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

Title: High upward fluxes of formic acid from a boreal forest canopy

Abstract

Abstract Eddy covariance fluxes of formic acid, HCOOH, were measured over a boreal forest canopy in spring/summer 2014. The HCOOH fluxes were bidirectional but mostly upward during daytime, in contrast to studies elsewhere that reported mostly downward fluxes. Downward flux episodes were explained well by modeled dry deposition rates. The sum of net observed flux and modeled dry deposition yields an upward “gross flux” of HCOOH, which could not be quantitatively explained by literature estimates of direct vegetative/soil emissions nor by efficient chemical production from other volatile organic compounds, suggesting missing or greatly underestimated HCOOH sources in the boreal ecosystem. We implemented a vegetative HCOOH source into the GEOS‐Chem chemical transport model to match our derived gross flux and evaluated the updated model against airborne and spaceborne observations. Model biases in the boundary layer were substantially reduced based on this revised treatment, but biases in the free troposphere remain unexplained.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [6];  [6]; ORCiD logo [7];  [2];  [6];  [2]
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Atmospheric Sciences; Univ. of Helsinki (Finland). Dept. of Physics
  2. Univ. of Washington, Seattle, WA (United States). Dept. of Atmospheric Sciences
  3. Estonian Univ. of Life Sciences, Tartu (Estonia). Dept. of Plant Physiology; Univ. of Helsinki (Finland). Dept. of Forest Sciences
  4. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Soil, Water, and Climate
  5. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
  6. Univ. of Helsinki (Finland). Dept. of Physics
  7. NASA Goddard Space Flight Center (GSFC), Greenbelt, MD (United States). Atmospheric Chemistry and Dynamics Lab.; Univ. of Maryland, Baltimore, MD (United States). Joint Center for Earth Systems Technology
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); European Commission (EU); National Science Foundation (NSF)
OSTI Identifier:
1392635
Alternate Identifier(s):
OSTI ID: 1402387
Grant/Contract Number:  
SC0011791; SC0006867; DE‐SC0006867
Resource Type:
Accepted Manuscript
Journal Name:
Geophysical Research Letters
Additional Journal Information:
Journal Volume: 43; Journal Issue: 17; Journal ID: ISSN 0094-8276
Publisher:
American Geophysical Union
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; formic acid; eddy covariance fluxes; chemical ionization mass spectrometry; boreal forest; biogenic emissions

Citation Formats

Schobesberger, Siegfried, Lopez-Hilfiker, Felipe D., Taipale, Ditte, Millet, Dylan B., D'Ambro, Emma L., Rantala, Pekka, Mammarella, Ivan, Zhou, Putian, Wolfe, Glenn M., Lee, Ben H., Boy, Michael, and Thornton, Joel A. High upward fluxes of formic acid from a boreal forest canopy. United States: N. p., 2016. Web. doi:10.1002/2016GL069599.
Schobesberger, Siegfried, Lopez-Hilfiker, Felipe D., Taipale, Ditte, Millet, Dylan B., D'Ambro, Emma L., Rantala, Pekka, Mammarella, Ivan, Zhou, Putian, Wolfe, Glenn M., Lee, Ben H., Boy, Michael, & Thornton, Joel A. High upward fluxes of formic acid from a boreal forest canopy. United States. https://doi.org/10.1002/2016GL069599
Schobesberger, Siegfried, Lopez-Hilfiker, Felipe D., Taipale, Ditte, Millet, Dylan B., D'Ambro, Emma L., Rantala, Pekka, Mammarella, Ivan, Zhou, Putian, Wolfe, Glenn M., Lee, Ben H., Boy, Michael, and Thornton, Joel A. Sun . "High upward fluxes of formic acid from a boreal forest canopy". United States. https://doi.org/10.1002/2016GL069599. https://www.osti.gov/servlets/purl/1392635.
@article{osti_1392635,
title = {High upward fluxes of formic acid from a boreal forest canopy},
author = {Schobesberger, Siegfried and Lopez-Hilfiker, Felipe D. and Taipale, Ditte and Millet, Dylan B. and D'Ambro, Emma L. and Rantala, Pekka and Mammarella, Ivan and Zhou, Putian and Wolfe, Glenn M. and Lee, Ben H. and Boy, Michael and Thornton, Joel A.},
abstractNote = {Abstract Eddy covariance fluxes of formic acid, HCOOH, were measured over a boreal forest canopy in spring/summer 2014. The HCOOH fluxes were bidirectional but mostly upward during daytime, in contrast to studies elsewhere that reported mostly downward fluxes. Downward flux episodes were explained well by modeled dry deposition rates. The sum of net observed flux and modeled dry deposition yields an upward “gross flux” of HCOOH, which could not be quantitatively explained by literature estimates of direct vegetative/soil emissions nor by efficient chemical production from other volatile organic compounds, suggesting missing or greatly underestimated HCOOH sources in the boreal ecosystem. We implemented a vegetative HCOOH source into the GEOS‐Chem chemical transport model to match our derived gross flux and evaluated the updated model against airborne and spaceborne observations. Model biases in the boundary layer were substantially reduced based on this revised treatment, but biases in the free troposphere remain unexplained.},
doi = {10.1002/2016GL069599},
journal = {Geophysical Research Letters},
number = 17,
volume = 43,
place = {United States},
year = {Sun Aug 14 00:00:00 EDT 2016},
month = {Sun Aug 14 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 28 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Chemodiversity of a Scots pine stand and implications for terpene air concentrations
journal, January 2012


