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Water is an important component of PM2.5 Many traditional SOA species are highly soluble and thus can be considered extractable Water can influence the partitioning of compounds traditionally considered insoluble in models Organic aerosol takes up water according to RH Organic aerosol interacts with inorganic water Deviations in ideality (solubility) must be considered.

In the U.S., the agricultural sector is the largest controllable source of several air pollutants, including ammonia (NH 3 ), which is a key precursor to PM 2.5 formation. Livestock waste is the dominant contributor to ammonia emissions. In contrast to most controllable air pollutants, satellite records show ammonia mixing ratios are rising. The number of confined animal feeding operations (CAFOs) that generate considerable livestock waste is also increasing. Spatial and temporal trends in USDA-reported animal numbers normalized by county area at medium and large CAFOs provide plausible explanations for patterns in satellite-derived NH 3 over the contiguous U.S. (CONUS). The correlation between summertime ammonia derived from the European Space Agency's (ESA) Infrared Atmospheric Sounding Interferometer (IASI) and CAFO animal unit density in 2017 is positive and significant ( r = 0.642; p ≈ 0). The temporal changes from 2002 to 2017 in animal unit density and NH 3 derived from NASA's Atmospheric Infrared Sounder (AIRS) are spatially similar. Trends and ambient concentrations of PM 2.5 mass in agricultural regions are difficult to assess relative to those of urban population centers given the sparseness of rural monitors in regulatory surface networks. Results suggest that in agricultural areas where ammonia concentrations and animal density are highest, air quality improvement lags behind the national average.

Fine particulate matter (PM 2.5 ) mass concentrations reported by regulatory networks are declining across the United States. It is well established that ammonium nitrate contributes substantially to the PM 2.5 mass in the western United States, and that Teflon filters commonly used by regulatory monitors are subject to negative mass artifacts due to ammonium nitrate volatilization. This study focuses on the San Joaquin Valley (SJV), an environmental justice (EJ) and agricultural region with persistently poor air quality. The SJV is a serious nonattainment area of PM 2.5 National Ambient Air Quality Standards (NAAQS) with substantial nitrate mass concentrations. We explicitly model the chemical thermodynamic equilibrium of the ammonium nitrate-nitric acid systems and quantify volatilization across California as a function of the deliquescence point relative humidity (%DRH). Nitrate loss is estimated at all federal reference method (FRM) and federal equivalent method (FEM) monitors from 2001 to 2021. Nearly 20% of PM 2.5 mass is lost from filters in the SJV area, especially during winter and fall when particulate nitrate mass is most abundant. All decadal PM 2.5 trends calculated from reported measurements in Kern, Tulare, and Fresno counties in the SJV show greater decline in PM 2.5 mass when nitrate loss is accounted for, up to a factor of 20 in Kern county. This suggests PM 2.5 mass concentrations reported in regulatory networks are biased low relative to the actual atmospheric burden, notably in an EJ area that lags behind most of the country's air quality improvements., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Particle chemical composition affects aerosol optical and physical properties in ways important for the fate, transport, and impact of atmospheric particulate matter. For example, hygroscopic constituents take up water to increase the physical size of a particle, which can alter the extinction properties and atmospheric lifetime. At the collocated AERosol RObotic NETwork (AERONET) and Interagency Monitoring of PROtected Visual Environments (IMPROVE) network monitoring stations in rural Bondville, Illinois, we employ a novel cloudiness determination method to compare measured aerosol physicochemical properties on predominantly cloudy and clear sky days from 2010 to 2019. On cloudy days, aerosol optical depth (AOD) is significantly higher than on clear sky days in all seasons. Measured Ångström exponents are significantly smaller on cloudy days, indicating physically larger average particle size for the sampled populations in all seasons except winter. Mass concentrations of fine particulate matter that include estimates of aerosol liquid water (ALW) are higher on cloudy days in all seasons but winter. More ALW on cloudy days is consistent with larger particle sizes inferred from Ångström exponent measurements. Aerosol chemical composition that affects hygroscopicity plays a determining impact on cloudy versus clear sky differences in AOD, Ångström exponents, and ALW. This work highlights the need for simultaneous collocated, high-time-resolution measurements of both aerosol chemical and physical properties, in particular at cloudy times when quantitative understanding of tropospheric composition is most uncertain., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Liquid water is a dominant and critical tropospheric constituent. Over polluted land masses low level cumulus clouds interact with boundary layer aerosol. The planetary boundary layer (PBL) is the lowest atmospheric layer and is directly influenced by Earth's surface. Water-aerosol interactions are critical to processes that govern the fate and transport of trace species in the Earth system and their impacts on air quality, radiative forcing, and regional hydrological cycling. In the PBL, air parcels rise adiabatically from the surface, and anthropogenically influenced hygroscopic aerosols take up water and serve as cloud condensation nuclei (CCN) to form clouds. Water-soluble gases partition to liquid water in wet aerosols and cloud droplets and undergo aqueous-phase photochemistry. Most cloud droplets evaporate, and low volatility material formed during aqueous phase chemistry remains in the condensed phase and adds to aerosol mass. The resulting cloud-processed aerosol has different physicochemical properties compared to the original CCN. Organic species that undergo multiphase chemistry in atmospheric liquid water transform gases to highly concentrated, nonideal ionic aqueous solutions and form secondary organic aerosol (SOA). In recent years, SOA formation modulated by atmospheric waters has received considerable interest.Key uncertainties are related to the chemical nature of hygroscopic aerosols that become CCN and their interaction with organic species. Gas-to-droplet or gas-to-aqueous aerosol partitioning of organic compounds is affected by the intrinsic chemical properties of the organic species in addition to the pre-existing condensed phase. Environmentally relevant conditions for atmospheric aerosol are nonideal. Salt identity and concentration, in addition to aerosol phase state, can dramatically affect organic gas miscibility for many compounds, in particular when ionic strength and salt molality are outside the bounds of limiting laws. For example, Henry's law and Debye-Hückel theory are valid only for dilute aqueous systems uncharacteristic of real atmospheric conditions. Chemical theory is incomplete, and at ambient conditions, this chemistry plays a determining role in total aerosol mass and particle size, controlling factors for air quality and climate-relevant aerosol properties.Accurate predictive skill to understand the impacts of societal choices and policies on air quality and climate requires that models contain correct chemical mechanisms and appropriate feedbacks. Globally, SOA is a dominant contributor to the atmospheric organic aerosol burden, and most mass can be traced back to precursor gas-phase volatile organic compounds (VOCs) emitted from the biosphere. However, organic aerosol concentrations in the Amazon Rainforest, the largest emitter of biogenic VOCs, are generally lower than in U.S. national parks. The Interagency Monitoring of Protected Visual Environments (IMPROVE) air quality network, with sites located predominantly in national parks, provides the longest continuous record of organic aerosol measurements in the U.S. Analysis of IMPROVE data provides a useful chemical climatology of changing air resources in response to environmental rules and shifting economic trends. IMPROVE data provides an excellent test bed for case studies to assess model skill to accurately predict changes in organic aerosol concentrations in the context of a changing climate.

