Fine Aerosol Acidity and Water during Summer in the Eastern North Atlantic
Abstract
Aerosol pH governs many important atmospheric processes that occur in the marine boundary layer, including regulating halogen and sulfur chemistries, and nutrient fertilization of surface ocean waters. In this study, we investigated the acidity of PM1 over the eastern North Atlantic during the Aerosol and Cloud Experiments in Eastern North Atlantic (ACE-ENA) aircraft campaign. The ISORROPIA-II thermodynamic model was used to predict PM1 pH and water. We first investigated the sensitivities of PM1 pH and water predictions to gas-phase NH3 and HNO3 concentrations. Our sensitivity analysis indicated that even though NH3 and HNO3 were present at very low concentrations in the eastern North Atlantic during the campaign, PM1 pH calculations can still be sensitive to NH3 concentrations. Specifically, NH3 was needed to constrain the pH of populations of PM1 that had low mass concentrations of NH4+ and non-volatile cations (NVCs). We next assumed that gas-phase NH3 and HNO3 concentrations during the campaign were 0.15 and 0.09 µg m-3, respectively, based on previous measurements conducted in the eastern North Atlantic. Using the assumption that PM1 were internally mixed (i.e., bulk PM1), we determined that PM1 pH ranged from 0.3–8.6, with a mean pH of 5.0 ± 2.3. The pH depended on both $$H^{+}_{air}$$ and $$W_{i}$$. $$H^{+}_{air}$$ was controlled primarily by the NVCs/SO42- molar ratio, while Wi was controlled by the SO42 mass concentration and RH. Changes in pH with altitude were driven primarily by changes in SO42-. Since aerosols in marine atmospheres are rarely internally mixed, the scenario where non-sea salt species and sea-salt species were present in two separate aerosol modes in the PM1 (i.e., completely externally mixed) was also considered. Smaller pH values were predicted for the aerosol mode comprised only of non-sea salt species compared to the bulk PM1 (difference of around 1 unit on average). This was due to the exclusion of sea-salt species (especially hygroscopic alkaline NVCs) in this aerosol mode, which led to increases in $$H^{+}_{air}$$ values and decreases in $$W_{i}$$ values. This result demonstrated that assumptions of aerosol mixing states can impact aerosol pH predictions substantially, which will have important implications for evaluating the nature and magnitude of pH-dependent atmospheric processes that occur in the marine boundary layer.
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); City Univ. of Hong Kong, Kowloon (Hong Kong); Washington Univ., St. Louis, MO (United States); Colorado State Univ., Fort Collins, CO (United States); Georgia Institute of Technology, Atlanta, GA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1813078
- Alternate Identifier(s):
- OSTI ID: 1813546; OSTI ID: 1837832
- Grant/Contract Number:
- DOE 333890; SC0020259; 333890
- Resource Type:
- Published Article
- Journal Name:
- Atmosphere (Basel)
- Additional Journal Information:
- Journal Name: Atmosphere (Basel) Journal Volume: 12 Journal Issue: 8; Journal ID: ISSN 2073-4433
- Publisher:
- MDPI AG
- Country of Publication:
- Switzerland
- Language:
- English
- Subject:
- 54 ENVIRONMENTAL SCIENCES; aerosol water; aerosol pH; aqueous phase; remote marine boundary layer; non-volatile cations
Citation Formats
Nah, Theodora, Yang, Junwei, Wang, Jian, Sullivan, Amy P., and Weber, Rodney J. Fine Aerosol Acidity and Water during Summer in the Eastern North Atlantic. Switzerland: N. p., 2021.
Web. doi:10.3390/atmos12081040.
Nah, Theodora, Yang, Junwei, Wang, Jian, Sullivan, Amy P., & Weber, Rodney J. Fine Aerosol Acidity and Water during Summer in the Eastern North Atlantic. Switzerland. https://doi.org/10.3390/atmos12081040
Nah, Theodora, Yang, Junwei, Wang, Jian, Sullivan, Amy P., and Weber, Rodney J. Fri .
"Fine Aerosol Acidity and Water during Summer in the Eastern North Atlantic". Switzerland. https://doi.org/10.3390/atmos12081040.
