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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
An important guide that highlights the multiphase chemical processes for students and professionals who want to learn more about aerosol chemistry Atmospheric Multiphase Reaction Chemistry provides the information and knowledge of multiphase chemical processes and offers a review of the fundamentals on gas-liquid equilibrium, gas phase reactions, bulk aqueous phase reactions, and gas-particle interface reactions related to formation of secondary aerosols. The authors--noted experts on the topic--also describe new particle formation, and cloud condensation nuclei activity. In addition, the text includes descriptions of field observations on secondary aerosols and PM2.5. Atmospheric aerosols play a critical role in air quality and climate change. There is growing evidence that the multiphase reactions involving heterogeneous reactions on the air-particle interface and the reactions in the bulk liquid phase of wet aerosol and cloud/fog droplets are important processes forming secondary aerosols in addition to gas-phase oxidation reactions to form low-volatile compounds. Comprehensive in scope, the book offers an understanding of the topic by providing a historical overview of secondary aerosols, the fundamentals of multiphase reactions, gas-phase reactions of volatile organic compounds, aqueous phase and air-particle interface reactions of organic compound. This important text: * Provides knowledge on multiphase chemical processes for graduate students and research scientists * Includes fundamentals on gas-liquid equilibrium, gas phase reactions, bulk aqueous phase reactions, and gas-particle interface reactions related to formation of secondary aerosols * Covers in detail reaction chemistry of secondary organic aerosols Written for students and research scientists in atmospheric chemistry and aerosol science of environmental engineering, Atmospheric Multiphase Reaction Chemistry offers an essential guide to the fundamentals of multiphase chemical processes.
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Table of Contents
Cover
Preface
1 Historical Background of Atmospheric Secondary Aerosol Research
1.1 Introduction
1.2 Secondary Inorganic Aerosols
1.3 Secondary Organic Aerosols
References
2 Fundamentals of Multiphase Chemical Reactions
2.1 Introduction
2.2 Gas–Liquid Phase Equilibrium and Equilibrium in Liquid Phase
2.3 Reactions in the Liquid Phase
2.4 Uptake Coefficient and Resistance Model
2.5 Physical Chemistry of Interface Reaction
2.6 Chemical Compositions and Physical Characters of Particles
References
3 Gas‐Phase Reactions Related to Secondary Organic Aerosols
3.1 Introduction
3.2 Ozone Reactions
3.3 OH Radical‐Induced Oxidation Reactions
3.4 NO3 Oxidation Reactions
References
4 Aqueous‐Phase Reactions Related to Secondary Organic Aerosols
4.1 Introduction
4.2 OH Radical Reactions
4.3 Nonradical Reactions
4.4 Formation Reactions of Organic Sulfates
4.5 Formation Reactions of Organic Nitrogen Compounds
References
5 Heterogeneous Oxidation Reactions at Organic Aerosol Surfaces
5.1 Introduction
5.2 Aging of Organic Aerosols in the Atmosphere
5.3 Reactions of Ozone
5.4 Reactions of OH Radicals
5.5 Reactions of NO3 Radicals
References
6 Reactions at the Air–Water and Air–Solid Particle Interface
6.1 Introduction
6.2 Molecular Pictures and Reactions at the Air–Water Interface
6.3 Air–Sea Salt Particle, Seawater, and Sulfate/Nitrate Aerosol Interface
6.4 Reactions on Snow/Ice Surface
6.5 Interface of Water and Mineral Dust, Quartz, and Metal Oxide Surface
References
7 Atmospheric New Particle Formation and Cloud Condensation Nuclei
7.1 Introduction
7.2 Classical Homogeneous Nucleation Theory
7.3 Atmospheric New Particle Formation
7.4 Aerosol Hygroscopicity and Cloud Condensation Nuclei
References
8 Field Observations of Secondary Organic Aerosols
8.1 Introduction
8.2 Global Budget of Aerosols
8.3 Analysis Methods of Ambient Aerosol Compositions
8.4 Marine Air
8.5 Forest Air
8.6 Urban/Rural Air
References
Index
End User License Agreement
List of Tables
Chapter 2
Table 2.1 Physical constants.
Table 2.2 Energy conversion table.
Table 2.3 Standard enthalpy of formation (
) and standard molar entropy (
) a...
Table 2.4 Henry's law constants of atmospheric molecules for watera (298 K).
Table 2.5 Heat of dissolution of atmospheric molecules for water (298 K).
Table 2.6 Equilibrium constants of aqueous ion dissociation reactions of atmo...
Table 2.7 Measured α
bulk
, Δ
H
obs
, Δ
S
obs
, and Δ
G
obs
(273 K) on water surface....
Table 2.8 Typical composition of seawater.
Chapter 3
Table 3.1 Reaction rate constants at 298 K and Arrhenius parameters of temper...
Table 3.2 Reaction rate constants at 298 K and Arrhenius parameters of temper...
Table 3.3 Reaction rate constants of stabilized Criegee intermediates at room...
Table 3.4 Yields of stabilized Criegee intermediates (SCI) in the reactions o...
Table 3.5 Yields of OH radicals in the ozone‐alkene reactions at room tempera...
Table 3.6 Rate constants at 298 K and temperature dependence parameters of th...
Table 3.7 Rate constants at 298 K and temperature dependence parameters of th...
Table 3.8 Yields of alkyl nitrate and hydroxyalkyl nitrate in the reaction of...
Table 3.9 Unimolecular decomposition rate of alkoxy radicals.
Table 3.10 Rate constants at 298 K and Arrhenius parameters for temperature d...
Chapter 4
Table 4.1 Absorption coefficients of hydrogen peroxide (H
2
O
2
) in the aqueous ...
Table 4.2 Absorption coefficients of nitrate ion (NO
3
−
) in the aqueous ...
