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Title: Role of pH in Aerosol Processes and Measurement Challenges

Abstract

pH is one of the most basic chemical properties of aqueous solution, but its measurement in nanoscale aerosol particles presents many challenges. The pH of aerosol particles is of growing interest in the atmospheric chemistry community because of its demonstrated effects on heterogeneous chemistry and human health, as well as potential effects on climate. The authors have shown that phase transitions of aerosol particles are sensitive to pH, focusing on systems that undergo liquid-liquid phase separation. Currently, aerosol pH is calculated indirectly from knowledge of species present in the gas and aerosol phases through the use of thermodynamic models. From these models, ambient aerosol is expected to be highly acidic (pH ~ 0-3). Direct measurements have focused on model systems due to the difficulty of this measurement. This area is one in which physical chemists should be encouraged to contribute because of the potential consequences for aerosol processes in the environment.

Authors:
ORCiD logo [1];  [1];  [1]
  1. Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1491413
Alternate Identifier(s):
OSTI ID: 1508822
Grant/Contract Number:  
DE SC0018032; SC0018032; AGS-1723290
Resource Type:
Published Article
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Volume: 123 Journal Issue: 7; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Freedman, Miriam Arak, Ott, Emily-Jean E., and Marak, Katherine E. Role of pH in Aerosol Processes and Measurement Challenges. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.8b10676.
Freedman, Miriam Arak, Ott, Emily-Jean E., & Marak, Katherine E. Role of pH in Aerosol Processes and Measurement Challenges. United States. doi:https://doi.org/10.1021/acs.jpca.8b10676
Freedman, Miriam Arak, Ott, Emily-Jean E., and Marak, Katherine E. Mon . "Role of pH in Aerosol Processes and Measurement Challenges". United States. doi:https://doi.org/10.1021/acs.jpca.8b10676.
@article{osti_1491413,
title = {Role of pH in Aerosol Processes and Measurement Challenges},
author = {Freedman, Miriam Arak and Ott, Emily-Jean E. and Marak, Katherine E.},
abstractNote = {pH is one of the most basic chemical properties of aqueous solution, but its measurement in nanoscale aerosol particles presents many challenges. The pH of aerosol particles is of growing interest in the atmospheric chemistry community because of its demonstrated effects on heterogeneous chemistry and human health, as well as potential effects on climate. The authors have shown that phase transitions of aerosol particles are sensitive to pH, focusing on systems that undergo liquid-liquid phase separation. Currently, aerosol pH is calculated indirectly from knowledge of species present in the gas and aerosol phases through the use of thermodynamic models. From these models, ambient aerosol is expected to be highly acidic (pH ~ 0-3). Direct measurements have focused on model systems due to the difficulty of this measurement. This area is one in which physical chemists should be encouraged to contribute because of the potential consequences for aerosol processes in the environment.},
doi = {10.1021/acs.jpca.8b10676},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 7,
volume = 123,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: https://doi.org/10.1021/acs.jpca.8b10676

Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Acidic aerosol can cause damage to the lungs through dissolution of metals, oxidative stress, and inflammation.

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Works referenced in this record:

Effect of Acidity on Secondary Organic Aerosol Formation from Isoprene
journal, August 2007

  • Surratt, Jason D.; Lewandowski, Michael; Offenberg, John H.
  • Environmental Science & Technology, Vol. 41, Issue 15
  • DOI: 10.1021/es0704176

Enhanced Iron Solubility at Low pH in Global Aerosols
journal, May 2018


Effects of Gas-Particle Partitioning on Refractive Index and Chemical Composition of m -Xylene Secondary Organic Aerosol
journal, March 2018

  • Li, Kun; Li, Junling; Wang, Weigang
  • The Journal of Physical Chemistry A, Vol. 122, Issue 12
  • DOI: 10.1021/acs.jpca.7b12792

pH Dependence of Liquid–Liquid Phase Separation in Organic Aerosol
journal, September 2016

  • Losey, Delanie J.; Parker, Robert G.; Freedman, Miriam Arak
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 19
  • DOI: 10.1021/acs.jpclett.6b01621

Spectroscopic Determination of Aerosol pH from Acid–Base Equilibria in Inorganic, Organic, and Mixed Systems
journal, July 2017

