A causal machine-learning framework for studying policy impact on air pollution: A case-study in COVID-19 lockdowns.

When studying the impact of policy interventions or natural experiments on air pollution, such as new environmental policies and opening or closing an industrial facility, careful statistical analysis is needed to separate causal changes from other confounding factors. Using COVID-19 lockdowns as a case-study, we present a comprehensive framework for estimating and validating causal changes from such perturbations. We propose using flexible machine learning-based comparative interrupted time series (CITS) models for estimating such a causal effect. We outline the assumptions required to identify causal effects, showing that many common methods rely on strong assumptions that are relaxed by machine learning models. For empirical validation, we also propose a simple diagnostic criterion, guarding against false effects in baseline years when there was no intervention. The framework is applied to study the impact of COVID-19 lockdowns on NO2 in the eastern US. The machine learning approaches guard against false effects better than common methods and suggest decreases in NO2 in Boston, New York City, Baltimore, and Washington D.C. The study showcases the importance of our validation framework in selecting a suitable method and the utility of a machine learning based CITS model for studying causal changes in air pollution time series.

Policy-Related Gains in Urban Air Quality May Be Offset by Increased Emissions in a Warming Climate.

Air quality policies have made substantial gains by reducing pollutant emissions from the transportation sector. In March 2020, New York City's activities were severely curtailed in response to the COVID-19 pandemic, resulting in 60-90% reductions in human activity. We continuously measured major volatile organic compounds (VOCs) during January-April 2020 and 2021 in Manhattan. Concentrations of many VOCs decreased significantly during the shutdown with variations in daily patterns reflective of human activity perturbations, resulting in a temporary ∼28% reduction in chemical reactivity. However, the limited effect of these dramatic measures was outweighed by larger increases in VOC-related reactivity during the anomalously warm spring 2021. This emphasizes the diminishing returns from transportation-focused policies alone and the risk of increased temperature-dependent emissions undermining policy-related gains in a warming climate.

Primary and Secondary Organic Aerosol Formation from Asphalt Pavements.

Asphalt is ubiquitous across cities and a source of organic compounds spanning a wide range of volatility and may be an overlooked source of urban organic aerosols. The emission rate and composition depend strongly on temperature, but emissions have been observed at both application temperatures and surface temperatures during warm sunny days. Here we report primary organic aerosol (POA) emissions and secondary organic aerosol (SOA) production from asphalt. We reheated real-world asphalt samples to application-relevant temperatures (∼130 °C) and typical summertime road-surface temperatures (∼55 °C) and then flushed the emitted vapors into an environmental oxidation chamber containing ammonium sulfate seed particles. SOA was then formed following the photo-oxidation of emissions under high-NOx conditions typical of urban atmospheres. We find that POA only forms at application temperature as it does not require further oxidation, whereas SOA forms under both conditions; with the resulting POA and SOA both being semi-volatile. While total OA formation rates were substantially greater under the limited time spent under application conditions, SOA formation from passive asphalt heating presents a potential long-term source, as heating continues for the lifetime of the road surface. This suggests that persistent asphalt solar heating is likely a considerable and continued source of summertime SOA in urban environments.

Oxidized and Unsaturated: Key Organic Aerosol Traits Associated with Cellular Reactive Oxygen Species Production in the Southeastern United States.

Exposure to ambient fine particulate matter (PM2.5) is associated with millions of premature deaths annually. Oxidative stress through overproduction of reactive oxygen species (ROS) is a possible mechanism for PM2.5-induced health effects. Organic aerosol (OA) is a dominant component of PM2.5 worldwide, yet its role in PM2.5 toxicity is poorly understood due to its chemical complexity. Here, through integrated cellular ROS measurements and detailed multi-instrument chemical characterization of PM in urban southeastern United States, we show that oxygenated OA (OOA), especially more-oxidized OOA, is the main OA type associated with cellular ROS production. We further reveal that highly unsaturated species containing carbon-oxygen double bonds and aromatic rings in OOA are major contributors to cellular ROS production. These results highlight the key chemical features of ambient OA driving its toxicity. As more-oxidized OOA is ubiquitous and abundant in the atmosphere, this emphasizes the need to understand its sources and chemical processing when formulating effective strategies to mitigate PM2.5 health impacts.

