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1. Urban aerosol chemistry at a land–water transition site during summer – Part 2: Aerosol pH and liquid water content

   https://doi.org/10.5194/acp-21-18271-2021  

   Battaglia Jr., Michael A. ; Balasus, Nicholas ; Ball, Katherine ; Caicedo, Vanessa ; Delgado, Ruben ; Carlton, Annmarie G. ; Hennigan, Christopher J. ( January 2021 , Atmospheric Chemistry and Physics)

   Abstract. Particle acidity (aerosol pH) is an important driver of atmospheric chemical processes and the resulting effects on human and environmentalhealth. Understanding the factors that control aerosol pH is critical when enacting control strategies targeting specific outcomes. This studycharacterizes aerosol pH at a land–water transition site near Baltimore, MD, during summer 2018 as part of the second Ozone Water-Land EnvironmentalTransition Study (OWLETS-2) field campaign. Inorganic fine-mode aerosol composition, gas-phase NH3 measurements, and all relevantmeteorological parameters were used to characterize the effects of temperature, aerosol liquid water (ALW), and composition on predictions ofaerosol pH. Temperature, the factor linked to the control of NH3 partitioning, was found to have the most significant effect on aerosol pHduring OWLETS-2. Overall, pH varied with temperature at a rate of −0.047 K−1 across all observations, though the sensitivity was−0.085 K−1 for temperatures > 293 K. ALW had a minor effect on pH, except at the lowest ALW levels(< 1 µg m−3), which caused a significant increase in aerosol acidity (decrease in pH). Aerosol pH was generally insensitive tocomposition (SO42-, SO42-:NH4+, total NH3 (Tot-NH3) = NH3 + NH4+), consistentwith recent studies in other locations. In a companion paper, the sources of episodic NH3 events (95th percentile concentrations,NH3 > 7.96 µg m−3) during the study are analyzed; aerosol pH was higher by only ∼ 0.1–0.2 pH unitsduring these events compared to the study mean. A case study was analyzed to characterize the response of aerosol pH to nonvolatile cations (NVCs)during a period strongly influenced by primary Chesapeake Bay emissions. Depending on the method used, aerosol pH was estimated to be either weakly(∼ 0.1 pH unit change based on NH3 partitioning calculation) or strongly (∼ 1.4 pH unit change based onISORROPIA thermodynamic model predictions) affected by NVCs. The case study suggests a strong pH gradient with size during the event and underscores the need to evaluate assumptions of aerosol mixing state applied to pH calculations. Unique features of this study, including the urban land–water transition site and the strong influence of NH3 emissions from both agricultural and industrial sources, add to the understanding of aerosol pH and its controlling factors in diverseenvironments. 

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2. Urban aerosol chemistry at a land–water transition site during summer – Part 1: Impact of agricultural and industrial ammonia emissions

   https://doi.org/10.5194/acp-21-13051-2021  

   Balasus, Nicholas ; Battaglia Jr., Michael A. ; Ball, Katherine ; Caicedo, Vanessa ; Delgado, Ruben ; Carlton, Annmarie G. ; Hennigan, Christopher J. ( January 2021 , Atmospheric Chemistry and Physics)

   Abstract. This study characterizes the impact of the Chesapeake Bay and associated meteorological phenomena on aerosol chemistry during the second Ozone Water-Land Environmental Transition Study (OWLETS-2) field campaign, which took place from 4 June to 5 July 2018. Measurements of inorganic PM2.5 composition, gas-phase ammonia (NH3), and an array of meteorological parameters were undertaken at Hart-Miller Island (HMI), a land–water transition site just east of downtown Baltimore on the Chesapeake Bay. The observations at HMI were characterized by abnormally high NH3 concentrations (maximum of 19.3 µg m−3, average of 3.83 µg m−3), which were more than a factor of 3 higher than NH3 levels measured at the closest atmospheric Ammonia Monitoring Network (AMoN) site (approximately 45 km away). While sulfate concentrations at HMI agreed quite well with those measured at a regulatory monitoring station 45 km away, aerosol ammonium and nitrate concentrations were significantly higher, due to the ammonia-rich conditions that resulted from the elevated NH3. The high NH3 concentrations were largely due to regional agricultural emissions, including dairy farms in southeastern Pennsylvania and poultry operations in the Delmarva Peninsula (Delaware–Maryland–Virginia). Reduced NH3 deposition during transport over the Chesapeake Bay likely contributed to enhanced concentrations at HMI compared to the more inland AMoN site. Several peak NH3 events were recorded, including the maximum NH3 observed during OWLETS-2, that appear to originate from a cluster of industrial sources near downtown Baltimore. Such events were all associated with nighttime emissions and advection to HMI under low wind speeds (< 1 m s−1) and stable atmospheric conditions. Our results demonstrate the importance of industrial sources, including several that are not represented in the emissions inventory, on urban air quality. Together with our companion paper, which examines aerosol liquid water and pH during OWLETS-2, we highlight unique processes affecting urban air quality of coastal cities that are distinct from continental locations. 

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3. Urban aerosol chemistry at a land-water transition site during summer – Part 1: Impact of agricultural and industrial ammonia emissions

   Balasus, N. ( January 2021 , Atmospheric chemistry and physics discussion)

   null (Ed.)

