as HVAC impacts.

Source and Chemistry of Hydroxymethanesulfonate (HMS) in Fairbanks, Alaska.

Fairbanks, Alaska, is a subarctic city with fine particle (PM2.5) concentrations that exceed air quality regulations in winter due to weak dispersion caused by strong atmospheric inversions, local emissions, and the unique chemistry occurring under the cold and dark conditions. Here, we report on observations from the winters of 2020 and 2021, motivated by our pilot study that showed exceptionally high concentrations of fine particle hydroxymethanesulfonate (HMS) or related sulfur(IV) species (e.g., sulfite and bisulfite). We deployed online particle-into-liquid sampler-ion chromatography (PILS-IC) in conjunction with a suite of instruments to determine HMS precursors (HCHO, SO2) and aerosol composition in general, with the goal to characterize the sources and sinks of HMS in wintertime Fairbanks. PM2.5 HMS comprised a significant fraction of PM2.5 sulfur (26-41%) and overall PM2.5 mass concentration of 2.8-6.8% during pollution episodes, substantially higher than what has been observed in other regions, likely due to the exceptionally low temperatures. HMS peaked in January, with lower concentrations in December and February, resulting from changes in precursors and meteorological conditions. Strong correlations with inorganic sulfate and organic mass during pollution events suggest that HMS is linked to processes responsible for poor air quality episodes. These findings demonstrate unique aspects of air pollution formation in cold and humid atmospheres.

Contrasting Chemical Complexity and the Reactive Organic Carbon Budget of Indoor and Outdoor Air.

Reactive organic carbon (ROC) comprises a substantial fraction of the total atmospheric carbon budget. Emissions of ROC fuel atmospheric oxidation chemistry to produce secondary pollutants including ozone, carbon dioxide, and particulate matter. Compared to the outdoor atmosphere, the indoor organic carbon budget is comparatively understudied. We characterized indoor ROC in a test house during unoccupied, cooking, and cleaning scenarios using various online mass spectrometry and gas chromatography measurements of gaseous and particulate organics. Cooking greatly impacted indoor ROC concentrations and bulk physicochemical properties (e.g., volatility and oxidation state), while cleaning yielded relatively insubstantial changes. Additionally, cooking enhanced the reactivities of hydroxyl radicals and ozone toward indoor ROC. We observed consistently higher median ROC concentrations indoors (≥223 µg C m-3) compared to outdoors (54 µg C m-3), demonstrating that buildings can be a net source of reactive carbon to the outdoor atmosphere, following its removal by ventilation. We estimate the unoccupied test house emitted 0.7 g C day-1 from ROC to outdoors. Indoor ROC emissions may thus play an important role in air quality and secondary pollutant formation outdoors, particularly in urban and suburban areas, and indoors during the use of oxidant-generating air purifiers.

Indoor black carbon and brown carbon concentrations from cooking and outdoor penetration: insights from the HOMEChem study.

Particle emissions from cooking are a major contributor to residential indoor air pollution and could also contribute to ambient concentrations. An important constituent of these emissions is light-absorbing carbon, including black carbon (BC) and brown carbon (BrC). This work characterizes the contributions of indoor and outdoor sources of BC and BrC to the indoor environment by concurrently measuring real-time concentrations of these air pollutants indoors and outdoors during the month-long HOMEChem study. The median indoor-to-outdoor ratios of BC and BrC during the periods of no activity inside the test house were 0.6 and 0.7, respectively. The absorption Ångström exponent was used to characterize light-absorbing particle emissions during different activities and ranged from 1.1 to 2.7 throughout the campaign, with the highest value (indicative of BrC-dominated emissions) observed during the preparation of a simulated Thanksgiving Day holiday style meal. An indoor BC exposure assessment shows that exposure for an occupant present in the kitchen area was ∼4 times higher during Thanksgiving Day experiments (primarily due to candle burning) when compared to the background conditions.

Modeling the Removal of Water-Soluble Trace Gases from Indoor Air via Air Conditioner Condensate.

Water-soluble trace gas (WSTG) loss from indoor air via air conditioning (AC) units has been observed in several studies, but these results have been difficult to generalize. In the present study, we designed a box model that can be used to investigate and estimate WSTG removal due to partitioning to AC coil condensate. We compared the model output to measurements of a suite of organic acids cycling in an indoor environment and tested the model by varying the input AC parameters. These tests showed that WSTG loss via AC cycling is influenced by Henry's law constant of the compound in question, which is controlled by air and water temperatures and the condensate pH. Air conditioning unit specifications also impact WSTG loss through variations in the sensible heat ratio, the effective recirculation rate of air through the unit, and the timing of coil and fan operation. These findings have significant implications for indoor modeling. To accurately model the fate of indoor WSTGs, researchers must either measure or otherwise account for these unique environmental and operational characteristics.