Total organic carbon (TOC) mass concentrations are decreasing across the contiguous United States (CONUS). We investigate decadal trends in organic carbon (OC) thermal fractions [OC1 (volatilizes at 140 °C), OC2 (280 °C), OC3 (480 °C), OC4 (580 °C)] and pyrolyzed carbon (PC), reported at 121 locations in the I nteragency M onitoring of Pro tected V isual E nvironments (IMPROVE) network from 2005 to 2015 for 23 regions across the CONUS. Reductions in PC and OC2 drive decreases in TOC (TOC = OC1 + OC2 + OC3 + OC4 + PC) mass concentrations. OC2 decreases by 40% from 2005 to 2015, and PC decreases by 34%. The largest absolute mass decreases occur in the eastern United States, and relative changes normalized to local concentrations are more uniform across the CONUS. OC is converted to organic mass (OM) using region- and season-specific OM:OC ratios. Simulations with GEOS-Chem reproduce OM trends and suggest that decreases across the CONUS are due to aerosol liquid water (ALW) chemistry. Individual model species, notably aerosol derived from isoprene oxidation products and formed in ALW, correlate significantly ( p < 0.05) with OM2, even in arid regions. These findings contribute to literature that suggests air quality rules aimed at SO 2 and NO x emissions induce the cobenefit of reducing organic particle mass through ALW chemistry, and these benefits extend beyond the eastern United States.