  • Craig, Rebecca L.; Nandy, Lucy; Axson, Jessica L.
  • The Journal of Physical Chemistry A, Vol. 121, Issue 30
  • DOI: 10.1021/acs.jpca.7b05261

Sources and light absorption of water-soluble organic carbon aerosols in the outflow from northern China
journal, January 2014

  • Kirillova, E. N.; Andersson, A.; Han, J.
  • Atmospheric Chemistry and Physics, Vol. 14, Issue 3
  • DOI: 10.5194/acp-14-1413-2014

Health effects of acid aerosols formed by atmospheric mixtures.
journal, February 1989

  • Kleinman, M. T.; Phalen, R. F.; Mautz, W. J.
  • Environmental Health Perspectives, Vol. 79
  • DOI: 10.1289/ehp.8979137

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
  • DOI: 10.5194/acp-15-2775-2015

A time-series analysis of acidic particulate matter and daily mortality and morbidity in the Buffalo, New York, region.
journal, February 2000

  • Gwynn, R. C.; Burnett, R. T.; Thurston, G. D.
  • Environmental Health Perspectives, Vol. 108, Issue 2
  • DOI: 10.1289/ehp.00108125

Solar Absorption by Aerosol-Bound Nitrophenols Compared to Aqueous and Gaseous Nitrophenols
journal, May 2016

  • Hinrichs, Ryan Z.; Buczek, Pawel; Trivedi, Jal J.
  • Environmental Science & Technology, Vol. 50, Issue 11
  • DOI: 10.1021/acs.est.6b00302

Direct Measurement of pH in Individual Particles via Raman Microspectroscopy and Variation in Acidity with Relative Humidity
journal, February 2016

  • Rindelaub, Joel D.; Craig, Rebecca L.; Nandy, Lucy
  • The Journal of Physical Chemistry A, Vol. 120, Issue 6
  • DOI: 10.1021/acs.jpca.5b12699

Variation in pH of Model Secondary Organic Aerosol during Liquid–Liquid Phase Separation
journal, April 2016

  • Dallemagne, Magda A.; Huang, Xiau Ya; Eddingsaas, Nathan C.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 18
  • DOI: 10.1021/acs.jpca.6b00275

A review on the human health impact of airborne particulate matter
journal, January 2015


Sensitivity of transatlantic dust transport to chemical aging and related atmospheric processes
journal, January 2017

  • Abdelkader, Mohamed; Metzger, Swen; Steil, Benedikt
  • Atmospheric Chemistry and Physics, Vol. 17, Issue 6
  • DOI: 10.5194/acp-17-3799-2017

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
  • DOI: 10.1038/ngeo2665

Aerosol-chamber study of the α-pinene/O3 reaction: influence of particle acidity on aerosol yields and products
journal, February 2004


Characterization and acid-mobilization study of iron-containing mineral dust source materials: IRON-CONTAINING DUST SOURCE MATERIALS
journal, March 2008

  • Cwiertny, David M.; Baltrusaitis, Jonas; Hunter, Gordon J.
  • Journal of Geophysical Research: Atmospheres, Vol. 113, Issue D5
  • DOI: 10.1029/2007JD009332

Reactive halogen chemistry in the troposphere
journal, January 2012

  • Saiz-Lopez, Alfonso; von Glasow, Roland
  • Chemical Society Reviews, Vol. 41, Issue 19
  • DOI: 10.1039/c2cs35208g

Phase separation in organic aerosol
journal, January 2017

  • Freedman, Miriam Arak
  • Chemical Society Reviews, Vol. 46, Issue 24
  • DOI: 10.1039/C6CS00783J

Size dependence of in situ pH in submicron atmospheric particles in Hong Kong
journal, January 2007


Chemical characteristics of acidic gas pollutants and PM2.5 species during hazy episodes in Seoul, South Korea
journal, September 2004


Composition of Air Pollution Particles and Oxidative Stress in Cells, Tissues, and Living Systems
journal, January 2012

  • Ghio, Andrew J.; Carraway, Martha Sue; Madden, Michael C.
  • Journal of Toxicology and Environmental Health, Part B, Vol. 15, Issue 1
  • DOI: 10.1080/10937404.2012.632359

Particle Phase Acidity and Oligomer Formation in Secondary Organic Aerosol
journal, December 2004

