Acknowledgments About the Authors
I Ozone in the Atmosphere .................................... 1
I-А Introduction ............................................... 1
I-B Historical Perspective of Atmospheric Ozone ................ 3
I-C Properties of the Earth's Atmosphere ....................... 7
I-C-l Chemical and Physical Properties .................... 7
I-C-2 Meteorology and Its Effects on Atmospheric Ozone ... 14
I-D Summary of Ambient Measurements of Tropospheric Ozone ..... 16
I-D-1 Measurements of Surface Ozone in Background and
Remote Locations ................................... 16
I-D-2 Measurements of Surface Ozone in Polluted Urban
Areas .............................................. 25
I-Е Summary of Measurements of Stratospheric Ozone ............ 31
I-F Ozone and Its Mechanisms of Formation and Destruction in
the Atmosphere ............................................ 33
I-F-l Ozone Formation and Destruction in the Unpolluted
Stratosphere ....................................... 33
I-F-2 Stratospheric Ozone Depletion: The Role of
Halocarbons ........................................ 38
I-F-2.1 Stratospheric Ozone Depletion and the
Montreal Protocol ............................. 40
I-F-3 Ozone Formation in the Troposphere ................. 44
I-F-A Ozone Destruction in the Troposphere ............... 47
I-G Major Sources of the Atmospheric Trace Gases
(NOx and VOCs) ............................................ 48
I-H Ozone and Climate ......................................... 54
I-H-l Contribution of Ozone to the Natural Greenhouse
Effect ............................................. 54
I-H-2 Contribution of Ozone to Radiative Forcing of
Climate Change ..................................... 57
I-H-3 Impact of Climate Change on Ozone .................. 58
I-I About the Material Covered in This Book ................... 59
II Mechanisms of Ozone Reactions in the Troposphere ......... 61
II-A Introduction ............................................. 61
II-B Ozone Photodecomposition and the Mechanism of HO
Radical Formation ......................................... 61
II-B-1 Absorption Cross Sections of Ozone ................ 62
II-B-2 Quantum Yields of O(1D) Formation in Ozone
Photodecomposition ................................ 63
II-B-3 Estimated Photolysis Frequencies j[O(1D)] for
Ozone Photodecomposition .......................... 65
II-B-4 Comparison of Measured and Calculated j[O(1D)]
Values ............................................ 65
II-C Mechanisms of the Ozone Reactions with Organic
Compounds ................................................. 67
II-C-1 Ozone Reactions with the Acyclic Mono-Alkenes ..... 67
II-C-2 Ozone Reactions with the Cyclic Alkenes ........... 84
II-C-3 Ozone Reactions with the Dienes ................... 86
II-D Mechanisms of O3 Reactions with Unsaturated Oxygenates ... 87
II-D-1 Ozone Reactions with the Unsaturated Alcohols ..... 87
II-D-2 Ozone Reactions with the Unsaturated Ethers ....... 88
II-D-3 Ozone Reactions with the Unsaturated Aldehydes .... 93
II-D-4 Ozone Reactions with the Unsaturated Ketones ...... 94
II-D-S Ozone Reactions with the Unsaturated Organic
Acids ............................................. 95
II-D-6 Ozone Reactions with the Unsaturated Esters ....... 96
II-E The Mechanisms of Reactions of the Criegee
Intermediates ............................................. 96
II-E-1 The Fragmentation Reactions of the Criegee
Intermediates ..................................... 96
II-E-1.1 Suggested Fragmentation Modes of the CH2OO4
Intermediate .................................. 97
II-E-1.2 Suggested Fragmentation Modes of the CH3HOO4
Intermediate .................................. 97
II-E-1.3 Suggested Fragmentation Modes of the
(CH3)2OO4 Intermediate ......................... 97
II-E-2 The Mechanism of HO Radical Formation in the
Reactions of Ozone with theAlkenes ................ 98
II-E-3 Reactions of the Stabilized Criegee
Intermediates ..................................... 99
II-E-3.1 The CH2OO and CH3CHOO Reactions with Water
Vapor ........................................ 107
II-E-3.2 Reaction of Criegee Intermediates with
Other Trace Gases ............................ 108
II-F Use of SARs in Ozone-Alkene Reactions ................... 108
II-F-1 Estimation of Rate Coefficients for the
Reactions of Ozone with the Alkenes .............. 108
II-F-2 An SAR Method of Estimating the Yield of HO