Observation and modelling of HO x radicals in a boreal forest
journal, January 2014

  • Hens, K.; Novelli, A.; Martinez, M.
  • Atmospheric Chemistry and Physics, Vol. 14, Issue 16
  • DOI: 10.5194/acp-14-8723-2014

Factors controlling regional differences in forest soil emission of nitrogen oxides (NO and N<sub>2</sub>O)
journal, January 2006


Exchange of atmospheric formic and acetic acids with trees and crop plants under controlled chamber and purified air conditions
journal, May 1998


Can chemical effects on cloud droplet number rival the first indirect effect?: CAN CHEMICAL EFFECTS ON CLOUD DROPLET NUMBER RIVAL INDIRECT EFFECT?
journal, September 2002

  • Nenes, Athanasios; Charlson, Robert J.; Facchini, M. Cristina
  • Geophysical Research Letters, Vol. 29, Issue 17
  • DOI: 10.1029/2002GL015295

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


Temperature and light dependence of the VOC emissions of Scots pine
journal, January 2005

  • Tarvainen, V.; Hakola, H.; Hellén, H.
  • Atmospheric Chemistry and Physics, Vol. 5, Issue 4
  • DOI: 10.5194/acp-5-989-2005

Temperature and light dependence of the VOC emissions of Scots pine
journal, January 2004

  • Tarvainen, V.; Hakola, H.; Hellén, H.
  • Atmospheric Chemistry and Physics Discussions, Vol. 4, Issue 5
  • DOI: 10.5194/acpd-4-6691-2004

Relative contribution of biogenic and anthropogenic sources to formic and acetic acids in the atmospheric boundary layer
journal, April 2001

  • Glasius, M.; Boel, C.; Bruun, N.
  • Journal of Geophysical Research: Atmospheres, Vol. 106, Issue D7
  • DOI: 10.1029/2000JD900676

The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions
journal, January 2012

  • Guenther, A. B.; Jiang, X.; Heald, C. L.
  • Geoscientific Model Development, Vol. 5, Issue 6
  • DOI: 10.5194/gmd-5-1471-2012

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

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species
journal, January 2006

  • Atkinson, R.; Baulch, D. L.; Cox, R. A.
  • Atmospheric Chemistry and Physics, Vol. 6, Issue 11
  • DOI: 10.5194/acp-6-3625-2006

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

A global model of natural volatile organic compound emissions
journal, January 1995

  • Guenther, Alex; Hewitt, C. Nicholas; Erickson, David
  • Journal of Geophysical Research, Vol. 100, Issue D5
  • DOI: 10.1029/94JD02950

Overview of the international project on biogenic aerosol formation in the boreal forest (BIOFOR)
journal, January 2001

  • Kulmala, M.; Hämeri, K.; Aalto, P. P.
  • Tellus B: Chemical and Physical Meteorology, Vol. 53, Issue 4
  • DOI: 10.3402/tellusb.v53i4.16601

The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions
journal, January 2012

