Effective Henry's Law Partitioning and the Salting Constant of Glyoxal in Aerosols Containing Sulfate

Autoren

Christopher J Kampf
Eleanor M Waxman
Jay G Slowik
Josef Dommen
Lisa Pfaffenberger
Arnaud P Praplan
André SH Prévôt
Urs Baltensperger
Thorsten Hoffmann
Rainer Volkamer

DOI

10.1021/es400083d

eISSN

1520-5851

ISSN

0013-936X

Ausgabe der Veröffentlichung

9

Zeitschrift

Environmental Science & Technology

Sprache

en

Online publication date

2013

Paginierung

4236 - 4244

Datum der Veröffentlichung

2013

Status

Published

Herausgeber

American Chemical Society (ACS)

Herausgeber URL

http://dx.doi.org/10.1021/es400083d

Datum der Datenerfassung

2023

Titel

Effective Henry’s Law Partitioning and the Salting Constant of Glyoxal in Aerosols Containing Sulfate

Ausgabe der Zeitschrift

47

Datenquelle: Crossref

Abstract

The reversible partitioning of glyoxal was studied in simulation chamber experiments for the first time by time-resolved measurements of gas-phase and particle-phase concentrations in sulfate-containing aerosols. Two complementary methods for the measurement of glyoxal particle-phase concentrations are compared: (1) an offline method utilizing filter sampling of chamber aerosols followed by HPLC-MS/MS analysis and (2) positive matrix factorization (PMF) analysis of aerosol mass spectrometer (AMS) data. Ammonium sulfate (AS) and internally mixed ammonium sulfate/fulvic acid (AS/FA) seed aerosols both show an exponential increase of effective Henry's law coefficients (KH,eff) with AS concentration (cAS, in mol kg(-1) aerosol liquid water, m = molality) and sulfate ionic strength, I(SO4(2-)) (m). A modified Setschenow plot confirmed that "salting-in" of glyoxal is responsible for the increased partitioning. The salting constant for glyoxal in AS is K(S)CHOCHO = (-0.24 ± 0.02) m(-1), and found to be independent of the presence of FA. The reversible glyoxal uptake can be described by two distinct reservoirs for monomers and higher molecular weight species filling up at characteristic time constants. These time constants are τ1 ≈ 10(2) s and τ2 ≈ 10(4) s at cAS < 12 m, and about 1-2 orders of magnitude slower at higher cAS, suggesting that glyoxal uptake is kinetically limited at high salt concentrations.

Addresses

Department of Chemistry and Biochemistry, University of Colorado, UCB 215, Boulder, Colorado, USA.

Autoren

Christopher J Kampf
Eleanor M Waxman
Jay G Slowik
Josef Dommen
Lisa Pfaffenberger
Arnaud P Praplan
André SH Prévôt
Urs Baltensperger
Thorsten Hoffmann
Rainer Volkamer

DOI

10.1021/es400083d

eISSN

1520-5851

Externe Identifier

PubMed Identifier: 23534917

Open access

false

ISSN

0013-936X

Ausgabe der Veröffentlichung

9

Zeitschrift

Environmental science & technology

Schlüsselwörter

Sulfates
Salts
Glyoxal
Aerosols
Chromatography, High Pressure Liquid
Tandem Mass Spectrometry

Sprache

eng

Medium

Print-Electronic

Online publication date

2013

Paginierung

4236 - 4244

Datum der Veröffentlichung

2013

Status

Published

Datum der Datenerfassung

2013

Titel

Effective Henry's law partitioning and the salting constant of glyoxal in aerosols containing sulfate.

Sub types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.
Journal Article

Ausgabe der Zeitschrift

47

Datenquelle: Europe PubMed Central

Abstract

The reversible partitioning of glyoxal was studied in simulation chamber experiments for the first time by time-resolved measurements of gas-phase and particle-phase concentrations in sulfate-containing aerosols. Two complementary methods for the measurement of glyoxal particle-phase concentrations are compared: (1) an offline method utilizing filter sampling of chamber aerosols followed by HPLC-MS/MS analysis and (2) positive matrix factorization (PMF) analysis of aerosol mass spectrometer (AMS) data. Ammonium sulfate (AS) and internally mixed ammonium sulfate/fulvic acid (AS/FA) seed aerosols both show an exponential increase of effective Henry's law coefficients (KH,eff) with AS concentration (cAS, in mol kg(-1) aerosol liquid water, m = molality) and sulfate ionic strength, I(SO4(2-)) (m). A modified Setschenow plot confirmed that "salting-in" of glyoxal is responsible for the increased partitioning. The salting constant for glyoxal in AS is K(S)CHOCHO = (-0.24 ± 0.02) m(-1), and found to be independent of the presence of FA. The reversible glyoxal uptake can be described by two distinct reservoirs for monomers and higher molecular weight species filling up at characteristic time constants. These time constants are τ1 ≈ 10(2) s and τ2 ≈ 10(4) s at cAS < 12 m, and about 1-2 orders of magnitude slower at higher cAS, suggesting that glyoxal uptake is kinetically limited at high salt concentrations.

Autoren

Christopher J Kampf
Eleanor M Waxman
Jay G Slowik
Josef Dommen
Lisa Pfaffenberger
Arnaud P Praplan
André SH Prévôt
Urs Baltensperger
Thorsten Hoffmann
Rainer Volkamer

Autoren-URL

https://www.ncbi.nlm.nih.gov/pubmed/23534917

DOI

10.1021/es400083d

eISSN

1520-5851

Ausgabe der Veröffentlichung

9

Zeitschrift

Environ Sci Technol

Schlüsselwörter

Aerosols
Chromatography, High Pressure Liquid
Glyoxal
Salts
Sulfates
Tandem Mass Spectrometry

Sprache

eng

Country

United States

Paginierung

4236 - 4244

Datum der Veröffentlichung

2013

Status

Published

Datum, an dem der Datensatz öffentlich gemacht wurde

2014

Titel

Effective Henry's law partitioning and the salting constant of glyoxal in aerosols containing sulfate.

Sub types

Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

Ausgabe der Zeitschrift

47

Datenquelle: PubMed

Effective Henry's Law Partitioning and the Salting Constant of Glyoxal in Aerosols Containing Sulfate

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