Table 4.3 Absorption coefficients of nitrite ion (NO
2
−
) in the aqueous ...
Table 4.4 Average concentrations of OH radicals in the cloud droplets and del...
Table 4.5 Rate constants of reactions of OH radicals with organic compounds i...
Table 4.6 Intrinsic Henry's constants (
K
H
),effective Henry's constants (
K
H
*
),...
Table 4.7 Bimolecular rate constants between H
2
O
2
and carbonyl compounds in a...
Chapter 5
Table 5.1 Comparison of fitting parameters for Eq. (5.1) to the reaction of s...
Chapter 6
Table 6.1 Aqueous bulk phase and aqueous surface concentrations of benzene an...
Table 6.2 Typical minerals in dust, chemical formulas, emission fluxes and at...
Chapter 8
Table 8.1 Estimates of global annual emissions of inorganic particulate matte...
Table 8.2 Estimates of global annual emissions of organic and carbonaceous pa...
List of Illustrations
Chapter 2
Figure 2.1 Schematic diagram of Gibbs energy change for the reaction
A ⇄ B
...
Figure 2.2 Schematic diagram of chemical reaction pathway passing through th...
Figure 2.3 Schematic potential energy change along the reaction coordinate f...
Figure 2.4 Schematic diagram of resistant model for gas–liquid multiphase re...
Figure 2.5 Schematic diagram of resistance model for gas‐liquid multiphase r...
Figure 2.6 Schematic diagram of resistance model for gas–liquid multiphase r...
Figure 2.7 Variation of surface tension of water with temperature.
Figure 2.8 Postulated free energy diagram for the liquid vapor interface (se...
Figure 2.9 Correlation of the experimental (•) and calculated (
⊞
) valu...
Figure 2.10 Element composition of atmospheric PM
10‐2.5
in the Yellow ...
Chart 2.1 Chemical structures of typical primary organic aerosols (POA) comp...
Chart 2.2 Chemical structure of typical secondary organic aerosols (SOAs) ob...
Figure 2.11 Mass spectra of the oligomers of Budapest (upper trace) and Mace...
Figure 2.12 Schematic plots of van Krevelen diagram for alcohols, carboxylic...
Figure 2.13 van Krevelen diagram for aerosols observed in the field campaign...
Figure 2.14 Vaporization enthalpies of n‐alkanes at 298 K from C
5
to C
29
as ...
Figure 2.15 Vapor pressure of organic compounds as a function of carbon numb...
Figure 2.16 SOA yield for α‐pinene as a function of the organic mass concent...
Figure 2.17 Partitioning of a collection of semi‐volatile compounds. Full ve...
Figure 2.18 Temperature dependence of partitioning of a collection of semi‐v...
Figure 2.19 Change of mass distribution as semi‐volatile organics are chemic...
Chapter 3
Figure 3.1 UV absorption spectrum of CH
2
OO.
Figure 3.2 IR absorption spectrum of CH
2
OO: experimental (blank circle) and ...
Figure 3.3 Molecular structure of CH
2
OO. The unit of distance (R) is nm, and...
Figure 3.4 Energy diagram for the C
2
H
4
+ O
3
reaction.
Figure 3.5 Primary internal energy distribution of CH
2
OO formed in the C
2
H
4
...
Figure 3.6 Energy diagram of unimolecular decomposition of CH
2
OO.
Chart 3.1 Structures of syn –and anti‐acetaldehyde oxide.
Figure 3.7 UV absorption spectra of syn‐ and anti‐CH
3
CHO.
Figure 3.8 Energy diagram of unimolecular decomposition of CH
3
CHOO (unit kca...
Figure 3.9 Molecular structure of CH
2
OO hydrate; CH
2
OO + H
2
O (M1), CH
2
OO + (...
Figure 3.10 Energy diagram of reaction pathways of CH
2
OO + H
2
O, and CH
2
OO + ...
Figure 3.11 Energy diagram of reaction pathways of (a) H
2
O
2
+ CH
2
OO (b) CH
3
O...
Figure 3.12 Energy diagram of reaction pathways of (a) CH
3
OO + CH
2
OO, and (b...
Figure 3.13 Negative‐ion mass spectra of (a) gas‐phase products and (b) filt...
Figure 3.14 Mass spectra of reaction products in the ozone reaction of
E
‐3–h...
Chart 3.2 Structures of syn– and anti‐vinylaldehyde oxide.
Reaction Scheme 3.1 Mechanism of the reaction of isoprene and O
3
.
Figure 3.15 Energy diagram of isoprene‐O
3
reaction. (a) O addition to the do...
Reaction Scheme 3.2 Mechanism of the chclohexene‐O
3
reaction.
Reaction Scheme 3.3 Mechanism of autoxidation processes in the cyclohexene‐O
Reaction Scheme 3.4 Formation mechanism of the gas‐phase products in the 1‐m...
Chart 3.3 Chemical structures of the products with multi‐functional groups o...
Reaction Scheme 3.5 Formation mechanism of gaseous products in the methylene...
Chart 3.4 Chemical structures of typical monoterpenes.
Reaction Scheme 3.6 Formation mechanism of gas‐ and particulate‐phase produc...
Reaction Scheme 3.7 Mechanism of the gas‐phase reaction of β‐pinene and ozon...
Figure 3.16 Energy diagrams of (a) nopinone formation from β‐pinene‐O
3
react...
Reaction Scheme 3.8 Formation mechanism of pinic acid in the ozone reaction ...
Reaction Scheme 3.9 Mechanism of the O
3
reaction with cyclic double bond (en...
Reaction Scheme 3.10 Mechanism of the O
3
reaction with side‐chain double bon...
Reaction Scheme 3.11 Mechanism of autoxidation reaction of alkyl‐type radica...