@article{osti_1813078,
title = {Fine Aerosol Acidity and Water during Summer in the Eastern North Atlantic},
author = {Nah, Theodora and Yang, Junwei and Wang, Jian and Sullivan, Amy P. and Weber, Rodney J.},
abstractNote = {Aerosol pH governs many important atmospheric processes that occur in the marine boundary layer, including regulating halogen and sulfur chemistries, and nutrient fertilization of surface ocean waters. In this study, we investigated the acidity of PM1 over the eastern North Atlantic during the Aerosol and Cloud Experiments in Eastern North Atlantic (ACE-ENA) aircraft campaign. The ISORROPIA-II thermodynamic model was used to predict PM1 pH and water. We first investigated the sensitivities of PM1 pH and water predictions to gas-phase NH3 and HNO3 concentrations. Our sensitivity analysis indicated that even though NH3 and HNO3 were present at very low concentrations in the eastern North Atlantic during the campaign, PM1 pH calculations can still be sensitive to NH3 concentrations. Specifically, NH3 was needed to constrain the pH of populations of PM1 that had low mass concentrations of NH4+ and non-volatile cations (NVCs). We next assumed that gas-phase NH3 and HNO3 concentrations during the campaign were 0.15 and 0.09 µg m-3, respectively, based on previous measurements conducted in the eastern North Atlantic. Using the assumption that PM1 were internally mixed (i.e., bulk PM1), we determined that PM1 pH ranged from 0.3–8.6, with a mean pH of 5.0 ± 2.3. The pH depended on both $H^{+}_{air}$ and $W_{i}$. $H^{+}_{air}$ was controlled primarily by the NVCs/SO42- molar ratio, while Wi was controlled by the SO42 mass concentration and RH. Changes in pH with altitude were driven primarily by changes in SO42-. Since aerosols in marine atmospheres are rarely internally mixed, the scenario where non-sea salt species and sea-salt species were present in two separate aerosol modes in the PM1 (i.e., completely externally mixed) was also considered. Smaller pH values were predicted for the aerosol mode comprised only of non-sea salt species compared to the bulk PM1 (difference of around 1 unit on average). This was due to the exclusion of sea-salt species (especially hygroscopic alkaline NVCs) in this aerosol mode, which led to increases in $H^{+}_{air}$ values and decreases in $W_{i}$ values. This result demonstrated that assumptions of aerosol mixing states can impact aerosol pH predictions substantially, which will have important implications for evaluating the nature and magnitude of pH-dependent atmospheric processes that occur in the marine boundary layer.},
doi = {10.3390/atmos12081040},
journal = {Atmosphere (Basel)},
number = 8,
volume = 12,
place = {Switzerland},
year = {Fri Aug 13 00:00:00 EDT 2021},
month = {Fri Aug 13 00:00:00 EDT 2021}
}
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Works referenced in this record:
Measurement of pH. Definition, standards, and procedures (IUPAC Recommendations 2002)
journal, January 2002
- Buck, R. P.; Rondinini, S.; Covington, A. K.
- Pure and Applied Chemistry, Vol. 74, Issue 11
The pH of deliquesced sea-salt aerosol in polluted marine air
journal, June 1998
- Keene, William C.; Savoie, Dennis L.
- Geophysical Research Letters, Vol. 25, Issue 12
Thermodynamic characterization of Mexico City aerosol during MILAGRO 2006
journal, January 2009
- Fountoukis, C.; Nenes, A.; Sullivan, A.
- Atmospheric Chemistry and Physics, Vol. 9, Issue 6
Ocean Ammonia Outgassing: Modulation by CO 2 and Anthropogenic Nitrogen Deposition
journal, October 2020
- Paulot, Fabien; Stock, Charles; John, Jasmin G.
- Journal of Advances in Modeling Earth Systems, Vol. 12, Issue 10
A critical evaluation of proxy methods used to estimate the acidity of atmospheric particles
journal, January 2015
- Hennigan, C. J.; Izumi, J.; Sullivan, A. P.
- Atmospheric Chemistry and Physics, Vol. 15, Issue 5
Influence of Atmospheric Processes on the Solubility and Composition of Iron in Saharan Dust
journal, June 2016
- Longo, Amelia F.; Feng, Yan; Lai, Barry
- Environmental Science & Technology, Vol. 50, Issue 13
Size-resolved aerosol pH over Europe during summer
journal, January 2021
- Kakavas, Stylianos; Patoulias, David; Zakoura, Maria
- Atmospheric Chemistry and Physics, Vol. 21, Issue 2
Clouds, Aerosols, and Precipitation in the Marine Boundary Layer: An Arm Mobile Facility Deployment
journal, March 2015
- Wood, Robert; Wyant, Matthew; Bretherton, Christopher S.
