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Errera Q., Daerden F., Chabrillat S., et al. (2008) 4D-Var assimilation of MIPAS chemical observations: Ozone and nitrogen dioxide analyses, Atmos. Chem. Phys., 8, 6169–6187.
Heald C. L., Jacob D. J., Jones D., et al. (2004) Comparative inverse analysis of satellite (MOPITT) and aircraft (TRACE-P) observations to estimate Asian sources of carbon monoxide, J. Geophys. Res., 109, D23306.
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A
Physical Constants and Other Data
A.1 General and Universal Constants
Base of natural logarithms 2.71828
π (Pi) 3.14159
Boltzmann’s constant 1.38066 × 10–23 J K–1
Molar gas constant 8.3144 J K–1 mol–1
Stefan–Boltzmann’s constant 5.67032 × 10–8 W m–2 K–4
Planck’s constant 6.62618 × 10–34 J s
Speed of light in vacuum 2.99792 × 108 m s–1
Gravitational constant 6.67259 × 10–11 m3 s–2 kg–1
Electron mass 9.1096 × 10–31 kg
Electron charge 1.6022 × 10–19 C
Atomic mass unit (amu) 1.66054 × 10–27 kg
Avogadro number 6.0221 × 1023 mol–1
A.2 Earth
Average radius 6.371 × 106 m
Surface area 5.10 × 1014 m2
Surface area (continents) 1.49 × 1014 m2
Surface area (oceans) 3.61 × 1014 m2
Average height of land 840 m
Average depth of oceans 3730 m
Acceleration of gravity (surface) 9.80665 m s–2
Mass of Earth 5.983 × 1024 kg
Mass of atmosphere 5.3 × 1018 kg
Eccentricity of Earth’s orbit 0.016750
Inclination of rotation axis 23.45° or 0.409 rad
Mean angular rotation rate 7.292 × 10–5 rad s–1
Earth orbital period 365.25463 days
Solar constant 1367 ± 2 W m–2
A.3 Dry Air
Average molar mass 28.97 g mol–1
Specific gas constant 287.05 J K–1 kg–1
Standard surface pressure 1.01325 × 105 Pa
Mass density at 0 °C and 101325 Pa 1.293 kg m–3
Number density at 0 °C and 101325 Pa 2.69 × 1025 m–3
Molar volume 0 °C and 101325 Pa 22.414 × 10–3 m3 mol–1
Specific heat at constant pressure (cp) 1004.64 J K–1 kg–1
Specific heat at constant volume (cv) 717.6 J K–1 kg–1
Poisson constant (cp/cv) 1.4
Index of refraction for air 1.000277
Dry diabatic lapse rate 9.75 K km–1
Speed of sound for standard conditions 343.15 m s–1
A.4 Water
Molecular weight 18.016 g mol–1
Gas constant for water vapor 461.6 J K–1 kg–1
Density of pure liquid water at 0 °C 1000 kg m–3
Density of ice at 0 °C 917 kg m–3
Density of water vapor at STP (0 °C, 1 atm) 0.803 kg m–3
Specific heat of water vapor at constant pressure 1952 J K–1 kg–1
Specific heat of water vapor at constant volume 1463 J K–1 kg–1
Specific heat of liquid water at 0 °C 4218 J K–1 kg–1
Specific heat of ice at 0 °C 2106 J K–1 kg–1
Latent heat of vaporization at 0 °C 2.501 × 106 J kg–1
Latent heat of vaporization at 100 °C 2.25 × 106 J kg–1
Latent heat of fusion at 0 °C 3.34 × 105 J kg–1
Latent heat of sublimation at 0 °C 2.83 × 106 J kg–1
Index or refraction for liquid water 1.336
Index of refraction for ice 1.312
Triple-point temperature of water 273.16 K
B
Units, Multiplying Prefixes, and Conversion Factors
B.1 International System of Units
Quantity Name of Unit Symbol Definition
Length Meter m
Mass Kilogram kg
Time Second s
Electrical current Ampere A
Temperature Kelvin K
Force Newton N kg m s–2
Pressure Pascal Pa N m–2
Energy Joule J kg m2 s–2
Power Watt W J s–1
Electrical potential Volt V W A–1
Electrical charge Coulomb C A s
Electrical resistance Ohm Ω V A–1
Electrical capacitance Farad F A s V–1
Frequency Hertz Hz s–1
Moles Mole mol
B.2 Multiplying Prefixes
Multiple Prefix Symbol Multiple Prefix Symbol
10–1 Deci d 101 Deca da
10–2 Centi c 102 Hecto h
10–3 Milli m 103 Kilo k
10–6 Micro μ 106 Mega M
10–9 Nano n 109 Giga G
10–12 Pico p 1012 Tera T
10–15 Femto f 1015 Peta P
10–18 Atto a 1018 Exa E
Wavelengths are typically expressed in micrometers (μm) or nanometers (nm). Wavenumbers are expressed in inverse centimeters (cm–1). Atmospheric pressure is often expressed in hectopascals (hPa), number densities in molecules per cubic centimeter (cm–3). Molar mixing ratios are given in percent, parts per million (ppm), parts per billion (ppbv), parts per trillion (pptv), or parts per quadrillion (ppqv). Mass mixing ratios are expressed in kilograms per kilogram or grams per kilogram.
