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Atmospheric Multiphase Chemistry
Atmospheric Multiphase Chemistry

Fundamentals of Secondary Aerosol Formation

Hajime Akimoto
National Institute for Environmental Studies
Tsukuba, Japan

Jun Hirokawa
Hokkaido University
Sapporo, Japan
This edition first published 2020
© 2020 John Wiley & Sons Ltd

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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

Set in 10/12pt WarnockPro by SPi Global, Chennai, India

Printed and bound by CPI Group (UK) Ltd, Croydon, CR0 4YY

10 9 8 7 6 5 4 3 2 1
 v

Contents

Preface xiii

1 Historical Background of Atmospheric Secondary Aerosol Research 1

1.1 Introduction 1
1.2 Secondary Inorganic Aerosols 1
1.2.1 Sulfate 2
1.2.2 Nitrate 3
1.3 Secondary Organic Aerosols 4
1.3.1 Photochemical Smog 5
1.3.2 Blue Haze 6
References 7

2 Fundamentals of Multiphase Chemical Reactions 13

2.1 Introduction 13
2.2 Gas–Liquid Phase Equilibrium and Equilibrium in Liquid Phase 13
2.2.1 Fundamentals of Thermodynamics 14
2.2.1.1 Internal Energy and Enthalpy 14
2.2.1.2 Entropy 16
2.2.1.3 Gibbs Energy 18
2.2.1.4 Chemical Potential 19
2.2.2 Chemical Equilibrium and Equilibrium Constant 21
2.2.2.1 Chemical Equilibrium 21
2.2.2.2 Equilibrium Constant of Gas-Phase Reaction 22
2.2.2.3 Equilibrium Constant of Liquid-Phase Reaction 24
2.2.2.4 Temperature Dependence of Equilibrium Constant 26
2.2.3 Gas–Liquid Equilibrium and Henry’s Law Constant 29
2.2.4 Hydration of Carbonyl Compounds and Effective Henry’s Law
Constant 31
2.2.5 pH and Equilibrium in the Aqueous Solution 32
2.2.5.1 Dissociation Equilibrium of Pure Water and pH 32
2.2.5.2 Ion Dissociation and Equilibrium in Aqueous Solution 33
2.3 Reactions in the Liquid Phase 35
2.3.1 Thermodynamics and Activity Coefficients of Nonideal Solutions 35
vi Contents

2.3.1.1 Salting-in, Salting-out 38

2.3.2 Chemical Kinetics of Aqueous-Phase Reaction 39
2.3.2.1 Diffusion Process and Chemical Reaction Kinetics 39
2.3.2.2 Transition State Theory of Solution Reaction and
Thermodynamic Expression 42
2.3.3 Cage Effect and Aqueous-Phase Solvent Effect 46
2.3.3.1 Cage Effect 46
2.3.3.2 Solvent Effect in the Aqueous Phase 48
2.4 Uptake Coefficient and Resistance Model 51
2.4.1 Accommodation Coefficient and Uptake Coefficient 52
2.4.2 Resistance Model 54
2.5 Physical Chemistry of Interface Reaction 56
2.5.1 Langmuir-Hinshelwood Mechanism and Eley-Rideal Mechanism 56
2.5.2 Resistance Model Including Interface Reaction 59
2.5.3 Surface Tension of Air–Water Interface and Thermodynamics of
Accommodation Coefficient 65
2.5.3.1 Surface Tension 65
2.5.3.2 Thermodynamics of Accommodation Coefficient at
Air–Water Interface 68
2.6 Chemical Compositions and Physical Characters of Particles 71
2.6.1 Elemental and Molecular Composition of Particles 72
2.6.1.1 Inorganic Elements and Compounds 72
2.6.1.2 Organic Compounds 74
2.6.1.3 van Krevelen Diagram 77
2.6.2 Molecular Composition and Vapor Pressure 78
2.6.3 Gas-Particle Partitioning and Volatility Basis Set Model 84
2.6.3.1 Gas-Particle Partitioning and SOA Formation Yield 84
2.6.3.2 Volatility Basis Set Model 88
2.6.3.3 Gas-Aqueous Phase Partitioning of Hydrophilic
Compounds 90
2.6.4 Phase State of Particles and Mass Transfer 93
References 95

3 Gas-Phase Reactions Related to Secondary Organic Aerosols 107

3.1 Introduction 107
3.2 Ozone Reactions 107
3.2.1 Properties and Reactions of Criegee Intermediates 108
3.2.1.1 Direct Detection of Criegee Intermediate and Molecular
Structure 110
3.2.1.2 Formation of CH2 OO in Ozone-Ethene Reaction 115
3.2.1.3 Formation of syn- and anti-CH3 CHOO in Ozone-Alkene
Reactions 118
3.2.2 Alkenes and Dialkenes 130
3.2.2.1 Ethene 130
3.2.2.2 >C3 Alkenes 132
3.2.2.3 1,3-Butadiene 134
3.2.3 Isoprene 135
 Contents vii