Evaluation of Calibration Approaches for Indoor Deployments of PurpleAir Monitors.

Low-cost air quality monitors are growing in popularity among both researchers and community members to understand variability in pollutant concentrations. Several studies have produced calibration approaches for these sensors for ambient air. These calibrations have been shown to depend primarily on relative humidity, particle size distribution, and particle composition, which may be different in indoor environments. However, despite the fact that most people spend the majority of their time indoors, little is known about the accuracy of commonly used devices indoors. This stems from the fact that calibration data for sensors operating in indoor environments are rare. In this study, we sought to evaluate the accuracy of the raw data from PurpleAir fine particulate matter monitors and for published calibration approaches that vary in complexity, ranging from simply applying linear corrections to those requiring co-locating a filter sample for correction with a gravimetric concentration during a baseline visit. Our data includes PurpleAir devices that were co-located in each home with a gravimetric sample for 1-week periods (265 samples from 151 homes). Weekly-averaged gravimetric concentrations ranged between the limit of detection (3 µg/m3) and 330 µg/m3. We found a strong correlation between the PurpleAir monitor and the gravimetric concentration (R>0.91) using internal calibrations provided by the manufacturer. However, the PurpleAir data substantially overestimated indoor concentrations compared to the gravimetric concentration (mean bias error ≥ 23.6 µg/m3 using internal calibrations provided by the manufacturer). Calibrations based on ambient air data maintained high correlations (R ≥ 0.92) and substantially reduced bias (e.g. mean bias error = 10.1 µg/m3 using a US-wide calibration approach). Using a gravimetric sample from a baseline visit to calibrate data for later visits led to an improvement over the internal calibrations, but performed worse than the simpler calibration approaches based on ambient air pollution data. Furthermore, calibrations based on ambient air pollution data performed best when weekly-averaged concentrations did not exceed 30 µg/m3, likely because the majority of the data used to train these models were below this concentration.

Limited Secondary Organic Aerosol Production from Acyclic Oxygenated Volatile Chemical Products.

Volatile chemical products (VCPs) have recently been identified as potentially important unconventional sources of secondary organic aerosol (SOA), in part due to the mitigation of conventional emissions such as vehicle exhaust. Here, we report measurements of SOA production in an oxidation flow reactor from a series of common VCPs containing oxygenated functional groups and at least one oxygen within the molecular backbone. These include two oxygenated aromatic species (phenoxyethanol and 1-phenoxy-2-propanol), two esters (butyl butyrate and butyl acetate), and four glycol ethers (carbitol, methyl carbitol, butyl carbitol, and hexyl carbitol). We measured gas- and particle-phase products with a suite of mass spectrometers and particle-sizing instruments. Only the aromatic VCPs produce SOA with substantial yields. For the acyclic VCPs, ether and ester functionality promotes fragmentation and hinders autoxidation, whereas aromatic rings drive SOA formation in spite of the presence of ether groups. Therefore, our results suggest that a potential strategy to reduce urban SOA from VCPs would be to reformulate consumer products to include less oxygenated aromatic compounds.

Oil sands operations as a large source of secondary organic aerosols.

Worldwide heavy oil and bitumen deposits amount to 9 trillion barrels of oil distributed in over 280 basins around the world, with Canada home to oil sands deposits of 1.7 trillion barrels. The global development of this resource and the increase in oil production from oil sands has caused environmental concerns over the presence of toxic compounds in nearby ecosystems and acid deposition. The contribution of oil sands exploration to secondary organic aerosol formation, an important component of atmospheric particulate matter that affects air quality and climate, remains poorly understood. Here we use data from airborne measurements over the Canadian oil sands, laboratory experiments and a box-model study to provide a quantitative assessment of the magnitude of secondary organic aerosol production from oil sands emissions. We find that the evaporation and atmospheric oxidation of low-volatility organic vapours from the mined oil sands material is directly responsible for the majority of the observed secondary organic aerosol mass. The resultant production rates of 45-84 tonnes per day make the oil sands one of the largest sources of anthropogenic secondary organic aerosols in North America. Heavy oil and bitumen account for over ten per cent of global oil production today, and this figure continues to grow. Our findings suggest that the production of the more viscous crude oils could be a large source of secondary organic aerosols in many production and refining regions worldwide, and that such production should be considered when assessing the environmental impacts of current and planned bitumen and heavy oil extraction projects globally.