Radical Formed in the Alkene-Ozone Reactions ..... 110
III The Oxides of Nitrogen: Their Relation
to Tropospheric Ozone .................................. 114
III-A Overview of Tropospheric "Odd Nitrogen" Chemistry ...... 114
III-B Reactions of NO with O3 and with HO2 ................... 116
III-C The Photodecomposition of NO2 and j(NO2)
Determination .......................................... 117
III-D Evaluation of the Mechanisms of the Major Reactions of
NO2 with Trace Gases in the Troposphere ................ 120
III-D-1 Reaction of NO2 with HO:HON02 Formation ......... 120
III-D-2 Reactions of NO2 with HO2, RO2 and RC(O)O2
Radicals: Reversible Peroxynitrate and
Peroxyacetyl nitrate Formation .................. 121
III-D-2.1 Loss Processes for HONO2, Organic Nitrates,
Peroxynitrates, and Peroxyacyl Nitrates:
Photolysis, Reaction with HO, and
Deposition .................................. 121
III-D-3 The Heterogeneous Formation of HONO and Its
Subsequent Losses ............................... 125
III-D-4 The Reaction of NO2 with O3 The Formation of
NO3 Radical ..................................... 126
III-D-5 NO2 + NO3 Reactions: N2O5 Formation and
Dissociation .................................... 126
III-D-5.1 Heterogeneous Reactions of N2O5 with
H2O and Halide Ions ......................... 126
III-E Evaluation of the Mechanisms of NO3 Radical Reactions .. 127
III-E-1 The Photodecomposition of NO3 [j(NO3] ........... 127
1II-E-2 Mechanism of the Reaction of NO3 with NO ........ 130
III-E-3 Rates and Mechanisms for Reactions of NO3 with
the Alkanes ..................................... 130
III-E-4 Rates and Mechanisms for Reactions of NO3 with
Haloalkanes ..................................... 131
III-Е-5 Rates and Mechanisms for Reactions of NO3 with
Alkenes, Haloalkenes, and Alkynes ............... 133
III-E-5.1 Rates and Mechanisms for Reactions of NO3
with Alkenes ................................ 133
III-E-S.2 Rates and Mechanisms for Reactions of NO3
with Haloalkenes ............................ 142
III-Е-5.3 Rates and Mechanisms for Reactions of NO3
with Alkynes ................................ 144
III-E-6 Rates and Mechanisms for the Reactions of NO3
with Aromatic Hydrocarbons ...................... 146
III-Е-7 Rates and Mechanisms for Reactions of NO3 with
the Oxygenates .................................. 146
III-E-7.1 Rates and Mechanisms for the Reactions of
NO3 with Alcohols ........................... 148
III-E-7.2 Rates and Mechanisms for the Reactions of
NO3 with Ethers ............................. 151
III-Е-7.3 Rates and Mechanisms for the Reactions of
NO3 with Aldehydes .......................... 154
III-Е-7.4 Rates and Mechanisms for the Reactions of
NO3 with Ketones ............................ 157
III-Е-7.5 Rates and Mechanisms for the Reactions of
NO3 with Organic Acids ...................... 159
III-Е-7.6 Rates and Mechanisms for the Reactions of
NO3 with Esters ............................. 160
III-E-7.7 Rates and Mechanisms for the Reactions of
NO3 with N-Atom-Containing Oxygenates ....... 160
III-E-8 Use of SARs to Estimate NO3 Rate Coefficients ... 161
III-E-8.1 SAR-Based Estimates of Rate Coefficients
for NO3 Reactions with the Alkanes and
Haloalkanes ................................. 162
III-E-8.2 SAR-Based Estimates of Rate Coefficients
for NO3 Reactions with Saturated,
Oxygenated Compounds (Aldehydes, Alcohols,
Ethers, Ketones, Esters, and Saturated
Multifunctional Species) .................... 163
III-E-8.3 SAR-Based Estimates of Rate Coefficients
for NO3 Reactions with the Alkenes,
Haloalkenes, and Alkynes .................... 166
III-E-8 4 SAR-Based Estimates of Rate Coefficients for
NO3 Reactions with Unsaturated Oxygenated
Compounds (Alcohols and Ethers) ............. 167
III-E-8.5 SAR-Based Estimates of Rate Coefficients
for NO3 Reactions with Unsaturated Carbonyl
Compound (Aldehydes, Ketones, Esters) ....... 169
IV The Hydroxy! Radical and Its Role in Ozone Formation .... 172
IV-A Introduction ............................................ 172
IV-A-1 Measurement of HO Radical Concentrations ........ 173
IV-B Mechanisms of HO Radical Reactions with Alkanes ......... 178
IV-C Mechanisms of HO Radical Reactions with Haloalkanes ..... 185
IV-D Mechanisms of HO Radical Reactions with Alkenes ......... 191
IV-D-1 HO Reactions with Mono-Alkenes ................... 191
IV-D-2 Mechanism of HO Addition to Alkenes ..............