Chart 3.5 Chemical structures of typical sesquiterpenes.
Chart 3.6 (a) β‐caryophyllene, (b) first‐generation products detected in the...
Reaction Scheme 3.12 Reaction mechanism of the isomerization pathway of 2‐hy...
Reaction Scheme 3.13 Reaction Scheme of OH‐induced oxidation of straight cha...
Reaction Scheme 3.14 Formation mechanism of formaldehyde, acrolein, and 4‐hy...
Reaction Scheme 3.15 Formation mechanism of furan in the OH‐induced oxidatio...
Reaction Scheme 3.16 Secondary formation mechanism of glyoxal, glycolaldehyd...
Reaction Scheme 3.17 Mechanism of the OH‐induced oxidation reaction of 1‐met...
Reaction Scheme 3.18 Reaction mechanism of primary production of MACR, MVK, ...
Reaction Scheme 3.19 Mechanism for OH and HO
2
radical formation in the OH ad...
Reaction Scheme 3.20 The mechanism of the OH‐induced oxidation reaction of (...
Reaction Scheme 3.21 Formation mechanism of metylglyoxal (MGLY), glycolaldeh...
Reaction Scheme 3.22 Reaction mechanism of the formation of MPAN, MAPA, MAEP...
Reaction Scheme 3.23 Reaction mechanism of the OH‐initiated oxidation of α‐p...
Reaction Scheme 3.24 Oxidation reaction mechanism of pinonaldehyde initiated...
Reaction Scheme 3.25 Reaction mechanism of oxidation of β‐pinene initiated b...
Reaction Scheme 3.26 Oxidation reaction mechanism of nopinone initiated by t...
Reaction Scheme 3.27 Oxidation reaction mechanism of limonene initiated by t...
Reaction Scheme 3.28 Example of oxidation reaction mechanism of limonene ini...
Reaction Scheme 3.29 Reaction mechanism of the OH‐initiated oxidation reacti...
Figure 3.17 UV absorption spectrum of hydroxycyclohexadienyl radical. Reprod...
Reaction Scheme 3.30 Mechanism of OH‐induced oxidation reaction of benzene i...
Figure 3.18 Energy diagram for the ring opening pathways of the reaction of ...
Reaction Scheme 3.31 Reaction mechanism of the OH‐initiated oxidation of tol...
Chart 3.7 Chemical structures of typical polycyclic aromatic compounds.
Reaction Scheme 3.32 Reaction mechanism of OH‐initiated oxidation of naphtha...
Figure 3.19 UV–VIS absorption spectrum of glyoxal.
Figure 3.20 Quantum yield of each process in the photolysis of glyoxal. Φ(to...
Figure 3.21 UV–VIS absorption spectrum of methylglyoxal (spectral resolution...
Figure 3.22 UV absorption spectrum of glycolaldehyde.
Figure 3.23 UV absorption spectrum of hydroxyacetone.
Reaction Scheme 3.33 Reaction mechanism of second‐generation SOA products fr...
Reaction Scheme 3.34 Mechanism of the α‐pinene reaction initiated by the add...
Reaction Scheme 3.35 Oxidation mechanism of β‐pinene initiated by the additi...
Reaction Scheme 3.36 Reaction mechanism of gas phase oxidation of limonene i...
Reaction Scheme 3.37 The pathways of the reaction of naphthalene and NO
3
rad...
Chapter 4
Figure 4.1 UV absorption spectrum of OH radical in the aqueous phase. Each d...
Chart 4.1 The structure of the optimized OH‐H
2
O clusters.
Figure 4.2 UV absorption spectrum of H
2
O
2
in the aqueous phase (298 K).
Figure 4.3 UV‐VIS absorption spectra of NO
3
−
and NO
2
−
in the aqu...
Figure 4.4 Wavelength dependence of quantum yield of OH in the photolysis of...
Reaction Scheme 4.1 Reaction mechanism of the OH‐induced oxidation of glyoxa...
Reaction Scheme 4.2 Formation mechanism of pyruvic acid in the OH‐induced re...
Figure 4.5 Absorption spectrum of pyruvic acid (dark) and phtalic acid (ligh...
Reaction Scheme 4.3 Reaction pathways of the OH‐induced oxidation reaction o...
Reaction Scheme 4.4 Reaction mechanism of the photolysis of pyruvic acid in ...
Reaction Scheme 4.5 Reaction mechanism of the OH‐induced oxidation of glycol...
Figure 4.6 Absorption spectrum of methacrolein (upper line), iso‐butylaldehy...
Reaction Scheme 4.6 Reaction mechanism of the OH‐induced reaction of MACR in...
Reaction Scheme 4.7 Reaction mechanism of the OH‐induced oxidation reaction ...
Reaction Scheme 4.8 Formation mechanism of oligomers in the OH‐induced oxida...
Reaction Scheme 4.9 Formation mechanism of dimethyl tartaric acid in the OH‐...
Reaction Scheme 4.10 Formation mechanism of oligomers in the OH‐induced oxid...
Reaction Scheme 4.11 Reaction mechanism of the acid catalyzed aldol reaction...
Chart 4.2 C
2
, C
3
organic sulfates ester identified in the ambient aerosols....
Chart 4.3 Hydroxy sulfates with MW = 250 identified in the OH oxidation of α...
Reaction Scheme 4.12 Reaction mechanism of ring‐opening hydration of epoxide...
Reaction Scheme 4.13 Formation mechanism of tetrol and hydroxy sulfate from ...
Chart 4.4 Chemical structures of imidazole and its derivatives formed in the...
Reaction Scheme 4.14 Mechanism of the formation of imidazoles in the reactio...
Reaction Scheme 4.15 Assumed mechanisms for the reactions of monohydrated gl...
Chapter 5
Chart 5.1 Chemical structures of (a) 17α(H),21β(H)‐hopane, (b) 17α(H),21β(H)...