3.2.4 Cycloalkenes 139

3.2.4.1 Cyclohexene 139
3.2.4.2 1-Methylcyclohexene 141
3.2.4.3 Methylenecyclohexane 144
3.2.5 Monoterpenes 144
3.2.5.1 α-Pinene 145
3.2.5.2 β-Pinene 148
3.2.5.3 Limonene 150
3.2.6 Sesquiterpenes 155
3.3 OH Radical-Induced Oxidation Reactions 160
3.3.1 Alkanes 160
3.3.1.1 Reactions of Alkyl Peroxy Radicals 165
3.3.1.2 Reactions of Alkoxy Radicals 165
3.3.2 Alkynes 170
3.3.3 Alkenes, Dialkenes, and Cycloalkenes 171
3.3.3.1 Alkenes 171
3.3.3.2 1,3-Butadiene 173
3.3.3.3 Cycloalkenes and Methylene cyclohexane 174
3.3.4 Isoprene 175
3.3.4.1 Fundamental Processes of OH-Induced Oxidation
Reaction 175
3.3.4.2 HOx Radicals Regeneration Reaction 178
3.3.4.3 Formation of Isoprene Hydroxy Hydroperoxide (ISOPOOH)
and Isoprene Epoxydiol (IEPOX) 179
3.3.4.4 Formation of Hydroxy Isoprene Nitrates 180
3.3.4.5 Reactions of Methyl Vinyl Ketone and Methacrolein 182
3.3.5 Monoterpenes 183
3.3.5.1 α-Pinene 183
3.3.5.2 β-Pinene 185
3.3.5.3 Limonene 187
3.3.6 Monocyclic Aromatic Hydrocarbons 189
3.3.6.1 Benzene 189
3.3.6.2 Toluene 192
3.3.7 Polycyclic Aromatic Hydrocarbons 195
3.3.7.1 Naphthalene 196
3.3.7.2 Other Polycyclic Aromatic Hydrocarbons 198
3.3.8 Carbonyl Compounds: OH Radical Reactions and Photolysis 199
3.3.8.1 Glyoxal 199
3.3.8.2 Methylglyoxal 202
3.3.8.3 Glycolaldehyde 204
3.3.8.4 Hydroxyacetone 207
3.4 NO3 Oxidation Reactions 209
3.4.1 Isoprene 209
3.4.2 Monoterpenes 213
3.4.2.1 α-Pinene 213
3.4.2.2 β-Pinene 214
3.4.2.3 Limonene 215
viii Contents

3.4.3 Monocyclic and Polycyclic Aromatic Hydrocarbons 217

3.4.3.1 Phenol, and Cresol 217
3.4.3.2 Naphthalene 218
3.4.3.3 Other Polycyclic Aromatic Hydrocarbons 219
References 219

4 Aqueous-Phase Reactions Related to Secondary Organic Aerosols 245

4.1 Introduction 245
4.2 OH Radical Reactions 246
4.2.1 UV Absorption Spectrum of OH Radicals in Aqueous Solution 246
4.2.2 Formation of OH Radicals in Cloud/Fog Droplets and Deliquescent
Aerosols 248
4.2.3 Reaction Rate Constants of OH Radicals in the Aqueous Phase 254
4.2.4 Reactions of Formaldehyde and OH Radical Chain Reaction 257
4.2.5 OH Radical Reactions and Photolysis of ≥C2 Carbonyl
Compounds 262
4.2.5.1 Glyoxal and Glyoxylic Acid 262
4.2.5.2 Methylglyoxal, Pyruvic Acid, and Acetic Acid 264
4.2.5.3 Glycolaldehyde and Glycolic Acid 267
4.2.5.4 Methacrolein and Methyl Vinyl Ketone 268
4.2.6 Oligomer Formation Reactions from ≥C2 Carbonyl Compounds 270
4.2.6.1 Glyoxal and Methylglyoxal 272
4.2.6.2 Methyl Vinyl Ketone and Methacrolein 273
4.3 Nonradical Reactions 275
4.3.1 Diels-Alder Reaction 276
4.3.2 Hemiacetal and Acetal Formation Reactions 277
4.3.2.1 Glyoxal 279
4.3.2.2 Methylglyoxal 280
4.3.2.3 1,4-Hydroxycarbonyl Compounds 281
4.3.3 Aldol Reaction 281
4.3.3.1 Acetaldehyde 282
4.3.3.2 Methylglyoxal 283
4.3.3.3 Methyl Vinyl Ketone and Methacrolein 284
4.3.4 Esterification Reactions 285
4.4 Formation Reactions of Organic Sulfates 287
4.4.1 C2 and C3 Carbonyl Compounds 287
4.4.2 Monoterpenes 288
4.4.3 Isoprene 291
4.4.4 Monocyclic and Polycyclic Aromatic Hydrocarbons 291
4.5 Formation Reactions of Organic Nitrogen Compounds 292
4.5.1 Organic Nitrates 292
4.5.2 Imidazoles 293
References 295

5 Heterogeneous Oxidation Reactions at Organic Aerosol Surfaces 309

5.1 Introduction 309
5.2 Aging of Organic Aerosols in the Atmosphere 309
 Contents ix

5.3 Reactions of Ozone 313

5.3.1 Oleic Acid and Unsaturated Long-Chain Carboxylic Acids 314
5.3.2 Squalene 316
5.3.3 Polycyclic Aromatic Hydrocarbons 318
5.4 Reactions of OH Radicals 320
5.4.1 Squalane and Long-Chain Alkanes 320
5.4.2 Levoglucosan, Erythritol, and Hopane 325
5.4.3 Saturated Dicarboxylic Acids 326
5.4.4 Squalene and Long-Chain Unsaturated Carboxylic Acids 328
5.4.5 Polycyclic Aromatic Hydrocarbons 330
5.5 Reactions of NO3 Radicals 332
5.5.1 Levoglucosan, Squalane, Long-Chain Alkane, and Alkanoic Acid 332
5.5.2 Squalene and Oleic Acid 334
5.5.3 Polycyclic Aromatic Hydrocarbons 334
References 336

6 Reactions at the Air–Water and Air–Solid Particle Interface 343

6.1 Introduction 343
6.2 Molecular Pictures and Reactions at the Air–Water Interface 344
6.2.1 Thermodynamics of Adsorption 345
6.2.1.1 OH, HO2 , and O3 346
6.2.1.2 Organic and Inorganic Compounds 348
6.2.2 Microscopic Picture of Molecules 349
6.2.2.1 Air–Pure Water Interface 350
6.2.2.2 Hydrophilic Organic Compounds 352
6.2.2.3 Amphiphilic Organic Compounds (Surfactants) 356
6.2.2.4 Hydrophobic Organic Compounds 357
6.2.2.5 NH3 and SO2 358
6.2.3 Reactions of O3 and Organic Compounds 359
6.2.3.1 Oleic Acid 360
6.2.3.2 Sesquiterpene Criegee Intermediates 360
6.2.3.3 Polycyclic Aromatic Hydrocarbons 361
6.2.4 Reactions of OH Radicals and Organic Compounds 362
6.2.4.1 Carboxylic and Dicarboxylic Acids 362
6.2.4.2 Organic Sulfur Compounds 364
6.3 Air–Sea Salt Particle, Seawater, and Sulfate/Nitrate Aerosol Interface 365
6.3.1 Microscopic View of Interface of Air and Alkaline Halide Aqueous
Solution 366
6.3.2 Reactions at the Interface of Sea Salt and Alkali Halide Aqueous
Solution 368
6.3.2.1 Reaction with O3 369
6.3.2.2 Reaction with OH Radicals 371
6.3.2.3 Uptake of HO2 Radicals 372
6.3.2.4 Reaction with N2 O5 372
6.3.2.5 Reaction with HNO3 373
6.3.3 Reactions of Organic Compounds at the Air–Seawater and Air–Sea
Salt Interface 375
x Contents