IV-D-3 HO Reactions with Dienes ......................... 206
IV-E Mechanisms of the HO Radical Reactions with the
Alkynes .................................................. 208
IV-E-1 Reaction of HO with Acetylene (Ethyne,HC≡CH) ..... 208
IV-E-2 Reaction of HO with Propyne (Methyl Acetylene,
CH3≡CH) .......................................... 208
IV-E-3 Reaction of HO with 1-Butyne (HC≡CCH2CH3) and
2-Butyne (CH3C≡CCH3) ............................. 208
IV-E-4 The Mechanism of HO Addition Reaction with
Alkynes .......................................... 208
IV-F Mechanisms of the HO Reactions with Aromatic
Hydrocarbons ............................................ 209
IV-G Mechanisms of the HO Reactions with the Alcohols ........ 211
IV-G-1 HO Reactions with Acyclic Alcohols ............... 211
IV-G-2 HO Reaction with Diols ........................... 227
IV-G-3 HO Reactions with Saturated Alcohols ............. 228
IV-G-4 HO Reactions with Aromatic Alcohols .............. 228
IV-G-5 HO Reactions with Unsaturated Alcohols ........... 228
TV-G-6 HO Reactions with Halogen-Atom-Substituted
Alcohols ......................................... 229
IV-H Mechanisms of Reactions of HO with Ethers ............... 230
IV-H-1 HO Reactions with Acyclic Ethers ................. 230
IV-H-2 HO Reactions with Difunctional Ethers ............ 251
IV-H-3 HO Reactions with Vinyl Ethers ................... 251
IV-H-4 HO Reactions with Cyclic Poly ethers ............. 251
TV-H-S HO Radical Reactions with Halogen-Atom-
Substituted Ethers ............................... 251
IV-I Mechanisms of Reaction of HO Radical with the
Aldehydes ................................................ 253
TV-I-1 HO Radical Reactions with Acyclic Aldehydes ...... 263
IV-I-2 HO Radical Reactions with Unsaturated Aldehydes .. 263
IV-I-3 HO Radical Reactions with Aromatic Aldehydes ..... 265
IV-I-4 HO Radical Reactions with Halogen-Atom-
Substituted Aldehydes ............................ 265
IV-I Mechanisms of HO Radical Reactions with Ketones ......... 265
IV-J-1 HO Radical Reactions with Acyclic Ketones ........ 266
IV-J-2 HO Radical Reactions with Hydroxyketones ......... 276
IV-J-3 HO Radical Reactions with Unsaturated Ketones .... 276
IV-J-4 HO Radical Reactions with Halogen-Atom-
Substituted Ketones .............................. 276
IV-K Mechanisms of Reaction of HO Radical with Organic
Acids and Acid Anhydrides ............................... 276
IV-L Mechanisms of Reaction of HO Radicals with Esters ....... 277
IV-L-1 HO Radical Reactions with Acyclic Esters ......... 277
IV-L-2 HO Radical Reactions with Unsaturated Esters ..... 279
IV-L-3 HO Radical Reactions with Halogen-Atom-
Substituted Esters ............................... 279
IV-M Mechanisms of Reactions of HO Radical with N-containing
Oxygenates ............................................... 280
IV-N Summary of HO Radical Reactions with Organic Compounds .. 296
IV-O Structure-Activity-Relations (SARs)for Estimating HO
Rate Coefficients ........................................ 296
V Mechanisms of Reactions of HO2 and RO2 Radicals .......... 315
V-A Introduction ............................................. 315
V-B Reactions of HO2 with NO and RO2 with NO ................. 317
V-B-l Kinetics of the HO2 + NO and the RO2 + NO
Reactions ......................................... 317
V-B-2 Products and Mechanisms of the HO2 + NO and RO2
+ NO Reactions .................................... 320