Recent laboratory studies have reported the formation of light-absorbing organic carbon compounds (brown carbon, BrC) in particles undergoing drying. Atmospheric particles undergo cycles of humidification and drying during vertical transport and through daily variations in temperature and humidity, which implies particle drying could potentially be an important source of BrC globally. In this work, we investigated BrC formation in ambient particles undergoing drying at a site in the eastern United States during summer. Aerosol BrC concentrations were linked to secondary organic aerosol (SOA) formation, consistent with seasonal expectations for this region. Measurements of water-soluble organic aerosol concentrations and light absorption (365 nm) were alternated between an unperturbed channel and a channel that dried particles to 41% or 35% relative humidity (RH), depending on the system configuration. The RH maintained in the dry channels was below most ambient RH levels observed throughout the study. We did not observe BrC formation in particles that were dried to either RH level. The results were consistent across two summers, spanning ∼5 weeks of measurements that included a wide range of RH conditions and organic and inorganic aerosol loadings. This work suggests that mechanisms aside from humidification-drying cycles are more important contributors to ambient particle BrC loadings. The implications of this work on the atmospheric budget of BrC are discussed.

Clouds are prevalent and alter PM 2.5 mass and chemical composition. Cloud-affected satellite retrievals are often removed from data products, hindering estimates of tropospheric chemical composition during cloudy times. We examine surface fine particulate matter (PM 2.5 ) chemical constituent concentrations in the Interagency Monitoring of PROtected Visual Environments network during Cloudy and Clear Sky times defined using Moderate Resolution Imaging Spectroradiometer (MODIS) cloud flags from 2010-2014 with a focus on differences in particle hygroscopicity and aerosol liquid water (ALW). Cloudy and Clear Sky periods exhibit significant differences in PM 2.5 and chemical composition that vary regionally and seasonally. In the eastern US, relative humidity alone cannot explain differences in ALW, suggesting emissions and in situ chemistry exert determining impacts. An implicit clear sky bias may hinder efforts to quantitatively to understand and improve model representation of aerosol-cloud interactions.

In this paper, we present an analytical framework to establish a closed-form relationship between electricity generation expansion planning decisions and the resulting negative health externalities. Typical electricity generation expansion planning models determine the optimal technology-capacity-investment strategy that minimizes total investment costs as well as fixed and variable operation and maintenance costs. However, the relationship between these long-term planning decisions and the associated health externalities is highly stochastic and nonlinear, and it is computationally expensive to evaluate. Thus, we developed a closed-form metamodel by executing computer-based experiments of a generation expansion planning model, and we analyzed the resulting model outputs in a United States Environmental Protection Agency (EPA) screening tool that approximates the associated human health externalities. Procedural guidance to verify the accuracy and to select key metamodel parameters to enhance its prediction capability is presented. Specifically, the metamodel presented in this paper can predict the resulting health damages of long-term power grid expansion decisions, thus, enabling researchers and policy makers to quickly assess the health implications of power grid expansion decisions with a high degree of certainty.

Models that accurately predict atmospheric composition and correctly respond to tested policy scenarios aid air quality managers in the development of effective strategies to protect human health. Controllable emissions from human activity interact with natural emissions from plants and trees from the biosphere through complex chemistry to form ozone (O 3 ) and organic fine particulate matter (PM 2.5 ), criteria air pollutants that induce a variety of adverse health effects. While organic gases emitted from plants and trees are natural, some fraction of the subsequent O 3 and PM 2.5 is not. Accurate assessment of the extent to which human activity and natural emissions interact to form pollution can be achieved when models are constructed from first principle chemical and physical laws, and tested and evaluated with laboratory and field observations. In the summer of 2013, hundreds of scientists descended on the southeast U.S. to coordinate an atmospheric chemistry campaign with the ultimate goal of understanding complex biosphere-atmosphere interactions, the subsequent formation of O 3 and PM 2.5 , and accurate incorporation of the chemistry into atmospheric models. A main finding from the campaign is that anthropogenic emissions facilitate formation of organic PM 2.5 derived from biogenic VOCs. This fraction of PM 2.5 is controllable pollution. Mechanistic insight from that campaign was recently incorporated into EPA's air quality model, improving the model representation of the atmospheric modeling and informing air quality management strategies for PM 2.5 . Emission reductions in SO 2 and NOx in the southeast U.S. are found to reduce non-fossil, presumably biogenic, organic PM 2.5 mass concentrations, suggesting existing Federal rules have been more successful than anticipated. Additional potential feedback mechanisms may become important as emissions reductions bring the atmosphere into new chemical regimes.