6.3.4 Microscopic View of the Interface of Air and Sulfate/Nitrate Aqueous

Solution 377
6.3.4.1 Sulfate Ion (SO4 2− ) 377
6.3.4.2 Nitrate Ion (NO3 − ) 378
6.4 Reactions on Snow/Ice Surface 379
6.4.1 Formation of NOy in the Photochemical Reaction of NO3 − 379
6.4.2 Formation of Inorganic Halogens on the Snow Ice and Sea Ice
Surface 382
6.4.2.1 Reaction with O3 382
6.4.2.2 Reaction with OH Radicals 383
6.4.2.3 Reactions with N2 O5 384
6.5 Interface of Water and Mineral Dust, Quartz, and Metal Oxide Surface 385
6.5.1 Microscopic View of Adsorbed Water on Mineral Surface 386
6.5.2 HONO Formation Reaction from NO2 on the Mineral Surface 390
6.5.2.1 Dark Reaction 390
6.5.2.2 Photochemical Reaction 392
6.5.3 Reaction of Organic Monolayer on Mineral Surface 394
References 396

7 Atmospheric New Particle Formation and Cloud Condensation Nuclei 415

7.1 Introduction 415
7.2 Classical Homogeneous Nucleation Theory 415
7.2.1 Homogeneous Nucleation in One-Component Systems 415
7.2.2 Homogeneous Nucleation in Two-Component Systems 419
7.3 Atmospheric New Particle Formation 422
7.3.1 New Particle Formation Rate and Growth Rate 422
7.3.2 Sulfuric Acid in New Particle Formation 425
7.3.3 Basic Substances in New Particle Formation 427
7.3.4 Organic Species in New Particle Formation 430
7.3.5 Other Species in New Particle Formation 433
7.3.5.1 Iodine Oxides 433
7.3.5.2 Atmospheric Ions 434
7.3.6 Field Observation of Nanoclusters 435
7.4 Aerosol Hygroscopicity and Cloud Condensation Nuclei 436
7.4.1 Köhler Theory 436
7.4.2 Nonideality of Solution in a Droplet 441
7.4.3 Hygroscopicity Parameter, 𝜅 442
References 446

8 Field Observations of Secondary Organic Aerosols453

8.1 Introduction 453
8.2 Global Budget of Aerosols 453
8.3 Analysis Methods of Ambient Aerosol Compositions 458
8.3.1 Positive Matrix Factorization 458
8.3.2 Mass Spectrum Peak Intensity and Elemental Ratio 459
8.3.3 Elemental Composition 460
8.4 Marine Air 461
 Contents xi

8.5 Forest Air 465

8.5.1 Amazon Tropical Forest 465
8.5.2 Finland Boreal Forest 469
8.6 Urban/Rural Air 472
8.6.1 Characterization of Ambient Aerosols 472
8.6.1.1 PMF Analysis 472
8.6.1.2 Mass Signal Intensity Ratio and Elemental Ratio 474
8.6.1.3 Particle Size Distribution 477
8.6.1.4 Elemental Composition 478
8.6.2 Molecular Composition 479
8.6.2.1 Dicarboxylic Acid 480
8.6.2.2 Plant Origin VOC Tracers 481
8.6.2.3 Anthropogenic VOC Tracer 484
8.6.2.4 Organic Sulfate 485
8.6.2.5 Organic Nitrates and Imidazoles 486
8.6.2.6 High-Molecular-Weight Compounds and Oligomers 489
References 493

Index 509
 xiii

Preface

Reaction kinetics and mechanism are a significant part of the fundamentals of atmo-
spheric 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 mul-
tiphase chemistry. Gas- and aqueous-phase reactions, heterogeneous oxidation pro-
cesses, 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 profession-
als who are interested in homogeneous and heterogeneous atmospheric reactions of
organic species related to aerosols.
xiv Preface

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 Akimoto

Jun Hirokawa
 1

Historical 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 absorp-
tion 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 mat-
ters 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 atmo-
spheric 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
Atmospheric Multiphase Chemistry: Fundamentals of Secondary Aerosol Formation,
First Edition. Hajime Akimoto and Jun Hirokawa.
© 2020 John Wiley & Sons Ltd. Published 2020 by John Wiley & Sons Ltd.
2 1 Historical Background of Atmospheric Secondary Aerosol Research

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 )2 CO3 ), ammonium sulfate ((NH4 )2 SO4 ), and sulfuric acid (H2 SO4 ) are formed
secondarily by the chemical reactions in the gas phase or in the fog water from atmo-
spheric 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 precip-
itation 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):
H2 O O2 NH4 +
SO2 −−−−→ SO3 2− −−−−n+−→ SO4 2− −−−−−→ (NH4 )2 SO4 (1.1)
M

The rate limiting stage of this process is the oxidation step of SO3 2− to SO4 2− , and the
oxidation by O2 had been studied for a long time (Fudakowski 1873; Backstrom 1934).
However, the oxidation rate of SO3 2− 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).
 1.2 Secondary Inorganic Aerosols 3