B.3 Conversion Factors
Area 1 ha = 104 m2
Volume 1 liter = 10–3 m3
Velocity 1 m s–1 = 3.6 km h–1 = 2.237 mi h–1
Force 1N = 105 dyn
Pressure 1 bar = 105 Pa =103 mb = 750.06 mm Hg
1 atm = 1.01325 × 105 Pa = 760 Torr
Energy 1 cal = 4.1855 J
1 eV = 1.6021 × 10–19 J
1 J =
1 N m = 107 erg = 0.239 cal
Power 1 W = 14.3353 cal min–1
Temperature T(°C) = T(K) – 273.15
T(°F) = 1.8 T(°C) + 32
Mixing ratios 1 ppb = 10–3 ppm
1 ppt = 10–3 ppb = 10–6 ppm
Logarithms ln x = 2.3026 log10 x
B.4 Commonly Used Units for Atmospheric Concentrations
Number density molecules cm–3
Mass density kg m–3
Mixing ratio (molar)a ppm ≡ ppmv ≡ μmol mol–1 ≡ 10–6 mol mol–1
ppb ≡ ppbv ≡ nmol mol–1 ≡ 10–9 mol mol–1
ppt ≡ pptv ≡ pmol mol–1 ≡ 10–12 mol mol–1
ppq ≡ ppqv ≡ fmol mol–1 ≡ 10–15 mol mol–1
Mixing ratio (mass) g g–1 ≡ g per g of air
g kg–1 ≡ g per kg of air
Partial pressure Pa, Torr (1 Torr = 133 Pa)
Column molecules cm–2,
Dobson Unit (1 DU = 2.69 × 1016 molecules cm–2)b
a Mixing ratios in the atmospheric chemistry literature denote molar fractions unless otherwise specified. Mol mol–1 is the SI unit but ppm, ppb, etc. are conventionally used. To avoid confusion with mass mixing ratios the conventional units are often written as ppmv, ppbv, etc. where v refers to volume (in an ideal gas such as the atmosphere, the number of moles is proportional to volume)
b The Dobson Unit was originally introduced and is still mainly used as a measure of the thickness of the ozone layer, with 1 DU corresponding to a 0.01 mm thick layer of pure ozone under standard conditions of temperature and pressure (0 °C, 1 atm).