- Bulletin of the American Meteorological Society, Vol. 96, Issue 3
Aerosol pH and its driving factors in Beijing
journal, January 2019
- Ding, Jing; Zhao, Pusheng; Su, Jie
- Atmospheric Chemistry and Physics, Vol. 19, Issue 12
Aircraft measurements of aerosol and trace gas chemistry in the eastern North Atlantic
journal, May 2021
- Zawadowicz, Maria A.; Suski, Kaitlyn; Liu, Jiumeng
- Atmospheric Chemistry and Physics, Vol. 21, Issue 10
The mass accommodation coefficient of ammonium nitrate aerosol
journal, August 1999
- Dassios, Konstandinos G.; Pandis, Spyros N.
- Atmospheric Environment, Vol. 33, Issue 18
Tropospheric chemistry of internally mixed sea salt and organic particles: Surprising reactivity of NaCl with weak organic acids: MIXED SEA SALT/ORGANICS PARTICLES
journal, August 2012
- Laskin, Alexander; Moffet, Ryan C.; Gilles, Mary K.
- Journal of Geophysical Research: Atmospheres, Vol. 117, Issue D15
Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA)
journal, February 2022
- Wang, Jian; Wood, Rob; Jensen, Michael P.
- Bulletin of the American Meteorological Society, Vol. 103, Issue 2
Refinements to the particle-into-liquid sampler (PILS) for ground and airborne measurements of water soluble aerosol composition
journal, March 2003
- Orsini, Douglas A.; Ma, Yilin; Sullivan, Amy
- Atmospheric Environment, Vol. 37, Issue 9-10
High aerosol acidity despite declining atmospheric sulfate concentrations over the past 15 years
journal, February 2016
- Weber, Rodney J.; Guo, Hongyu; Russell, Armistead G.
- Nature Geoscience, Vol. 9, Issue 4
Role of pH in Aerosol Processes and Measurement Challenges
journal, November 2018
- Freedman, Miriam Arak; Ott, Emily-Jean E.; Marak, Katherine E.
- The Journal of Physical Chemistry A, Vol. 123, Issue 7
Inland Sea Spray Aerosol Transport and Incomplete Chloride Depletion: Varying Degrees of Reactive Processing Observed during SOAS
journal, August 2017
- Bondy, Amy L.; Wang, Bingbing; Laskin, Alexander
- Environmental Science & Technology, Vol. 51, Issue 17
An interlaboratory comparison of aerosol inorganic ion measurements by ion chromatography: implications for aerosol pH estimate
journal, January 2020
- Xu, Jingsha; Song, Shaojie; Harrison, Roy M.
- Atmospheric Measurement Techniques, Vol. 13, Issue 11
Relationships between ozone and carbon monoxide at surface sites in the North Atlantic region
journal, June 1998
- Parrish, D. D.; Trainer, M.; Holloway, J. S.
- Journal of Geophysical Research: Atmospheres, Vol. 103, Issue D11
Predicting the relative humidities of liquid-liquid phase separation, efflorescence, and deliquescence of mixed particles of ammonium sulfate, organic material, and water using the organic-to-sulfate mass ratio of the particle and the oxygen-to-carbon elemental ratio of the organic component
journal, January 2011
- Bertram, A. K.; Martin, S. T.; Hanna, S. J.
- Atmospheric Chemistry and Physics, Vol. 11, Issue 21
Global and regional model simulations of atmospheric ammonia
journal, April 2020
- Khan, M. A. H.; Lowe, D.; Derwent, R. G.
- Atmospheric Research, Vol. 234
Estimates of aerosol species scattering characteristics as a function of relative humidity
journal, June 2001
- Malm, William C.; Day, Derek E.
- Atmospheric Environment, Vol. 35, Issue 16
Observational constraints on particle acidity using measurements and modelling of particles and gases
journal, January 2017
- Murphy, J. G.; Gregoire, P. K.; Tevlin, A. G.
- Faraday Discussions, Vol. 200
A Study of Processes that Govern the Maintenance of Aerosols in the Marine Boundary Layer
journal, April 1999
- Katoshevski, David; Nenes, Athanasios; Seinfeld, John H.
- Journal of Aerosol Science, Vol. 30, Issue 4
Aerosol pH in the marine boundary layer
journal, March 1998
- Keene, William C.; Sander, Rolf; Pszenny, Alexander A. P.
- Journal of Aerosol Science, Vol. 29, Issue 3
A study of gas-aerosol equilibrium and aerosol pH in the remote marine boundary layer during the First Aerosol Characterization Experiment (ACE 1)
journal, July 2000
- Fridlind, A. M.; Jacobson, M. Z.
