I‐Ting Ku

, 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.

Abstract We present emission measurements of volatile organic compounds (VOCs) for western U.S. wildland fires made on the NSF/NCAR C‐130 research aircraft during the Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE‐CAN) field campaign in summer 2018. VOCs were measured with complementary instruments onboard the C‐130, including a proton‐transfer‐reaction time‐of‐flight mass spectrometer (PTR‐ToF‐MS) and two gas chromatography (GC)‐based methods. Agreement within combined instrument uncertainties (<60%) was observed for most co‐measured VOCs. GC‐based measurements speciated the isomeric contributions to selected PTR‐ToF‐MS ion masses and generally showed little fire‐to‐fire variation. We report emission ratios (ERs) and emission factors (EFs) for 161 VOCs measured in 31 near‐fire smoke plume transects of 24 specific individual fires sampled in the afternoon when burning conditions are typically most active. Modified combustion efficiency (MCE) ranged from 0.85 to 0.94. The measured campaign‐average total VOC EF was 26.1 ± 6.9 g kg −1 , approximately 67% of which is accounted for by oxygenated VOCs. The 10 most abundantly emitted species contributed more than half of the total measured VOC mass. We found that MCE alone explained nearly 70% of the observed variance for total measured VOC emissions ( r 2 = 0.67) and >50% for 57 individual VOC EFs representing more than half the organic carbon mass. Finally, we found little fire‐to‐fire variability for the mass fraction contributions of individual species to the total measured VOC emissions, suggesting that a single speciation profile can describe VOC emissions for the wildfires in coniferous ecosystems sampled during WE‐CAN.

Abstract Reactive nitrogen ( N r ) within smoke plumes plays important roles in the production of ozone, the formation of secondary aerosols, and deposition of fixed N to ecosystems. The Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE‐CAN) field campaign sampled smoke from 23 wildfires throughout the western U.S. during summer 2018 using the NSF/NCAR C‐130 research aircraft. We empirically estimate N r normalized excess mixing ratios and emission factors from fires sampled within 80 min of estimated emission and explore variability in the dominant forms of N r between these fires. We find that reduced N compounds comprise a majority (39%–80%; median = 66%) of total measured reactive nitrogen ( ΣN r ) emissions. The smoke plumes sampled during WE‐CAN feature rapid chemical transformations after emission. As a result, within minutes after emission total measured oxidized nitrogen ( Σ NO y ) and measured total Σ NH x (NH 3 + p NH 4 ) are more robustly correlated with modified combustion efficiency (MCE) than NO x and NH 3 by themselves. The ratio of ΣNH x /ΣNO y displays a negative relationship with MCE, consistent with previous studies. A positive relationship with total measured ΣN r suggests that both burn conditions and fuel N content/volatilization differences contribute to the observed variability in the distribution of reduced and oxidized N r . Additionally, we compare our in situ field estimates of N r EFs to previous lab and field studies. For similar fuel types, we find Σ NH x EFs are of the same magnitude or larger than lab‐based NH 3 EF estimates, and Σ NO y EFs are smaller than lab NO x EFs.

With large primary emissions of nitrogen-containing compounds, wildfires impact the tropospheric oxidizing capacity, ozone (O3), and formation of secondary organic and inorganic aerosol. The fate of reactive nitrogen in daytime fresh wildfire plumes was examined using airborne measurements over the western U.S. during the Wildfire Experiment for Cloud chemistry, Aerosol absorption, and Nitrogen (WE-CAN) campaign in the summer of 2018 together with a photochemical box model. For four wildfire plumes sampled in a pseudo-Lagrangian manner, the model predicts that the majority of emitted NOx (96 ± 2%) is converted into peroxyacetyl nitrate (PAN) (27 ± 8%) and the sum of gas and particulate HNO3 (29 ± 5%) within a few hours of plume evolution. In two of the plumes with the highest initial NOx and HONO, the default model significantly underestimates the observed dilution-normalized decay rate of NOx with plume age. We investigated several potential causes of this discrepancy and found that the model likely does not accurately represent the formation of a suite of oxidized organic nitrogen species such as alkyl and acyl peroxynitrates in these fire plumes, consistent with a suite of organic nitrogen compounds measured by chemical ionization mass spectrometry. This organic nitrogen reservoir can be similar in magnitude to that of PAN and thus represents an important fate of NOx with uncertain impacts on downwind O3 and aerosol nitrate formation depending on whether these are acyl peroxynitrates (APNs), alkyl nitrates (RONO2), or nitro-aromatics.

As large-scale peat burning emissions can severely impact the environment and human health, it is crucial to assess the characteristics of smoke aerosol at the source and at down-wind locations. From March until late summer in 2014, the Tver region, north of the city of Moscow, was considerably affected by long-lasting peat bog fires. Peat bog smoldering emissions from three types of smoke (underground, inside grass, and above grass) were analyzed by an extensive suite of instrumentation that sampled and measured their optical and chemical properties. The particle composition was characterized by organic species with high OC/EC ratios (10–20), with water-soluble organic carbon (WSOC) and levoglucosan (Lev) comprising the largest fraction, up to 30 and 9%, respectively, of the OC. Aliphatic, aromatic, carbonyl, and carboxylate functionalities in the underground smoke were enriched by nitro compounds, and brown carbon (BrC) was identified by a high Absorption Angstrom Exponent (AAE) of 4.1. Organic “tar balls” in the peat smoke were more abundant (78.5%) than individual Ca-rich (e.g., Ca-oxides or carbonates), Fe-rich (e.g., Fe-oxides), and Al-rich (e.g., alumosilicates) particles. Peat smoke plumes affected an urban site in Moscow in August 2014, with ambient PM10 mass loadings reaching up to 97 µg m–3 and OC, EC, and ionic species accounting for a large percentage of the total aerosol enhancement. With the transport of air masses from the peat bog region to Moscow, the OC/EC ratio and AAE reached peak values of 7 and 1.3, respectively. Levoglucosan served as a molecular marker of the impact of peat smoldering, approaching a maximum ambient concentration of 108 ng m–3. WSOC correlated well with Lev, indicating secondary organic aerosol (SOA) formation associated with peat burning emissions. Spectral absorbance features showed characteristics similar to peat burning and traffic source emissions during fire and non-fire related days, confirming the potential effect of transported peat smoke on air quality in megacities.