HCOOH in the Remote Atmosphere: Constraints from Atmospheric Tomography (ATom) Airborne Observations
Abstract
Formic acid (HCOOH) is an important component of atmospheric acidity but its budget is poorly understood, with prior observations implying substantial missing sources. Here, we combine pole-to-pole airborne observations from the Atmospheric Tomography Mission (ATom) with a chemical transport model (GEOS-Chem CTM) and back-trajectory analyses to provide the first global in situ characterization of HCOOH in the remote atmosphere. ATom reveals sub-100 ppt HCOOH concentrations over most of the remote oceans, punctuated by large enhancements associated with continental outflow. Enhancements correlate with known combustion tracers and trajectory-based fire influences. The GEOS-Chem model underpredicts these in-plume HCOOH enhancements, but elsewhere, we find no broad indication of a missing HCOOH source in the background free troposphere. We conclude that missing nonfire HCOOH precursors inferred previously are predominantly short-lived. We find indications of a wet scavenging underestimate in the model consistent with a positive HCOOH bias in the tropical upper troposphere. Observations reveal episodic evidence of ocean HCOOH uptake, which is well-captured by GEOS-Chem; however, despite its strong seawater undersaturation, HCOOH is not consistently depleted in the remote marine boundary layer. Over 50 fire and mixed plumes were intercepted during ATom with widely varying transit times and source regions. HCOOH:CO-normalized excess mixing ratios in these plumes range from 3.4 to >50 ppt/ppb CO and are often over an order of magnitude higher than expected primary emission ratios. HCOOH is thus a major reactive organic carbon reservoir in the aged plumes sampled during ATom, implying important missing pathways for in-plume HCOOH production.
Department
Earth Systems Research Center
Publication Date
5-13-2021
Journal Title
ACS Earth and Space Chemistry
Publisher
ACS Publications
Digital Object Identifier (DOI)
Version of Record: https://dx.doi.org/10.1021/acsearthspacechem.1c00049
Document Type
Article
Recommended Citation
Chen, X., D. B. Millet, J. A. Neuman, P. R. Veres, E. A. Ray, R. Commane, B. Daube, K. McKain, J. P. Schwarz, J. M. Katich, K. D. Froyd, G. P. Schill, M. J. Kim, J. D. Crounse, H. M. Allen, E. C. Apel, R. S. Hornbrook, D. R. Blake, B. A. Nault, P. Campuzano-Jost, J.-L. Jimenez, and J. E. Dibb (2021), HCOOH in the remote atmosphere: Constraints from Atmospheric Tomography (ATom) airborne observations, ACS Earth and Space Chemistry, https://doi.org/10.1021/acsearthspacechem.1c00049.
Comments
This is an author manuscript of an article published by ACS Publications in ACS Earth and Space Chemistry in 2021, available online: https://dx.doi.org/10.1021/acsearthspacechem.1c00049