Development and Performance Evaluation of a Low-Cost Portable PM2.5 Monitor for Mobile Deployment.

The concentration of fine particulate matter (PM2.5) is known to vary spatially across a city landscape. Current networks of regulatory air quality monitoring are too sparse to capture these intra-city variations. In this study, we developed a low-cost (60 USD) portable PM2.5 monitor called Smart-P, for use on bicycles, with the goal of mapping street-level variations in PM2.5 concentration. The Smart-P is compact in size (85 × 85 × 42 mm) and light in weight (147 g). Data communication and geolocation are achieved with the cyclist's smartphone with the help of a user-friendly app. Good agreement was observed between the Smart-P monitors and a regulatory-grade monitor (mean bias error: −3.0 to 1.5 µg m−3 for the four monitors tested) in ambient conditions with relative humidity ranging from 38 to 100%. Monitor performance decreased in humidity > 70% condition. The measurement precision, represented as coefficient of variation, was 6 to 9% in stationary mode and 6% in biking mode across the four tested monitors. Street tests in a city with low background PM2.5 concentrations (8 to 9 µg m−3) and in two cities with high background concentrations (41 to 74 µg m−3) showed that the Smart-P was capable of observing local emission hotspots and that its measurement was not sensitive to bicycle speed. The low-cost and user-friendly nature are two features that make the Smart-P a good choice for empowering citizen scientists to participate in local air quality monitoring.

Evaluating Indoor Air Chemical Diversity, Indoor-to-Outdoor Emissions, and Surface Reservoirs Using High-Resolution Mass Spectrometry.

Detailed offline speciation of gas- and particle-phase organic compounds was conducted using gas/liquid chromatography with traditional and high-resolution mass spectrometers in a hybrid targeted/nontargeted analysis. Observations were focused on an unoccupied home and were compared to two other indoor sites. Observed gas-phase organic compounds span the volatile to semivolatile range, while functionalized organic aerosols extend from intermediate volatility to ultra-low volatility, including a mix of oxygen, nitrogen, and sulfur-containing species. Total gas-phase abundances of hydrocarbon and oxygenated gas-phase complex mixtures were elevated indoors and strongly correlated in the unoccupied home. While gas-phase concentrations of individual compounds generally decreased slightly with greater ventilation, their elevated ratios relative to controlled emissions of tracer species suggest that the dilution of gas-phase concentrations increases off-gassing from surfaces and other indoor reservoirs, with volatility-dependent responses to dynamically changing environmental factors. Indoor-outdoor emissions of gas-phase intermediate-volatility/semivolatile organic hydrocarbons from the unoccupied home averaged 6-11 mg h-1, doubling with ventilation. While the largest single-compound emissions observed were furfural (61-275 mg h-1) and acetic acid, observations spanned a wide range of individual volatile chemical products (e.g., terpenoids, glycol ethers, phthalates, other oxygenates), highlighting the abundance of long-lived reservoirs resulting from prior indoor use or materials, and their gradual transport outdoors.

Waste Containment Ponds Are a Major Source of Secondary Organic Aerosol Precursors from Oil Sands Operations.

The surface mining and bitumen extraction of oil sands (OS) generates over one million barrels of heavy oil each day in the Alberta Oil Sands Region of Canada. Recent observations suggest that emissions from OS development contribute to secondary organic aerosol (SOA) formation, but the chemical composition, mass fluxes, and sources of those emissions are poorly delineated. Here, we simulated OS extraction and used comprehensive two-dimensional gas chromatography to quantify and characterize direct air emissions, bitumen froth, residual wastewater, and tailings components, ultimately enabling fate modeling of over 1500 chromatographic features simultaneously. During the non-ice cover season, tailings ponds emissions contributed 15 000-72 000 metric tonnes of hydrocarbon SOA precursors, translating to 3000-13 000 tonnes of SOA, whereas direct emissions during the extraction process itself were notably smaller (960 ± 500 tonnes SOA yr-1). These results suggest that tailings pond waste management practices should be targeted to reduce environmental emissions.