In 1970s, the importance of the reaction of O3 and H2 O2 , 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 H2 O2 . Later studies on these aqueous phase reactions revealed that the oxidation
by H2 O2 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 SO4 2− 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
OH + SO2 + M → HOSO2 + M (1.2)
HOSO2 + O2 → HO2 + SO3 (1.3)
SO3 + H2 O + M → H2 SO4 + M (1.4)
HO2 + NO → NO2 + OH (1.5)
This implies that the HOSO2 forms H2 SO4 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 )2 SO4 )
or ammonium bisulfate (NH4 HSO4 ), and a part of them exists as sulfuric acid (H2 SO4 )
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 SO4 2− (Junge 1954; Lee and Patterson 1969). For
example, the equivalent-basis fractions of SO4 2− 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:
OH + NO2 + M → HNO3 + M, (1.6)
4 1 Historical Background of Atmospheric Secondary Aerosol Research

is one order of magnitude larger than the reaction, OH + SO2 + M, under the atmo-
spheric 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
N2 O5 formed via NO3 by the reaction of O3 and NO2 (Orel and Seinfeld 1977):
NO2 + O3 → NO3 + O2 (1.7)
NO2 + NO3 + M → N2 O5 + M (1.8)
N2 O5 + H2 O → 2 HNO3 (1.9)
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 heteroge-
neous 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 night-
time (Richards 1983; Heikes and Thompson 1983).
The gaseous nitric acid, ammonia, and ammonium nitrate formed from them are
thought to be in equilibrium:
NH3 (g) + HNO3 (g) ⇆ NH4 NO3 (s), (1.10)
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 NH4 NO3 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:
NaCl(s) + HNO3 (g) → NaNO3 (s) + HCl(g). (1.11)
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 NH4 NO3 in submicron parti-
cles 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).
 1.3 Secondary Organic Aerosols 5

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 oxy-
genated 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 pol-
lution 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 particu-
larly 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 oxidiz-
ing 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 atmo-
spheric 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 cyclo-
hexene, 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
6 1 Historical Background of Atmospheric Secondary Aerosol Research

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 SO4 2− and OA, and
temperature-dependent gas-solid equilibrium of NH4 NO3 (Day, Malm, and Kreiden-
weis 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 anthro-
pogenic 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.
 References 7

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 13

Fundamentals of Multiphase Chemical Reactions

2.1 Introduction
Chemical reaction systems in the atmosphere are composed of homogeneous reactions
in the gas phase, homogeneous liquid-phase reactions in deliquescent aerosol particles
and water droplets, and heterogeneous reactions at the particle surface. Among them,
physicochemical fundamentals of photochemistry and kinetics in the homogenous gas
phase reactions have already been well established in principle, and detailed explana-
tion has been given in a previous book by one of the present authors (Akimoto 2016)
and many textbooks introduced therein. In contrast, many aspects of atmospheric mul-
tiphase chemical reactions, including uptake of chemical species from gas phase to par-
ticle surface, heterogeneous reactions at the surface, and homogeneous aqueous phase
reactions, have not yet been well established. In this chapter, fundamentals of physi-
cal chemistry relevant to the formation and transformation of atmospheric aerosols are
described. The values of physical constants appearing in this book and the conversion
factors of energy units between kJ, kcal, and eV are given in Tables 2.1 and 2.2.
In this chapter, fundamentals of optical properties, such as scattering of light and
photoabsorption by atmospheric fine particles, and the photochemistry related to the
photolysis at the surface of fine particles are not covered. The former topics are covered
by the textbook by Mishchenko et al. (2002) and Kokhanovsky (2008), but the system-
atic research on the latter topic has not been developed well and is still open to future
research.

2.2 Gas–Liquid Phase Equilibrium and Equilibrium in Liquid

Phase
In the gas–liquid phase equilibrium, the experimental discovery that the amount of
gaseous molecules dissolving into the liquid phase is proportional to the partial pressure
of the substance in the gas phase was made by a British chemist, William Henry (1803),
and the proportional constant is called Henry’s law constant after his name. The Henry’s
law constant is an important parameter in atmospheric chemistry, which describes the
partitioning of trace chemical species between the air and the cloud/fog and aqueous
aerosol particles. Before the specific discussion of Henry’s law constant and ion disso-
ciation, general treatment of thermodynamics of chemical equilibrium is described in
this section as underlying bases.
Atmospheric Multiphase Chemistry: Fundamentals of Secondary Aerosol Formation,
First Edition. Hajime Akimoto and Jun Hirokawa.
© 2020 John Wiley & Sons Ltd. Published 2020 by John Wiley & Sons Ltd.
14 2 Fundamentals of Multiphase Chemical Reactions

Table 2.1 Physical constants.

Constants Values

Boltzmann constant (k B ) 1.3807 × 10−23 J K−1

Plank constant (h) 6.6261 × 10−34 J s
Light velocity (in vacuum) (c) 2.9979 × 108 m s−1
Avogadro constant (N A ) 6.0221 × 1023 mol−1
Gas constant (R) 8.3145 J K−1 mol−1 = 0.082058 L atm K−1 mol−1

Table 2.2 Energy conversion table.

kJ mol−1 kcal mol−1 eV

kJ mol−1 = 1 × 0.2390 × 0.01036

kcal mol−1 = × 4.184 1 × 0.04337
eV = × 96.49 × 23.06 1

2.2.1 Fundamentals of Thermodynamics

2.2.1.1 Internal Energy and Enthalpy
If we represent the internal energy (the sum of kinetic and potential energy of atoms,
molecules, and ions constituting the system) by U, the work done from the surroundings
to the system by w, and the heat applied from the surroundings to the system by q, the
changes of internal energy ΔU is expressed as
ΔU = q + w (2.1)
from the first law of thermodynamics. Putting the infinitesimal changes of U, w, and q
as dU, δw, and δq, we obtain
dU = δq + δw (2.2)
from Eq. (2.1). Here, considering only the work done by the change of volume V by dV
against the external pressure pext , δw is expressed as
δw = −pext dV . (2.3)
For the reversible change, keeping the equilibrium between the system and the
surroundings, the pressure of the system p is equal to the pressure of the surroundings
pext , so that p = pext and Eq. (2.3) can be rewritten by
δwrev = −p dV , (2.4)
and Eq. (2.2) becomes
dU = δq − pdV . (2.5)
For the constant volume change (dV = 0),
dU = δq, (2.6)
 2.2 Gas–Liquid Phase Equilibrium and Equilibrium in Liquid Phase 15