Atmospheric models that accurately describe the fate and transport of trace species for the right reasons aid in the development of effective air-quality management strategies that safeguard human health. Controllable emissions facilitate the formation of biogenic secondary organic aerosol (BSOA) to enhance the atmospheric fine particulate matter (PM 2.5 ) burden. Previous modeling with the EPA's Community Multiscale Air Quality (CMAQ) model predicted that anthropogenic primary organic aerosol (POA) emissions had the greatest impact on BSOA. That experiment included formation processes involving semivolatile partitioning but not aerosol liquid water (ALW), a ubiquitous PM constituent. We conduct 17 summertime CMAQ simulations with updated chemistry and evaluate changes in BSOA due to the removal of individual pollutants and source sectors for the contiguous U.S. CMAQ predicts SO 2 from electricity generating units, and mobile source NO X emissions have the largest impacts on BSOA. The removal of anthropogenic NO X , SO 2 , and POA emissions during the simulation reduces the nationally averaged BSOA by 23, 14, and 8% and PM 2.5 by 9.2, 14, and 5.3%, respectively. ALW mass concentrations decrease by 10 and 35% in response to the removal of NO X and SO 2 emissions. This work contributes chemical insight into ancillary benefits of Federal NO X and SO 2 rules that concurrently reduce organic PM 2.5 mass.

Elevated water vapor (H 2 O v ) mole fractions were occassionally observed downwind of Indianapolis, IN, and the Washington, D.C.-Baltimore, MD, area during airborne mass balance experiments conducted during winter months between 2012 and 2015. On days when an urban H 2 O v excess signal was observed, H 2 O v emissions estimates range between 1.6 × 10 4 and 1.7 × 10 5 kg s -1 , and account for up to 8.4% of the total (background + urban excess) advected flow of atmospheric boundary layer H 2 O v from the urban study sites. Estimates of H 2 O v emissions from combustion sources and electricity generation facility cooling towers are 1-2 orders of magnitude smaller than the urban H 2 O v emission rates estimated from observations. Instances of urban H 2 O v enhancement could be a result of differences in snowmelt and evaporation rates within the urban area, due in part to larger wintertime anthropogenic heat flux and land cover differences, relative to surrounding rural areas. More study is needed to understand why the urban H 2 O v excess signal is observed on some days, and not others. Radiative transfer modeling indicates that the observed urban enhancements in H 2 O v and other greenhouse gas mole fractions contribute only 0.1°C day -1 to the urban heat island at the surface. This integrated warming through the boundary layer is offset by longwave cooling by H 2 O v at the top of the boundary layer. While the radiative impacts of urban H 2 O v emissions do not meaningfully influence urban heat island intensity, urban H 2 O v emissions may have the potential to alter downwind aerosol and cloud properties., Competing Interests: The authors declare no competing financial interest.

The lack of statistically robust relationships between IEPOX (isoprene epoxydiol)-derived SOA (IEPOX SOA) and aerosol liquid water and pH observed during the 2013 Southern Oxidant and Aerosol Study (SOAS) emphasizes the importance of modeling the whole system to understand the controlling factors governing IEPOX SOA formation. We present a mechanistic modeling investigation predicting IEPOX SOA based on Community Multiscale Air Quality (CMAQ) model algorithms and a recently introduced photochemical box model, simpleGAMMA. We aim to (1) simulate IEPOX SOA tracers from the SOAS Look Rock ground site, (2) compare the two model formulations, (3) determine the limiting factors in IEPOX SOA formation, and (4) test the impact of a hypothetical sulfate reduction scenario on IEPOX SOA. The estimated IEPOX SOA mass variability is in similar agreement (r 2 ∼ 0.6) with measurements. Correlations of the estimated and measured IEPOX SOA tracers with observed aerosol surface area (r 2 ∼ 0.5-0.7), rate of particle-phase reaction (r 2 ∼ 0.4-0.7), and sulfate (r 2 ∼ 0.4-0.5) suggest an important role of sulfate in tracer formation via both physical and chemical mechanisms. A hypothetical 25% reduction of sulfate results in ∼70% reduction of IEPOX SOA formation, reaffirming the importance of aqueous phase chemistry in IEPOX SOA production.