C
International Reference Atmosphere
Elevation Temperature Pressure Relative
density Kinematic
viscosity Thermal
conductivity Speed of sound
z
[m] T
[K] p
[Pa]
×105 ρ/ρ0 ν
[m2 s–1]
×10–5 κ
[W m–1 K–1]
×10–2 c
[m s–1]
–1500 297.9 1.2070 1.1522 1.301 2.611 346.0
–1000 294.7 1.1393 1.0996 1.352 2.585 344.1
–500 291.4 1.0748 1.0489 1.405 2.560 342.2
0 288.15 1.01325 1.0000 1.461 2.534 340.3
500 284.9 0.9546 0.9529 1.520 2.509 338.4
1000 281.7 0.8988 0.9075 1.581 2.483 336.4
1500 278.4 0.8456 0.8638 1.646 2.457 334.5
2000 275.2 0.7950 0.8217 1.715 2.431 332.5
2500 271.9 0.7469 0.7812 1.787 2.405 330.6
3000 268.7 0.7012 0.7423 1.863 2.379 328.6
3500 265.4 0.6578 0.7048 1.943 2.353 326.6
4000 262.2 0.6166 0.6689 2.028 2.327 324.6
4500 258.9 0.5775 0.6343 2.117 2.301 322.6
5000 255.7 0.5405 0.6012 2.211 2.275 320.5
5500 252.4 0.5054 0.5694 2.311 2.248 318.5
6000 249.2 0.4722 0.5389 2.416 2.222 316.5
6500 245.9 0.4408 0.5096 2.528 2.195 314.4
7000 242.7 0.4111 0.4817 2.646 2.169 312.3
7500 239.5 0.3830 0.4549 2.771 2.142 310.2
8000 236.2 0.3565 0.4292 2.904 2.115 308.1
8500 233.0 0.3315 0.4047 3.046 2.088 306.0
9000 229.7 0.3080 0.3813 3.196 2.061 303.8
9500 226.5 0.2858 0.3589 3.355 2.034 301.7
10 000 223.3 0.2650 0.3376 3.525 2.007 299.8
10 500 220.0 0.2454 0.3172 3.706 1.980 297.4
11 000 216.8 0.2270 0.2978 3.899 1.953 295.2
11 500 216.7 0.2098 0.2755 4.213 1.952 295.1
12 000 216.7 0.1940 0.2546 4.557 1.952 295.1
12 500 216.7 0.1793 0.2354 4.930 1.952 295.1
13 000 216.7 0.1658 0.2176 5.333 1.952 295.1
13 500 216.7 0.1533 0.2012 5.768 1.952 295.1
14 000 216.7 0.1417 0.1860 6.239 1.952 295.1
14 500 216.7 0.1310 0.1720 6.749 1.952 295.1
15 000 216.7 0.1211 0.1590 7.300 1.952 295.1
15 500 216.7 0.1120 0.1470 7.895 1.952 295.1
16 000 216.7 0.1035 0.1359 8.540 1.952 295.1
16 500 216.7 0.09572 0.1256 9.237 1.952 295.1
17 000 216.7 0.08850 0.1162 9.990 1.952 295.1
17 500 216.7 0.08182 0.1074 10.805 1.952 295.1
18 000 216.7 0.07565 0.09930 11.686 1.952 295.1
18 500 216.7 0.06995 0.09182 12.639 1.952 295.1
19 000 216.7 0.06467 0.08489 13.670 1.952 295.1
19 500 216.7 0.05980 0.07850 14.784 1.952 295.1
20 000 216.7 0.05529 0.07258 15.989 1.952 295.1
22 000 218.6 0.04047 0.05266 22.201 1.968 296.4
24 000 220.6 0.02972 0.03832 30.743 1.985 297.7
26 000 222.5 0.02188 0.02797 42.439 2.001 299.1
28 000 224.5 0.01616 0.02047 58.405 2.018 300.4
30 000 226.5 0.01197 0.01503 80.134 2.034 301.7
D
Chemical Mechanism
This appendix lists important chemical and photolysis reactions occurring in the troposphere and stratosphere, including rate constants and typical photolysis frequencies. It is based on a mechanism described by Emmons et al. (2010) and Lamarque et al. (2012). Many rate constants in the mechanism are simplified and uncertain. More comprehensive and detailed information with references can be found in various compilations, including the regularly updated NASA Jet Propulsion Laboratory (JPL) Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies and the International Union of Pure and Applied Chemistry (IUPAC) Evaluated Kinetic Data for Atmospheric Chemistry. See also The Atmospheric Chemist’s Companion by P. Warneck and J. Williams (Springer, 2012). Chemical mechanisms used in models often vary in their lumping of larger organic species and their oxidation products. The present mechanism lumps alkanes and alkenes with four or more carbon atoms, lumps aromatic hydrocarbons as toluene, and also includes isoprene and a lumped terpene (α-pinene). The chemical reactivity of the lumped species is chosen to approximately represent the average reactivity of the different individual hydrocarbons that are accounted for by the lumped species. The mechanism symbols identify individual species in the computer code for the mechanism and are sometimes used in atmospheric chemistry jargon (PAN, for example) but have otherwise no meaning. The “common names” may depart from IUPAC nomenclature but represent standard usage in the atmospheric chemistry literature.