and if we write the supplied heat under the constant volume as qV ,

ΔU = qV . (2.7)
Thus, the internal energy change is equal to the supplied heat under the constant
volume.
Meanwhile, when the volume changes (dV ≠ 0),
δq = dU + pdV (2.8)
from Eq. (2.5). Defining the enthalpy H of the system as
H = U + pV , (2.9)
the infinitesimal change of H is expressed by
dH = dU + pdV + V dp. (2.10)
For the constant pressure change (dp = 0), from the above formula and Eq. (2.8),
dH = dU + pdV = δq. (2.11)
Therefore, if we write the heat supplied to the system under the constant pressure
as qP ,
ΔH = qP . (2.12)
Thus, the enthalpy change is equal to the supplied heat to the system under the constant
pressure.
Since most of atmospheric chemical reactions proceed under the constant pressure,
enthalpy is one of the most important thermochemical quantities for considering atmo-
spheric chemistry. Enthalpy change accompanying chemical reactions is called reaction
enthalpy and represented by Δr H. Here, the suffix r of Δr stands for the change accom-
panying with chemical reaction. The reaction with Δr H = qP < 0 (heat is released from
the system to the surroundings) is called exothermic reaction while the reaction with
Δr H = qP > 0 (heat is absorbed by the system from the surroundings) is called endother-
mic reaction.
In general, reaction enthalpy is represented by the values when the reactants and prod-
ucts are in the standard state (also called reference state). In this case, it is called standard
reaction enthalpy and represented by Δr H ∘ . Here, the superscript ∘ represents the stan-
dard state. The standard state means that the state of the substance is under the pressure
of 1 bar = 105 Pa (definition by the recommendation of IUPAC in 1982. Previously, it
was defined at 0 ∘ C and 1 atm = 1.013 × 105 Pa). However, for ions in the aqueous solu-
tion, standard state is defined as a hypothetical ideal dilute solution with the molality of
1 mol kg−1 (cf. Section 2.2.2). According to the new definition, temperature is not spec-
ified, but usually reference temperature 298.15 K (25 ∘ C) is selected and the standard
reaction enthalpy is represented by Δr H 298 ∘ .
Reaction enthalpy is decided by the difference between the total enthalpy of
reactants and products, and does not depend on the intermediate process (Hess’s law).
For instance, considering the chemical reaction,
𝜈A A + 𝜈B B → 𝜈C C + 𝜈D D, (2.13)
16 2 Fundamentals of Multiphase Chemical Reactions

where 𝜈 i (i = A, B, C, and D) is the stoichiometric number of reactants and products,

the standard reaction enthalpy of this reaction is expressed as
Δ H ∘ = [𝜈 H ∘ (C) + 𝜈 H ∘ (D)] − [𝜈 H ∘ (A) + 𝜈 H ∘ (B)],
r C D A B (2.14)
using the enthalpy per mole (molar enthalpy) of the reactants and products in their stan-
dard state, H ∘ (i) (i = A, B, C, and D). For more general chemical reactions, it can be
written as
∑ ∑
Δ H∘ =
r 𝜈 H ∘ (i) −
i 𝜈 H ∘ (i). i (2.15)
products reactants

Equations (2.14) and (2.15) are the “definition” of standard reaction enthalpy, which
is practically obtained by using standard enthalpy of formation Δf H ∘ of reactants and
products. The standard enthalpy of formation is the enthalpy change when 1 mol of a
compound is formed from the constituent elements in the most stable state at 1 bar and
the specified temperature (usually 298.15 K). Here, the standard enthalpies of formation
of the most stable form of the elements are prescribed as zero at all temperatures.
For example, Δf H ∘ of gaseous H2 , N2 , O2 , liquid Hg, Br2 , and solid Na, Si, I2 at 1 bar,
298.15 K are all zero. For carbon, Δf H ∘ of the most stable graphite rather than diamond
is taken to be zero. For ions in the aqueous solution, Δf H ∘ of hydrogen ion H+ in the
standard state mentioned above is prescribed as zero. Standard enthalpy of formation
Δf H 0 ∘ and Δf H 298 ∘ of compounds of interest in atmospheric chemistry at 0 and 298.15 K
are given in many literatures (e.g. Finlayson-Pitts and Pitts 2000; Burkholder et al. 2015;
Akimoto 2016). Table 2.3 lists the standard enthalpy of formation Δf H ∘ 298 (kJ mol−1 )
of compounds related to the formation of inorganic and organic aerosols. Referring to
the table, standard reaction enthalpy can be calculated from Δf H ∘ of each reactant and
product by
∑ ∑
Δ H∘ =
r 𝜈 Δ H ∘ (i) −
i f 𝜈 Δ H ∘ (i).i f (2.16)
products reactants

2.2.1.2 Entropy
According to the second law of thermodynamics, the spontaneous reaction proceeds
to the direction fulfilling the following inequality between the amount of infinitesimal
change in thermodynamical entropy dS, incremental heat of exchange with the sur-
roundings δq (δq > 0 when heat is transferred to the system from the surroundings),
and the temperature T:
δq
dS ≥ . (2.17)
T
The equality holds for reversible change. Thus, expressing the heat quantity going in and
out in the reversible change as δqrev , the relationship holds:
δqrev
dS = (2.18)
T
This equation also serves as the definition of entropy. Substituting the relation-
ship δqrev = TdS derived from Eq. (2.18) and Eq. (2.4) to Eq. (2.2), the first law of
thermodynamics for the reversible change is expressed by
dU = TdS − pdV . (2.19)
 2.2 Gas–Liquid Phase Equilibrium and Equilibrium in Liquid Phase 17

The entropy of perfect crystals of pure substances is zero at T = 0 K, which is known as

the third law of thermodynamics. The molar entropy of compounds and elements at the
temperature T is called standard entropy and expressed by S∘ . Table 2.3 cites standard
entropy S298 ∘ (J K−1 mol−1 ) at 298.15 K together with the standard enthalpy of formation
Δf H 298 ∘ .
Using S∘ , the standard reaction entropy Δr S∘ can be defined as
∑ ∑
Δr S∘ = 𝜈i S∘ (i) − 𝜈i S∘ (i) (2.20)
products reactants

similarly to the standard reaction enthalpy given in Eq. (2.15).

