Sensitivity of air quality to vehicle ammonia emissions in the United States.

The US Environmental Protection Agency (EPA) estimates on-road vehicles emissions using the Motor Vehicle Emission Simulator (MOVES). We developed updated ammonia emission rates for MOVES based on road-side exhaust emission measurements of light-duty gasoline and heavy-duty diesel vehicles. The resulting nationwide on-road vehicle ammonia emissions are 1.8, 2.1, 1.8, and 1.6 times higher than the MOVES3 estimates for calendar years 2010, 2017, 2024, and 2035, respectively, primarily due to an increase in light-duty gasoline vehicle NH3 emission rates. We conducted an air quality simulation using the Community Multi-Scale Air Quality (CMAQv5.3.2) model to evaluate the sensitivity of modeled ammonia and fine particulate matter (PM2.5) concentrations in calendar year 2017 using the updated on-road vehicle ammonia emissions. The average monthly urban ammonia ambient concentrations increased by up to 2.3 ppbv in January and 3.0 ppbv in July. The updated on-road NH3 emission rates resulted in better agreement of modeled ammonia concentrations with 2017 annual average ambient ammonia measurements, reducing model bias by 5.8 % in the Northeast region. Modeled average winter PM2.5 concentrations increased in urban areas, including enhancements of up to 0.5 µg/m3 in the northeast United States. The updated ammonia emission rates have been incorporated in MOVES4 and will be used in future versions of the NEI and EPA's modeling platforms.

Secondary Organic Aerosol Formation from Volatile Chemical Product Emissions: Model Parameters and Contributions to Anthropogenic Aerosol.

Volatile chemical products (VCP) are an increasingly important source of hydrocarbon and oxygenated volatile organic compound (OVOC) emissions to the atmosphere, and these emissions are likely to play an important role as anthropogenic precursors for secondary organic aerosol (SOA). While the SOA from VCP hydrocarbons is often accounted for in models, the formation, evolution, and properties of SOA from VCP OVOCs remain uncertain. We use environmental chamber data and a kinetic model to develop SOA parameters for 10 OVOCs representing glycols, glycol ethers, esters, oxygenated aromatics, and amines. Model simulations suggest that the SOA mass yields for these OVOCs are of the same magnitude as widely studied SOA precursors (e.g., long-chain alkanes, monoterpenes, and single-ring aromatics), and these yields exhibit a linear correlation with the carbon number of the precursor. When combined with emissions inventories for two megacities in the United States (US) and a US-wide inventory, we find that VCP VOCs react with OH to form 0.8-2.5× as much SOA, by mass, as mobile sources. Hydrocarbons (terpenes, branched and cyclic alkanes) and OVOCs (terpenoids, glycols, glycol ethers) make up 60-75 and 25-40% of the SOA arising from VCP use, respectively. This work contributes to the growing body of knowledge focused on studying VCP VOC contributions to urban air pollution.

2002-2017 anthropogenic emissions data for air quality modeling over the United States.

The United States Environmental Protection Agency (US EPA) has developed a set of annual North American emissions data for multiple air pollutants across 18 broad source categories for 2002 through 2017. The sixteen new annual emissions inventories were developed using consistent input data and methods across all years. When a consistent method or tool was not available for a source category, emissions were estimated by scaling data from the EPA's 2017 National Emissions Inventory with scaling factors based on activity data and/or emissions control information. The emissions datasets are designed to support regional air quality modeling for a wide variety of human health and ecological applications. The data were developed to support simulations of the EPA's Community Multiscale Air Quality model but can also be used by other regional scale air quality models. The emissions data are one component of EPA's Air Quality Time Series Project which also includes air quality modeling inputs (meteorology, initial conditions, boundary conditions) and outputs (e.g., ozone, PM2.5 and constituent species, wet and dry deposition) for the Conterminous US at a 12 km horizontal grid spacing.

Reactive organic carbon air emissions from mobile sources in the United States.

