Conversion of gaseous nitrogen dioxide to nitrate and nitrite on aqueous surfactants

Takashi Kinugawa, Shinichi Enami, Akihiro Yabushita, Masahiro Kawasaki, Michael R. Hoffmann, Agustín J. Colussi

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

The hydrolytic disproportionation of gaseous NO2 on water's surface (2 NO2 + H2O → HONO + NO3 - + H+) (R1) has long been deemed to play a key, albeit unquantifiable role in tropospheric chemistry. We recently found that (R1) is dramatically accelerated by anions in experiments performed on aqueous microjets monitored by online electrospray mass spectrometry. This finding let us rationalize unresolved discrepancies among previous laboratory results and suggested that under realistic environmental conditions (R1) should be affected by everpresent surfactants. Herein, we report that NO2(g) uptake is significantly enhanced by cationic surfactants, weakly inhibited by fulvic acid (FA, a natural polycarboxylic acid) and anionic surfactants, and unaffected by 1-octanol. Surfactants appear to modulate interfacial anion coverage via electrostatic interactions with charged headgroups. We show that (R1) should be the dominant mechanism for the heterogeneous conversion of NO2(g) to HONO under typical atmospheric conditions throughout the day. The photoinduced reduction of NO2 into HONO on airborne soot might play a limited role during daytime.

Original languageEnglish
Pages (from-to)5144-5149
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume13
Issue number11
DOIs
Publication statusPublished - Mar 21 2011

Fingerprint

Nitrogen Dioxide
nitrogen dioxide
nitrites
Nitrites
Surface-Active Agents
Nitrates
Anions
nitrates
surfactants
1-Octanol
Soot
Anionic surfactants
Cationic surfactants
Coulomb interactions
Mass spectrometry
anions
acids
Acids
Water
soot

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Conversion of gaseous nitrogen dioxide to nitrate and nitrite on aqueous surfactants. / Kinugawa, Takashi; Enami, Shinichi; Yabushita, Akihiro; Kawasaki, Masahiro; Hoffmann, Michael R.; Colussi, Agustín J.

In: Physical Chemistry Chemical Physics, Vol. 13, No. 11, 21.03.2011, p. 5144-5149.

Research output: Contribution to journalArticle

Kinugawa, Takashi ; Enami, Shinichi ; Yabushita, Akihiro ; Kawasaki, Masahiro ; Hoffmann, Michael R. ; Colussi, Agustín J. / Conversion of gaseous nitrogen dioxide to nitrate and nitrite on aqueous surfactants. In: Physical Chemistry Chemical Physics. 2011 ; Vol. 13, No. 11. pp. 5144-5149.
@article{a08bc0ad4ba74fc49b014256cb68f083,
title = "Conversion of gaseous nitrogen dioxide to nitrate and nitrite on aqueous surfactants",
abstract = "The hydrolytic disproportionation of gaseous NO2 on water's surface (2 NO2 + H2O → HONO + NO3 - + H+) (R1) has long been deemed to play a key, albeit unquantifiable role in tropospheric chemistry. We recently found that (R1) is dramatically accelerated by anions in experiments performed on aqueous microjets monitored by online electrospray mass spectrometry. This finding let us rationalize unresolved discrepancies among previous laboratory results and suggested that under realistic environmental conditions (R1) should be affected by everpresent surfactants. Herein, we report that NO2(g) uptake is significantly enhanced by cationic surfactants, weakly inhibited by fulvic acid (FA, a natural polycarboxylic acid) and anionic surfactants, and unaffected by 1-octanol. Surfactants appear to modulate interfacial anion coverage via electrostatic interactions with charged headgroups. We show that (R1) should be the dominant mechanism for the heterogeneous conversion of NO2(g) to HONO under typical atmospheric conditions throughout the day. The photoinduced reduction of NO2 into HONO on airborne soot might play a limited role during daytime.",
author = "Takashi Kinugawa and Shinichi Enami and Akihiro Yabushita and Masahiro Kawasaki and Hoffmann, {Michael R.} and Colussi, {Agust{\'i}n J.}",
year = "2011",
month = "3",
day = "21",
doi = "10.1039/c0cp01497d",
language = "English",
volume = "13",
pages = "5144--5149",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "11",

}

TY - JOUR

T1 - Conversion of gaseous nitrogen dioxide to nitrate and nitrite on aqueous surfactants

AU - Kinugawa, Takashi

AU - Enami, Shinichi

AU - Yabushita, Akihiro

AU - Kawasaki, Masahiro

AU - Hoffmann, Michael R.

AU - Colussi, Agustín J.

PY - 2011/3/21

Y1 - 2011/3/21

N2 - The hydrolytic disproportionation of gaseous NO2 on water's surface (2 NO2 + H2O → HONO + NO3 - + H+) (R1) has long been deemed to play a key, albeit unquantifiable role in tropospheric chemistry. We recently found that (R1) is dramatically accelerated by anions in experiments performed on aqueous microjets monitored by online electrospray mass spectrometry. This finding let us rationalize unresolved discrepancies among previous laboratory results and suggested that under realistic environmental conditions (R1) should be affected by everpresent surfactants. Herein, we report that NO2(g) uptake is significantly enhanced by cationic surfactants, weakly inhibited by fulvic acid (FA, a natural polycarboxylic acid) and anionic surfactants, and unaffected by 1-octanol. Surfactants appear to modulate interfacial anion coverage via electrostatic interactions with charged headgroups. We show that (R1) should be the dominant mechanism for the heterogeneous conversion of NO2(g) to HONO under typical atmospheric conditions throughout the day. The photoinduced reduction of NO2 into HONO on airborne soot might play a limited role during daytime.

AB - The hydrolytic disproportionation of gaseous NO2 on water's surface (2 NO2 + H2O → HONO + NO3 - + H+) (R1) has long been deemed to play a key, albeit unquantifiable role in tropospheric chemistry. We recently found that (R1) is dramatically accelerated by anions in experiments performed on aqueous microjets monitored by online electrospray mass spectrometry. This finding let us rationalize unresolved discrepancies among previous laboratory results and suggested that under realistic environmental conditions (R1) should be affected by everpresent surfactants. Herein, we report that NO2(g) uptake is significantly enhanced by cationic surfactants, weakly inhibited by fulvic acid (FA, a natural polycarboxylic acid) and anionic surfactants, and unaffected by 1-octanol. Surfactants appear to modulate interfacial anion coverage via electrostatic interactions with charged headgroups. We show that (R1) should be the dominant mechanism for the heterogeneous conversion of NO2(g) to HONO under typical atmospheric conditions throughout the day. The photoinduced reduction of NO2 into HONO on airborne soot might play a limited role during daytime.

UR - http://www.scopus.com/inward/record.url?scp=79952137716&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=79952137716&partnerID=8YFLogxK

U2 - 10.1039/c0cp01497d

DO - 10.1039/c0cp01497d

M3 - Article

C2 - 21279216

AN - SCOPUS:79952137716

VL - 13

SP - 5144

EP - 5149

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 11

ER -