V-C Reactions of HO2 + NO2 and RO2 + NO2 ...................... 324
V-D Reactions of HO2 + HO2 and HO2 + RO2 ...................... 326
V-E Reactions of HO2 with NO3 and RO2 with NO3 ................ 331
V-F Reactions of HO2 with RO2 and HO2 with ClO,
BrO, IO .................................................. 332
V-G Reactions of HO2 with O3 and RO2 with O3 .................. 335
V-H Reactions of RO2 with RO2 and RO2 with R'O2 ............... 336
V-H-1 Introduction ...................................... 336
V-H-2 Kinetics of RO2 Reactions with RO2 and RO2 with
R'O2 .............................................. 337
V-H-3 Products of the RO2 Reaction with RO2 and RO2
with R'O2 ......................................... 340
V-I R02 Unimolecular Reactions ............................... 343
V-I-l RO2 → QOOH Isomerization .......................... 343
V-I-2 Decomposition Reactions of the a-Hydroxy-Peroxy
Radicals .......................................... 346
VI Mechanisms of Reactions of the RO Radicals ............... 347
VI-A Introduction ............................................. 347
VI-B Modes of Alkoxy Radical Reactions in the Atmosphere ...... 348
VI-B-1 Alkoxy Radical Reactions with O2 ................. 348
VI-B-2 Unimolecular Decomposition Reactions of the
Alkoxy Radicals .................................. 349
VI-B-2.1 Unimolecular Decomposition of RR'R"CO•
Radicals ..................................... 349
VI-B-2.2 Unimolecular Decomposition of Acyloxy
Radicals [RC(O)O•] ........................... 352
VI-B-2.3 Unimolecular Isomerization Reactions of the
Alkoxy Radicals .............................. 352
VI-B-2.4 Unimolecular Decomposition of RCHCIO•
Radicals ..................................... 357
VI-B-2.5 Unimolecular Decomposition of RC(O)OCH(0•)R'
Radicals ..................................... 357
VI-B-2.6 Chemical Activation in the Chemistry of
Alkoxy Radicals .............................. 358
VI-C Reaction Rate Coefficients and Atmospheric Fate of
Selected Alkoxy Radicals ................................. 360
VI-C-I Reaction of the Methoxy Radical (CH3O•) .......... 360
VI-C-2 Reaction of the Ethoxy Radical (C2H5O•) .......... 361
VI-C-3 Reactions of the 1-Propoxy Radical (n-Propoxy
Radical, n-C3H7O•) ................................ 361
VI-C-4 Reactions of the 2-Propoxy Radical [iso-Propoxy
Radical, CH3CH(0•)CH3] ............................ 362
VI-C-5 Reactions of the 1-Butoxy Radical (n-Butoxy
Radical CH3CH2CH2CH2O•) ........................... 363
VI-C-6 Reactions of the 2-Butoxy Radical [sec-Butoxy
Radical, CH3CH(O•)CH2CH3] ......................... 364
VI-C-7 Reactions of the 2-Methyl-2-Propoxy Radical
[tert-Butoxy Radical, (CH3)3CO•] .................. 365
VI-C-8 Reactions of the 2-Methyl-l-Propoxy Radical
[iso-Butoxy Radical, (CH3)2CHCH2O•] ............... 365
VI-C-9 Reactions of the 1-Pentoxy Radical (n-Pentoxy
Radical, CH3CH2CH2CH2CH2O•) ....................... 366
VI-C-10 Reactions of the 2-Pentoxy Radical [CH3CH2CH2CH
(0•)CH3] .......................................... 366
VI-C-11 Reactions of the 3-Pentoxy Radical [CH3CH2CH(O•)
CH2CH3] ........................................... 367
VI-C-12 Reactions of the 2,2-Dimethyl-l-Propoxy Radical
[Neopentoxy Radical, (CH3)3CCH2O•] ................ 367
VI-C-13 Reactions of the 2-Methyl-2-Butoxy Radical
[CH3CH2(O•)(CH3)2 ................................. 368
VI-C-14 Reactions of the 2-Methoxy-l-Butoxy Radical