  • Guenther, A. B.; Jiang, X.; Heald, C. L.
  • Geoscientific Model Development Discussions, Vol. 5, Issue 2
  • DOI: 10.5194/gmdd-5-1503-2012

Towards a comprehensive emission inventory of terpenoids from boreal ecosystems
journal, July 2007


A Large Underestimate of Formic Acid from Tropical Fires: Constraints from Space-Borne Measurements
journal, May 2016

  • Chaliyakunnel, S.; Millet, D. B.; Wells, K. C.
  • Environmental Science & Technology, Vol. 50, Issue 11
  • DOI: 10.1021/acs.est.5b06385

A revised parameterization for gaseous dry deposition in air-quality models
journal, January 2003


HCOOH measurements from space: TES retrieval algorithm and observed global distribution
journal, January 2014

  • Cady-Pereira, K. E.; Chaliyakunnel, S.; Shephard, M. W.
  • Atmospheric Measurement Techniques, Vol. 7, Issue 7
  • DOI: 10.5194/amt-7-2297-2014

Atmospheric formic acid from formicine ants: a preliminary assessment
journal, September 1988


Testing the hypothesis on the relationship between aerodynamic roughness length and albedo using vegetation structure parameters
journal, May 2011

  • Cho, Jaeil; Miyazaki, Shin; Yeh, Pat J. -F.
  • International Journal of Biometeorology, Vol. 56, Issue 2
  • DOI: 10.1007/s00484-011-0445-2

Gas-phase products and secondary aerosol yields from the ozonolysis of ten different terpenes
journal, January 2006

  • Lee, Anita; Goldstein, Allen H.; Keywood, Melita D.
  • Journal of Geophysical Research, Vol. 111, Issue D7
  • DOI: 10.1029/2005JD006437

Chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulfate
journal, January 1986


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

Diurnal cycles of formic and acetic acids in the northern part of the Guayana shield, Venezuela
journal, July 1991

  • Hartmann, W. R.; Santana, M.; Hermoso, M.
  • Journal of Atmospheric Chemistry, Vol. 13, Issue 1
  • DOI: 10.1007/BF00048100

A high-resolution mass spectrometer to measure atmospheric ion composition
journal, January 2010

  • Junninen, H.; Ehn, M.; Petäjä, T.
  • Atmospheric Measurement Techniques, Vol. 3, Issue 4
  • DOI: 10.5194/amt-3-1039-2010

Turbulence Statistics Inside and Over Forest: Influence on Footprint Prediction
journal, November 2003

  • Rannik, Ü.; Markkanen, T.; Raittila, J.
  • Boundary-Layer Meteorology, Vol. 109, Issue 2
  • DOI: 10.1023/A:1025404923169

Hydrocarbon fluxes above a Scots pine forest canopy: measurements and modeling
journal, January 2007

  • Rinne, J.; Taipale, R.; Markkanen, T.
  • Atmospheric Chemistry and Physics, Vol. 7, Issue 12
  • DOI: 10.5194/acp-7-3361-2007

Rapid deposition of oxidized biogenic compounds to a temperate forest
journal, January 2015

  • Nguyen, Tran B.; Crounse, John D.; Teng, Alex P.
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 5
  • DOI: 10.1073/pnas.1418702112

Effect of thinning on surface fluxes in a boreal forest: THINNING AND SURFACE FLUXES IN BOREAL FOREST
journal, April 2005

  • Vesala, T.; Suni, T.; Rannik, Ü.
  • Global Biogeochemical Cycles, Vol. 19, Issue 2
  • DOI: 10.1029/2004GB002316

Atmospheric formic acid from formicine ants: a preliminary assessment
journal, November 1988


Gas-Phase OH Oxidation of Monoterpenes: Gaseous and Particulate Products
journal, January 2001

  • Larsen, Bo. R.; Di Bella, Dario; Glasius, Marianne
  • Journal of Atmospheric Chemistry, Vol. 38, Issue 3, p. 231-276
  • DOI: 10.1023/A:1006487530903

Tools for quality assessment of surface-based flux measurements
journal, January 1996


Eddy covariance fluxes of acyl peroxy nitrates (PAN, PPN and MPAN) above a Ponderosa pine forest
journal, January 2009