∘ ) and standard molar entropy (S∘ ) at 298.15 K and

Table 2.3 Standard enthalpy of formation (Δf H298 298
1 bar.

Chemical ∘
𝚫f H298 ∘
S298 Chemical ∘
𝚫f H298 ∘
S298
species (kJ mol−1 ) (J K−1 mol−1 ) species (kJ mol−1 ) (J K−1 mol−1 )

H 218.0 114.7 HCO 44.2 224.3

H2 0.00 130.7 CH2 O (HCHO) −109.0 218.8
O(3 P) 249.2 161.1 HC(O)OH −378.6 248.2
O2 0.00 205.2 CH2 OO (Criegee Int.) 110
O3 141.7 239.0 CH2 O2 (dioxirane) 5.0
OH 37.5 183.7 CH3 OH (g) −201.0 239.9
HO2 11.9 228.1 CH3 OH (l) −239.1
H2 O (g) −241.8 188.8 CH3 OOH −136.8 276.5
H2 O (l) −285.8 70.0 HCN 132 201.8
H2 O2 −135.9 234.5 CH3 CN 74.0 245.1
NH2 186.2 194.9 CH3 ONO −64.0 284.3
NH3 −45.9 192.8 CH3 ONO2 −122.2 301.9
NO 91.1 210.8 CH3 OONO2 −62.8
NO2 34.0 240.2 C2 H2 227.4 200.9
NO3 74.7 258.4 C2 H4 52.4 219.3
N2 O 3 88.6 314.7 C2 H5 120.9 250.5
N2 O 4 11.1 304.5 C2 H6 −83.9 229.2
N2 O 5 14.4 353.5 CH3 CHO −166.1 264.0
HNO 109.2 220.9 C2 H5 OH −234.8 281.6
HNO2 (HONO) −78.5 254.1 CH3 OCH3 −184.1 267.3
HNO3 (HONO2 ) −134.3 266.9 CH3 C(O)OH −253 283.4
HO2 NO2 −52.7 297 (CHO)2 −212
CH3 146.7 194.0 CH3 OOCH3 −125.5 308.4
CH4 −74.5 186.4 CH3 C(O)OONO2 (PAN) −240.1
CO −11.5 197.7 C3 H6 166.1 266.6
CO2 −393.5 213.8 n- C3 H7 101.3
(Continued)
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The Project Gutenberg eBook of Jack Derringer
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Title: Jack Derringer

A tale of deep water

Author: Basil Lubbock

Release date: November 1, 2023 [eBook #71996]

Language: English

Original publication: London: John Murray, 1906

Credits: Hekula03, Graeme Mackreth and the Online Distributed

Proofreading Team at https://www.pgdp.net (This file was
produced from images generously made available by The
Internet Archive)

*** START OF THE PROJECT GUTENBERG EBOOK JACK

DERRINGER ***
JACK DERRINGER
 JACK DERRINGER

A TALE OF DEEP WATER

By BASIL LUBBOCK
AUTHOR OF "ROUND THE HORN BEFORE THE MAST"

LONDON

JOHN MURRAY, ALBEMARLE STREET, W.