[CH3CH2CH(CH3)CH2O•] .............................. 368
VI-C-15 Reactions of the 2-Hexoxy Radical
[CH3CH2CH2CH2CH(O•)СН3] ........................... 368
VI-C-16 Reactions of the 3-Hexoxy Radical [CH3CH2CH(O•)
CH2CH2CH3] ........................................ 369
VI-C-17 Reactions of the 1-Hexoxy Radical [n-Hexoxy
Radial, CH3CH2CH2CH2CH2CH2O•] ..................... 369
VI-C-18 Reactions of the 2-Methyl-2-Pentoxy Radical
[CH3CH2CH2C(O•)(CH3)2 ............................. 369
VI-C-19 Reactions of the 4-Methyl-l-Pentoxy Radical
[CH3)2CHCH2CH2CH2O•] ............................... 370
VI-C-20 Reactions of the 5-Methyl-2-Hexoxy Radical
[(CH3)2CHCH2CH2CH(O•)CH3] ......................... 370
VI-C-21 Reactions of the 2-Methyl-2-Hexoxy Radical
[CH3CH2CH2CH2C(O•)(CH3)2 .......................... 370
Vl-C-22 Reactions of the 2,5-Dimethyl-2-Hexoxy Radical
[CH3)2CHCH2CH2C(O•)(CH3)2] ........................ 370
VI-C-23 Reaction of the Cyclopentoxy Radical ............. 371
VI-C-24 Reactions of the Cyclohexoxy Radical ............. 371
VI-C-25 Reactions of the 4-Methyl-Cyclohexoxy Radical .... 371
VI-C-26 Reactions of Other Five- and Six-Carbon Alkoxy
Radicals ......................................... 372
VI-C-27 Reactions of the 2-Hydoxy-Ethoxy Radical
(HOCH2CH2O•) ..................................... 372
VI-C-28 Reactions of the CH3OCH2O•
Radical .......................................... 372
VI-C-29 Reactions of the CH3CH2OCH(0•)CH3
Radical .......................................... 373
VI-C-30 Reactions of the CH3C(O)CH2O•
Radical .......................................... 374
VII The Impact of Inorganic Trace Gases on Ozone in the
Atmosphere ............................................... 375
VII-A Introduction ........................................... 375
VII-B Sources and Sinks of Atmospheric Carbon Dioxide (CO2)
and Carbon Monoxide (CO) ................................. 375
VII-B-1 Levels of Atmospheric CO2 and the Global
Carbon Cycle: A Brief Overview .................. 375
VII-B-2 Atmospheric Budget and Chemistry of Carbon
Monoxide ........................................ 376
VII-B-2.1 Sources of CO to the Atmosphere ............. 376
VII-B-2.2 Loss of CO via Reaction with HO:
A Significant Source of HO2 ................. 376
VII-C Tropospheric Chemistry of Inorganic Halogen Species .... 376
VII-C-1 Sources of Inorganic Halogens to the
Troposphere ..................................... 377
VII-C-2 Tropospheric Inorganic Halogen Cycles ........... 377
VII-C-3 Reactions of Cl Atoms with the Hydrocarbons ..... 380
VII-C-3.1 Reactions of Cl Atoms with Alkanes .......... 380
VII-C-3.2 Reactions of Cl Atoms with Haloalkanes ...... 380
VII-C-3.3 Reactions of Cl Atoms with Alkenes .......... 383
VII-C-3.4 Reactions of Cl Atoms with Aromatic
Hydrocarbons ................................ 384
VII-C-4 Reactions of Cl Atoms with Oxygenates ........... 385
VII-C-4.1 Reactions of Cl Atoms with Alcohols ......... 385
VII-C-4.2 Reactions of Cl Atoms with Ethers ........... 388
VII-C-4.3 Reactions of Cl Atoms with Aldehydes ........ 392
VII-C-4.4 Reactions of Cl Atoms with Ketones .......... 392
VII-C-4.S Reactions of Cl Atoms with Organic Acids .... 394
VLl-C-4.6 Reactions of Cl Atoms with Esters ........... 396
VII-C-4.7 Reactions of Cl Atoms with N-Atom-
Containing Oxygenates ....................... 399
VII-C-S Structure-Activity Relations (SARs)for
Reactions of CI Atoms with Organic Species ...... 400
