Secondary brown carbon formation via the dicarbonyl imine pathway: nitrogen heterocycle formation and synergistic effects

Abstract

<p>We observe nitrogen heterocycles to be common secondary brown carbon chromophores formed by dicarbonyls<italic>via</italic>the imine pathway, and synergistic effects in mixed dicarbonyl reaction systems.</p>

Autoren

CJ Kampf
A Filippi
C Zuth
T Hoffmann
T Opatz

DOI

10.1039/c6cp03029g

eISSN

1463-9084

ISSN

1463-9076

Ausgabe der Veröffentlichung

27

Zeitschrift

Physical Chemistry Chemical Physics

Sprache

en

Online publication date

2016

Paginierung

18353 - 18364

Status

Published online

Herausgeber

Royal Society of Chemistry (RSC)

Herausgeber URL

http://dx.doi.org/10.1039/c6cp03029g

Datum der Datenerfassung

2024

Titel

Secondary brown carbon formation via the dicarbonyl imine pathway: nitrogen heterocycle formation and synergistic effects

Ausgabe der Zeitschrift

18

Datenquelle: Crossref

Abstract

Dicarbonyls are known to be important precursors of so-called atmospheric brown carbon, significantly affecting aerosol optical properties and radiative forcing. In this systematic study we report the formation of light-absorbing nitrogen containing compounds from simple 1,2-, 1,3-, 1,4-, and 1,5-dicarbonyl + amine reactions. A combination of spectrophotometric and mass spectrometric techniques was used to characterize reaction products in solutions mimicking atmospheric particulates. Experiments with individual dicarbonyls and dicarbonyl mixtures in ammonium sulfate and glycine solutions demonstrate that nitrogen heterocycles are common structural motifs of brown carbon chromophores formed in such reaction systems. 1,4- and 1,5-dicarbonyl reaction systems, which were used as surrogates for terpene ozonolysis products, showed rapid formation of light-absorbing material and products with absorbance maxima at ∼450 nm. Synergistic effects on absorbance properties were observed in mixed (di-)carbonyl experiments, as indicated by the formation of a strong absorber in ammonium sulfate solutions containing acetaldehyde and acetylacetone. This cross-reaction oligomer shows an absorbance maximum at 385 nm, relevant for the actinic flux region of the atmosphere. This study demonstrates the complexity of secondary brown carbon formation via the imine pathway and highlights that cross-reactions with synergistic effects have to be considered an important pathway for atmospheric BrC formation.

Addresses

Institut für Anorganische und Analytische Chemie, Johannes Gutenberg-Universität Mainz, 55128 Mainz, Germany. kampfc@uni-mainz.de.

Autoren

CJ Kampf
A Filippi
C Zuth
T Hoffmann
T Opatz

DOI

10.1039/c6cp03029g

eISSN

1463-9084

Externe Identifier

PubMed Identifier: 27334793

Funding acknowledgements

Deutsche Forschungsgemeinschaft: KA 4008/1-1

Open access

false

ISSN

1463-9076

Ausgabe der Veröffentlichung

27

Zeitschrift

Physical chemistry chemical physics : PCCP

Sprache

eng

Medium

Print-Electronic

Online publication date

2016

Paginierung

18353 - 18364

Datum der Veröffentlichung

2016

Status

Published

Datum der Datenerfassung

2016

Titel

Secondary brown carbon formation via the dicarbonyl imine pathway: nitrogen heterocycle formation and synergistic effects.

Sub types

Journal Article

Ausgabe der Zeitschrift

18

Datenquelle: Europe PubMed Central

Abstract

Dicarbonyls are known to be important precursors of so-called atmospheric brown carbon, significantly affecting aerosol optical properties and radiative forcing. In this systematic study we report the formation of light-absorbing nitrogen containing compounds from simple 1,2-, 1,3-, 1,4-, and 1,5-dicarbonyl + amine reactions. A combination of spectrophotometric and mass spectrometric techniques was used to characterize reaction products in solutions mimicking atmospheric particulates. Experiments with individual dicarbonyls and dicarbonyl mixtures in ammonium sulfate and glycine solutions demonstrate that nitrogen heterocycles are common structural motifs of brown carbon chromophores formed in such reaction systems. 1,4- and 1,5-dicarbonyl reaction systems, which were used as surrogates for terpene ozonolysis products, showed rapid formation of light-absorbing material and products with absorbance maxima at ∼450 nm. Synergistic effects on absorbance properties were observed in mixed (di-)carbonyl experiments, as indicated by the formation of a strong absorber in ammonium sulfate solutions containing acetaldehyde and acetylacetone. This cross-reaction oligomer shows an absorbance maximum at 385 nm, relevant for the actinic flux region of the atmosphere. This study demonstrates the complexity of secondary brown carbon formation via the imine pathway and highlights that cross-reactions with synergistic effects have to be considered an important pathway for atmospheric BrC formation.

Autoren

CJ Kampf
A Filippi
C Zuth
T Hoffmann
T Opatz

Autoren-URL

https://www.ncbi.nlm.nih.gov/pubmed/27334793

DOI

10.1039/c6cp03029g

eISSN

1463-9084

Ausgabe der Veröffentlichung

27

Zeitschrift

Phys Chem Chem Phys

Sprache

eng

Country

England

Paginierung

18353 - 18364

Datum der Veröffentlichung

2016

Status

Published

Datum, an dem der Datensatz öffentlich gemacht wurde

2018

Titel

Secondary brown carbon formation via the dicarbonyl imine pathway: nitrogen heterocycle formation and synergistic effects.

Sub types

Journal Article

Ausgabe der Zeitschrift

18

Datenquelle: PubMed

Secondary brown carbon formation via the dicarbonyl imine pathway: nitrogen heterocycle formation and synergistic effects

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