Statistical field calibration of a low-cost PM2.5 monitoring network in Baltimore.

Low-cost air pollution monitors are increasingly being deployed to enrich knowledge about ambient air-pollution at high spatial and temporal resolutions. However, unlike regulatory-grade (FEM or FRM) instruments, universal quality standards for low-cost sensors are yet to be established and their data quality varies widely. This mandates thorough evaluation and calibration before any responsible use of such data. This study presents evaluation and field-calibration of the PM2.5 data from a network of low-cost monitors currently operating in Baltimore, MD, which has only one regulatory PM2.5 monitoring site within city limits. Co-location analysis at this regulatory site in Oldtown, Baltimore revealed high variability and significant overestimation of PM2.5 levels by the raw data from these monitors. Universal laboratory corrections reduced the bias in the data, but only partially mitigated the high variability. Eight months of field co-location data at Oldtown were used to develop a gain-offset calibration model, recast as a multiple linear regression. The statistical model offered substantial improvement in prediction quality over the raw or lab-corrected data. The results were robust to the choice of the low-cost monitor used for field-calibration, as well as to different seasonal choices of training period. The raw, lab-corrected and statistically-calibrated data were evaluated for a period of two months following the training period. The statistical model had the highest agreement with the reference data, producing a 24-hour average root-mean-square-error (RMSE) of around 2 µg m -3. To assess transferability of the calibration equations to other monitors in the network, a cross-site evaluation was conducted at a second co-location site in suburban Essex, MD. The statistically calibrated data once again produced the lowest RMSE. The calibrated PM2.5 readings from the monitors in the low-cost network provided insights into the intra-urban spatiotemporal variations of PM2.5 in Baltimore.

Compact, Automated, Inexpensive, and Field-Deployable Vacuum-Outlet Gas Chromatograph for Trace-Concentration Gas-Phase Organic Compounds.

The identification and quantification of gas-phase organic compounds, such as volatile organic compounds (VOCs), frequently use gas chromatography (GC), which typically requires high-purity compressed gases. We have developed a new instrument for trace-concentration measurements of VOCs and intermediate-volatility compounds of up to 14 carbon atoms in a fully automated (computer-free), independent, low-cost, compact GC-based system for the quantitative analysis of complex mixtures without the need for compressed, high-purity gases or expensive detectors. Through adsorptive analyte preconcentration, vacuum GC, photoionization detectors, and need-based water-vapor control, we enable sensitive and selective measurements with picogram-level limits of detection (i.e., under 15 ppt in a 4 L sample for most compounds). We validate performance against a commercial pressurized GC, including resolving challenging isomers of similar volatility, such as ethylbenzene and  m/ p-xylene. We employ vacuum GC across the whole column with filtered air as a carrier gas, producing long-term system stability and performance over a wide range of analytes. Through theory and experiments, we present variations in analyte diffusivities in the mobile phase, analyte elution temperatures, optimal linear velocities, and separation-plate heights with vacuum GC in air at different pressures, and we optimize our instrument to exploit these differences. At 2-6 psia, the molecular diffusion coefficients are 6.4-2.1 times larger and the elution temperatures are 39-92 °C lower than with pressurized GC with helium (at 30 psig) depending on the molecular structure, and we find a wide range of optimal linear velocities (up to 60 cm s-1) that are faster with broader tolerances than with pressurized-N2 GC.

Effects of Molecular-Level Compositional Variability in Organic Aerosol on Phase State and Thermodynamic Mixing Behavior.

