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 (
), 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.
The acidity of aqueous atmospheric solutions is a key parameter driving both the partitioning of semi-volatile acidic and basic trace gases and their aqueous-phase chemistry. In addition, the acidity ...of atmospheric aqueous phases, e.g., deliquesced aerosol particles, cloud, and fog droplets, is also dictated by aqueous-phase chemistry. These feedbacks between acidity and chemistry have crucial implications for the tropospheric lifetime of air pollutants, atmospheric composition, deposition to terrestrial and oceanic ecosystems, visibility, climate, and human health. Atmospheric research has made substantial progress in understanding feedbacks between acidity and multiphase chemistry during recent decades. This paper reviews the current state of knowledge on these feedbacks with a focus on aerosol and cloud systems, which involve both inorganic and organic aqueous-phase chemistry. Here, we describe the impacts of acidity on the phase partitioning of acidic and basic gases and buffering phenomena. Next, we review feedbacks of different acidity regimes on key chemical reaction mechanisms and kinetics, as well as uncertainties and chemical subsystems with incomplete information. Finally, we discuss atmospheric implications and highlight the need for future investigations, particularly with respect to reducing emissions of key acid precursors in a changing world, and the need for advancements in field and laboratory measurements and model tools.
The Acidity of Atmospheric Particles and Clouds Pye, Havala O T; Nenes, Athanasios; Alexander, Becky ...
Atmospheric chemistry and physics,
04/2020, Letnik:
20, Številka:
8
Journal Article
Recenzirano
Odprti dostop
Acidity, defined as pH, is a central component of aqueous chemistry. In the atmosphere, the acidity of condensed phases (aerosol particles, cloud water, and fog droplets) governs the phase ...partitioning of semi-volatile gases such as HNO
, NH
, HCl, and organic acids and bases as well as chemical reaction rates. It has implications for the atmospheric lifetime of pollutants, deposition, and human health. Despite its fundamental role in atmospheric processes, only recently has this field seen a growth in the number of studies on particle acidity. Even with this growth, many fine particle pH estimates must be based on thermodynamic model calculations since no operational techniques exist for direct measurements. Current information indicates acidic fine particles are ubiquitous, but observationally-constrained pH estimates are limited in spatial and temporal coverage. Clouds and fogs are also generally acidic, but to a lesser degree than particles, and have a range of pH that is quite sensitive to anthropogenic emissions of sulfur and nitrogen oxides, as well as ambient ammonia. Historical measurements indicate that cloud and fog droplet pH has changed in recent decades in response to controls on anthropogenic emissions, while the limited trend data for aerosol particles indicates acidity may be relatively constant due to the semi-volatile nature of the key acids and bases and buffering in particles. This paper reviews and synthesizes the current state of knowledge on the acidity of atmospheric condensed phases, specifically particles and cloud droplets. It includes recommendations for estimating acidity and pH, standard nomenclature, a synthesis of current pH estimates based on observations, and new model calculations on the local and global scale.
Fine particle pollution, PM
, is associated with increased risk of death from cardiorespiratory diseases. A multidecadal shift in the United States (U.S.) PM
composition towards organic aerosol as ...well as advances in predictive algorithms for secondary organic aerosol (SOA) allows for novel examinations of the role of PM
components on mortality. Here we show SOA is strongly associated with county-level cardiorespiratory death rates in the U.S. independent of the total PM
mass association with the largest associations located in the southeastern U.S. Compared to PM
, 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 PM
, 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 PM
requires consideration of SOA.
Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor ...and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustion sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds-water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May-June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 μg m
). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73μg m
, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.
Gasoline- and diesel-fueled engines are ubiquitous sources of air pollution in urban environments. They emit both primary particulate matter and precursor gases that react to form secondary ...particulate matter in the atmosphere. In this work, we updated the organic aerosol module and organic emissions inventory of a three-dimensional chemical transport model, the Community Multiscale Air Quality Model (CMAQ), using recent, experimentally derived inputs and parameterizations for mobile sources. The updated model included a revised volatile organic compound (VOC) speciation for mobile sources and secondary organic aerosol (SOA) formation from unspeciated intermediate volatility organic compounds (IVOCs). The updated model was used to simulate air quality in southern California during May and June 2010, when the California Research at the Nexus of Air Quality and Climate Change (CalNex) study was conducted. Compared to the Traditional version of CMAQ, which is commonly used for regulatory applications, the updated model did not significantly alter the predicted organic aerosol (OA) mass concentrations but did substantially improve predictions of OA sources and composition (e.g., POA-SOA split), as well as ambient IVOC concentrations. The updated model, despite substantial differences in emissions and chemistry, performed similar to a recently released research version of CMAQ (Woody et al., 2016) that did not include the updated VOC and IVOC emissions and SOA data. Mobile sources were predicted to contribute 30-40 % of the OA in southern California (half of which was SOA), making mobile sources the single largest source contributor to OA in southern California. The remainder of the OA was attributed to non-mobile anthropogenic sources (e.g., cooking, biomass burning) with biogenic sources contributing to less than 5 % to the total OA. Gasoline sources were predicted to contribute about 13 times more OA than diesel sources; this difference was driven by differences in SOA production. Model predictions highlighted the need to better constrain multi-generational oxidation reactions in chemical transport models.