  • Wolfe, G. M.; Thornton, J. A.; Yatavelli, R. L. N.
  • Atmospheric Chemistry and Physics, Vol. 9, Issue 2
  • DOI: 10.5194/acp-9-615-2009

Investigation of secondary formation of formic acid: urban environment vs. oil and gas producing region
journal, January 2015


Satellite evidence for a large source of formic acid from boreal and tropical forests
journal, December 2011

  • Stavrakou, T.; Müller, J-F.; Peeters, J.
  • Nature Geoscience, Vol. 5, Issue 1
  • DOI: 10.1038/ngeo1354

Overview of the field measurement campaign in Hyytiälä, August 2001 in the framework of the EU project OSOA
journal, January 2004

  • Boy, M.; Petäjä, T.; Dal Maso, M.
  • Atmospheric Chemistry and Physics, Vol. 4, Issue 3
  • DOI: 10.5194/acp-4-657-2004

A novel method for online analysis of gas and particle composition: description and evaluation of a Filter Inlet for Gases and AEROsols (FIGAERO)
journal, January 2014

  • Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.
  • Atmospheric Measurement Techniques, Vol. 7, Issue 4
  • DOI: 10.5194/amt-7-983-2014

Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature)
journal, January 2006

  • Guenther, A.; Karl, T.; Harley, P.
  • Atmospheric Chemistry and Physics Discussions, Vol. 6, Issue 1
  • DOI: 10.5194/acpd-6-107-2006

Parameterization of surface resistances to gaseous dry deposition in regional-scale numerical models
journal, January 1989


Gas-phase products and secondary aerosol yields from the photooxidation of 16 different terpenes
journal, January 2006

  • Lee, Anita; Goldstein, Allen H.; Kroll, Jesse H.
  • Journal of Geophysical Research, Vol. 111, Issue D17
  • DOI: 10.1029/2006JD007050

Tropospheric Emission Spectrometer (TES) satellite validations of ammonia, methanol, formic acid, and carbon monoxide over the Canadian oil sands
journal, January 2015

  • Shephard, M. W.; McLinden, C. A.; Cady-Pereira, K. E.
  • Atmospheric Measurement Techniques Discussions, Vol. 8, Issue 9
  • DOI: 10.5194/amtd-8-9503-2015

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

Simulation Chamber Studies of the Atmospheric Oxidation of 2-Methyl-3-Buten-2-ol: Reaction with Hydroxyl Radicals and Ozone Under a Variety of Conditions
journal, November 2006

  • Carrasco, N.; Doussin, J. F.; O’Connor, M.
  • Journal of Atmospheric Chemistry, Vol. 56, Issue 1
  • DOI: 10.1007/s10874-006-9041-y

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

Footprint prediction of scalar fluxes from analytical solutions of the diffusion equation
journal, March 1990

  • Schuepp, P. H.; Leclerc, M. Y.; MacPherson, J. I.
  • Boundary-Layer Meteorology, Vol. 50, Issue 1-4
  • DOI: 10.1007/BF00120530

Succession, Forest Fragmentation, and the Distribution of Wood Ants
journal, March 1996


Measurement of weak organic acidity in precipitation from remote areas of the world
journal, June 1983

  • Keene, William C.; Galloway, James N.; Holden, J. David
  • Journal of Geophysical Research: Oceans, Vol. 88, Issue C9
  • DOI: 10.1029/JC088iC09p05122

Exchange of short-chain monocarboxylic acids by vegetation at a remote tropical forest site in Amazonia
journal, January 2002


Abundances and Flux Estimates of Volatile Organic Compounds from a Dairy Cowshed in Germany
journal, January 2008

  • Ngwabie, Ngwa Martin; Schade, Gunnar W.; Custer, Thomas G.
  • Journal of Environment Quality, Vol. 37, Issue 2
  • DOI: 10.2134/jeq2006.0417

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

A large and ubiquitous source of atmospheric formic acid
journal, January 2015

  • Millet, D. B.; Baasandorj, M.; Farmer, D. K.
  • Atmospheric Chemistry and Physics, Vol. 15, Issue 11
  • DOI: 10.5194/acp-15-6283-2015

The effect of atmospheric nitric acid vapor on cloud condensation nucleus activation
journal, January 1993