The molecular-level composition and structure of organic aerosol (OA) affect its chemical/physical properties, transformations, and impacts. Here, we use the molecular-level chemical composition of functionalized OA from three diverse field sites to evaluate the effect of molecular-level compositional variability on OA phase state and thermodynamic mixing favorability. For these ambient sites, modeled aerosol phase state ranges from liquid to semisolid. The observed variability in OA composition has some effect on resulting phase state, but other factors like the presence of inorganic ions, aerosol liquid water, and internal versus external mixing with water are determining factors in whether these particles exist as liquids, semisolids, or solids. Organic molecular composition plays a more important role in determining phase state for phase-separated (verus well-mixed) systems. Similarly, despite the observed OA compositional differences, the thermodynamic mixing favorability for OA samples with aerosol liquid water, isoprene oxidation products, or monoterpene oxidation products remains fairly consistent within each campaign. Mixing of filter-sampled OA and isoprene or monoterpene oxidation products is often favorable in both seasons, while mixing with water is generally unfavorable.

Bouncier Particles at Night: Biogenic Secondary Organic Aerosol Chemistry and Sulfate Drive Diel Variations in the Aerosol Phase in a Mixed Forest.

Aerosol phase state is critical for quantifying aerosol effects on climate and air quality. However, significant challenges remain in our ability to predict and quantify phase state during its evolution in the atmosphere. Herein, we demonstrate that aerosol phase (liquid, semisolid, solid) exhibits a diel cycle in a mixed forest environment, oscillating between a viscous, semisolid phase state at night and liquid phase state with phase separation during the day. The viscous nighttime particles existed despite higher relative humidity and were independently confirmed by bounce factor measurements and atomic force microscopy. High-resolution mass spectrometry shows the more viscous phase state at night is impacted by the formation of terpene-derived and higher molecular weight secondary organic aerosol (SOA) and smaller inorganic sulfate mass fractions. Larger daytime particulate sulfate mass fractions, as well as a predominance of lower molecular weight isoprene-derived SOA, lead to the liquid state of the daytime particles and phase separation after greater uptake of liquid water, despite the lower daytime relative humidity. The observed diel cycle of aerosol phase should provoke rethinking of the SOA atmospheric lifecycle, as it suggests diurnal variability in gas-particle partitioning and mixing time scales, which influence aerosol multiphase chemistry, lifetime, and climate impacts.

Review of Urban Secondary Organic Aerosol Formation from Gasoline and Diesel Motor Vehicle Emissions.

Secondary organic aerosol (SOA) is formed from the atmospheric oxidation of gas-phase organic compounds leading to the formation of particle mass. Gasoline- and diesel-powered motor vehicles, both on/off-road, are important sources of SOA precursors. They emit complex mixtures of gas-phase organic compounds that vary in volatility and molecular structure-factors that influence their contributions to urban SOA. However, the relative importance of each vehicle type with respect to SOA formation remains unclear due to conflicting evidence from recent laboratory, field, and modeling studies. Both are likely important, with evolving contributions that vary with location and over short time scales. This review summarizes evidence, research needs, and discrepancies between top-down and bottom-up approaches used to estimate SOA from motor vehicles, focusing on inconsistencies between molecular-level understanding and regional observations. The effect of emission controls (e.g., exhaust aftertreatment technologies, fuel formulation) on SOA precursor emissions needs comprehensive evaluation, especially with international perspective given heterogeneity in regulations and technology penetration. Novel studies are needed to identify and quantify "missing" emissions that appear to contribute substantially to SOA production, especially in gasoline vehicles with the most advanced aftertreatment. Initial evidence suggests catalyzed diesel particulate filters greatly reduce emissions of SOA precursors along with primary aerosol.

Ethylene glycol emissions from on-road vehicles.

Ethylene glycol (HOCH2CH2OH), used as engine coolant for most on-road vehicles, is an intermediate volatility organic compound (IVOC) with a high Henry's law coefficient. We present measurements of ethylene glycol (EG) vapor in the Caldecott Tunnel near San Francisco, using a proton transfer reaction mass spectrometer (PTR-MS). Ethylene glycol was detected at mass-to-charge ratio 45, usually interpreted as solely coming from acetaldehyde. EG concentrations in bore 1 of the Caldecott Tunnel, which has a 4% uphill grade, were characterized by infrequent (approximately once per day) events with concentrations exceeding 10 times the average concentration, likely from vehicles with malfunctioning engine coolant systems. Limited measurements in tunnels near Houston and Boston are not conclusive regarding the presence of EG in sampled air. Previous PTR-MS measurements in urban areas may have overestimated acetaldehyde concentrations at times due to this interference by ethylene glycol. Estimates of EG emission rates from the Caldecott Tunnel data are unrealistically high, suggesting that the Caldecott data are not representative of emissions on a national or global scale. EG emissions are potentially important because they can lead to the formation of secondary organic aerosol following oxidation in the atmospheric aqueous phase.

Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions.

Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to secondary organic aerosol (SOA) in urban areas. Their relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region's fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies.

Lubricating oil dominates primary organic aerosol emissions from motor vehicles.

Motor vehicles are major sources of primary organic aerosol (POA), which is a mixture of a large number of organic compounds that have not been comprehensively characterized. In this work, we apply a recently developed gas chromatography mass spectrometry approach utilizing "soft" vacuum ultraviolet photoionization to achieve unprecedented chemical characterization of motor vehicle POA emissions in a roadway tunnel with a mass closure of >60%. The observed POA was characterized by number of carbon atoms (NC), number of double bond equivalents (NDBE) and degree of molecular branching. Vehicular POA was observed to predominantly contain cycloalkanes with one or more rings and one or more branched alkyl side chains (≥80%) with low abundances of n-alkanes and aromatics (<5%), similar to "fresh" lubricating oil. The gas chromatography retention time data indicates that the cycloalkane ring structures are most likely dominated by cyclohexane and cyclopentane rings and not larger cycloalkanes. High molecular weight combustion byproducts, that is, alkenes, oxygenates, and aromatics, were not present in significant amounts. The observed carbon number and chemical composition of motor vehicle POA was consistent with lubricating oil being the dominant source from both gasoline and diesel-powered vehicles, with an additional smaller contribution from unburned diesel fuel and a negligible contribution from unburned gasoline.

Total organic carbon measurements reveal major gaps in petrochemical emissions reporting.

Anthropogenic organic carbon emissions reporting has been largely limited to subsets of chemically speciated volatile organic compounds. However, new aircraft-based measurements revealed total gas-phase organic carbon emissions that exceed oil sands industry-reported values by 1900% to over 6300%, the bulk of which was due to unaccounted-for intermediate-volatility and semivolatile organic compounds. Measured facility-wide emissions represented approximately 1% of extracted petroleum, resulting in total organic carbon emissions equivalent to that from all other sources across Canada combined. These real-world observations demonstrate total organic carbon measurements as a means of detecting unknown or underreported carbon emissions regardless of chemical features. Because reporting gaps may include hazardous, reactive, or secondary air pollutants, fully constraining the impact of anthropogenic emissions necessitates routine, comprehensive total organic carbon monitoring as an inherent check on mass closure.

Long-term trends in motor vehicle emissions in u.s. urban areas.

A fuel-based approach is used to estimate long-term trends (1990-2010) in carbon monoxide (CO) emissions from motor vehicles. Non-methane hydrocarbons (NMHC) are estimated using ambient NMHC/CO ratios after controlling for nonvehicular sources. Despite increases in fuel use of ∼10-40%, CO running exhaust emissions from on-road vehicles decreased by ∼80-90% in Los Angeles, Houston, and New York City, between 1990 and 2010. The ratio of NMHC/CO was found to be 0.24 ± 0.04 mol C/mol CO over time in Los Angeles, indicating that both pollutants decreased at a similar rate and were improved by similar emission controls, whereas on-road data from other cities suggest rates of reduction in NMHC versus CO emissions may differ somewhat. Emission ratios of CO/NOx (nitrogen oxides = NO + NO2) and NMHC/NOx decreased by a factor of ∼4 between 1990 and 2007 due to changes in the relative emission rates of passenger cars versus diesel trucks, and slight uptick thereafter, consistent across all urban areas considered here. These pollutant ratios are expected to increase in future years due to (1) slowing rates of decrease in CO and NMHC emissions from gasoline vehicles and (2) significant advances in control of diesel NOx emissions.