Reactivity of aminophenols in forming nitrogen-containing brown carbon from iron-catalyzed reactions

Hind A. Al-Abadleh; Fatemeh Motaghedi; Wisam Mohammed; Md Sohel Rana; Kotiba A. Malek; Dewansh Rastogi; Akua A. Asa-Awuku; Marcelo I. Guzman

doi:10.1038/s42004-022-00732-1

Reactivity of aminophenols in forming nitrogen-containing brown carbon from iron-catalyzed reactions

Hind A. Al-Abadleh, Fatemeh Motaghedi, Wisam Mohammed, Md Sohel Rana, Kotiba A. Malek, Dewansh Rastogi, Akua A. Asa-Awuku, Marcelo I. Guzman

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

Nitrogen-containing organic carbon (NOC) in atmospheric particles is an important class of brown carbon (BrC). Redox active NOC like aminophenols received little attention in their ability to form BrC. Here we show that iron can catalyze dark oxidative oligomerization of o- and p-aminophenols under simulated aerosol and cloud conditions (pH 1–7, and ionic strength 0.01–1 M). Homogeneous aqueous phase reactions were conducted using soluble Fe(III), where particle growth/agglomeration were monitored using dynamic light scattering. Mass yield experiments of insoluble soot-like dark brown to black particles were as high as 40%. Hygroscopicity growth factors (κ) of these insoluble products under sub- and super-saturated conditions ranged from 0.4–0.6, higher than that of levoglucosan, a prominent proxy for biomass burning organic aerosol (BBOA). Soluble products analyzed using chromatography and mass spectrometry revealed the formation of ring coupling products of o- and p-aminophenols and their primary oxidation products. Heterogeneous reactions of aminophenol were also conducted using Arizona Test Dust (AZTD) under simulated aging conditions, and showed clear changes to optical properties, morphology, mixing state, and chemical composition. These results highlight the important role of iron redox chemistry in BrC formation under atmospherically relevant conditions.

Original language	English
Article number	112
Journal	Communications Chemistry
Volume	5
Issue number	1
DOIs	https://doi.org/10.1038/s42004-022-00732-1
State	Published - Dec 2022

Bibliographical note

Funding Information:
The authors acknowledge funding from the Natural Science and Engineering Council of Canada (NSERC) and to the U.S.A. National Science Foundation under award 1903744 to M.I.G. For technical assistance, the authors would like to thank Dr. Kitaev at Laurier for DLS, Drs. Smith and Goodfellow from the MS facility at the University of Waterloo for MALDI-TOF-MS, Dr. Castel from the Department of Chemical Engineering at the University of Waterloo for TGA, Dr. Andrei and Victoria Jarvis from the Canadian Centre for Electron Microscopy and MAX Diffraction Facility at McMaster University.

Publisher Copyright:
© 2022, The Author(s).

Funding

The authors acknowledge funding from the Natural Science and Engineering Council of Canada (NSERC) and to the U.S.A. National Science Foundation under award 1903744 to M.I.G. For technical assistance, the authors would like to thank Dr. Kitaev at Laurier for DLS, Drs. Smith and Goodfellow from the MS facility at the University of Waterloo for MALDI-TOF-MS, Dr. Castel from the Department of Chemical Engineering at the University of Waterloo for TGA, Dr. Andrei and Victoria Jarvis from the Canadian Centre for Electron Microscopy and MAX Diffraction Facility at McMaster University.

Funders	Funder number
National Science Foundation Arctic Social Science Program	1903744
National Science Foundation Arctic Social Science Program
Natural Sciences and Engineering Research Council of Canada
University of Waterloo
Department of Chemical Engineering, Universiti Teknologi Petronas

ASJC Scopus subject areas

General Chemistry
Environmental Chemistry
Biochemistry
Materials Chemistry

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title = "Reactivity of aminophenols in forming nitrogen-containing brown carbon from iron-catalyzed reactions",

abstract = "Nitrogen-containing organic carbon (NOC) in atmospheric particles is an important class of brown carbon (BrC). Redox active NOC like aminophenols received little attention in their ability to form BrC. Here we show that iron can catalyze dark oxidative oligomerization of o- and p-aminophenols under simulated aerosol and cloud conditions (pH 1–7, and ionic strength 0.01–1 M). Homogeneous aqueous phase reactions were conducted using soluble Fe(III), where particle growth/agglomeration were monitored using dynamic light scattering. Mass yield experiments of insoluble soot-like dark brown to black particles were as high as 40%. Hygroscopicity growth factors (κ) of these insoluble products under sub- and super-saturated conditions ranged from 0.4–0.6, higher than that of levoglucosan, a prominent proxy for biomass burning organic aerosol (BBOA). Soluble products analyzed using chromatography and mass spectrometry revealed the formation of ring coupling products of o- and p-aminophenols and their primary oxidation products. Heterogeneous reactions of aminophenol were also conducted using Arizona Test Dust (AZTD) under simulated aging conditions, and showed clear changes to optical properties, morphology, mixing state, and chemical composition. These results highlight the important role of iron redox chemistry in BrC formation under atmospherically relevant conditions.",

