DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Investigating the Tropospheric Chemistry of Acetic Acid Using the Global 3‐D Chemistry Transport Model, STOCHEM‐CRI

Abstract

Abstract Acetic acid (CH 3 COOH) is one of the most abundant carboxylic acids in the troposphere. In the study, the tropospheric chemistry of CH 3 COOH is investigated using the 3‐D global chemistry transport model, STOCHEM‐CRI. The highest mixing ratios of surface CH 3 COOH are found in the tropics by as much as 1.6 ppb in South America. The model predicts the seasonality of CH 3 COOH reasonably well and correlates with some surface and flight measurement sites, but the model drastically underpredicts levels in urban and midlatitudinal regions. The possible reasons for the underprediction are discussed. The simulations show that the lifetime and global burden of CH 3 COOH are 1.6–1.8 days and 0.45–0.61 Tg, respectively. The reactions of the peroxyacetyl radical (CH 3 CO 3 ) with the hydroperoxyl radical (HO 2 ) and other organic peroxy radicals (RO 2 ) are found to be the principal sources of tropospheric CH 3 COOH in the model, but the model‐measurement discrepancies suggest the possible unknown or underestimated sources which can contribute large fractions of the CH 3 COOH burden. The major sinks of CH 3 COOH in the troposphere are wet deposition, dry deposition, and OH loss. However, the reactionmore » of CH 3 COOH with Criegee intermediates is proposed to be a potentially significant chemical loss process of tropospheric CH 3 COOH that has not been previously accounted for in global modeling studies. Inclusion of this loss process reduces the tropospheric CH 3 COOH level significantly which can give even larger discrepancies between model and measurement data, suggesting that the emissions inventory and the chemical production sources of CH 3 COOH are underpredicted even more so in current global models.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [2]; ORCiD logo [2];  [1];  [3]; ORCiD logo [1]
  1. School of Chemistry University of Bristol Bristol UK
  2. Combustion Research Facility Sandia National Laboratories Livermore CA USA
  3. Jet Propulsion Laboratory California Institute of Technology Pasadena CA USA
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1454283
Alternate Identifier(s):
OSTI ID: 1454284; OSTI ID: 1459928
Report Number(s):
SAND2018-6899J
Journal ID: ISSN 2169-897X
Grant/Contract Number:  
DE‐AC02‐05CH11231; AC04-94AL85000
Resource Type:
Published Article
Journal Name:
Journal of Geophysical Research: Atmospheres
Additional Journal Information:
Journal Name: Journal of Geophysical Research: Atmospheres Journal Volume: 123 Journal Issue: 11; Journal ID: ISSN 2169-897X
Publisher:
American Geophysical Union (AGU)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Khan, M. Anwar H., Lyons, Kyle, Chhantyal‐Pun, Rabi, McGillen, Max R., Caravan, Rebecca L., Taatjes, Craig A., Orr‐Ewing, Andrew J., Percival, Carl J., and Shallcross, Dudley E. Investigating the Tropospheric Chemistry of Acetic Acid Using the Global 3‐D Chemistry Transport Model, STOCHEM‐CRI. United States: N. p., 2018. Web. doi:10.1029/2018JD028529.
Khan, M. Anwar H., Lyons, Kyle, Chhantyal‐Pun, Rabi, McGillen, Max R., Caravan, Rebecca L., Taatjes, Craig A., Orr‐Ewing, Andrew J., Percival, Carl J., & Shallcross, Dudley E. Investigating the Tropospheric Chemistry of Acetic Acid Using the Global 3‐D Chemistry Transport Model, STOCHEM‐CRI. United States. https://doi.org/10.1029/2018JD028529
Khan, M. Anwar H., Lyons, Kyle, Chhantyal‐Pun, Rabi, McGillen, Max R., Caravan, Rebecca L., Taatjes, Craig A., Orr‐Ewing, Andrew J., Percival, Carl J., and Shallcross, Dudley E. Wed . "Investigating the Tropospheric Chemistry of Acetic Acid Using the Global 3‐D Chemistry Transport Model, STOCHEM‐CRI". United States. https://doi.org/10.1029/2018JD028529.
@article{osti_1454283,
title = {Investigating the Tropospheric Chemistry of Acetic Acid Using the Global 3‐D Chemistry Transport Model, STOCHEM‐CRI},
author = {Khan, M. Anwar H. and Lyons, Kyle and Chhantyal‐Pun, Rabi and McGillen, Max R. and Caravan, Rebecca L. and Taatjes, Craig A. and Orr‐Ewing, Andrew J. and Percival, Carl J. and Shallcross, Dudley E.},
abstractNote = {Abstract Acetic acid (CH 3 COOH) is one of the most abundant carboxylic acids in the troposphere. In the study, the tropospheric chemistry of CH 3 COOH is investigated using the 3‐D global chemistry transport model, STOCHEM‐CRI. The highest mixing ratios of surface CH 3 COOH are found in the tropics by as much as 1.6 ppb in South America. The model predicts the seasonality of CH 3 COOH reasonably well and correlates with some surface and flight measurement sites, but the model drastically underpredicts levels in urban and midlatitudinal regions. The possible reasons for the underprediction are discussed. The simulations show that the lifetime and global burden of CH 3 COOH are 1.6–1.8 days and 0.45–0.61 Tg, respectively. The reactions of the peroxyacetyl radical (CH 3 CO 3 ) with the hydroperoxyl radical (HO 2 ) and other organic peroxy radicals (RO 2 ) are found to be the principal sources of tropospheric CH 3 COOH in the model, but the model‐measurement discrepancies suggest the possible unknown or underestimated sources which can contribute large fractions of the CH 3 COOH burden. The major sinks of CH 3 COOH in the troposphere are wet deposition, dry deposition, and OH loss. However, the reaction of CH 3 COOH with Criegee intermediates is proposed to be a potentially significant chemical loss process of tropospheric CH 3 COOH that has not been previously accounted for in global modeling studies. Inclusion of this loss process reduces the tropospheric CH 3 COOH level significantly which can give even larger discrepancies between model and measurement data, suggesting that the emissions inventory and the chemical production sources of CH 3 COOH are underpredicted even more so in current global models.},
doi = {10.1029/2018JD028529},
journal = {Journal of Geophysical Research: Atmospheres},
number = 11,
volume = 123,
place = {United States},
year = {Wed Jun 13 00:00:00 EDT 2018},
month = {Wed Jun 13 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1029/2018JD028529

Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Evaluation of the global oceanic isoprene source and its impacts on marine organic carbon aerosol
journal, January 2009

  • Arnold, S. R.; Spracklen, D. V.; Williams, J.
  • Atmospheric Chemistry and Physics, Vol. 9, Issue 4
  • DOI: 10.5194/acp-9-1253-2009

A study of global atmospheric budget and distribution of acetone using global atmospheric model STOCHEM-CRI
journal, July 2015


Atmospheric formic and acetic acids: An overview
journal, May 1999

  • Khare, Puja; Kumar, N.; Kumari, K. M.
  • Reviews of Geophysics, Vol. 37, Issue 2
  • DOI: 10.1029/1998RG900005

Criegee intermediates and their impacts on the troposphere
journal, January 2018

  • Khan, M. A. H.; Percival, C. J.; Caravan, R. L.
  • Environmental Science: Processes & Impacts, Vol. 20, Issue 3
  • DOI: 10.1039/C7EM00585G

Atmospheric concentrations of formic and acetic acid and related compounds in eastern and northern Austria
journal, January 1988


Short-chain oxygenated VOCs: Emission and uptake by plants and atmospheric sources, sinks, and concentrations
journal, April 2007


Compilation of Henry's law constants (version 4.0) for water as solvent
journal, January 2015


Computational Study on the Existence of Organic Peroxy Radical-Water Complexes (RO 2 ·H 2 O)
journal, February 2008