  • Gao, Song; Ng, Nga L.; Keywood, Melita
  • Environmental Science & Technology, Vol. 38, Issue 24
  • DOI: 10.1021/es049125k

Iron dissolution and speciation in atmospheric mineral dust: Metal-metal synergistic and antagonistic effects
journal, August 2018


Observations and implications of liquid–liquid phase separation at high relative humidities in secondary organic material produced by α -pinene ozonolysis without inorganic salts
journal, January 2016

  • Renbaum-Wolff, Lindsay; Song, Mijung; Marcolli, Claudia
  • Atmospheric Chemistry and Physics, Vol. 16, Issue 12
  • DOI: 10.5194/acp-16-7969-2016

Acidity of Aerosols during Winter Heavy Haze Events in Beijing and Gucheng, China
journal, February 2018

  • Chi, Xiyuan; He, Pengzhen; Jiang, Zhuang
  • Journal of Meteorological Research, Vol. 32, Issue 1
  • DOI: 10.1007/s13351-018-7063-4

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
  • DOI: 10.1039/C7FD00086C

Organic aerosol growth by acid-catalyzed heterogeneous reactions of octanal in a flow reactor
journal, May 2003


Conversion of Iodide to Hypoiodous Acid and Iodine in Aqueous Microdroplets Exposed to Ozone
journal, September 2013

  • Pillar, Elizabeth A.; Guzman, Marcelo I.; Rodriguez, Jose M.
  • Environmental Science & Technology, Vol. 47, Issue 19
  • DOI: 10.1021/es401700h

Nanotoxicology: An Emerging Discipline Evolving from Studies of Ultrafine Particles
journal, July 2005

  • Oberdörster, Günter; Oberdörster, Eva; Oberdörster, Jan
  • Environmental Health Perspectives, Vol. 113, Issue 7
  • DOI: 10.1289/ehp.7339

Heterogeneous Reaction of Gaseous Ozone with Aqueous Iodide in the Presence of Aqueous Organic Species
journal, May 2010

  • Hayase, Sayaka; Yabushita, Akihiro; Kawasaki, Masahiro
  • The Journal of Physical Chemistry A, Vol. 114, Issue 19
  • DOI: 10.1021/jp101985f

Particle water and pH in the eastern Mediterranean: source variability and implications for nutrient availability
journal, January 2016

  • Bougiatioti, Aikaterini; Nikolaou, Panayiota; Stavroulas, Iasonas
  • Atmospheric Chemistry and Physics, Vol. 16, Issue 7
  • DOI: 10.5194/acp-16-4579-2016

An Association between Air Pollution and Mortality in Six U.S. Cities
journal, December 1993


Weak Acids Enhance Halogen Activation on Atmospheric Water’s Surfaces
journal, May 2011

  • Hayase, Sayaka; Yabushita, Akihiro; Kawasaki, Masahiro
  • The Journal of Physical Chemistry A, Vol. 115, Issue 19
  • DOI: 10.1021/jp2021775

Tropospheric Halogen Chemistry: Sources, Cycling, and Impacts
journal, February 2015

  • Simpson, William R.; Brown, Steven S.; Saiz-Lopez, Alfonso
  • Chemical Reviews, Vol. 115, Issue 10
  • DOI: 10.1021/cr5006638

A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients
journal, January 2008

  • Zuend, A.; Marcolli, C.; Luo, B. P.
  • Atmospheric Chemistry and Physics, Vol. 8, Issue 16
  • DOI: 10.5194/acp-8-4559-2008

Heterogeneous SOA yield from ozonolysis of monoterpenes in the presence of inorganic acid
journal, March 2007


The Effects of Organic Species on the Hygroscopic Behaviors of Inorganic Aerosols
journal, June 2002

  • Choi, Man Yee; Chan, Chak K.
  • Environmental Science & Technology, Vol. 36, Issue 11
  • DOI: 10.1021/es0113293

Effects of High Acidity on Phase Transitions of an Organic Aerosol
journal, March 2018

  • Losey, Delanie J.; Ott, Emily-Jean E.; Freedman, Miriam Arak
  • The Journal of Physical Chemistry A, Vol. 122, Issue 15
  • DOI: 10.1021/acs.jpca.8b00399

Pathways of sulfate enhancement by natural and anthropogenic mineral aerosols in China
journal, December 2014