D.1 Chemical Species and Definitions of Symbols
D.1.1 Inorganic Gas-Phase Species
Chemical formula Common name
O(3P) Ground state “triplet-P” atomic oxygen
O(1D) Excited state “singlet-D” atomic oxygen
O3 Ozone
N2O Nitrous oxide
NO Nitric oxide
NO2 Nitrogen dioxide
NO3 Nitrate radical
HONO Nitrous acid
HNO3 Nitric acid
HNO4 Pernitric acid
N2O5 Dinitrogen pentoxide
H Atomic hydrogen
H2 Molecular hydrogen
OH Hydroxyl radical
HO2 Hydroperoxy radical
H2O2 Hydrogen peroxide
CO Carbon monoxide
SO2 Sulfur dioxide
NH3 Ammonia
Cl Chlorine atom
ClO Chlorine monoxide
OClO Chlorine dioxide
Cl2O2 Chlorine monoxide dimer
Cl2 Molecular chlorine
HCl Hydrogen chloride
HOCl Hypochlorous acid
ClONO2 Chlorine nitrate
ClNO2 Nitryl chloride
Br Bromine atom
BrO Bromine monoxide
Br2 Molecular bromine
BrCl Bromine monochloride
HBr Hydrogen bromide
HOBr Hypobromous acid
BrONO2 Bromine nitrate
D.1.2 Organic Gas-Phase Species
Mechanism symbol Chemical formula Common name
C1 species
CH4 CH4 Methane
CH3O2 CH3O2 Methylperoxy radical
CH3OOH
CH3OOH Methylhydroperoxide
CH2O CH2O Formaldehyde
CH3OH CH3OH Methanol
HCOOH HCOOH Formic acid
C2 species
C2H4 C2H4 Ethene
C2H6 C2H6 Ethane
C2H2 C2H2 Acetylene
CH3CHO CH3CHO Acetaldehyde
C2H5OH C2H5OH Ethanol
EO HOCH2CH2O Hydroxy ethene oxy radical
EO2 HOCH2CH2O2 Hydroxy ethene peroxy radical
CH3COOH CH3COOH Acetic acid
GLYOXAL HCOCHO Glyoxal
GLYALD HOCH2CHO Glycolaldehyde
C2H5O2 C2H5O2 Ethylperoxy radical
C2H5OOH C2H5OOH Ethylhydroperoxide
CH3CO3 CH3CO3 Peroxyacetyl radical
CH3COOOH CH3C(O)OOH Peracetic acid
PAN CH3C(O)OONO2 Peroxyacetyl nitrate
DMS (CH3)2S Dimethylsulfide
C3 species
C3H6 C3H6 Propene
C3H8 C3H8 Propane
C3H7O2 C3H7O2 Propylperoxy radical
C3H7OOH C3H7OOH Propylhydroperoxide
PO2 e.g., CH3CH(OO)CH2OH Hydroxyl propene peroxy radicals
POOH e.g., CH3CH(OOH)CH2OH Hydroxyl propene peroxide
CH3COCH3 CH3COCH3 Acetone
HYAC CH3COCH2OH Hydroxyacetone
CH3COCHO CH3COCHO Methylglyoxal
AO2 CH3COCH2O2 Acetone peroxy radical
AOOH CH3COCH2OOH Acetone hydroperoxide
ONIT CH3COCH2ONO2 Organic nitrate
C4 species
BIGENE C4H8 Lumped >C3 alkene
ENEO2 e.g., CH3CH(OH)CH(OO)CH3 Lumped alkene peroxy radical
MEK CH3C(O)CH2CH3 Methyl ethyl ketone
MEKO2 CH3COCH(OO)CH3 MEK peroxy radical
MEKOOH CH3COCH(OOH)CH3 MEK hydroperoxide
MVK CH2CHCOCH3 Methyl vinyl ketone
MACR CH2CCH3CHO Methacrolein
MPAN CH2CCH3CO3NO2 Methacryloyl peroxynitrate
MACRO2 e.g., CH3COCH(OO)CH2OH MVK + MACR peroxy radical
MACROOH e.g., CH3COCH(OOH)CH2OH MVK + MACR hydroperoxide
MCO3 CH2CCH3CO3 MACR peroxyacyl radical
Modeling of Atmospheric Chemistry Page 66