Abstract
Terrestrial ecosystems are simultaneously the largest source and a major sink of volatile organic compounds (VOCs) to the global atmosphere, and these two-way fluxes are an important source of uncertainty in current models. Here, we apply high-resolution mass spectrometry (proton transfer reaction-quadrupole interface time-of-flight; PTR-QiTOF) to measure ecosystem-atmosphere VOC fluxes across the entire detected mass range (m/z 0-335) over a mixed temperate forest and use the results to test how well a state-of-science chemical transport model (GEOS-Chem CTM) is able to represent the observed reactive carbon exchange. We show that ambient humidity fluctuations can give rise to spurious VOC fluxes with PTR-based techniques and present a method to screen for such effects. After doing so, 377 of the 636 detected ions exhibited detectable gross fluxes during the study, implying a large number of species with active ecosystem-atmosphere exchange. We introduce the reactivity flux as a measure of how Earth-atmosphere fluxes influence ambient OH reactivity and show that the upward total VOC (-VOC) carbon and reactivity fluxes are carried by a far smaller number of species than the downward fluxes. The model underpredicts the -VOC carbon and reactivity fluxes by 40-60% on average. However, the observed net fluxes are dominated (90% on a carbon basis, 95% on a reactivity basis) by known VOCs explicitly included in the CTM. As a result, the largest CTM uncertainties in simulating VOC carbon and reactivity exchange for this environment are associated with known rather than unrepresented species. This conclusion pertains to the set of species detectable by PTR-TOF techniques, which likely represents the majority in terms of carbon mass and OH reactivity, but not necessarily in terms of aerosol formation potential. In the case of oxygenated VOCs, the model severely underpredicts the gross fluxes and the net exchange. Here, unrepresented VOCs play a larger role, accounting for ∼30% of the carbon flux and ∼50% of the reactivity flux. The resulting CTM biases, however, are still smaller than those that arise from uncertainties for known and represented compounds.
Original language | English (US) |
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Pages (from-to) | 764-777 |
Number of pages | 14 |
Journal | ACS Earth and Space Chemistry |
Volume | 2 |
Issue number | 8 |
DOIs | |
State | Published - Aug 16 2018 |
Bibliographical note
Publisher Copyright:© Copyright 2018 American Chemical Society.
Keywords
- chemical transport model
- deposition
- eddy covariance
- emissions
- flux
- reactivity
- volatile organic compounds
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Atmospheric formic acid measurements from the 2016 PROPHET-AMOS campaign at the University of Michigan Biological Station
Millet, D. B. & Alwe, H., Data Repository for the University of Minnesota, 2018
DOI: 10.13020/D6JQ3R, http://hdl.handle.net/11299/200898
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