On the sources and sinks of atmospheric VOCs: an integrated analysis of recent aircraft campaigns over North America

Xin Chen, Dylan B. Millet, Hanwant B. Singh, Armin Wisthaler, Eric C. Apel, Elliot L Atlas, Donald R. Blake, Ilann Bourgeois, Steven S. Brown, John D. Crounse, Joost A. De Gouw, Frank M. Flocke, Alan Fried, Brian G. Heikes, Rebecca S. Hornbrook, Tomas Mikoviny, Kyung Eun Min, Markus Müller, J. Andrew Neuman, Daniel W. O'sullivanJeff Peischl, Gabriele G. Pfister, Dirk Richter, James M. Roberts, Thomas B. Ryerson, Stephen R. Shertz, Chelsea R. Thompson, Victoria Treadaway, Patrick R. Veres, James Walega, Carsten Warneke, Rebecca A. Washenfelder, Petter Weibring, Bin Yuan

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to (i) characterize the VOC budget and (ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70&thinsp;% and 95&thinsp;% of annually emitted VOC carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2<span classCombining double low line"inline-formula">×</span> larger source of nonmethane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half of the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In<span idCombining double low line"page9098"/> the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC abundance (<span classCombining double low line"inline-formula">R2Combining double low line0.36</span>) and reactivity (<span classCombining double low line"inline-formula">R2Combining double low line0.54</span>). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (<span classCombining double low line"inline-formula">ĝ1/4</span>&thinsp;60&thinsp;%), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL&thinsp;:&thinsp;FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene <span classCombining double low line"inline-formula">+</span> oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation.

Original languageEnglish (US)
Pages (from-to)9097-9123
Number of pages27
JournalAtmospheric Chemistry and Physics
Volume19
Issue number14
DOIs
StatePublished - Jul 17 2019
Externally publishedYes

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volatile organic compound
aircraft
troposphere
biogenic emission
boundary layer
analysis
North America
formaldehyde
oxidation
acetaldehyde
isoprene
formic acid
ethane
EOS
ketone
acetone
ventilation
methanol
methane
tracer

ASJC Scopus subject areas

  • Atmospheric Science

Cite this

On the sources and sinks of atmospheric VOCs : an integrated analysis of recent aircraft campaigns over North America. / Chen, Xin; Millet, Dylan B.; Singh, Hanwant B.; Wisthaler, Armin; Apel, Eric C.; Atlas, Elliot L; Blake, Donald R.; Bourgeois, Ilann; Brown, Steven S.; Crounse, John D.; De Gouw, Joost A.; Flocke, Frank M.; Fried, Alan; Heikes, Brian G.; Hornbrook, Rebecca S.; Mikoviny, Tomas; Min, Kyung Eun; Müller, Markus; Andrew Neuman, J.; O'sullivan, Daniel W.; Peischl, Jeff; Pfister, Gabriele G.; Richter, Dirk; Roberts, James M.; Ryerson, Thomas B.; Shertz, Stephen R.; Thompson, Chelsea R.; Treadaway, Victoria; Veres, Patrick R.; Walega, James; Warneke, Carsten; Washenfelder, Rebecca A.; Weibring, Petter; Yuan, Bin.

In: Atmospheric Chemistry and Physics, Vol. 19, No. 14, 17.07.2019, p. 9097-9123.