Mobile sources are responsible for a substantial controllable portion of the reactive organic carbon (ROC) emitted to the atmosphere, especially in urban environments of the United States. We update existing methods for calculating mobile source organic particle and vapor emissions in the United States with over a decade of laboratory data that parameterize the volatility and organic aerosol (OA) potential of emissions from on-road vehicles, nonroad engines, aircraft, marine vessels, and locomotives. We find that existing emission factor information from Teflon filters combined with quartz filters collapses into simple relationships and can be used to reconstruct the complete volatility distribution of ROC emissions. This new approach consists of source-specific filter artifact corrections and state-of-the-science speciation including explicit intermediate-volatility organic compounds (IVOCs), yielding the first bottom-up volatility-resolved inventory of US mobile source emissions. Using the Community Multiscale Air Quality model, we estimate mobile sources account for 20 %-25 % of the IVOC concentrations and 4.4 %-21.4 % of ambient OA. The updated emissions and air quality model reduce biases in predicting fine-particle organic carbon in winter, spring, and autumn throughout the United States (4.3 %-11.3 % reduction in normalized bias). We identify key uncertain parameters that align with current state-of-the-art research measurement challenges.

Human-health impacts of controlling secondary air pollution precursors.

Exposure to ozone and fine particle (PM2.5) air pollution results in premature death. These pollutants are predominantly secondary in nature and can form from nitrogen oxides (NOX), sulfur oxides (SOX), and volatile organic compounds (VOCs). Predicted health benefits for emission reduction scenarios often incompletely account for VOCs as precursors as well as the secondary organic aerosol (SOA) component of PM2.5. Here, we show that anthropogenic VOC emission reductions are more than twice as effective as equivalent fractional reductions of SOX or NOX at reducing air pollution-associated cardiorespiratory mortality in the United States. A 25% reduction in anthropogenic VOC emissions from 2016 levels is predicted to avoid 13,000 premature deaths per year, and most (85%) of the VOC-reduction benefits result from reduced SOA with the remainder from ozone. While NOX (-5.7 ± 0.2 % yr-1) and SOX (-12 ± 1 % yr-1) emissions have declined precipitously across the U.S. since 2002, anthropogenic VOC emissions (-1.8 ± 0.3 % yr-1) and concentrations of non-methane organic carbon (-2.4 ± 1.0 % yr-1) have changed less. This work indicates preferentially controlling VOCs could yield significant benefits to human health.

Volatile Chemical Product Enhancements to Criteria Pollutants in the United States.

Volatile chemical products (VCPs) are a significant source of reactive organic carbon emissions in the United States with a substantial fraction (>20% by mass) serving as secondary organic aerosol (SOA) precursors. Here, we incorporate a new nationwide VCP inventory into the Community Multiscale Air Quality (CMAQ) model with VCP-specific updates to better model air quality impacts. Model results indicate that VCPs mostly enhance anthropogenic SOA in densely populated areas with population-weighted annual average SOA increasing 15-30% in Southern California and New York City due to VCP emissions (contribution of 0.2-0.5 µg m-3). Annually, VCP emissions enhance total population-weighted PM2.5 by ∼5% in California, ∼3% in New York, New Jersey, and Connecticut, and 1-2% in most other states. While the maximum daily 8 h ozone enhancements from VCP emissions are more modest, their influence can cause a several ppb increase on select days in major cities. Printing Inks, Cleaning Products, and Paints and Coatings product use categories contribute ∼75% to the modeled VCP-derived SOA and Cleaning Products, Paints and Coatings, and Personal Care Products contribute ∼81% to the modeled VCP-derived ozone. Overall, VCPs enhance multiple criteria pollutants throughout the United States with the largest impacts in urban cores.

Secondary organic aerosol association with cardiorespiratory disease mortality in the United States.