Figure 5.1 Seasonal variation of monthly averaged concentration ratio of hop...
Figure 5.2 Seasonal variation of concentration ratio of levoglucosan/EC at C...
Figure 5.3 Summary plot showing
f
44
vs.
f
60
for the field measurements. The ...
Figure 5.4 Ratios of reactive/stable PAHs (BaP/BeP and BaA/Chr) during the c...
Reaction Scheme 5.1 Proposed scheme for the heterogeneous reaction of O
3
and...
Chart 5.2 Chemical structures of (a) squalene, (b) squalane, and (c) n‐octac...
Reaction Scheme 5.2 Proposed reaction mechanism of forming volatile products...
Figure 5.5 Pseudo‐first‐order rate coefficients (k
I
obs
) as a function of gas...
Reaction Scheme 5.3 Proposed mechanism for the heterogeneous reaction of par...
Reaction Scheme 5.4 Reaction pathways of the OH‐initiated heterogeneous oxid...
Figure 5.6 Distribution of positional isomers of functionalization products ...
Reaction Scheme 5.5 Reaction pathways of OH‐induced oxidation of polyol.
Reaction Scheme 5.6 Reaction pathways of OH‐induced oxidation of levoglucosa...
Reaction Scheme 5.7 Proposed mechanism of OH‐initiated oxidation of suberic ...
Reaction Scheme 5.8 Proposed major reaction pathways of heterogeneous reacti...
Chart 5.3 Chemical structures of (a) oleic acid, (b) linoleic acid, and (c) ...
Reaction Scheme 5.9 Proposed reaction mechanism for the OH‐initiated heterog...
Reaction Scheme 5.10 Proposed reaction mechanism for the OH‐initiated oxidat...
Reaction Scheme 5.11 Proposed reaction mechanism for the NO
3
‐initiated heter...
Reaction Scheme 5.12 Proposed mechanism of heterogeneous reaction of NO
3
and...
Chapter 6
Figure 6.1 Atmospheric water regimes on aerosols. The scale varies from nm t...
Figure 6.2 Conceptual schematic of the typical aqueous aerosol droplet inter...
Figure 6.3 Molecular dynamics simulations of free energy for transfer from t...
Figure 6.4 Free energy (Δ
G
) change for transfer from the air to the bulk wat...
Figure 6.5 (a)–(d) Sum‐frequency generation (SFG) spectra of the air–water i...
Figure 6.6 Typical orientation of H
2
O in each frequency region represented w...
Figure 6.7 (a) Experimental and (b) computational SSP‐polarized vibrational ...
Figure 6.8 Schematic illustration of the possible structures for (a) the vap...
Figure 6.9 Schematic illustration of the possible orientations of (a) carbon...
Figure 6.10 Observed vibrational SFG spectra (light gray) of the OH and CH s...
Figure 6.11 The schematic orientation of surface‐active organic molecules at...
Figure 6.12 Reaction mechanism of Criegee intermediate from α‐humulene –O
3
r...
Figure 6.13Figure 6.13 Schematic energy profile for the reaction of O
3
with ...
Figure 6.14 Signal intensity ratios of HOOC‐R
n
‐COO
−
in the presence ve...
Figure 6.15 Vibrational sum frequency (SFG) spectra of NaF, NaCl, NaBr, and ...
Figure 6.16 Snapshots and number desities of Na
+
, F
−
, Cl
−
, B...
Figure 6.17 Decay in uptake coefficient (γ) with reaction time for the surfa...
Figure 6.18 SFG spectra of CH stretching vibrations of natural marine water ...
Figure 6.19 SFG spectra of 1 M aqueous (NH
4
)
2
SO
4
solution compared to neat w...
Figure 6.20 Schematic view of relative surface propensities of different ion...
Figure 6.21 Absorption spectra and molar absorption coefficient for (a) 10 m...
Figure 6.22 Uptake coefficient (γ) vs. pH for the reaction of O
3
with frozen...
Figure 6.23 The dependence of the yields of ClNO
2
and Br
2
as a function of C...
Figure 6.24 (a) ATR‐FTIR spectra following the water uptake on SiO
2
at diffe...
Figure 6.25 Vibrational SFG spectra of water/α‐quartz interface at various b...
Figure 6.26 Schematic illustrations of the orientations of water molecules i...
Figure 6.27 (a) Absorption cross section data of HNO
3
on fused silica based ...
Figure 6.28 Schematic structure of C8 = silane SAM on silicone.
Chapter 7
Figure 7.1 Gibbs energy change for nucleation, Δ
G
, as a function of the clus...
Figure 7.2 Typical new particle formation event observed in Hyytiälä, Finlan...
Figure 7.3 Comparison of atmospheric nucleation rates obtained during the Qu...
Figure 7.4 Mass defect is plotted against mass‐to‐charge ratio,
m
/
z
, obtaine...
Figure 7.5 Schematic description of main size regimes of atmospheric neutral...
Figure 7.6 An example of a Köhler curve representing the relation between su...
Figure 7.7 Relationship between the O : C ratio and hygroscopicity,
κ
or
...
Figure 7.8 Organic hygroscopicity,
κ
org
, plotted as a function of O : C...
Chapter 8
Figure 8.1 Schematic diagram of bilinear factor analysis of mass spectral ma...
Figure 8.2 Schematic diagram of 2D‐VBS framework for OA aging. The x axis is...
Figure 8.3 Seasonal differences in aerosol mass‐diameter distribution in cle...
Figure 8.4 Seasonal differences in size distribution of number density of su...
Figure 8.5 Seasonal variation in accumulation mode mass concentration in cle...
Figure 8.6 Seasonal variation of the mass concentrations of water‐soluble or...