  • Clark, Jared; English, Alecia M.; Hansen, Jaron C.
  • The Journal of Physical Chemistry A, Vol. 112, Issue 7
  • DOI: 10.1021/jp077266d

How is surface ozone in Europe linked to Asian and North American NOx emissions?
journal, October 2008


Global data set of biogenic VOC emissions calculated by the MEGAN model over the last 30 years
journal, January 2014

  • Sindelarova, K.; Granier, C.; Bouarar, I.
  • Atmospheric Chemistry and Physics, Vol. 14, Issue 17
  • DOI: 10.5194/acp-14-9317-2014

Global atmospheric budget of acetaldehyde: 3-D model analysis and constraints from in-situ and satellite observations
journal, January 2010

  • Millet, D. B.; Guenther, A.; Siegel, D. A.
  • Atmospheric Chemistry and Physics, Vol. 10, Issue 7
  • DOI: 10.5194/acp-10-3405-2010

Considerations regarding sources for formic and acetic acids in the troposphere
journal, January 1986

  • Keene, William C.; Galloway, James N.
  • Journal of Geophysical Research, Vol. 91, Issue D13
  • DOI: 10.1029/JD091iD13p14466

Acidic gases (HCOOH, CH 3 COOH, HNO 3 , HCl, and SO 2 ) and related aerosol species at a high mountain Alpine site (4360 m elevation) in Europe
journal, January 2007

  • Preunkert, S.; Legrand, M.; Jourdain, B.
  • Journal of Geophysical Research, Vol. 112, Issue D23
  • DOI: 10.1029/2006JD008225

Measurements of formic and acetic acid levels in the vapour phase at Dayalbagh, Agra, India
journal, October 1996


Importance of secondary sources in the atmospheric budgets of formic and acetic acids
journal, January 2011

  • Paulot, F.; Wunch, D.; Crounse, J. D.
  • Atmospheric Chemistry and Physics, Vol. 11, Issue 5
  • DOI: 10.5194/acp-11-1989-2011

C 1 −C 5 Organic Acid Emissions from an SI Engine:  Influence of Fuel and Air/Fuel Equivalence Ratio
journal, July 2001

  • Zervas, E.; Montagne, X.; Lahaye, J.
  • Environmental Science & Technology, Vol. 35, Issue 13
  • DOI: 10.1021/es000237v

Carboxylic acids in gas and particulate phase above the Atlantic Ocean
journal, June 2000

  • Baboukas, E. D.; Kanakidou, M.; Mihalopoulos, N.
  • Journal of Geophysical Research: Atmospheres, Vol. 105, Issue D11
  • DOI: 10.1029/1999JD900977

Distribution and fate of selected oxygenated organic species in the troposphere and lower stratosphere over the Atlantic
journal, February 2000

  • Singh, H.; Chen, Y.; Tabazadeh, A.
  • Journal of Geophysical Research: Atmospheres, Vol. 105, Issue D3
  • DOI: 10.1029/1999JD900779

A model for studies of tropospheric ozone and nonmethane hydrocarbons: Model evaluation of ozone-related species
journal, January 2003


The composition of precipitation in remote areas of the world
journal, January 1982

  • Galloway, James N.; Likens, Gene E.; Keene, William C.
  • Journal of Geophysical Research, Vol. 87, Issue C11
  • DOI: 10.1029/JC087iC11p08771

A Common Representative Intermediates (CRI) mechanism for VOC degradation. Part 2: Gas phase mechanism reduction
journal, October 2008


Atmospheric evolution of organic aerosol: ATMOSPHERIC EVOLUTION OF ORGANIC AEROSOL
journal, November 2004

  • Molina, M. J.; Ivanov, A. V.; Trakhtenberg, S.
  • Geophysical Research Letters, Vol. 31, Issue 22
  • DOI: 10.1029/2004GL020910

Formic acid and acetic acid: Emissions, atmospheric formation and dry deposition at two southern California locations
journal, December 1992


Organic acids in Southern California air: ambient concentrations, mobile source emissions, in situ formation and removal processes
journal, December 1989