Fine particle pollution, PM2.5, is associated with increased risk of death from cardiorespiratory diseases. A multidecadal shift in the United States (U.S.) PM2.5 composition towards organic aerosol as well as advances in predictive algorithms for secondary organic aerosol (SOA) allows for novel examinations of the role of PM2.5 components on mortality. Here we show SOA is strongly associated with county-level cardiorespiratory death rates in the U.S. independent of the total PM2.5 mass association with the largest associations located in the southeastern U.S. Compared to PM2.5, county-level variability in SOA across the U.S. is associated with 3.5× greater per capita county-level cardiorespiratory mortality. On a per mass basis, SOA is associated with a 6.5× higher rate of mortality than PM2.5, and biogenic and anthropogenic carbon sources both play a role in the overall SOA association with mortality. Our results suggest reducing the health impacts of PM2.5 requires consideration of SOA.

Reactive organic carbon emissions from volatile chemical products.

Volatile chemical products (VCPs) are an increasingly important source of anthropogenic reactive organic carbon (ROC) emissions. Among these sources are everyday items, such as personal care products, general cleaners, architectural coatings, pesticides, adhesives, and printing inks. Here, we develop VCPy, a new framework to model organic emissions from VCPs throughout the United States, including spatial allocation to regional and local scales. Evaporation of a species from a VCP mixture in the VCPy framework is a function of the compound-specific physiochemical properties that govern volatilization and the timescale relevant for product evaporation. We introduce two terms to describe these processes: evaporation timescale and use timescale. Using this framework, predicted national per capita organic emissions from VCPs are 9.5 kg per person per year (6.4 kg C per person per year) for 2016, which translates to 3.05 Tg (2.06 Tg C), making VCPs a dominant source of anthropogenic organic emissions in the United States. Uncertainty associated with this framework and sensitivity to select parameters were characterized through Monte Carlo analysis, resulting in a 95 % confidence interval of national VCP emissions for 2016 of 2.61-3.53 Tg (1.76-2.38 Tg C). This nationwide total is broadly consistent with the U.S. EPA's 2017 National Emission Inventory (NEI); however, county-level and categorical estimates can differ substantially from NEI values. VCPy predicts higher VCP emissions than the NEI for approximately half of all counties, with 5 % of all counties having greater than 55 % higher emissions. Categorically, application of the VCPy framework yields higher emissions for personal care products (150 %) and paints and coatings (25 %) when compared to the NEI, whereas pesticides (-54 %) and printing inks (-13 %) feature lower emissions. An observational evaluation indicates emissions of key species from VCPs are reproduced with high fidelity using the VCPy framework (normalized mean bias of -13 % with r =0.95). Sector-wide, the effective secondary organic aerosol yield and maximum incremental reactivity of VCPs are 5.3 % by mass and 1.58 gO3 g-1, respectively, indicating VCPs are an important, and likely to date underrepresented, source of secondary pollution in urban environments.

Modeling secondary organic aerosol formation from volatile chemical products.

Volatile chemical products (VCPs) are commonly-used consumer and industrial items that are an important source of anthropogenic emissions. Organic compounds from VCPs evaporate on atmospherically relevant time scales and include many species that are secondary organic aerosol (SOA) precursors. However, the chemistry leading to SOA, particularly that of intermediate volatility organic compounds (IVOCs), has not been fully represented in regional-scale models such as the Community Multiscale Air Quality (CMAQ) model, which tend to underpredict SOA concentrations in urban areas. Here we develop a model to represent SOA formation from VCP emissions. The model incorporates a new VCP emissions inventory and employs three new classes of emissions: siloxanes, oxygenated IVOCs, and nonoxygenated IVOCs. VCPs are estimated to produce 1.67 µg m-3 of noontime SOA, doubling the current model predictions and reducing the SOA mass concentration bias from -75% to -58% when compared to observations in Los Angeles in 2010. While oxygenated and nonoxygenated intermediate volatility VCP species are emitted in similar quantities, SOA formation is dominated by the nonoxygenated IVOCs. Formaldehyde and SOA show similar relationships to temperature and bias signatures indicating common sources and/or chemistry. This work suggests that VCPs contribute up to half of anthropogenic SOA in Los Angeles and models must better represent SOA precursors from VCPs to predict the urban enhancement of SOA.