Isoprene epoxydiol (IEPOX), glyoxal, and methylglyoxal are ubiquitous water-soluble organic gases (WSOGs) that partition to aerosol liquid water (ALW) and clouds to form aqueous secondary organic aerosol (aqSOA). Recent laboratory-derived Setschenow (or salting) coefficients suggest glyoxal's potential to form aqSOA is enhanced by high aerosol salt molality, or "salting-in". In the southeastern U.S., aqSOA is responsible for a significant fraction of ambient organic aerosol, and correlates with sulfate mass. However, the mechanistic explanation for this correlation remains elusive, and an assessment of the importance of different WSOGs to aqSOA is currently missing. We employ EPA's CMAQ model to the continental U.S. during the Southern Oxidant and Aerosol Study (SOAS) to compare the potential of glyoxal, methylglyoxal, and IEPOX to partition to ALW, as the initial step toward aqSOA formation. Among these three studied compounds, IEPOX is a dominant contributor, ∼72% on average in the continental U.S., to potential aqSOA mass due to Henry's Law constants and molecular weights. Glyoxal contributes significantly, and application of the Setschenow coefficient leads to a greater than 3-fold model domain average increase in glyoxal's aqSOA mass potential. Methylglyoxal is predicted to be a minor contributor. Acid or ammonium - catalyzed ring-opening IEPOX chemistry as well as sulfate-driven ALW and the associated molality may explain positive correlations between SOA and sulfate during SOAS and illustrate ways in which anthropogenic sulfate could regulate biogenic aqSOA formation, ways not presently included in atmospheric models but relevant to development of effective control strategies.

Laboratory studies of atmospheric chemistry characterize the nature of atmospherically relevant processes down to the molecular level, providing fundamental information used to assess how human activities drive environmental phenomena such as climate change, urban air pollution, ecosystem health, indoor air quality, and stratospheric ozone depletion. Laboratory studies have a central role in addressing the incomplete fundamental knowledge of atmospheric chemistry. This article highlights the evolving science needs for this community and emphasizes how our knowledge is far from complete, hindering our ability to predict the future state of our atmosphere and to respond to emerging global environmental change issues. Laboratory studies provide rich opportunities to expand our understanding of the atmosphere via collaborative research with the modeling and field measurement communities, and with neighboring disciplines.

This paper describes the development and implementation of an extendable aqueous-phase chemistry option (AQCHEM -KMT(I)) for the Community Multiscale Air Quality (CMAQ) modeling system, version 5.1. Here, the Kinetic PreProcessor (KPP), version 2.2.3, is used to generate a Rosenbrock solver (Rodas3) to integrate the stiff system of ordinary differential equations (ODEs) that describe the mass transfer, chemical kinetics, and scavenging processes of CMAQ clouds. CMAQ's standard cloud chemistry module (AQCHEM) is structurally limited to the treatment of a simple chemical mechanism. This work advances our ability to test and implement more sophisticated aqueous chemical mechanisms in CMAQ and further investigate the impacts of microphysical parameters on cloud chemistry. Box model cloud chemistry simulations were performed to choose efficient solver and tolerance settings, evaluate the implementation of the KPP solver, and assess the direct impacts of alternative solver and kinetic mass transfer on predicted concentrations for a range of scenarios. Month-long CMAQ simulations for winter and summer periods over the US reveal the changes in model predictions due to these cloud module updates within the full chemical transport model. While monthly average CMAQ predictions are not drastically altered between AQCHEM and AQCHEM-KMT, hourly concentration differences can be significant. With added in-cloud secondary organic aerosol (SOA) formation from biogenic epoxides (AQCHEM-KMTI), normalized mean error and bias statistics are slightly improved for 2-methyltetrols and 2-methylglyceric acid at the Research Triangle Park measurement site in North Carolina during the Southern Oxidant and Aerosol Study (SOAS) period. The added in-cloud chemistry leads to a monthly average increase of 11-18 % in "cloud" SOA at the surface in the eastern United States for June 2013., Competing Interests: Competing interests. The authors declare that they have no conflict of interest.

Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM/OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM/OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH > SRH led to increased SOA concentrations,· particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties· such as the OM/OC and hygroscopicity parameter ( κ org ), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically derived semivolatile species in the Community Multiscale Air Quality (CMAQ) model were highly water soluble and expected to contribute to water-soluble organic carbon (WSOC). Organic aerosol and SOA precursors were abundant at night, but additional improvements in daytime organic aerosol are needed to close the model-measurement gap. When taking into account deviations from ideality, including both inorganic (when RH > SRH) and organic water in the organic partitioning medium reduced the mean bias in SOA for routine monitoring networks and improved model performance compared to observations from SOAS. Property updates from this work will be released in CMAQ v5.2.