Figure 8.7 Time series of particle mass concentrations at Santarem (eastern ...
Figure 8.8 Diurnal variation of emission fluxes (top) and mixing ratios (bot...
Figure 8.9 Statistical factors HOA, OOA‐1, OOA‐2, and OOA‐3 identified by PM...
Figure 8.10 Three modal structure of number size distribution of submicron a...
Figure 8.11 Mass spectra of OOA‐1, OOA‐2, and HOA from the three component P...
Figure 8.12 Diurnal patterns of five OA factors determined by PMF analysis o...
Figure 8.13 Average ratios of total mass composition deduced from PMF analys...
Figure 8.14 (a)
f
44
vs.
f
43
for the OOA components from different sites. (b)...
Figure 8.15 Diurnal averages of atomic O/C, H/C, N/C, and OM/OC for the samp...
Figure 8.16 O/C for ambient aerosol sampled at the ground site and by air pl...
Figure 8.17 (a) Scatter plot of OM/OC vs. O/C for all ambient and chamber OA...
Figure 8.18 The average size distribution of m/z 57, m/z 4, C
4
H
9
+
and su...
Figure 8.19 Van Krevelen diagram for detected ions in the aerosol samples fr...
Figure 8.20 Normalized relative abundances for each elemental group with res...
Chart 8.1 Dicarboxylic acids and related compounds observed in the ambient o...
Chart 8.2 Dicarboxylic acids and related compounds derived from α‐ or β‐pine...
Figure 8.21 Produced organic carbon concentration as a function of aerosol a...
Chart 8.3 IEPOX and other isoprene‐derived compounds observed in urban ambie...
Chart 8.4 DHOPA derived from toluene observed in ambient aerosols.
Chart 8.5 Monoterpene‐derived organic sulfate observed in ambient aerosols....
Chart 8.6 Isoprene‐derived organic sulfate observed in ambient aerosols.
Chart 8.7 α‐pinene and isoprene‐derived organic nitrates observed in ambient...
Chart 8.8 Proposed molecular structures of monoterpene and isoprene‐derived ...
Chart 8.9 Imidazoles observed in ambient aerosols.
Figure 8.22 Mass spectra of (a) HMWC fraction of Mace Head aerosol, and (b) ...
Figure 8.23 UV‐VIS Spectrum of HMWC extracted from the WSOC at Mace Head....
Reaction Scheme 8.1 Proposed formation mechanism for the MW358 and 344 compo...
Guide
Cover
Table of Contents
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Atmospheric Multiphase Chemistry
Fundamentals of Secondary Aerosol Formation
Hajime Akimoto
National Institute for Environmental StudiesTsukuba, Japan
Jun Hirokawa
Hokkaido UniversitySapporo, Japan
Copyright
This edition first published 2020
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Library of Congress Cataloging‐in‐Publication Data
Names: Akimoto, Hajime, author. | Hirokawa, Jun, author.
Title: Atmospheric multiphase chemistry : fundamentals of secondary aerosol
formation / Hajime Akimoto, Jun Hirokawa.
Description: First edition. | Hoboken, NJ : Wiley‐Blackwell, 2020. |
Includes bibliographical references and index.
Identifiers: LCCN 2019051976 (print) | LCCN 2019051977 (ebook) | ISBN
9781119422426 (hardback) | ISBN 9781119422396 (adobe pdf) | ISBN
9781119422402 (epub)
Subjects: LCSH: Atmospheric aerosols. | Chemical reactions. | Multiphase
flow.
Classification: LCC QC882.42 .A45 2020 (print) | LCC QC882.42 (ebook) |
DDC 551.51/13–dc23
LC record available at https://lccn.loc.gov/2019051976
LC ebook record available at https://lccn.loc.gov/2019051977
Cover Design: Wiley
Cover Image: © Daniel Haug/Getty Images
Preface
Reaction kinetics and mechanism are a significant part of the fundamentals of atmospheric chemistry. The chemical reaction system in the atmosphere is composed of homogeneous reactions in the gas and liquid phases and heterogeneous processes involving particle surfaces. Among them, the study of gas‐phase homogeneous reaction system in the atmosphere has evolved since the Chapman theory in the 1930s to explain the stratospheric ozone layer, and developed dramatically after 1970s with photochemical air pollution as a trigger. It is now almost established and summarized in many bibliographies, including a book by one of present authors (H.A.) discussed in Chapter 3.
In contrast, although the heterogeneous reaction system in the atmosphere has developed substantially with acid rain and stratospheric ozone hole as turning points, the studies have long been confined mainly to inorganic species. The research field of aerosols and heterogeneous kinetics has undergone dramatic changes since the 2000s, when the importance of secondary organic aerosols as cloud condensation nuclei was pointed out. Also, secondary organic aerosols have been recognized as important as inorganic sulfate and nitrate as a constituent of PM2.5, which is concerned from the point of human health.
The formation mechanism of secondary organic aerosols involves condensation of reaction products of homogeneous gas‐phase reactions, uptake of the gas‐phase products onto the particle surface, complex formation and reaction at the interface, homogeneous aqueous‐phase reaction, and evaporation from a particle to the gas phase. We call series of these processes multiphase reaction chemistry.
This book intends to serve as a reference book on fundamentals of atmospheric multiphase chemistry. Gas‐ and aqueous‐phase reactions, heterogeneous oxidation processes, and air–water interface and solid particle surface reactions related to secondary organic aerosol formation are first described. After that, new particle formation, cloud condensation nucleus activity, and field observation of organic aerosols are discussed. The book can serve as a comprehensive reference for graduate students and professionals who are interested in homogeneous and heterogeneous atmospheric reactions of organic species related to aerosols.
The field of atmospheric multiphase chemistry is still a rapidly developing research area. Many studies described in this book have not become fully established, and future revisions are likely.