1906
 PRINTED BY
HAZELL, WATSON AND VINEY, LD.,
LONDON AND AYLESBURY.
 PREFACE
I have endeavoured in this book to paint sea life as it really is, as it
can be seen on any deep-water sailing-ship of the present day,
without glossing over the hardships, the hard knocks, the hard
words, and the continual struggle and strife of it all. At the same time
I have tried to hint at the glamour and fascination which the sea
breathes into such souls as respond to its mighty call.
As to the queer collection of flotsam which found itself in the down-
easter's foc's'le, I can assure my readers that this mixed crowd is in
no way unusual; in fact, I am quite certain that the greater number of
sailing ships "bound deep water" at the present moment are manned
by crews of an even worse mixture of nationalities, trades, and
creeds than formed the complement of the Higgins, which, for a ship
sailing out of San Francisco, when seamen were scarce, was
singularly lucky in finding so many bona-fide sailormen amongst her
crew.
My reader may ask if the brutality described still goes on on
American ships. All I can say is that several of the Yankee Cape
Horn fleet are still notorious for it, their officers excusing themselves
on the plea that only by the harshest measures can they preserve
discipline amongst the hard-cut citizens of all nations who form
American crews.
Many of the episodes in this book, including the cowpuncher's
frontier yarns, I have taken from fact, and the treatment of the knifing
dago by the bucko mate in Chapter IV. actually occurred in every
detail.
As regards the moon-blindness, I have no doubt I shall have to bear
with many scoffers and unbelievers, but this I know, that few men
who have been used to sleeping in the open, whether sailors or
landsmen, will be amongst them. Many a time have I hauled a
sleeping man out of the glare of the tropical moon for fear of its
direful beams, and many a time have I had the like service done to
me. Few old seamen but have some strange yarn to spin anent the
strange effects of the moon upon the human countenance exposed
to its sinister rays: in most cases it is some hours' or some days'
moon-blindness; sometimes it is a queer contraction of the muscles
on the side of the face exposed; and I have even heard of cases of
idiocy put down to the same cause. Certain it is that the cold beams
of our world's satellite are not to be trusted. Why, do they not even
poison fish or meat if left exposed to the mercy of their baleful glitter?
I must apologise for the sentimental part of this book, but apparently
in a work of fiction a certain amount of sentiment is considered
necessary, even in a sea yarn. However, if my reader finds it not to
his taste, he can skip. We've all learnt to do that, some time or other.
BASIL LUBBOCK.
CONTENTS
PART I
CHAPTER I
"THE YANKEE
HELL-SHIP" 3
CHAPTER II
"THE RULE
OF THE
BELAYING-
PIN" 13
CHAPTER III
"THE USE OF
A SHEATH-
KNIFE" 27
CHAPTER IV
"BARBARISM" 37
CHAPTER V
"IN THE
WATCHES OF
THE NIGHT" 48
CHAPTER VI
"THE FATAL
RED LEAD" 59
CHAPTER VII
"IN THE
SECOND
DOG-WATCH" 75
CHAPTER VIII
"ON THE 89
FOC'S'LE
HEAD"
CHAPTER IX
"THE GLORY
OF THE
STARS" 99
CHAPTER X
"STUDPOKER
BOB'S
MALADY" 109
CHAPTER XI
"THE
STORMFIEND" 118
CHAPTER XII
"A CALL FOR
NERVE" 132
CHAPTER XIII
"THE MAN
WITH THE
GUN" 143
PART II
CHAPTER I
"ADRIFT" 157
CHAPTER II
"THE
OCMULGEE" 167
CHAPTER III
"THE
BURNING OF
THE SOUTH
SEAMAN" 179
CHAPTER IV
"THE OPEN
BOAT" 194
CHAPTER V
"THE SPELL
OF THE
MOON" 209
CHAPTER VI
"THE ATOLL" 218
CHAPTER VII
"LOYOLA" 230
CHAPTER VIII
"THE FIGHT
ON THE
SANDS" 239
CHAPTER IX
"THE
LYNCHING" 253
CHAPTER X
"THE BLACK
ADDER" 272
CHAPTER XI
"A SEA FIGHT
UNDER THE
STARS" 291
CHAPTER XII
"THE PLUCK
OF WOMAN" 303
CHAPTER XIII
"PAPEETE" 318
PART I
 CHAPTER I
"THE YANKEE HELL-SHIP"
Bucking Broncho awoke to the familiar cry of "Roll out, roll
out, show a leg!" and thinking it was the call of the Round Up Boss in
the early morning, he opened his eyes and sat up.
The sight that met his gaze considerably astonished him, and the
foc's'le, with its double row of bunks, its stuffy atmosphere, and its
swinging oil-lamp, he mistook for some mining-camp shanty.
Slowly his half-shut eyes took in the details of the gloomy den, into
which the grey light of dawn had as yet hardly penetrated.
Round him lay men in every condition of drunkenness, some prone
upon the deck, others hanging half in and half out of their bunks, all
apparently still in the stupors of a late carouse.
Stretched upon a chest right under his bunk lay a ghastly object
clothed in greasy, blood-stained rags, which but for its hoarse rattling
breathing he would have taken for a corpse.
From the bunk above him came a spasmodic grunt at intervals,
sudden and unexpected, whilst opposite him a cadaverous-looking
deadbeat in a miner's shirt whistled discordantly through a hawk-like,
fiery-tinted nose.
As his eyes grew accustomed to the dim light he discovered other
forms scattered in a variety of grotesque attitudes amongst the litter
of chests and sea-bags on the deck, and through the open door he
beheld a man, in a pair of overalls, sluicing himself with a bucket of
water.
Then a gigantic form with a hairy face of kindly aspect blocked up
the doorway, and in hurricane tones besought the snoring crowd to
tumble up and man the capstan. Advancing into the foc's'le, this
leather-lunged apparition coolly and methodically began to haul the
insensible scarecrows out of their bunks, and to shake them until
their teeth rattled.
"Say, stranger, whatever's the hock kyard to all this? What be you-
alls aimin' for to do?" inquired Bucking Broncho in his soft Western
drawl, as he watched the big man handling the drunks.
"Just you tumble out, my son, and get outside, or you'll reap a skinful
of trouble. You'll get the hang o' things quick enough by-and-by,"
returned the other shortly.
"I'm clean stampeded in my intellec' complete," declared the cowboy;
"but assuming you're the boss of this outfit, your word goes; I plays
your hand, stranger, an' I rolls out."
The big, hairy-faced man was too busy pushing, pommelling,
thumping, and hustling the rest of the inmates to take any more
notice of Bucking Broncho, who, gaining the door, stared round in
amazement as he found himself upon the deck of a large sailing-
ship.
The cowpuncher, who had only seen "blue water" on two occasions
in his life, had been shanghaied aboard the notorious Yankee
skysail-yard clipper Silas K. Higgins, the hottest hell-ship under the
Stars and Stripes.
The last of the wheat fleet, this vessel had been lying at anchor in
San Francisco Bay for some weeks, delayed from sailing for want of
a crew, which her bad name made impossible for her to get except
by foul means.
With lavish hands her "old man" scattered his blood-money amongst
the boarding-house runners and crimps, and then patiently awaited
the result.
Slowly but surely his crew began to arrive, heels first to a man, some
drugged, some sandbagged, some set upon and kidnapped along
the water-front.
Night after night boats sneaked up to the gangway grating and
deposited insensible bundles of rags, which the ghoulish traders in
blood callously slung aboard.
But before signing the note, the experienced mate took care to