On high electricity demand days, when air quality is often poor, regional transmission organizations (RTOs), such as PJM Interconnection, ensure reliability of the grid by employing peak-use electric generating units (EGUs). These "peaking units" are exempt from some federal and state air quality rules. We identify RTO assignment and peaking unit classification for EGUs in the Eastern U.S. and estimate air quality for four emission scenarios with the Community Multiscale Air Quality (CMAQ) model during the July 2006 heat wave. Further, we population-weight ambient values as a surrogate for potential population exposure. Emissions from electricity reliability networks negatively impact air quality in their own region and in neighboring geographic areas. Monitored and controlled PJM peaking units are generally located in economically depressed areas and can contribute up to 87% of hourly maximum PM2.5 mass locally. Potential population exposure to peaking unit PM2.5 mass is highest in the model domain's most populated cities. Average daily temperature and national gross domestic product steer peaking unit heat input. Air quality planning that capitalizes on a priori knowledge of local electricity demand and economics may provide a more holistic approach to protect human health within the context of growing energy needs in a changing world.

Water is a ubiquitous and abundant component of atmospheric aerosols. It influences light scattering, the hydrological cycle, atmospheric chemistry, and secondary particulate matter (PM) formation. Despite the critical importance of aerosol liquid water, mass concentrations are not well-known. Using speciated ion and meteorological data from the Southeastern Aerosol Research and Characterization network, we employ the thermodynamic model ISORROPIAv2.1 to estimate water mass concentrations and evaluate trends from 2001 to 2012 in urban and rural locations. The purpose of this study is to better understand the historical trends of aerosol liquid water in the southeast U.S. in the context of improved air quality and recently noted reductions in particulate organic carbon (OC). Aerosol water mass concentrations decrease by ∼79% from 2001 to 2012 in the region. Decreases are more prominent in rural than in urban areas. Fractional contribution of water to PM also decreases during the same time period, and this is consistent with recently noted improvements in visibility. These findings agree with the hypotheses that aerosol liquid water facilitates formation of biogenic secondary organic aerosol (SOA) and that biogenically derived SOA is modulated in the presence of anthropogenic perturbations.

Underprediction of peak ambient pollution by air quality models hinders development of effective strategies to protect health and welfare. The U.S. Environmental Protection Agency's community multiscale air quality (CMAQ) model routinely underpredicts peak ozone and fine particulate matter (PM2.5) concentrations. Temporal misallocation of electricity sector emissions contributes to this modeling deficiency. Hourly emissions are created for CMAQ by use of temporal profiles applied to annual emission totals unless a source is matched to a continuous emissions monitor (CEM) in the National Emissions Inventory (NEI). More than 53% of CEMs in the Pennsylvania-New Jersey-Maryland (PJM) electricity market and 45% nationally are unmatched in the 2008 NEI. For July 2006, a United States heat wave with high electricity demand, peak electric sector emissions, and elevated ambient PM2.5 mass, we match hourly emissions for 267 CEM/NEI pairs in PJM (approximately 49% and 12% of unmatched CEMs in PJM and nationwide) using state permits, electricity dispatch modeling and CEMs. Hourly emissions for individual facilities can differ up to 154% during the simulation when measurement data is used rather than default temporalization values. Maximum CMAQ PM2.5 mass, sulfate, and elemental carbon predictions increase up to 83%, 103%, and 310%, at the surface and 51%, 75%, and 38% aloft (800 mb), respectively.

Aerosol liquid water (ALW) influences aerosol radiative properties and the partitioning of gas-phase water-soluble organic compounds (WSOCg) to the condensed phase. A recent modeling study drew attention to the anthropogenic nature of ALW in the southeastern United States, where predicted ALW is driven by regional sulfate. Herein, we demonstrate that ALW in the Po Valley, Italy, is also anthropogenic but is driven by locally formed nitrate, illustrating regional differences in the aerosol components responsible for ALW. We present field evidence for the influence of controllable ALW on the lifetimes and atmospheric budgets of reactive organic gases and note the role of ALW in the formation of secondary organic aerosol (SOA). Nitrate is expected to increase in importance due to increased emissions of nitrate precursors, as well as policies aimed at reducing sulfur emissions. We argue that the impacts of increased particulate nitrate in future climate and air quality scenarios may be under predicted because they do not account for the increased potential for SOA formation in nitrate-derived ALW, nor do they account for the impacts of this ALW on reactive gas budgets and gas-phase photochemistry.