VII-C-S.l SARs in the Reaction of CI Atoms with
Alkanes ..................................... 400
VII-C-S.2 SARs in the Reaction of CI Atoms with
Saturated Alcohols and Ethers ............... 400
VII-C-5.3 SARs in Reactions of CI Atoms with
Saturated Carbonyl Compounds ................ 401
VII-C-S.4 SARs in Reaction of CI Atoms with
Unsaturated Compounds ....................... 405
VII-C-6 Reactions of Br Atoms with Organic Compounds:
An Overview ..................................... 405
VII-C-6.1 Reactions of Br Atoms with Alkanes .......... 406
VII-C-6.2 Reactions of Br Atoms with Alkenes and
Alkynes ..................................... 406
VII-C-6.3 Reactions of Br Atoms with Aromatic
Hydrocarbons ................................ 407
VII-C-6.4 Reactions of Br Atoms with Alcohols and
Ethers ...................................... 407
VII-C-6.5 Reactions of Br Atoms with Aldehydes ........ 407
VII-C-6.6 Reactions of Br Atoms with Ketones, Acids,
and Esters .................................. 409
VII-C-6.7 Polar Surface Ozone Depletion Events:
A Special Case .............................. 409
VII-C-7 Reaction of Iodine Atoms with Organic
Compounds ....................................... 411
VII-D Atmospheric Reactions of Sulfur Compounds .............. 412
VII-D-1 Sources of Atmospheric Sulfur Compounds ......... 412
VII-D-2 Loss Processes for SO2 and SO3 .................. 412
VII-D-3 Atmospheric Oxidation of Reduced Sulfur
Species: H2S, CH3SH, CH3SCH3, CH3SSCH3 ........... 414
VII-D-3.1 Atmospheric Oxidation of H2S ................ 414
VII-D-3.2 Atmospheric Oxidation of CH3SH
(Methanethiol, Methyl Mercaptan) ............ 414
VII-D-3.3 Atmospheric Oxidation of CH3SCH3 (Dimethyl
Sulfide, DMS) ............................... 418
VII-D-3.4 Atmospheric Oxidation of CH3SSCH3
(Dimethyl Disulfide) ........................ 420
VII-D-4 Atmospheric Chemistry of COS and CS2 ............ 421
VII-D-4.1 Atmospheric Chemistry of Carbonyl Sulfide
(OCS) ....................................... 421
VII-D-4.2 Atmospheric Chemistry of Carbonyl
Disulfide (CS2) ............................. 423
VIII Photodecomposition of Light-Absorbing Oxygenates and
Its Influence on Ozone Levels in the Atmosphere .......... 425
VIII-A Introduction .......................................... 425
VIII-B Photolysis Frequency (j-Value) of Molecules and
Their Photochemical Lifetimes (1/j) ...................... 425
VIII-C The Mechanisms of Photodecomposition of Aldehydes .... 428
VIII-C-1 Mechanism of Photodecomposition of
Formaldehyde ................................... 428
VIII-C-2 Mechanisms of Photodecomposition of Higher
Acyclic Aldehydes .............................. 433
VIII-C-3 Photodecomposition Pathways of Aldehydes
Containing Additional Functional Groups ........ 435
VIII-C-3.1 Photodecomposition of Unsaturated
Aldehydes ................................. 435
VIII-C-3.2 Photodecompositions of HO- and Halogen-
Atom-Substituted Aldehydes ................ 437
VIIl-C-3.3 Photodecomposition of Acyclic Dials
(Dicarbonyls) ............................. 438
VIII-D Mechanisms of Photodecomposition of Ketones in the
Troposphere .............................................. 440
VIII-D-1 Mechanisms of Photodissociation of Acetone
within the Troposphere .......................... 442
VIII-D-2 Mechanisms of the Atmospheric
Photodecomposition of Larger Acyclic Ketones .... 446
VIII-D-2.1 RC(O)R' + hv → RCO + R': Process (I) ...... 446