  • Kulmala, M.; Laaksonen, A.; Korhonen, P.
  • Journal of Geophysical Research, Vol. 98, Issue D12
  • DOI: 10.1029/93JD02070

An Iodide-Adduct High-Resolution Time-of-Flight Chemical-Ionization Mass Spectrometer: Application to Atmospheric Inorganic and Organic Compounds
journal, May 2014

  • Lee, Ben H.; Lopez-Hilfiker, Felipe D.; Mohr, Claudia
  • Environmental Science & Technology, Vol. 48, Issue 11
  • DOI: 10.1021/es500362a

Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature)
journal, January 2006

  • Guenther, A.; Karl, T.; Harley, P.
  • Atmospheric Chemistry and Physics, Vol. 6, Issue 11
  • DOI: 10.5194/acp-6-3181-2006

Cryogenic trapping of atmospheric organic acids under laboratory and field conditions
journal, May 1997


Overview of the international project on biogenic aerosol formation in the boreal forest (BIOFOR)
journal, September 2001


Overview of the field measurement campaign in Hyytiala, August 2001 in the framework of the EU project OSOA
journal, July 2003


HCOOH measurements from space: TES retrieval algorithm and observed global distribution
journal, February 2014

  • Cady-Pereira, K. E.; Chaliyakunnel, S.; Shephard, M. W.
  • Atmospheric Measurement Techniques Discussions
  • DOI: 10.5194/amtd-7-1975-2014

Towards a comprehensive emission inventory of terpenoids from boreal ecosystems
journal, July 2007


Hydrocarbon fluxes above a Scots pine forest canopy: Measurements and modeling
journal, February 2007


Eddy covariance fluxes of acyl peroxy nitrates (PAN, PPN, and MPAN) above a Ponderosa pine forest
journal, September 2008

  • Wolfe, G. M.; Yatavelli, R. L. N.; Thornton, J. A.
  • Atmospheric Chemistry and Physics Discussions
  • DOI: 10.5194/acpd-8-17495-2008

Works referencing / citing this record:

Tropospheric sources and sinks of gas-phase acids in the Colorado Front Range
journal, January 2018

  • Mattila, James M.; Brophy, Patrick; Kirkland, Jeffrey
  • Atmospheric Chemistry and Physics, Vol. 18, Issue 16
  • DOI: 10.5194/acp-18-12315-2018

Oxidation of Volatile Organic Compounds as the Major Source of Formic Acid in a Mixed Forest Canopy
journal, March 2019

  • Alwe, Hariprasad D.; Millet, Dylan B.; Chen, Xin
  • Geophysical Research Letters, Vol. 46, Issue 5
  • DOI: 10.1029/2018gl081526

Temporal variation of VOC fluxes measured with PTR-TOF above a boreal forest
journal, January 2018

  • Schallhart, Simon; Rantala, Pekka; Kajos, Maija K.
  • Atmospheric Chemistry and Physics, Vol. 18, Issue 2
  • DOI: 10.5194/acp-18-815-2018

Physicochemical uptake and release of volatile organic compounds by soil in coated-wall flow tube experiments with ambient air
journal, January 2019


Semi-volatile and highly oxygenated gaseous and particulate organic compounds observed above a boreal forest canopy
journal, January 2018

  • Lee, Ben H.; Lopez-Hilfiker, Felipe D.; D'Ambro, Emma L.
  • Atmospheric Chemistry and Physics, Vol. 18, Issue 15
  • DOI: 10.5194/acp-18-11547-2018

High gas-phase mixing ratios of formic and acetic acid in the High Arctic
journal, January 2018

  • Mungall, Emma L.; Abbatt, Jonathan P. D.; Wentzell, Jeremy J. B.
  • Atmospheric Chemistry and Physics, Vol. 18, Issue 14
  • DOI: 10.5194/acp-18-10237-2018

Molecular identification of organic vapors driving atmospheric nanoparticle growth
journal, September 2019


Temporal variation of VOC fluxes measured with PTR-TOF above a boreal forest
journal, June 2017

  • Schallhart, Simon; Rantala, Pekka; Kajos, Maija K.
  • Atmospheric Chemistry and Physics Discussions
  • DOI: 10.5194/acp-2017-394