This study presents a first attempt to investigate the roles of fire aerosols in ozone (O(3)) photochemistry using an online coupled meteorology-chemistry model, the Weather Research and Foresting model with Chemistry (WRF-Chem). Four 1-month WRF-Chem simulations for August 2007, with and without fire emissions, were carried out to assess the sensitivity of O(3) predictions to the emissions and subsequent radiative feedbacks associated with large-scale fires in the Western United States (U.S.). Results show that decreases in planetary boundary layer height (PBLH) resulting from the radiative effects of fire aerosols and increases in emissions of nitrogen oxides (NO(x)) and volatile organic compounds (VOCs) from the fires tend to increase modeled O(3) concentrations near the source. Reductions in downward shortwave radiation reaching the surface and surface temperature due to fire aerosols cause decreases in biogenic isoprene emissions and J(NO(2)) photolysis rates, resulting in reductions in O(3) concentrations by as much as 15%. Thus, the results presented in this study imply that considering the radiative effects of fire aerosols may reduce O(3) overestimation by traditional photochemical models that do not consider fire-induced changes in meteorology; implementation of coupled meteorology-chemistry models are required to simulate the atmospheric chemistry impacted by large-scale fires.

Biogenic volatile organic compounds (BVOCs) contribute substantially to atmospheric carbon, exerting influence on air quality and climate. Two widely used models, the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the Biogenic Emission Inventory System (BEIS) are employed to generate emissions for application in the CMAQ air quality model. Predictions of isoprene, monoterpenes, ozone, formaldehyde, and secondary organic carbon (SOC) are compared to surface and aloft measurements made during an intensive study in the Ozarks, a large isoprene emitting region. MEGAN and BEIS predict spatially similar emissions but magnitudes differ. The total VOC reactivity of the emissions, as developed for the CB05 gas-phase chemical mechanism, is a factor of 2 different between the models. Isoprene estimates by CMAQ-MEGAN are higher and more variable than surface and aloft measurements, whereas CMAQ-BEIS predictions are lower. CMAQ ozone predictions are similar and compare well with measurements using either MEGAN or BEIS. However, CMAQ-MEGAN overpredicts formaldehyde. CMAQ-BEIS SOC predictions are lower than observational estimates for every sample. CMAQ-MEGAN underpredicts SOC ∼ 80% of the time, despite overprediction of precursor VOCs. CMAQ-MEGAN isoprene predictions improve when prognostically predicted solar radiation is replaced with the GEWEX satellite product. CMAQ-BEIS does not exhibit similar photosensitivity.

Numerous scientific upgrades to the representation of secondary organic aerosol (SOA) are incorporated into the Community Multiscale Air Quality (CMAQ) modeling system. Additions include several recently identified SOA precursors: benzene, isoprene, and sesquiterpenes; and pathways: in-cloud oxidation of glyoxal and methylglyoxal, particle-phase oligomerization, and acid enhancement of isoprene SOA. NO(x)-dependent aromatic SOA yields are also added along with new empirical measurements of the enthalpies of vaporization and organic mass-to-carbon ratios. For the first time, these SOA precursors, pathways and empirical parameters are included simultaneously in an air quality model for an annual simulation spanning the continental U.S. Comparisons of CMAQ-modeled secondary organic carbon (OC(sec)) with semiempirical estimates screened from 165 routine monitoring sites across the U.S. indicate the new SOA module substantially improves model performance. The most notable improvement occurs in the central and southeastern U.S. where the regionally averaged temporal correlations (r) between modeled and semiempirical OC(sec) increase from 0.5 to 0.8 and 0.3 to 0.8, respectively, when the new SOA module is employed. Wintertime OC(sec) results improve in all regions of the continental U.S. and the seasonal and regional patterns of biogenic SOA are better represented.

The implicit assumption that biogenic secondary organic aerosol (SOA) is natural and can not be controlled hinders effective air quality management. Anthropogenic pollution facilitates transformation of naturally emitted volatile organic compounds (VOCs) to the particle phase, enhancing the ambient concentrations of biogenic secondary organic aerosol (SOA). It is therefore conceivable that some portion of ambient biogenic SOA can be removed by controlling emissions of anthropogenic pollutants. Direct measurement of the controllable fraction of biogenic SOA is not possible, but can be estimated through 3-dimensional photochemical air quality modeling. To examine this in detail, 22 CMAQ model simulations were conducted over the continental U.S. (August 15 to September 4, 2003). The relative contributions of five emitted pollution classes (i.e., NO(x), NH(3), SO(x), reactive non methane carbon (RNMC) and primary carbonaceous particulate matter (PCM)) on biogenic SOA were estimated by removing anthropogenic emissions of these pollutants, one at a time and all together. Model results demonstrate a strong influence of anthropogenic emissions on predicted biogenic SOA concentrations, suggesting more than 50% of biogenic SOA in the eastern U.S. can be controlled. Because biogenic SOA is substantially enhanced by controllable emissions, classification of SOA as biogenic or anthropogenic based solely on VOC origin is not sufficient to describe the controllable fraction.