Atmospheric organic aerosol (OA) has important impacts on climate and human health but its sources remain poorly understood. Biogenic monoterpenes and sesquiterpenes are important precursors of ...secondary organic aerosol (SOA), but the amounts and pathways of SOA generation from these precursors are not well constrained by observations. We propose that the less-oxidized oxygenated organic aerosol (LO-OOA) factor resolved from positive matrix factorization (PMF) analysis on aerosol mass spectrometry (AMS) data can be used as a surrogate for fresh SOA from monoterpenes and sesquiterpenes in the southeastern US. This hypothesis is supported by multiple lines of evidence, including lab-in-the-field perturbation experiments, extensive ambient ground-level measurements, and state-of-the-art modeling. We performed lab-in-the-field experiments in which the ambient air is perturbed by the injection of selected monoterpenes and sesquiterpenes, and the subsequent SOA formation is investigated. PMF analysis on the perturbation experiments provides an objective link between LO-OOA and fresh SOA from monoterpenes and sesquiterpenes as well as insights into the sources of other OA factors. Further, we use an upgraded atmospheric model and show that modeled SOA concentrations from monoterpenes and sesquiterpenes could reproduce both the magnitude and diurnal variation of LO-OOA at multiple sites in the southeastern US, building confidence in our hypothesis. We estimate the annual average concentration of SOA from monoterpenes and sesquiterpenes in the southeastern US to be roughly 2 μg m
.
Per- and polyfluoroalkyl substances (PFASs) have been released into the environment for decades, yet contributions of air emissions to total human exposure, from inhalation and drinking water ...contamination via deposition, are poorly constrained. The atmospheric transport and fate of a PFAS mixture from a fluoropolymer manufacturing facility in North Carolina were investigated with the Community Multiscale Air Quality (CMAQ) model applied at high resolution (1 km) and extending ∼150 km from the facility. Twenty-six explicit PFAS compounds, including GenX, were added to CMAQ using current best estimates of air emissions and relevant physicochemical properties. The new model, CMAQ-PFAS, predicts that 5% by mass of total emitted PFAS and 2.5% of total GenX are deposited within ∼150 km of the facility, with the remainder transported out. Modeled air concentrations of total GenX and total PFAS around the facility can reach 24.6 and 8500 ng m–3 but decrease to ∼0.1 and ∼10 ng m–3 at 35 km downwind, respectively. We find that compounds with acid functionality have higher deposition due to enhanced water solubility and pH-driven partitioning to aqueous media. To our knowledge, this is the first modeling study of the fate of a comprehensive, chemically resolved suite of PFAS air emissions from a major manufacturing source.
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
0.95). Sector-wide, the effective secondary organic aerosol yield and maximum incremental reactivity of VCPs are 5.3 % by mass and 1.58 gO
g
, respectively, indicating VCPs are an important, and likely to date underrepresented, source of secondary pollution in urban environments.
Several models were used to describe the partitioning of ammonia, water, and organic compounds between the gas and particle phases for conditions in the southeastern US during summer 2013. Existing ...equilibrium models and frameworks were found to be sufficient, although additional improvements in terms of estimating pure-species vapor pressures are needed. Thermodynamic model predictions were consistent, to first order, with a molar ratio of ammonium to sulfate of approximately 1.6 to 1.8 (ratio of ammonium to 2× sulfate,
≈ 0.8 to 0.9) with approximately 70% of total ammonia and ammonium (NH
) in the particle. Southeastern Aerosol Research and Characterization Network (SEARCH) gas and aerosol and Southern Oxidant and Aerosol Study (SOAS) Monitor for AeRosols and Gases in Ambient air (MARGA) aerosol measurements were consistent with these conditions. CMAQv5.2 regional chemical transport model predictions did not reflect these conditions due to a factor of 3 overestimate of the nonvolatile cations. In addition, gas-phase ammonia was overestimated in the CMAQ model leading to an even lower fraction of total ammonia in the particle. Chemical Speciation Network (CSN) and aerosol mass spectrometer (AMS) measurements indicated less ammonium per sulfate than SEARCH and MARGA measurements and were inconsistent with thermodynamic model predictions. Organic compounds were predicted to be present to some extent in the same phase as inorganic constituents, modifying their activity and resulting in a decrease in H
(H
in μgm
air), increase in ammonia partitioning to the gas phase, and increase in pH compared to complete organic vs. inorganic liquid-liquid phase separation. In addition, accounting for nonideal mixing modified the pH such that a fully interactive inorganic-organic system had a pH roughly 0.7 units higher than predicted using traditional methods (pH = 1.5 vs. 0.7). Particle-phase interactions of organic and inorganic compounds were found to increase partitioning towards the particle phase (vs. gas phase) for highly oxygenated (O : C≥0.6) compounds including several isoprene-derived tracers as well as levoglu-cosan but decrease particle-phase partitioning for low O: C, monoterpene-derived species.
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