  • Grosjean, Daniel
  • Environmental Science & Technology, Vol. 23, Issue 12
  • DOI: 10.1021/es00070a009

Formic and acetic acid over the central Amazon region, Brazil: 1. Dry season
journal, January 1988

  • Andreae, M. O.; Talbot, R. W.; Andreae, T. W.
  • Journal of Geophysical Research, Vol. 93, Issue D2
  • DOI: 10.1029/JD093iD02p01616

Effects of additional nonmethane volatile organic compounds, organic nitrates, and direct emissions of oxygenated organic species on global tropospheric chemistry
journal, January 2007

  • Ito, Akinori; Sillman, Sanford; Penner, Joyce E.
  • Journal of Geophysical Research, Vol. 112, Issue D6
  • DOI: 10.1029/2005JD006556

Mechanism of the OH-Initiated Oxidation of Hydroxyacetone over the Temperature Range 236−298 K
journal, June 2006

  • Butkovskaya, Nadezhda I.; Pouvesle, Nicolas; Kukui, Alexander
  • The Journal of Physical Chemistry A, Vol. 110, Issue 21
  • DOI: 10.1021/jp056345r

Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry
journal, January 2009

  • Pan, X.; Underwood, J. S.; Xing, J. -H.
  • Atmospheric Chemistry and Physics, Vol. 9, Issue 12
  • DOI: 10.5194/acp-9-3851-2009

A Common Representative Intermediates (CRI) mechanism for VOC degradation. Part 3: Development of a secondary organic aerosol module
journal, April 2009


Equilibrium constant of the HO 2 -H 2 O complex formation and kinetics of HO 2 + HO 2 -H 2 O: Implications for tropospheric chemistry
journal, January 2006

  • Kanno, Nozomu; Tonokura, Kenichi; Koshi, Mitsuo
  • Journal of Geophysical Research, Vol. 111, Issue D20
  • DOI: 10.1029/2005JD006805

Determination of organic acids (C1-C10) in the atmosphere, motor exhausts, and engine oils
journal, November 1985

  • Kawamura, Kimitaka.; Ng, Lai Ling.; Kaplan, Isaac R.
  • Environmental Science & Technology, Vol. 19, Issue 11
  • DOI: 10.1021/es00141a010

A Common Representative Intermediates (CRI) mechanism for VOC degradation. Part 1: Gas phase mechanism development
journal, October 2008


A modeling study of secondary organic aerosol formation from sesquiterpenes using the STOCHEM global chemistry and transport model: SOA FORMATION FROM SESQUITERPENES
journal, April 2017

  • Khan, M. A. H.; Jenkin, M. E.; Foulds, A.
  • Journal of Geophysical Research: Atmospheres, Vol. 122, Issue 8
  • DOI: 10.1002/2016JD026415

Gaseous formic and acetic acids in the atmosphere of Yokohama, Japan
journal, April 1992

  • Schultz Tokos, J. J.; Tanaka, S.; Morikami, T.
  • Journal of Atmospheric Chemistry, Vol. 14, Issue 1-4
  • DOI: 10.1007/BF00115225

Link between isoprene and secondary organic aerosol (SOA): Pyruvic acid oxidation yields low volatility organic acids in clouds
journal, January 2006

  • Carlton, Annmarie G.; Turpin, Barbara J.; Lim, Ho-Jin
  • Geophysical Research Letters, Vol. 33, Issue 6
  • DOI: 10.1029/2005GL025374

Acid generation in the troposphere by gas-phase chemistry
journal, September 1983

  • Calvert, Jack G.; Stockwell, William R.
  • Environmental Science & Technology, Vol. 17, Issue 9
  • DOI: 10.1021/es00115a727

Atmospheric formic and acetic acids in Venezuela
journal, May 1996


Carboxylic acids in the rural continental atmosphere over the eastern United States during the Shenandoah Cloud and Photochemistry Experiment
journal, January 1995