VIII-D-2.2 Ketone Photodissociation into Enol and
Alkene Products: Process (II) .............. 447
VIII-D-3 Photodecomposition ofKetene (CH2=C=0) .......... 448
VIII-D-4 Photodecomposition of Some HO- and Halogen-
Atom-Substituted Ketones ....................... 448
VIII-D-5 Photodecomposition Pathways for Some
Difunctional Ketones ........................... 449
VIII-D-6 Photodecomposition of Carbonyl Halides,
Formyl Halides, and Acetyl Halides ............. 451
VIII-E The Photodecomposition of N-Atom-Containing
Compounds ................................................ 451
VIII-E-1 Photodecomposition oftheAlkyl Nitrates ......... 452
VIII-E-2 Photodecomposition of the Peroxyacyl Nitrates
(RC(O)OON02) ................................... 453
VIII-E-3 The Role of HONO in Ozone Generation in Urban
Atmospheres .................................... 454
VIII-E-4 Photodecomposition of Other N-Atom-Containing
Oxygenates and Other Photochemically Active
Trace Gases .................................... 455
VIII-F Summary of Photochemical Processes in the
Troposphere .............................................. 457
IX Chemical Mechanisms for Air Quality Modeling and
Their Applications ....................................... 465
IX-A Development of Mechanisms for Air Quality Modeling ...... 465
IX-A-1 Requirements for Mechanisms for Air Quality
Modeling, Their Development, and an Overview
of the Types of Mechanisms Available ............. 465
IX-A-2 Computer-Generated and Detailed Explicit
Mechanisms ....................................... 468
IX-A-3 Condensed Mechanisms (EKMA, Carbon Bond,
SAPRAC, RADM/RACM) ............................... 469
IX-B Methods of Assessing the Influence of VOCs and NOx on
Ozone Generation Using Computer Models ................... 473
IX-B-1 Process Analysis and the Sensitivity of Ozone
Formation to VOC and NOx ......................... 473
IX-B-2 O3, PAN, HNO3, H2O2, HO and HO2 Isopleths:
VOC and NOx Sensitivity .......................... 476
IX-B-3 Methods of Sensitivity and Process Analysis for
Mechanism Assessment ............................. 477
IX-B-4 NOx and VOC Sensitivity and Indicator Ratios for
NOx and VOC ...................................... 480
IX-C Computer Assessment of the Effects of [H20],
Temperature, and Clouds on O3 Generation ................. 481
IX-D Simulation of the Effects of CH2O, CO,
SO2, NO3 and N2O5 on O3 Generation ........................ 484
IX-E Measures of Ozone Formation Reactivity .................. 487
LX-E-1 Incremental Reactivity: MIR and MOIR ............. 487
IX-E-1.1 Maximum Ozone Incremental Reactivity: MOIR ... 487
IX-E-1.2 Maximum Incremental Reactivity: MIR .......... 487
IX-E-1.3 Comparison of MOIR and MIRValues ............. 488
IX-E-2 Photochemical Ozone Creation Potential (POCP) .... 489
IX-F Modeling of Secondary Inorganic Aerosol and Organic
Aerosol Formation ........................................ 490
IX-G Potential Deficiencies of Atmospheric Chemistry
Mechanisms as Implemented in Air Quality Models .......... 493
IX-H Future Development of Atmospheric Chemical Mechanisms
for Air Quality Modeling ................................. 496
References .................................................... 497
Author Index .................................................. 549
Subject Index ................................................. 575
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