  • Huang, Xin; Song, Yu; Zhao, Chun
  • Journal of Geophysical Research: Atmospheres, Vol. 119, Issue 24
  • DOI: 10.1002/2014JD022301

Global analysis of nitrogen and phosphorus limitation of primary producers in freshwater, marine and terrestrial ecosystems
journal, December 2007


Enhancement of Gaseous Iodine Emission by Aqueous Ferrous Ions during the Heterogeneous Reaction of Gaseous Ozone with Aqueous Iodide
journal, March 2013

  • Sakamoto, Yosuke; Enami, Shinichi; Tonokura, Kenichi
  • The Journal of Physical Chemistry A, Vol. 117, Issue 14
  • DOI: 10.1021/jp308407j

Particle Growth by Acid-Catalyzed Heterogeneous Reactions of Organic Carbonyls on Preexisting Aerosols
journal, September 2003

  • Jang, Myoseon; Carroll, Brian; Chandramouli, Bharadwaj
  • Environmental Science & Technology, Vol. 37, Issue 17
  • DOI: 10.1021/es021005u

Coupling of organic and inorganic aerosol systems and the effect on gas–particle partitioning in the southeastern US
journal, January 2018

  • Pye, Havala O. T.; Zuend, Andreas; Fry, Juliane L.
  • Atmospheric Chemistry and Physics, Vol. 18, Issue 1
  • DOI: 10.5194/acp-18-357-2018

Organic aerosol and global climate modelling: a review
journal, January 2005

  • Kanakidou, M.; Seinfeld, J. H.; Pandis, S. N.
  • Atmospheric Chemistry and Physics, Vol. 5, Issue 4
  • DOI: 10.5194/acp-5-1053-2005

Atmospheric acidification of mineral aerosols: a source of bioavailable phosphorus for the oceans
journal, January 2011

  • Nenes, A.; Krom, M. D.; Mihalopoulos, N.
  • Atmospheric Chemistry and Physics, Vol. 11, Issue 13
  • DOI: 10.5194/acp-11-6265-2011

High levels of ammonia do not raise fine particle pH sufficiently to yield nitrogen oxide-dominated sulfate production
journal, September 2017


Liquid–liquid phase separation in organic particles containing one and two organic species: importance of the average O : C
journal, January 2018

  • Song, Mijung; Ham, Suhan; Andrews, Ryan J.
  • Atmospheric Chemistry and Physics, Vol. 18, Issue 16
  • DOI: 10.5194/acp-18-12075-2018

Liquid–liquid phase separation in atmospherically relevant particles consisting of organic species and inorganic salts
journal, January 2014

  • You, Yuan; Smith, Mackenzie L.; Song, Mijung
  • International Reviews in Physical Chemistry, Vol. 33, Issue 1
  • DOI: 10.1080/0144235X.2014.890786

Evolution of Organic Aerosols in the Atmosphere
journal, December 2009


Br 2 Production from the Heterogeneous Reaction of Gas-Phase OH with Aqueous Salt Solutions:  Impacts of Acidity, Halide Concentration, and Organic Surfactants
journal, September 2006

  • Frinak, Elizabeth K.; Abbatt, Jonathan P. D.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 35
  • DOI: 10.1021/jp063165o

Aerosol microdroplets exhibit a stable pH gradient
journal, June 2018

  • Wei, Haoran; Vejerano, Eric P.; Leng, Weinan
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 28
  • DOI: 10.1073/pnas.1720488115

The formation, properties and impact of secondary organic aerosol: current and emerging issues
journal, January 2009

  • Hallquist, M.; Wenger, J. C.; Baltensperger, U.
  • Atmospheric Chemistry and Physics, Vol. 9, Issue 14
  • DOI: 10.5194/acp-9-5155-2009

Persistent sulfate formation from London Fog to Chinese haze
journal, November 2016

  • Wang, Gehui; Zhang, Renyi; Gomez, Mario E.
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 48
  • DOI: 10.1073/pnas.1616540113

Iron dissolution kinetics of mineral dust at low pH during simulated atmospheric processing
journal, January 2011

  • Shi, Z.; Bonneville, S.; Krom, M. D.
  • Atmospheric Chemistry and Physics, Vol. 11, Issue 3
  • DOI: 10.5194/acp-11-995-2011