  • Talbot, Robert W.; Mosher, Byard W.; Heikes, Brian G.
  • Journal of Geophysical Research, Vol. 100, Issue D5
  • DOI: 10.1029/95JD00507

Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications
journal, March 2014

  • Welz, Oliver; Eskola, Arkke J.; Sheps, Leonid
  • Angewandte Chemie International Edition, Vol. 53, Issue 18
  • DOI: 10.1002/anie.201400964

Temperature-Dependence of the Rates of Reaction of Trifluoroacetic Acid with Criegee Intermediates
journal, June 2017

  • Chhantyal-Pun, Rabi; McGillen, Max R.; Beames, Joseph M.
  • Angewandte Chemie International Edition, Vol. 56, Issue 31
  • DOI: 10.1002/anie.201703700

Organic acids over equatorial Africa: Results from DECAFE 88
journal, January 1992

  • Helas, Gunter; Bingemer, Heinz; Andreae, Meinrat O.
  • Journal of Geophysical Research, Vol. 97, Issue D6
  • DOI: 10.1029/91JD01438

Rethinking the global secondary organic aerosol (SOA) budget: stronger production, faster removal, shorter lifetime
journal, January 2016

  • Hodzic, Alma; Kasibhatla, Prasad S.; Jo, Duseong S.
  • Atmospheric Chemistry and Physics, Vol. 16, Issue 12
  • DOI: 10.5194/acp-16-7917-2016

Carboxylic acids in the troposphere, occurrence, sources, and sinks: A review
journal, December 1996


Criegee Intermediate–Alcohol Reactions, A Potential Source of Functionalized Hydroperoxides in the Atmosphere
journal, December 2017


Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime
journal, January 2015

  • Hodzic, A.; Madronich, S.; Kasibhatla, P. S.
  • Atmospheric Chemistry and Physics, Vol. 15, Issue 16
  • DOI: 10.5194/acp-15-9253-2015

Sources and sinks of formic, acetic, and pyruvic acids over central Amazonia: 2. Wet season
journal, January 1990

  • Talbot, R. W.; Andreae, M. O.; Berresheim, H.
  • Journal of Geophysical Research, Vol. 95, Issue D10
  • DOI: 10.1029/JD095iD10p16799

The second Hadley Centre coupled ocean-atmosphere GCM: model description, spinup and validation
journal, February 1997

  • Johns, T. C.; Carnell, R. E.; Crossley, J. F.
  • Climate Dynamics, Vol. 13, Issue 2
  • DOI: 10.1007/s003820050155

Gaseous oxygenated hydrocarbons in the remote marine troposphere
journal, January 1990

  • Arlander, D. W.; Cronn, D. R.; Farmer, J. C.
  • Journal of Geophysical Research, Vol. 95, Issue D10
  • DOI: 10.1029/JD095iD10p16391

Calibration and intercomparison of acetic acid measurements using proton-transfer-reaction mass spectrometry (PTR-MS)
journal, January 2012

  • Haase, K. B.; Keene, W. C.; Pszenny, A. A. P.
  • Atmospheric Measurement Techniques, Vol. 5, Issue 11
  • DOI: 10.5194/amt-5-2739-2012

Photochemistry of biogenic emissions over the Amazon forest
journal, January 1988

  • Jacob, Daniel J.; Wofsy, Steven C.
  • Journal of Geophysical Research, Vol. 93, Issue D2
  • DOI: 10.1029/JD093iD02p01477

Permutation reactions of organic peroxy radicals in the troposphere
journal, January 1990

  • Madronich, Sasha; Calvert, Jack G.
  • Journal of Geophysical Research, Vol. 95, Issue D5
  • DOI: 10.1029/JD095iD05p05697

Photochemical Aging of Light-Absorbing Secondary Organic Aerosol Material
journal, March 2013

  • Sareen, Neha; Moussa, Samar G.; McNeill, V. Faye
  • The Journal of Physical Chemistry A, Vol. 117, Issue 14
  • DOI: 10.1021/jp309413j