Finally, we would like to acknowledge Drs. Michihiro Mochida, Satoshi Inomata, Kei Sato, Yasuhiro Sadanaga, and Shinichi Enami, who read the manuscript in their respective parts and gave us valuable comments.
October, 2019
Hajime AkimotoJun Hirokawa
1Historical Background of Atmospheric Secondary Aerosol Research
1.1 Introduction
Trace components in the tropospheric atmosphere consist of gaseous molecules and particulate matters. Most of gaseous molecules in the atmosphere do not have absorption bands in the visible region. Some species such as ozone and nitrogen dioxide have the absorption, but they are invisible to the naked eye under the normal atmospheric conditions because their absorbance are small. In contrast, since the particulate matters intercept sunlight and small particles scatter strongly the solar radiation, they are captured easily by the naked eye as haze. Thus, particulate matters in the atmosphere called atmospheric aerosols have been studied from relatively early days in relation to air pollution historically.
These atmospheric aerosols are divided broadly into the primary species released directly from emission sources and the secondary compounds formed by chemical reactions in the atmosphere. Further, secondary particulate matter can be classified into secondary inorganic aerosol and secondary organic aerosol (SOA).
This book aims at the understanding of chemical reactions forming secondary aerosols in the gas phase, in the liquid phase, and at their interface, particularly focusing on organic aerosols. Therefore, most of the descriptions are focused on organic species, and inorganic species are addressed whenever necessary. As for the formation of secondary inorganic aerosols, detailed discussion has been given by the textbook of Seinfeld and Pandis (2016).
In this chapter, historical background of research on atmospheric secondary aerosols, including inorganic aerosols, is described looking back before 1980s, when the atmospheric chemistry was founded as one of the academic fields of the global environmental sciences.
1.2 Secondary Inorganic Aerosols
The first capture of atmospheric secondary inorganic aerosol such as nitrate and sulphate was in the form of precipitation component, and their historical reviews are available by Eriksson (1952a, 1952b) and Möller (2008). First discovery of nitrate in precipitation was made by Marggraf (1751), a German chemist, and mineral species (silica and lime), sea salt component (sodium and chloride), ammonium, and organics as brown residue were also detected together with nitrate. It was the earlier half of nineteenth century when Liebig (1835) advocated a theory that atmospheric nitrogen compounds deposited on ground are essential to plant growth as nutrient salt absorbed by roots, leading to a revolution of agricultural chemistry. Thus, atmospheric nitrate, the main component of the plant nutrient, had been discovered from long ago as a precipitation constituent (Miller 1905; Eriksson 1952a; Möller 2008). On the other hand, the discovery of sulphate was delayed nearly 100 years after that of nitrate. From the view point of air pollution in Manchester, UK, Smith (1852) described based on the analysis of precipitation that three kinds of air can be found: (i) with carbonate of ammonia in the remote field; (ii) with sulphate of ammonia in the suburbs; and (iii) with sulfuric acid in the urban area (Cowling 1982). The described ammonium carbonate ((NH4)2CO3), ammonium sulfate ((NH4)2SO4), and sulfuric acid (H2SO4) are formed secondarily by the chemical reactions in the gas phase or in the fog water from atmospheric trace gaseous species, CO2, NH3, and SO2. These aerosols are water‐soluble, and recognized as major components of “acid rain” after taken into precipitation. Incidentally, the term of acid rain was used for the first time in the monograph of Smith (1872) as accredited by Cowling (1982). Since then, the measurement of nitrate and ammonium had been made in many places in Europe in the latter half of nineteenth century from the interest of agricultural chemistry, while sulfate had been measured in the eastern part of United States since the 1910s (Cowling 1982).
Hydrogen ion concentration (pH) has been measured since the 1950s, started in Europe and United States, over a wide area. Owing to these wide‐area observations, spatial distribution and temporal trends of pH and chemical components of precipitation became to be known well in Europe (Emanuelsson et al. 1954; Barrett and Brodin 1955; Odén 1976) and North America (Junge and Werby 1958; Gorham and Gordon 1960; Cogbill 1976). The acid rain causing acidification of lakes and rivers and their impact on fishery was then brought up as a social problem internationally. The quantitative research on the formation of sulfate and nitrate as secondary inorganic aerosol had been developed rapidly as “acid rain” became social concern.
1.2.1 Sulfate
In the earlier studies on acid rain, it was thought that sulfur dioxide (SO2), primary air pollutants whose atmospheric concentration had increased rapidly after the Industrial Revolution, was taken up into fog water droplets and converted to sulfate by oxidation in the aqueous phase (Junge and Ryan 1958; Junge 1963):
The rate limiting stage of this process is the oxidation step of SO32− to SO42−, and the oxidation by O2 had been studied for a long time (Fudakowski 1873; Backstrom 1934). However, the oxidation rate of SO32− by O2 was found to be very slow (Fuller and Crist 1941; Brimblecombe and Spedding 1974). Therefore, this reaction is not important for O2 alone as the oxidation reaction of SO2 in the atmosphere, but it was found that the reaction is accelerated by the coexistence of trace metal ions such as Fe3+, Cu2+, and Mn2+ (Reinders and Vles 1925; Junge and Ryan 1958; Brimblecombe and Spedding 1974; Hegg and Hobbs 1978). The effects of transition metal ions on the SO2 oxidation in the aqueous phase still leaves a lot of unknowns, and the studies are ongoing (Deguillaume et al. 2005; Harris et al. 2013; Herrmann et al. 2015).