The influence of solvent and pH on determination of the light absorption properties of water-soluble brown carbon
journal, July 2017


The contribution of outdoor air pollution sources to premature mortality on a global scale
journal, September 2015


Quantification of SO 2 Oxidation on Interfacial Surfaces of Acidic Micro-Droplets: Implication for Ambient Sulfate Formation
journal, July 2018

  • Hung, Hui-Ming; Hsu, Mu-Ni; Hoffmann, Michael R.
  • Environmental Science & Technology, Vol. 52, Issue 16
  • DOI: 10.1021/acs.est.8b01391

N2O5 Oxidizes Chloride to Cl2 in Acidic Atmospheric Aerosol
journal, August 2008


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


Technical note: Comparison and interconversion of pH based on different standard states for aerosol acidity characterization
journal, January 2018


Health effects of acid aerosols on North American children: pulmonary function.
journal, May 1996

  • Raizenne, M.; Neas, L. M.; Damokosh, A. I.
  • Environmental Health Perspectives, Vol. 104, Issue 5
  • DOI: 10.1289/ehp.96104506

Liquid–liquid phase separation in particles containing secondary organic material free of inorganic salts
journal, January 2017

  • Song, Mijung; Liu, Pengfei; Martin, Scot T.
  • Atmospheric Chemistry and Physics, Vol. 17, Issue 18
  • DOI: 10.5194/acp-17-11261-2017

Thermodynamics of multicomponent, miscible, ionic solutions. Mixtures including unsymmetrical electrolytes
journal, November 1992

  • Clegg, Simon L.; Pitzer, Kenneth S.; Brimblecombe, Peter
  • The Journal of Physical Chemistry, Vol. 96, Issue 23
  • DOI: 10.1021/j100202a074

Cloud activation of single-component organic aerosol particles
journal, January 2002

  • Raymond, Timothy M.
  • Journal of Geophysical Research, Vol. 107, Issue D24
  • DOI: 10.1029/2002JD002159

Secondary organic aerosol formation from <i>m</i>-xylene, toluene, and benzene
journal, January 2007

  • Ng, N. L.; Kroll, J. H.; Chan, A. W. H.
  • Atmospheric Chemistry and Physics, Vol. 7, Issue 14
  • DOI: 10.5194/acp-7-3909-2007

Atmospheric processing of iron carried by mineral dust
journal, January 2013

  • Nickovic, S.; Vukovic, A.; Vujadinovic, M.
  • Atmospheric Chemistry and Physics, Vol. 13, Issue 18
  • DOI: 10.5194/acp-13-9169-2013

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
  • DOI: 10.5194/acp-4-147-2004

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
  • DOI: 10.1021/acs.est.6b06151

Diabetes Enhances Vulnerability to Particulate Air Pollution–Associated Impairment in Vascular Reactivity and Endothelial Function
journal, June 2005


Respiratory Hospital Admissions and Summertime Haze Air Pollution in Toronto, Ontario: Consideration of the Role of Acid Aerosols
journal, May 1994


CCN Activity and Hygroscopic Growth of Organic Aerosols Following Reactive Uptake of Ammonia
journal, February 2008

  • Dinar, E.; Anttila, T.; Rudich, Y.
  • Environmental Science & Technology, Vol. 42, Issue 3
  • DOI: 10.1021/es071874p

Fine-particle water and pH in the southeastern United States
journal, January 2015


Direct Determination of Aerosol pH: Size-Resolved Measurements of Submicrometer and Supermicrometer Aqueous Particles
journal, September 2018


Effect of the Urban Heat Island on Aerosol pH
journal, November 2017

  • Battaglia, Michael A.; Douglas, Sarah; Hennigan, Christopher J.
  • Environmental Science & Technology, Vol. 51, Issue 22
  • DOI: 10.1021/acs.est.7b02786

Exposure of Lung Epithelial Cells to Photochemically Aged Secondary Organic Aerosol Shows Increased Toxic Effects
journal, June 2018

  • Chowdhury, Pratiti Home; He, Quanfu; Lasitza Male, Tatyana
  • Environmental Science & Technology Letters, Vol. 5, Issue 7
  • DOI: 10.1021/acs.estlett.8b00256

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
  • DOI: 10.1002/2016JD025311

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