Atmospheric transformation of enols: A potential secondary source of carboxylic acids in the urban troposphere
journal, January 2007

  • Archibald, Alex T.; McGillen, Max R.; Taatjes, Craig A.
  • Geophysical Research Letters, Vol. 34, Issue 21
  • DOI: 10.1029/2007GL031032

Unimolecular decay strongly limits the atmospheric impact of Criegee intermediates
journal, January 2017

  • Vereecken, L.; Novelli, A.; Taraborrelli, D.
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 47
  • DOI: 10.1039/C7CP05541B

Carboxylic acids in clouds at a high-elevation forested site in central Virginia
journal, January 1995

  • Keene, William C.; Mosher, Byard W.; Jacob, Daniel J.
  • Journal of Geophysical Research, Vol. 100, Issue D5
  • DOI: 10.1029/94JD01247

Emission of formic and acetic acids from tropical Savanna soils
journal, September 1991

  • Sanhueza, Eugenio; Andreae, Meinrat O.
  • Geophysical Research Letters, Vol. 18, Issue 9
  • DOI: 10.1029/91GL01565

Biosphere/Atmosphere interactions: Integrated research in a European coniferous forest ecosystem
journal, January 1992

  • Enders, G.; Dlugi, R.; Steinbrecher, R.
  • Atmospheric Environment. Part A. General Topics, Vol. 26, Issue 1
  • DOI: 10.1016/0960-1686(92)90269-Q

Global Budget and Distribution of Peroxyacetyl Nitrate (PAN) for Present and Preindustrial Scenarios
journal, March 2017

  • Khan, M. Anwar; Cooke, Michael; Utembe, Steven
  • International Journal of Earth & Environmental Sciences, Vol. 2, Issue 1
  • DOI: 10.15344/2456-351X/2017/130

Atmospheric Wet Deposition in Remote Regions: Benchmarks for Environmental Change
journal, August 2015

  • Keene, William C.; Galloway, James N.; Likens, Gene E.
  • Journal of the Atmospheric Sciences, Vol. 72, Issue 8
  • DOI: 10.1175/JAS-D-14-0378.1

Atmospheric Oxidation Pathways of Acetic Acid
journal, April 2006

  • Rosado-Reyes, Claudette M.; Francisco, Joseph S.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 13
  • DOI: 10.1021/jp0567974

Chemical characteristics and sources of organic acids in precipitation at a semi-urban site in Southwest China
journal, January 2011


Isoprene Forms Secondary Organic Aerosol through Cloud Processing:  Model Simulations
journal, June 2005

  • Lim, Ho-Jin; Carlton, Annmarie G.; Turpin, Barbara J.
  • Environmental Science & Technology, Vol. 39, Issue 12
  • DOI: 10.1021/es048039h

Formic acid and acetic acid in the western Sierra Nevada, California
journal, August 1993

  • Harrington, Robert F.; Gertler, Alan W.; Grosjean, Daniel
  • Atmospheric Environment. Part A. General Topics, Vol. 27, Issue 12
  • DOI: 10.1016/0960-1686(93)90289-B

Atmospheric concentrations of carboxylic acids and related compounds at a semiurban site
journal, January 1995


Photodegradation of Secondary Organic Aerosol Particles as a Source of Small, Oxygenated Volatile Organic Compounds
journal, September 2016

  • Malecha, Kurtis T.; Nizkorodov, Sergey A.
  • Environmental Science & Technology, Vol. 50, Issue 18
  • DOI: 10.1021/acs.est.6b02313

Atmospheric geochemistry of formic and acetic acids at a mid-latitude temperate site
journal, January 1988

  • Talbot, R. W.; Beecher, K. M.; Harriss, R. C.
  • Journal of Geophysical Research, Vol. 93, Issue D2
  • DOI: 10.1029/JD093iD02p01638

Criegee Intermediate Reactions with Carboxylic Acids: A Potential Source of Secondary Organic Aerosol in the Atmosphere
journal, June 2018