- Journal of Geophysical Research: Atmospheres, Vol. 105, Issue D13
Mixed Chloride Aerosols and their Atmospheric Implications: A Review
journal, January 2017
- Wang, Hao; Wang, Xinfeng; Yang, Xue
- Aerosol and Air Quality Research, Vol. 17, Issue 4
Multiphase buffer theory explains contrasts in atmospheric aerosol acidity
journal, September 2020
- Zheng, Guangjie; Su, Hang; Wang, Siwen
- Science, Vol. 369, Issue 6509
A general circulation model based calculation of HCl and ClNO 2 production from sea salt dechlorination: Reactive Chlorine Emissions Inventory
journal, April 1999
- Erickson, David J.; Seuzaret, Christophe; Keene, William C.
- Journal of Geophysical Research: Atmospheres, Vol. 104, Issue D7
The 2nd Aerosol Characterization Experiment (ACE-2): general overview and main results
journal, January 2000
- Raes, Frank; Bates, Timothy; McGovern, Frank
- Tellus B: Chemical and Physical Meteorology, Vol. 52, Issue 2
Reactive intermediates revealed in secondary organic aerosol formation from isoprene
journal, December 2009
- Surratt, J. D.; Chan, A. W. H.; Eddingsaas, N. C.
- Proceedings of the National Academy of Sciences, Vol. 107, Issue 15
The underappreciated role of nonvolatile cations in aerosol ammonium-sulfate molar ratios
journal, January 2018
- Guo, Hongyu; Nenes, Athanasios; Weber, Rodney J.
- Atmospheric Chemistry and Physics, Vol. 18, Issue 23
Marine boundary layer aerosol in the eastern North Atlantic: seasonal variations and key controlling processes
journal, January 2018
- Zheng, Guangjie; Wang, Yang; Aiken, Allison C.
- Atmospheric Chemistry and Physics, Vol. 18, Issue 23
Sulfate, nitrate, methanesulfonate, chloride, ammonium, and sodium measurements from ship, island, and aircraft during the Atlantic Stratocumulus Transition Experiment/Marine Aerosol Gas Exchange
journal, February 1996
- Huebert, Barry J.; Zhuang, Liangzhong; Howell, Steven
- Journal of Geophysical Research: Atmospheres, Vol. 101, Issue D2
Heterogeneous Atmospheric Aerosol Production by Acid-Catalyzed Particle-Phase Reactions
journal, October 2002
- Jang, M.
- Science, Vol. 298, Issue 5594
Fine particles in the global troposphere A review
journal, March 1989
- Heintzenberg, Jost
- Tellus B: Chemical and Physical Meteorology, Vol. 41, Issue 2
Quantitative Time-Resolved Monitoring of Nitrate Formation in Sea Salt Particles Using a CCSEM/EDX Single Particle Analysis
journal, December 2002
- Laskin, Alexander; Iedema, Martin J.; Cowin, James P.
- Environmental Science & Technology, Vol. 36, Issue 23
Fine particle pH and gas–particle phase partitioning of inorganic species in Pasadena, California, during the 2010 CalNex campaign
journal, January 2017
- Guo, Hongyu; Liu, Jiumeng; Froyd, Karl D.
- Atmospheric Chemistry and Physics, Vol. 17, Issue 9
The acidity of atmospheric particles and clouds
journal, January 2020
- Pye, Havala O. T.; Nenes, Athanasios; Alexander, Becky
- Atmospheric Chemistry and Physics, Vol. 20, Issue 8
Atmospheric aerosol models for systems including the ions H + , NH 4 + , Na + , SO 4 2− , NO 3 − , Cl − , Br − , and H 2 O
journal, January 2002
- Wexler, Anthony S.
- Journal of Geophysical Research, Vol. 107, Issue D14
Investigation of global particulate nitrate from the AeroCom phase III experiment
journal, January 2017
- Bian, Huisheng; Chin, Mian; Hauglustaine, Didier A.
- Atmospheric Chemistry and Physics, Vol. 17, Issue 21
Water-soluble ions species of size-resolved aerosols: Implications for the atmospheric acidity in São Paulo megacity, Brazil
journal, November 2016
- Vieira-Filho, Marcelo; Pedrotti, Jairo J.; Fornaro, Adalgiza
- Atmospheric Research, Vol. 181
Effects of water-soluble organic carbon on aerosol pH
journal, January 2019
- Battaglia Jr., Michael A.; Weber, Rodney J.; Nenes, Athanasios
- Atmospheric Chemistry and Physics, Vol. 19, Issue 23
Aerosols in an arid environment: The role of aerosol water content, particulate acidity, precursors, and relative humidity on secondary inorganic aerosols
journal, January 2019
- Wang, Haiting; Ding, Jing; Xu, Jiao
- Science of The Total Environment, Vol. 646
A Microorifice Uniform Deposit Impactor (MOUDI): Description, Calibration, and Use
journal, January 1991
- Marple, Virgil A.; Rubow, Kenneth L.; Behm, Steven M.