In 1970s, the importance of the reaction of O3 and H2O2, formed secondarily in the photochemically polluted atmosphere, was pointed out. The pioneering studies were made by Penkett and Garland (1974), Erickson et al. (1977), and Larson et al. (1978) for O3, and by Mader (1958), Hoffmann and Edwards (1975), and Penkett et al. (1979) for H2O2. Later studies on these aqueous phase reactions revealed that the oxidation by H2O2 is more important at lower pH than 7, and those of O3 become important in the higher pH region. Details of these aqueous‐phase reactions are summarized in the textbooks by Akimoto (2016, pp. 363–372), and Seinfeld and Pandis (2016).
Atmospheric oxidation reactions of SO2 to SO42− were studied earlier for the aqueous‐phase reactions, and the gas‐phase reactions was noted later by Cox and Penkett (1972). The years of 1970s are the era that OH radical chain reactions were proposed and demonstrated to cause photochemical air pollution (Akimoto 2016, pp. 288–290). The importance of the reaction of SO2 and OH for the oxidation of SO2 was deduced based on the measured rate constant of the reaction (Eggleton and Cox 1978; Davis et al. 1979). Later, Stockwell and Calvert (1983) showed the oxidation process of SO2 with OH as
This implies that the HOSO2 forms H2SO4 without terminating the OH chain reaction. The SO2 oxidation mechanism in the gas‐phase has thus been established. Although the relative importance of gas‐ and aqueous‐phase reactions varies widely, depending on meteorological conditions. It is thought in general that both processes are important (Barrie et al. 2001). Most of sulfate in particles exist as ammonium sulfate ((NH4)2SO4) or ammonium bisulfate (NH4HSO4), and a part of them exists as sulfuric acid (H2SO4) when NH3 is in short stoichiometrically as observed in the sub‐micron particles in many urban samples (van den Heuvel and Mason 1963; Ludwig and Robinson 1965; Wagman, Lee, and Axt 1967).
1.2.2 Nitrate
The measurement of nitrate (NO3−) in precipitation has been reported in United States early in 1920s from the interest in agricultural chemistry (Wilson 1926). Its atmospheric concentrations increased rapidly, accompanying with the rapid increase of fossil fuel combustion. It has been monitored since the 1950s as an important secondary inorganic aerosol next to SO42− (Junge 1954; Lee and Patterson 1969). For example, the equivalent‐basis fractions of SO42− and NO3− in precipitation in Eastern United States in early 1960s are reported as ca. 60% and ca. 20%, respectively (Likens and Bormann 1974). Particularly, large amounts of nitrates were reported, together with sulfate and organic aerosols existing in photochemical smog mentioned in the next section (Renzetti and Doyle 1959; Lundgren 1970; Appel et al. 1978).
Since the rate constant of the reaction:
is one order of magnitude larger than the reaction, OH + SO2 + M, under the atmospheric conditions, and the Henry's law constant of NO2 is two orders of magnitude smaller than SO2 (Table 2.2), nitric acid (HNO3) in the atmosphere is thought to be formed in the gas phase and then taken into the aqueous phase (Orel and Seinfeld 1977). Meanwhile, a formation pathway other than 1.6 is considered to be the hydrolysis of N2O5 formed via NO3 by the reaction of O3 and NO2 (Orel and Seinfeld 1977):
The rate constant of Reaction (1.9) in the gas phase as a homogeneous reaction is very small, <2.0 × 10−21 cm3 molecule−1 s−1 (Burkholder et al. 2015), and the heterogeneous reaction on the particle surface is thought to be more important (Mozurkewich and Calvert 1988). The NO3 radical involved in this reaction process has absorption bands in the visible region and photolysed easily by sunlight, so that the formation of HNO3 by this heterogeneous reaction process is thought to be important in the nighttime (Richards 1983; Heikes and Thompson 1983).
The gaseous nitric acid, ammonia, and ammonium nitrate formed from them are thought to be in equilibrium:
and comparison between model estimate based on the thermodynamic parameters (Stelson et al. 1979) and field observation for the formation of nitrate have been made (Harrison and Pio 1983; Hildemann et al. 1984). Reaction (1.10) is reversible reaction, and the particulate NH4NO3 increases with the decrease of temperature, and thus the concentration ratio of nitrate is known to increase in winter and at dawn. Multiphase models that treat sulfuric and nitric acid simultaneously have been developed in 1980s (Bassett and Seinfeld 1983; Saxena et al. 1983).
Gaseous HNO3 reacts with sea salt (NaCl) on the surface to give sodium nitrate by releasing HCl:
Although it has been presumed that the reaction causes the decrease of chlorine to sodium ratio in the sea salt in the vicinity of continents and brings the nitrate in coarse particles (Robbins et al. 1959), the reaction has been validated by laboratory experiments only after the latter half of 1990s (De Haan and Finlayson‐Pitts 1997; Wahner et al. 1998). Thus, nitrates have the characteristics that they exist as NH4NO3 in submicron particles in the inland and as NaNO3 in coarse particles (2–8 μm) in the coastal urban area (Lee and Patterson 1969; Cronn et al. 1977).
1.3 Secondary Organic Aerosols
Existence of organic materials in the precipitation was noted by Marggraf (1751) in the middle of eighteenth century, and they were more clearly identified as humic acid‐like substances in the first half of the nineteenth century (Lampadius 1837; Möller 2008). However, the trigger to wide concern on the particulate organic compounds was the discovery of carcinogenic polyaromatic hydrocarbons (PAHs) in the diesel exhaust and urban atmosphere in the middle of twentieth century (e.g. Waller 1952; Kotin et al. 1954; Stocks and Campbell 1955; Wynder and Hoffmann 1965). Further findings of many oxygenated compounds in the atmospheric aerosols were made in the photochemical smog.