ascertain if his new hand still breathed, for more than once in the
past he had had dead men palmed off upon him. Then, if satisfied
after his careful scrutiny, he ordered the watchman to drag the
shanghaied man forward whilst he ticked off Able-bodied Seaman
Jones or Smith, whichever name happened to come first on his list.
The Higgins had been waiting two days for her last man when
Bucking Broncho fell a victim to the manhunters.
The cowpuncher, discovered in Chinatown busy celebrating his first
night off the prairie, was pounced upon by these vultures as "an easy
thing." Skilfully they drugged him, cheerfully they possessed
themselves of his wad of notes, then, overcome by the humour of
the idea, instead of substituting the trade rags for his clothes as
usual in shanghai-ing men, they slung him aboard an hour after
midnight in all the glory of chaps and spurs.
Thus, with her complement gained at last, the Higgins was about to
get under weigh.
Wholly oblivious of the events of the past night, thanks to the
strength of the dope, with buzzing head and half-fuddled senses the
cowboy stood gazing stupidly at the scene before him.
"I'm shorely plumb locoed," he muttered. "What for of a play is this
I'm into?"
Overhearing this, the man sluicing himself turned round.
"Bit muzzy still, mate——" he began, and then stopped in surprise.
This man formed a big contrast to the broken-looking crowd in the
foc's'le.
As he stood there in the morning light, stripped as he was to the
waist, he looked the beau ideal of health: the muscles on his arms
and shoulders stretched the skin till it shone, and heightened the
artistic effect of the beautiful Japanese tattooing which, in the shape
of dragons, butterflies, Geisha girls, and other quaint designs, made
a picture gallery of his body.
Six foot high at least, he stood lightly on his feet with the careless
grace of one used to a heaving deck.
A peculiar look of devil-may-care good nature stamped his clean-cut,
deeply tanned features, yet there was a keen glint of shrewdness in
his blue eyes, decision in his firm chin and resolute lips, with just a
touch of martial fierceness in the twirl of his small moustache.
No tenderfoot this man, though there was no mistaking his
nationality. "A d——d Britisher" was written large all over him. Bare-
footed though he was, in well-worn dungarees, with leather belt and
sheath-knife, his birth was plain as his nationality.
In England they would use one word to describe him—the one word
"rolling-stone"; but in the world not one but a dozen words would be
required—frontiersman, sailor, soldier, gold-miner, cowboy, hunter,
scout, prospector, explorer, and many more, all marked "dangerous"
in the catalogue of professions, for the "rolling-stone" takes to
dangers and hardships just as a city man does to dollars and
comforts. And who shall lay the blame? It's all in the blood, whether
you take your strain from Francis Drake the buccaneer or Shylock
the Jew.
Such was the man who faced Broncho—just a British rolling-stone, a
modern freelance, a sea rover.
As he spoke, Bucking Broncho gave him a keen look, and then cried
out:
"I'm a coyote if it ain't Derringer Jack. Shake, old pard, you-alls ain't
shorely forget Bucking Broncho?"
"Think I'd forget an old pal like that; no, Broncho, so sure as you
remember me."
"Which I shorely does. I makes a bet I tells them brands o' yours on
the skyline."
As they gripped hands Jack Derringer remarked:
"You've strayed a long way off your range, Broncho; shanghaied, I
suppose? Well, you've run against bad luck here. It's a rough deal
aboard this ship."
"What for of a game is it?"
"Quien sabe? Pretty tough, I expect, old man; you're a sailor outward
bound——"
"The hell you say!"
"Yes; I'll watch your hand as well as I can, but, mind you, Broncho,
no gun-play whatever happens, or you'll reap more lead than if you'd
got the whole of the Tucson Stranglers on your trail."
"I shorely notes your play, Jack; I'm the last gent to go fosterin' idees
of bloodshed. This here deadfall draws the cinch some tight an'
painful, but you can gamble I ain't going to plunge none before the
draw; I'll just watch the deal a whole lot."
"That's bueno! Roll a small loop and don't stir up the range more'n
you can help; trouble comes a-hooping and don't need looking for.
How are you feeling after that poisoned grog?"
"Pretty rocky," replied the cowpuncher.
"Stuff your head into that," said the rover, pointing to the bucket of
water which he had drawn a short while before.
"I guess you had better get out of those buckskins," he went on
gravely, as Broncho tried the saltwater cure. "Bit of boarding-house
runner's wit sending you aboard in them; but I'll fit you out. I expect
you've only got the usual rag-bag, like the rest."
"Seems to me I've got my horns locked in a re-ather tough
proposition. I shore aims to be resigned. The ways of Providence is
that various an' spreadeagle that as a man of savvy I comes in blind
an' stands pat," remarked the cowboy, as they retired into the
foc's'le.
Perhaps before he gets rid of his cowpuncher attire for the blue
dungarees of the 'fore-mast Jack, a short description might be
welcome.
He was arrayed in full cowboy get-up, just as he had ridden into
Frisco. He wore a fringed and silk-ornamented buckskin shirt, deeply
fringed leather chaparegos, and long-heeled cowpuncher boots, on
which jingled great Mexican spurs. Round his neck he had the usual
gay silk handkerchief, and on his head a brand new Stetson hat.
A loose belt full of cartridges swung a 45-calibre revolver low down
upon his hip. This had evidently been overlooked by the crimps, and,
at a glance from Jack Derringer, he hastily tucked it under his shirt
out of sight.
In appearance Bucking Broncho was a man of medium height, with
good shoulders, none too square, but broad enough.
He was lean and muscular, with the firm flesh of a man in perfect
health and training. There was not an ounce of fat on his whole body.
His skin was darkened and toughened by long contact with wind,
sun, and alkali.
His eyes were of that blue-grey so often seen in men of cool nerve,
who, though used to danger and ready to dare anything, are yet
long-headed and full of resource. He kept them half-shut from long
squinting in the bright sun of the south-west.
His rather heavy moustache had been sunburnt and bleached to a
raw gold colour.
It took but a short time to convert the cowboy into the sailor in flannel
shirt and overalls, with a belt, minus revolver and cartridges, but with
a sailor's sheath-knife instead.
Whilst he was changing his attire, being lavishly supplied with
clothes from Jack Derringer's big sea-chest, his head was fast
clearing and the drugging was losing its stupefying effect.
Calmly he reviewed the situation, and, used to the vicissitudes of the
West, treated his change of fortune with the stoical philosophy of a
frontiersman.
By the time that Broncho was arrayed afresh, the last of the poor
drunks had been dragged from the foc's'le. Then, as Jack and the
cowboy emerged, they came face to face with a big square chunk of
a man, with eyebrows so thick and bushy that they almost hid his
fierce, bloodshot little eyes.