- Aerosol Science and Technology, Vol. 14, Issue 4
Iron mobilization in mineral dust: Can anthropogenic SO 2 emissions affect ocean productivity?
journal, January 2003
- Meskhidze, N.
- Geophysical Research Letters, Vol. 30, Issue 21
Halogen cycling and aerosol pH in the Hawaiian marine boundary layer
journal, January 2004
- Pszenny, A. A. P.; Moldanová, J.; Keene, W. C.
- Atmospheric Chemistry and Physics, Vol. 4, Issue 1
Highly Acidic Ambient Particles, Soluble Metals, and Oxidative Potential: A Link between Sulfate and Aerosol Toxicity
journal, February 2017
- Fang, Ting; Guo, Hongyu; Zeng, Linghan
- Environmental Science & Technology, Vol. 51, Issue 5
A study of acidity on PM2.5 in Hong Kong using online ionic chemical composition measurements
journal, December 2011
- Xue, Jian; Lau, Alexis K. H.; Yu, Jian Zhen
- Atmospheric Environment, Vol. 45, Issue 39
Aqueous-phase chemical processes in deliquescent sea-salt aerosols: A mechanism that couples the atmospheric cycles of S and sea salt
journal, January 1992
- Chameides, W. L.; Stelson, A. W.
- Journal of Geophysical Research, Vol. 97, Issue D18
Global oceanic emission of ammonia: Constraints from seawater and atmospheric observations
journal, August 2015
- Paulot, F.; Jacob, D. J.; Johnson, M. T.
- Global Biogeochemical Cycles, Vol. 29, Issue 8
Modeling and Characterization of a Particle-into-Liquid Sampler (PILS)
journal, July 2006
- Sorooshian, Armin; Brechtel, Fred J.; Ma, Yilin
- Aerosol Science and Technology, Vol. 40, Issue 6
The effect of dioctyl phthalate films on the ammonium nitrate aerosol evaporation rate
journal, January 2000
- Cruz, Celia N.; Dassios, Konstandinos G.; Pandis, Spyros N.
- Atmospheric Environment, Vol. 34, Issue 23
Chemical transport models often underestimate inorganic aerosol acidity in remote regions of the atmosphere
journal, May 2021
- Nault, Benjamin A.; Campuzano-Jost, Pedro; Day, Douglas A.
- Communications Earth & Environment, Vol. 2, Issue 1
ISORROPIA II: a computationally efficient thermodynamic equilibrium model for K<sup>+</sup>–Ca<sup>2+</sup>–Mg<sup>2+</sup>–NH<sub>4</sub><sup>+</sup>–Na<sup>+</sup>–SO<sub>4</sub><sup>2−</sup>–NO<sub>3</sub><sup>−</sup>–Cl<sup>−</sup>–H<sub>2</sub>O aerosols
journal, January 2007
- Fountoukis, C.; Nenes, A.
- Atmospheric Chemistry and Physics, Vol. 7, Issue 17
Fine-particle water and pH in the southeastern United States
journal, January 2015
- Guo, H.; Xu, L.; Bougiatioti, A.
- Atmospheric Chemistry and Physics, Vol. 15, Issue 9
The physical characteristics of sulfur aerosols
journal, January 1978
- Whitby, Kenneth T.
- Atmospheric Environment (1967), Vol. 12, Issue 1-3
Fine particle pH and the partitioning of nitric acid during winter in the northeastern United States: PARTICLE PH AND NITRIC ACID PARTITIONING
journal, September 2016
- Guo, Hongyu; Sullivan, Amy P.; Campuzano-Jost, Pedro
- Journal of Geophysical Research: Atmospheres, Vol. 121, Issue 17
Factors determining the formation of secondary inorganic aerosol: a case study in the Po Valley (Italy)
journal, January 2013
- Squizzato, S.; Masiol, M.; Brunelli, A.
- Atmospheric Chemistry and Physics, Vol. 13, Issue 4
Effect of ammonia on fine-particle pH in agricultural regions of China: comparison between urban and rural sites
journal, January 2020
- Wang, Shenbo; Wang, Lingling; Li, Yuqing
- Atmospheric Chemistry and Physics, Vol. 20, Issue 5
Kinetics and Products of the Acid-Catalyzed Ring-Opening of Atmospherically Relevant Butyl Epoxy Alcohols
journal, August 2010
- Eddingsaas, Nathan C.; VanderVelde, David G.; Wennberg, Paul O.
- The Journal of Physical Chemistry A, Vol. 114, Issue 31