Mounting evidence suggests that low-volatility (particle-phase) organic compounds form in the atmosphere through aqueous phase reactions in clouds and aerosols. Although some models have begun including secondary organic aerosol (SOA) formation through cloud processing, validation studies that compare predictions and measurements are needed. In this work, agreement between modeled organic carbon (OC) and aircraft measurements of water soluble OC improved for all 5 of the compared ICARTT NOAA-P3 flights during August when an in-cloud SOA (SOAcld) formation mechanism was added to CMAQ (a regional-scale atmospheric model). The improvement was most dramatic for the August 14th flight, a flight designed specifically to investigate clouds. During this flight the normalized mean bias for layer-averaged OC was reduced from -64 to -15% and correlation (r) improved from 0.5 to 0.6. Underpredictions of OC aloft by atmospheric models may be explained, in part, by this formation mechanism (SOAcld). OC formation aloft contributes to long-range pollution transport and has implications to radiative forcing, regional air quality and climate.

Electrospray ionization mass spectrometry (ESI-MS) was used to investigate product formation in laboratory experiments designed to study secondary organic aerosol (SOA) formation in clouds. It has been proposed that water soluble aldehydes derived from aromatics and alkenes, including isoprene, oxidize further in cloud droplets forming organic acids and, upon droplet evaporation, SOA. Pyruvic acid is an important aqueous-phase intermediate. Time series samples from photochemical batch aqueous phase reactions of pyruvic acid and hydrogen peroxide were analyzed for product formation. In addition to the monomers predicted by the reaction scheme, products consistent with an oligomer system were found when pyruvic acid and OH radical were both present. No evidence of oligomer formation was found in a standard mix composed of pyruvic, glyoxylic, and oxalic acids prepared in the same matrix as the samples analyzed using the same instrument conditions. The distribution of high molecular weight products is consistent with oligomers composed of the mono-, oxo-, and di-carboxylic acids expected from the proposed reaction scheme.

Isoprene accounts for more than half of non-methane volatile organics globally. Despite extensive experimentation, homogeneous formation of secondary organic aerosol (SOA) from isoprene remains unproven. Herein, an incloud process is identified in which isoprene produces SOA. Interstitial oxidation of isoprene produces water-soluble aldehydes that react in cloud droplets to form organic acids. Upon cloud evaporation new organic particulate matter is formed. Cloud processing of isoprene contributes at least 1.6 Tg yr(-1) to a global biogenic SOA production of 8-40 Tg yr(-1). We conclude that cloud processing of isoprene is an important contributor to SOA production, altering the global distribution of hygroscopic organic aerosol and cloud condensation nuclei.

The U.S. Environmental Protection Agency (EPA) Quality Assurance (QA) Guidance Document 2.12: Monitoring PM2.5 in Ambient Air Using Designated Reference or Class I Equivalent Methods (Document 2.12) requires conditioning of PM2.5 filters at 20-23 degrees C and 30-40% relative humidity (RH) for 24 hr prior to gravimetric analysis. Variability of temperature and humidity may not exceed +/-2 degrees C and +/-5% RH during the conditioning period. The quality assurance team at EPA Region 2's regional laboratory designed a PM2.5 weighing facility that operates well within these strict performance requirements. The traditional approach to meeting the performance requirements of Document 2.12 for PM2.5 filter analysis is to build a walk-in room, with costs typically exceeding $100,000. The initial one-time capital cost for the laboratory at EPA's Edison, NJ, facility was approximately $24,000. Annual costs [e.g., National Institute of Standards and Technology (NIST) recertifications and nitrogen replacement cylinders used for humidity control] are approximately $500. The average 24-hr variabilities in temperature and RH in the Region 2 weighing chamber are small, +/-0.2 degrees C and +/-0.8% RH, respectively. The mass detection limit for the PM2.5 weighing system of 47-mm stretched Teflon (lab blank) filters is 6.3 microg. This facility demonstrates an effective and economical example for states and other organizations planning PM2.5 weighing facilities.