Improving Predictions of Indoor Aerosol Concentrations of Outdoor Origin by Considering the Phase Change of Semivolatile Material Driven by Temperature and Mass-Loading Gradients.

Outdoor aerosols experience environmental changes as they are transported indoors, including outdoor-to-indoor temperature and mass-loading gradients, which can reduce or enhance their indoor concentrations due to repartitioning driven by changes in thermodynamic equilibrium states. However, the complexity required to model repartitioning typically hinders its inclusion in studies predicting indoor exposure to ambient aerosols. To facilitate exposure predictions, this work used an explicit thermodynamic indoor aerosol model to simulate outdoor-to-indoor aerosol repartitioning typical for residential and office buildings across the 16 U.S. climate zones over an annual time horizon. Results demonstrate that neglecting repartitioning when predicting indoor concentrations can produce errors of up to 80-100% for hydrocarbon-like organic aerosol, 40-60% for total organic aerosol, 400% for ammonium nitrate, and 60% (typically 3 µg/m3) for the total PM2.5 aerosol. Underpredictions were more likely for buildings in hotter than colder regions, and for residences than offices, since both cooler indoor air and more meaningful residential organic aerosol concentrations encourage condensation of semivolatile organics. Furthermore, a method for computing correction factors to more easily account for thermodynamic repartitioning is provided. Applying these correction factors to mechanical-only aerosol predictions significantly reduced errors to <0.5 µg/m3 for the total indoor PM2.5 while bypassing explicit thermodynamic simulations.

Emerging investigator series: chemical and physical properties of organic mixtures on indoor surfaces during HOMEChem.

Organic films on indoor surfaces serve as a medium for reactions and for partitioning of semi-volatile organic compounds and thus play an important role in indoor chemistry. However, the chemical and physical properties of these films are poorly characterized. Here, we investigate the chemical composition of an organic film collected during the HOMEChem campaign, over three cumulative weeks in the kitchen, using both Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) and offline Aerosol Mass Spectrometry (AMS). We also characterize the viscosity of this film using a model based on molecular formulas as well as poke-flow measurements. We find that the film contains organic material similar to cooking organic aerosol (COA) measured during the campaign using on-line AMS. However, the average molecular formula observed using FT-ICR MS is ∼C50H90O11, which is larger and more oxidized than fresh COA. Solvent extracted film material is a low viscous semisolid, with a measured viscosity <104 Pa s. This is much lower than the viscosity model predicts, which is parametrized with atmospherically relevant organic molecules, but sensitivity tests demonstrate that including unsaturation can explain the differences. The presence of unsaturation is supported by reactions of film material with ozone. In contrast to the solvent extract, manually removed material appears to be highly viscous, highlighting the need for continued work understanding both viscosity measurements as well as parameterizations for modeled viscosity of indoor organic films.

Urban Emissions of Nitrogen Oxides, Carbon Monoxide, and Methane Determined from Ground-Based Measurements in Philadelphia.

Nitrogen oxides (NOX) and methane impact air quality through the promotion of ozone formation, and methane is also a strong greenhouse gas. Despite the importance of these pollutants, emissions in urban areas are poorly quantified. We present measurements of NOX, CH4, CO, and CO2 made at Drexel University in Philadelphia along with NOX and CO observations at two roadside monitors. Because CO2 concentrations in the winter result almost entirely from combustion with negligible influence from photosynthesis and respiration, we are able to infer fleet-averaged fuel-based emission factors (EFs) for NOX and CO, similar in some ways to how EFs are determined from tunnel studies. Comparison of the inferred NOX and CO fuel-based EF to the National Emissions Inventory (NEI) suggests errors in NEI emissions of either NOX, CO, or both. From the measurements of CH4 and CO2, which are not emitted by the same sources, we infer the ratio of CH4 emissions (from leaks in the natural gas infrastructure) to CO2 emissions (from fossil fuel combustion) in Philadelphia. Comparison of the CH4/CO2 emission ratios to emission inventories from the Environmental Protection Agency suggests underestimates in CH4 emissions by almost a factor of 4. These results demonstrate the need for the addition of long-term observations of CH4 and CO2 to existing monitoring networks in urban areas to better constrain emissions and complement existing measurements of NOX and CO.

Spatial and temporal scales of variability for indoor air constituents.

Historically air constituents have been assumed to be well mixed in indoor environments, with single point measurements and box modeling representing a room or a house. Here we demonstrate that this fundamental assumption needs to be revisited through advanced model simulations and extensive measurements of bleach cleaning. We show that inorganic chlorinated products, such as hypochlorous acid and chloramines generated via multiphase reactions, exhibit spatial and vertical concentration gradients in a room, with short-lived ⋅OH radicals confined to sunlit zones, close to windows. Spatial and temporal scales of indoor constituents are modulated by rates of chemical reactions, surface interactions and building ventilation, providing critical insights for better assessments of human exposure to hazardous pollutants, as well as the transport of indoor chemicals outdoors.

Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry.

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.