author = "Al-Abadleh, {Hind A.} and Fatemeh Motaghedi and Wisam Mohammed and Rana, {Md Sohel} and Malek, {Kotiba A.} and Dewansh Rastogi and Asa-Awuku, {Akua A.} and Guzman, {Marcelo I.}",

note = "Funding Information: The authors acknowledge funding from the Natural Science and Engineering Council of Canada (NSERC) and to the U.S.A. National Science Foundation under award 1903744 to M.I.G. For technical assistance, the authors would like to thank Dr. Kitaev at Laurier for DLS, Drs. Smith and Goodfellow from the MS facility at the University of Waterloo for MALDI-TOF-MS, Dr. Castel from the Department of Chemical Engineering at the University of Waterloo for TGA, Dr. Andrei and Victoria Jarvis from the Canadian Centre for Electron Microscopy and MAX Diffraction Facility at McMaster University. Publisher Copyright: {\textcopyright} 2022, The Author(s).",

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T1 - Reactivity of aminophenols in forming nitrogen-containing brown carbon from iron-catalyzed reactions

AU - Al-Abadleh, Hind A.

AU - Motaghedi, Fatemeh

AU - Mohammed, Wisam

AU - Rana, Md Sohel

AU - Malek, Kotiba A.

AU - Rastogi, Dewansh

AU - Asa-Awuku, Akua A.

AU - Guzman, Marcelo I.

N1 - Funding Information: The authors acknowledge funding from the Natural Science and Engineering Council of Canada (NSERC) and to the U.S.A. National Science Foundation under award 1903744 to M.I.G. For technical assistance, the authors would like to thank Dr. Kitaev at Laurier for DLS, Drs. Smith and Goodfellow from the MS facility at the University of Waterloo for MALDI-TOF-MS, Dr. Castel from the Department of Chemical Engineering at the University of Waterloo for TGA, Dr. Andrei and Victoria Jarvis from the Canadian Centre for Electron Microscopy and MAX Diffraction Facility at McMaster University. Publisher Copyright: © 2022, The Author(s).

PY - 2022/12

Y1 - 2022/12

N2 - Nitrogen-containing organic carbon (NOC) in atmospheric particles is an important class of brown carbon (BrC). Redox active NOC like aminophenols received little attention in their ability to form BrC. Here we show that iron can catalyze dark oxidative oligomerization of o- and p-aminophenols under simulated aerosol and cloud conditions (pH 1–7, and ionic strength 0.01–1 M). Homogeneous aqueous phase reactions were conducted using soluble Fe(III), where particle growth/agglomeration were monitored using dynamic light scattering. Mass yield experiments of insoluble soot-like dark brown to black particles were as high as 40%. Hygroscopicity growth factors (κ) of these insoluble products under sub- and super-saturated conditions ranged from 0.4–0.6, higher than that of levoglucosan, a prominent proxy for biomass burning organic aerosol (BBOA). Soluble products analyzed using chromatography and mass spectrometry revealed the formation of ring coupling products of o- and p-aminophenols and their primary oxidation products. Heterogeneous reactions of aminophenol were also conducted using Arizona Test Dust (AZTD) under simulated aging conditions, and showed clear changes to optical properties, morphology, mixing state, and chemical composition. These results highlight the important role of iron redox chemistry in BrC formation under atmospherically relevant conditions.

AB - Nitrogen-containing organic carbon (NOC) in atmospheric particles is an important class of brown carbon (BrC). Redox active NOC like aminophenols received little attention in their ability to form BrC. Here we show that iron can catalyze dark oxidative oligomerization of o- and p-aminophenols under simulated aerosol and cloud conditions (pH 1–7, and ionic strength 0.01–1 M). Homogeneous aqueous phase reactions were conducted using soluble Fe(III), where particle growth/agglomeration were monitored using dynamic light scattering. Mass yield experiments of insoluble soot-like dark brown to black particles were as high as 40%. Hygroscopicity growth factors (κ) of these insoluble products under sub- and super-saturated conditions ranged from 0.4–0.6, higher than that of levoglucosan, a prominent proxy for biomass burning organic aerosol (BBOA). Soluble products analyzed using chromatography and mass spectrometry revealed the formation of ring coupling products of o- and p-aminophenols and their primary oxidation products. Heterogeneous reactions of aminophenol were also conducted using Arizona Test Dust (AZTD) under simulated aging conditions, and showed clear changes to optical properties, morphology, mixing state, and chemical composition. These results highlight the important role of iron redox chemistry in BrC formation under atmospherically relevant conditions.

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JF - Communications Chemistry

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M1 - 112

ER -

Reactivity of aminophenols in forming nitrogen-containing brown carbon from iron-catalyzed reactions

Abstract

Bibliographical note

Funding

ASJC Scopus subject areas

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