   This study characterizes the impact of the Chesapeake Bay and associated meteorological phenomena on aerosol chemistry during the second Ozone Water-Land Environmental Transition Study (OWLETS-2) field campaign during summer 2018. Measurements of inorganic PM2.5 composition, gas-phase ammonia (NH3), and an array of meteorological parameters were undertaken at Hart-Miller Island (HMI), a land-water transition site just east of downtown Baltimore on the Chesapeake Bay. The observations at HMI were characterized by abnormally high NH3 concentrations (maximum of 19.3 μg m-3, average of 3.83 μg m-3), which were more than a factor of three higher than NH3 levels measured at the closest Atmospheric Ammonia Network (AMoN) site (approximately 45 km away). While sulfate concentrations at HMI agreed quite well with those measured at a regulatory monitoring station 45 km away, aerosol ammonium and nitrate concentrations were significantly higher, due to the ammonia-rich conditions that resulted from the elevated NH3. The high NH3 concentrations were largely due to regional agricultural emissions, including dairy farms in southeastern Pennsylvania and poultry operations in the Delmarva Peninsula (Delaware-Maryland-Virginia). Reduced NH3 deposition during transport over the Chesapeake Bay likely contributed to enhanced concentrations at HMI compared to the more inland AMoN site. Several peak NH3 events were recorded, including the maximum NH3 observed during OWLETS-2, that appear to originate from a cluster of industrial sources near downtown Baltimore. Such events were all associated with nighttime emissions and advection to HMI under low 15 wind speeds (< 1 m s-1) and stable atmospheric conditions. Our results demonstrate the importance of industrial sources, including several that are not represented in the emissions inventory, on urban air quality. Together with our companion paper, which examines aerosol liquid water and pH during OWLETS-2, we highlight unique processes affecting urban air quality of coastal cities that are distinct from continental locations. 

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4. Soil NH3 emissions across an aridity, soil pH, and N deposition gradient in southern California

   https://doi.org/10.1525/elementa.2022.00123  

   Krichels, Alexander H. ; Homyak, Peter M. ; Aronson, Emma L. ; Sickman, James O. ; Botthoff, Jon ; Greene, Aral C. ; Andrews, Holly M. ; Shulman, Hannah ; Piper, Stephanie ; Jenerette, G. Darrel ( January 2023 , Elem Sci Anth)

   Soil ammonia (NH3) emissions are seldom included in ecosystem nutrient budgets; however, they may represent substantial pathways for ecosystem nitrogen (N) loss, especially in arid regions where hydrologic N losses are comparatively small. To characterize how multiple factors affect soil NH3 emissions, we measured NH3 losses from 6 dryland sites along a gradient in soil pH, atmospheric N deposition, and rainfall. We also enriched soils with ammonium (NH4+), to determine whether N availability would limit emissions, and measured NH3 emissions with passive samplers in soil chambers following experimental wetting. Because the volatilization of NH3 is sensitive to pH, we hypothesized that NH3 emissions would be higher in more alkaline soils and that they would increase with increasing NH4+ availability. Consistent with this hypothesis, average soil NH3 emissions were positively correlated with average site pH (R2 = 0.88, P = 0.004), ranging between 0.77 ± 0.81 µg N-NH3 m−2 h−1 at the least arid and most acidic site and 24.2 ± 16.0 µg N-NH3 m−2 h−1 at the most arid and alkaline site. Wetting soils while simultaneously adding NH4+ increased NH3 emissions from alkaline and moderately acidic soils (F1,35 = 14.7, P < 0.001), suggesting that high N availability can stimulate NH3 emissions even when pH is less than optimal for NH3 volatilization. Thus, both pH and N availability act as proximate controls over NH3 emissions suggesting that these N losses may limit how much N accumulates in arid ecosystems. 

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5. The acidity of atmospheric particles and clouds

   https://doi.org/10.5194/acp-20-4809-2020  

   Pye, Havala O. ; Nenes, Athanasios ; Alexander, Becky ; Ault, Andrew P. ; Barth, Mary C. ; Clegg, Simon L. ; Collett Jr., Jeffrey L. ; Fahey, Kathleen M. ; Hennigan, Christopher J. ; Herrmann, Hartmut ; et al ( January 2020 , Atmospheric Chemistry and Physics)

   Abstract. Acidity, defined as pH, is a central component of aqueouschemistry. In the atmosphere, the acidity of condensed phases (aerosolparticles, cloud water, and fog droplets) governs the phase partitioning ofsemivolatile gases such as HNO3, NH3, HCl, and organic acids andbases as well as chemical reaction rates. It has implications for theatmospheric lifetime of pollutants, deposition, and human health. Despiteits fundamental role in atmospheric processes, only recently has this fieldseen a growth in the number of studies on particle acidity. Even with thisgrowth, many fine-particle pH estimates must be based on thermodynamic modelcalculations since no operational techniques exist for direct measurements.Current information indicates acidic fine particles are ubiquitous, butobservationally constrained pH estimates are limited in spatial and temporalcoverage. Clouds and fogs are also generally acidic, but to a lesser degreethan particles, and have a range of pH that is quite sensitive toanthropogenic emissions of sulfur and nitrogen oxides, as well as ambientammonia. Historical measurements indicate that cloud and fog droplet pH haschanged in recent decades in response to controls on anthropogenicemissions, while the limited trend data for aerosol particles indicateacidity may be relatively constant due to the semivolatile nature of thekey acids and bases and buffering in particles. This paper reviews andsynthesizes the current state of knowledge on the acidity of atmosphericcondensed phases, specifically particles and cloud droplets. It includesrecommendations for estimating acidity and pH, standard nomenclature, asynthesis of current pH estimates based on observations, and new modelcalculations on the local and global scale. 

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