Research output: Contribution to journalArticle

Chen, X, Millet, DB, Singh, HB, Wisthaler, A, Apel, EC, Atlas, EL, Blake, DR, Bourgeois, I, Brown, SS, Crounse, JD, De Gouw, JA, Flocke, FM, Fried, A, Heikes, BG, Hornbrook, RS, Mikoviny, T, Min, KE, Müller, M, Andrew Neuman, J, O'sullivan, DW, Peischl, J, Pfister, GG, Richter, D, Roberts, JM, Ryerson, TB, Shertz, SR, Thompson, CR, Treadaway, V, Veres, PR, Walega, J, Warneke, C, Washenfelder, RA, Weibring, P & Yuan, B 2019, 'On the sources and sinks of atmospheric VOCs: an integrated analysis of recent aircraft campaigns over North America', Atmospheric Chemistry and Physics, vol. 19, no. 14, pp. 9097-9123. https://doi.org/10.5194/acp-19-9097-2019
Chen, Xin ; Millet, Dylan B. ; Singh, Hanwant B. ; Wisthaler, Armin ; Apel, Eric C. ; Atlas, Elliot L ; Blake, Donald R. ; Bourgeois, Ilann ; Brown, Steven S. ; Crounse, John D. ; De Gouw, Joost A. ; Flocke, Frank M. ; Fried, Alan ; Heikes, Brian G. ; Hornbrook, Rebecca S. ; Mikoviny, Tomas ; Min, Kyung Eun ; Müller, Markus ; Andrew Neuman, J. ; O'sullivan, Daniel W. ; Peischl, Jeff ; Pfister, Gabriele G. ; Richter, Dirk ; Roberts, James M. ; Ryerson, Thomas B. ; Shertz, Stephen R. ; Thompson, Chelsea R. ; Treadaway, Victoria ; Veres, Patrick R. ; Walega, James ; Warneke, Carsten ; Washenfelder, Rebecca A. ; Weibring, Petter ; Yuan, Bin. / On the sources and sinks of atmospheric VOCs : an integrated analysis of recent aircraft campaigns over North America. In: Atmospheric Chemistry and Physics. 2019 ; Vol. 19, No. 14. pp. 9097-9123.
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author = "Xin Chen and Millet, {Dylan B.} and Singh, {Hanwant B.} and Armin Wisthaler and Apel, {Eric C.} and Atlas, {Elliot L} and Blake, {Donald R.} and Ilann Bourgeois and Brown, {Steven S.} and Crounse, {John D.} and {De Gouw}, {Joost A.} and Flocke, {Frank M.} and Alan Fried and Heikes, {Brian G.} and Hornbrook, {Rebecca S.} and Tomas Mikoviny and Min, {Kyung Eun} and Markus M{\"u}ller and {Andrew Neuman}, J. and O'sullivan, {Daniel W.} and Jeff Peischl and Pfister, {Gabriele G.} and Dirk Richter and Roberts, {James M.} and Ryerson, {Thomas B.} and Shertz, {Stephen R.} and Thompson, {Chelsea R.} and Victoria Treadaway and Veres, {Patrick R.} and James Walega and Carsten Warneke and Washenfelder, {Rebecca A.} and Petter Weibring and Bin Yuan",
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TY - JOUR

T1 - On the sources and sinks of atmospheric VOCs

T2 - an integrated analysis of recent aircraft campaigns over North America

AU - Chen, Xin

AU - Millet, Dylan B.

AU - Singh, Hanwant B.

AU - Wisthaler, Armin

AU - Apel, Eric C.

AU - Atlas, Elliot L

AU - Blake, Donald R.

AU - Bourgeois, Ilann

AU - Brown, Steven S.

AU - Crounse, John D.

AU - De Gouw, Joost A.

AU - Flocke, Frank M.

AU - Fried, Alan

AU - Heikes, Brian G.

AU - Hornbrook, Rebecca S.

AU - Mikoviny, Tomas

AU - Min, Kyung Eun

AU - Müller, Markus

AU - Andrew Neuman, J.

AU - O'sullivan, Daniel W.

AU - Peischl, Jeff

AU - Pfister, Gabriele G.

AU - Richter, Dirk

AU - Roberts, James M.

AU - Ryerson, Thomas B.

AU - Shertz, Stephen R.

AU - Thompson, Chelsea R.

AU - Treadaway, Victoria

AU - Veres, Patrick R.

AU - Walega, James

AU - Warneke, Carsten

AU - Washenfelder, Rebecca A.

AU - Weibring, Petter

AU - Yuan, Bin

PY - 2019/7/17

Y1 - 2019/7/17

N2 - We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to (i) characterize the VOC budget and (ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70&thinsp;% and 95&thinsp;% of annually emitted VOC carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2× larger source of nonmethane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half of the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC abundance (R2Combining double low line0.36) and reactivity (R2Combining double low line0.54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (ĝ1/4&thinsp;60&thinsp;%), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL&thinsp;:&thinsp;FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene + oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation.

AB - We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to (i) characterize the VOC budget and (ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70&thinsp;% and 95&thinsp;% of annually emitted VOC carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2× larger source of nonmethane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half of the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC abundance (R2Combining double low line0.36) and reactivity (R2Combining double low line0.54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (ĝ1/4&thinsp;60&thinsp;%), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL&thinsp;:&thinsp;FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene + oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation.

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