1.3.1 Photochemical Smog
In the middle of the 1940s, new type of smog totally different from conventional air pollution due to SO2, sulfate, and coal fly ash, spread in Los Angeles basin, and became a social problem by causing visibility reduction, eye and throat irritation, and particularly big damage to agriculture (Middleton et al. 1950; Finlayson‐Pitts and Pitts 2000). Although the cause of so‐named Los Angeles smog was unexplained at the beginning, Haagen‐Smit (1952), and Haagen‐Smit, Bradley and Fox (1956) elucidated for the first time that it is ascribed to the toxic substances, including ozone and other strongly oxidizing compounds so‐named photochemical oxidants, formed by the solar irradiation to the mixtures of nitrogen oxides and non‐methane hydrocarbons (NMHCs) emitted from automobile exhaust. Such atmospheric photochemical processes were systematized by Leighton (1961), and his book, Photochemistry of Air Pollution is now a classic of atmospheric photochemistry. Los Angeles smog was later called photochemical smog (e.g. Rogers 1958), and the term, photochemical air pollution, is now widely used including more general concept (e.g. Robinson 1972).
In photochemical smog, other than gaseous oxidants, many kinds of organic aerosols together with sulfate and nitrate were found as particulate matter, and these were shown to be SOAs, formed by the photo‐irradiation of the mixtures of NOx and NMHCs such as auto exhaust (Mader et al. 1952; Renzetti and Doyle 1959). Incidentally, the NMHC was used as a general term for the collectives of short‐lived hydrocarbons, excluding methane, which has a longer atmospheric lifetime of nearly 10 years and does not contribute to urban photochemical air pollution directly. Recently, instead of NMHC, the term nonmethane volatile organic compounds (NMVOC) has been more widely used to include oxygen‐containing organic compounds other than hydrocarbons. From the early days of the study on the formation mechanism of photochemical smog, there was interest in what kinds of hydrocarbons generate SOAs more effectively. Studies of Haagen‐Smit (1952) showed that cyclic hydrocarbons with double bonds such as cyclohexene, indene, and cyclopentadiene easily form low‐volatile oxygenated compounds with higher yields of aerosols, since the multiple functional groups are introduced by the ring‐opening reactions. This was later confirmed by O'Brien, Holmes, and Bokian (1975), and they reported α‐pinene having a cyclic double bond and dialkenes such as isoprene form aerosols with the higher yields, and monocyclic aromatic hydrocarbons such as xylenes also form aerosols with the lower yields.
In the organic aerosols, particulate alkanes, alkenes, alkylbenzenes, naphthalene, etc. were detected as primary organic aerosols (POAs) released directly from emission sources, and pinonic acid, adipic acid, phenols, alkyl nitrates, etc. as SOA formed in the atmosphere. Primary aerosols are not correlated with ozone, but the secondary aerosols have a high correlation with ozone and have peak concentration in early afternoon. Such clear distinction between the POA and SOA was made in the middle of 1970s (Appel, Colodny, and Wesolowski 1976; Cronn et al. 1977). These early studies showed that alcohols, carboxylic acids, and carbonyl compounds are included in the aerosols by use of infrared absorption spectroscopy and mass spectrometry (Cukor et al. 1972; Ciaccio et al. 1974; Cronn et al. 1977). Also, it was revealed that atmospheric carbonaceous aerosol sampled in California consisted of elemental carbon (EC) and organic carbon (OC) (Appel, Colodny and Wesolowski 1976).
1.3.2 Blue Haze
It is experienced for a long time that the atmosphere in the boundary layer over forests is covered by blue haze after the air is cleaned by rain in summer. In 1950s, a botanist, Went (1960a) addressed the interest to this phenomenon from the viewpoint of atmospheric aerosols. In the “Blue Mountains” near Sydney, Australia, and “Blue Ridges” near the Smoky Mountains in Tennessee, United States, such blue haze are often visible (Ferman, Wolff, and Kelly 1981). Went (1960a) mentioned that a similar phenomenon in Tuscany, Italy, was described in a note by Leonardo da Vinci a long time ago in sixteenth century. This kind of haze is not natural dust or mist, nor the effects of biomass burning or air pollution, and can be seen in dry air irrelevant to water vapor. From these considerations Went (1960a) concluded that blue haze is due to the Tyndall effect described by Tyndall (1869) in the middle of nineteenth century, a phenomenon that a light path can be seen bright from an oblique due to scatter of light by fine particles in air. He proposed that when the fine particles with a diameter of the order of 0.1 μm exist in the atmosphere, blue light in the solar light is effectively scattered and blue haze is visible.
As for the possibility of formation of such sub‐micron fine particles over the clean forests, Went (1960b) suggested that the photochemical smog reaction of hydrocarbons such as terpenes and isoprene emitted by plants. However, atmospheric concentrations of such biogenic hydrocarbons were not known in early 1960s. They were measured for the first time by Rasmussen and Went (1965), and total concentration of isoprene and terpenes up to ∼10 ppbv was reported in several forest highlands in United States.
Later measurement of chemical composition of field aerosols at Great Smoky Mountains showed that the main component of fine particles is sulfate and the fraction of organic compounds are relatively small (Stevens et al. 1980; Ferman, Wolff, and Kelly 1981) in those days. Seasonality of the aerosol components were shown that concentrations of sulfate and organic aerosols are high in summer and that of nitrate is high in winter, reflecting the photochemical formation of SO42− and OA, and temperature‐dependent gas‐solid equilibrium of NH4NO3 (Day, Malm, and Kreidenweis 1997). Meanwhile, although the measurement of chemical analysis of aerosols in Blue Mountains in Australia is scarce, solvent extracted organics contains n‐alkane, n‐alkanoic acid, and n‐alcohol, which compose lipids contained in plant wax (Simoneit et al. 1991).
It is interesting to note that the prototype of SOA formation from biogenic and anthropogenic hydrocarbons was thus shown in early studies more than 50 years ago. The research on SOA has been developed extensively after the year of 2000 being related to the interests in the impact on human health of PM2.5 and in the climate impact of aerosols.
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