4/9/2017

Chapter 8
Global Atmospheric Change
Chuyang Y. Tang
tangc@[Link]
2859 1976

Atmosphere of the Earth

Stratosphere
• Absorption of solar energy by O2  T inversion
• Poor vertical mixing

Mesosphere
• Good air mixing

Stratosphere
• Dry air
99.9% • UV absorption by ozone  T inversion
of • Poor vertical mixing
mass • Pollutants remain in stratosphere for long time
Troposphere
• 80% of mass, almost all water vapor, clouds
• T decreases at 5-7 C/km
• Turbulent, strong vertical mixing
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Atmosphere of the Earth

Constituent Formula Concentration (ppm)
Nitrogen N2 780,800
Oxygen O2 209,500
Argon Ar 9,300
Carbon dioxide CO2 380 Greenhouse gases
Neon Ne 18
Helium He 5.2
Methane CH4 1.7
Krypton Kr 1.1
Nitrous oxide N2O 0.3
Hydrogen H2 0.5
Ozone O3 0.04
UV protection
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Temperature Anomaly
NASA Goddard Institute for Space Studies (GISS)

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[Link]

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A simple temprature Solar radiation reaching earth

SR2
model (S = 1370 W/m2)

Reflected
by Earth
SR2 
Absorbed
(the Earth
by Earth
albedo,
SR2 (1-)
 = 0.31)

SR2 (1-) =  4R2 Te4

[Link]
 4R2 Te4  Te = 254 K = - 19 C
(actual average T = 15 C)

Stefan-Boltzmann constant
 = 5.67 x 10-8 W/m2-K4 11

The greenhouse effect

IR window
(7-13 µm)

[Link]

Absorption of IR radiation (thermal radiation) from the

Earth by the atmosphere. A significant portion of the
absorbed energy is re-radiated back to the Earth.

Greenhouse gases: absorbing wavelengths > 4 µm.

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[Link]

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The greenhouse effect

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[Link]

Greenhouse gases
• Water vapor
• Carbon dioxide (CO2)
• Nitrous oxide (N2O)
• Methane (CH4)
• Ozone (O3)
• Halogenated hydrocarbons
• Chlorofluorocarbons (CFCs)
• Hydrochlorofluorocarbons (HCFCs)
• Hydrofluorocarbons (HFCs)
• Carbon tetrachloride (CCl4)
• Methylchloroform (CH3CCl3)

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CO2 in the atmosphere

[Link]
[Link]
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Carbon cycle
• Atmosphere: 750 GtC (@360 ppm) Atmosphere net gain 3.2  0.2 GtC/yr
• Vegetation: 610 GtC
• Ocean: 39,000 GtC

6.3  0.4 2.2  0.8 2.9  1.1 2.4  0.8

Fossil fuel Land-use Land uptake Oceans
& cement change

Of 8.5 GtC/yr emitted through anthropogenic activities,

3.2 GtC/yr remains in the atmosphere.

Airborne fraction = 3.2/8.5 x 100% = 38%

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[Link]

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Carbon emission
• 1 ppm CO2 = 2.12 GtC (see ex. 8.2)

Ex. 8.3
• Suppose global emission in Gt/yr:
• 2.2 (land use)
• 7.9 (fossil fuel)
• 0.5 (cement),
• Assume airborne fraction = 0.38

•  CO2 = 10.1 GtC/yr x 0.38 / (2.12 GtC/ppm CO2) = 1.8 ppm CO2/yr

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Other greenhouse gases and aerosols

• Methane (CH4)
• 600 Mt methane/yr emitted, ~ 60% from human activities
• Natural decomposition of organic matter in anaerobic conditions
• Agriculture, fossil fuel use, waste disposal
• 1750 ppb (compared to preindustrial concentration 750 ppb)
• Absorption band ~ 7.7 µm, a potent greenhouse gas
• Relatively short residence time: 9-15 yrs
•  Removal of methane could be effective in reducing global warming
CH4 + OH radical + 9 O2  CO2 + 0.5 H2 + 2 H2O + 5 O3
A positive feedback loop
Release methane frozen in permafrost
Production of more
Global warming methane
Anaerobic decomposition of organic
matter in permafrost
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Other greenhouse gases and aerosols

• Nitrous oxide (N2O)
• 9 Mt N2O /yr from natural source, and 6 Mt N2O /yr from human activities
• Released during nitrification

NH4+  N2  N2O  NO2-  NO3-

• 320 ppb (compared to preindustrial concentration of 275 ppb)
• Absorption band ~ 7.8 and ~ 8.6 µm, potent greenhouse gas
• Long residence time: ~ 120 yrs  long lasting effect
• Removed in stratosphere by photolysis

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Other greenhouse gases and aerosols

• Halocarbons (Trade name: Freon)
• Carbon based molecules with
halogens (F, Cl, or Br)
• Halocarbons are entirely
emitted due to human
activities
• C-F, C-Cl, C-Br bonds absorb IR
 greenhouse effect
• Halocarbons containing Cl or Br
are responsible for
stratospheric ozone depletion

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Other greenhouse gases and aerosols

• Chlorofluorocarbons (CFCs)
• Nontoxic, nonflammable, nonreactive, not water soluble
•  difficult to remove from atmosphere  long life time
• Removal in stratosphere: photolysis by short wavelength solar radiation (this releases Cl
that destroys ozone)
• CFCs were used as refrigerant, aerosol propellant, and in making foamed plastics. Most
uses of CFCs are now banned or severely restricted by the Montreal Protocol.
• Hydrochlorofluorocarbons (HCFCs)
• Introduced as (temporary) replacements for CFCs
• Addition of H in the molecules  can be chemically destroyed  shorter life time than
CFCs
• Potent greenhouse gas + some potential for ozone destruction
• Hydrofluorocarbons (HFCs)
• No Cl  not an ozone destructor
• CH2FCF3 (HFC-134a) is a popular car refrigerant
• Life time 14.6 yrs, 1400 times as potent as CO2
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Other greenhouse gases and aerosols

• Perfluorocarbons (PFCs)
• Contains only C and F  not an ozone destructor
• Extremely stable, nonflammable, zero ozone depletion potential
• Lifetime 50,000 yrs, global warming potential 6,500 times of CO2
• Halons (CF3Br; CF2ClBr)
• Contains Br  ozone destroying compound
• Non-toxic
• Used in fire extinguishers
• Very stable molecules  destroyed by photolysis in stratosphere

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Other greenhouse gases and aerosols

• Ozone (O3)
• Strong absorption band at 9 µm
• Strong variation of concentration over time, location
• In troposphere
• Ozone is formed by photochemical reactions VOCs + NOx + sunlight  photochemical smog
• High concentration in Northern Hemisphere
• Seasonable variation, higher concentration in
summer
• In stratosphere,
• Decreasing ozone concentrations due to attacks by
chlorine and bromine released by UV-exposed CFCs
and halons
• Ozone depletion led to ozone hole over Antarctica
• Opens the atmospheric window  offset some
global warming caused by halocarbon emissions

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Other greenhouse gases and aerosols

• Aerosols
• Particles < 10 µm, including both solid particles and liquid particles (e.g., condensation of SO 2)
• Shorter lifetime: Days to weeks in troposphere; a few years in stratosphere
• Strong regional variation in concentration
• Both heating and cooling effects
• Reflect incoming solar radiation back into space (cooling)
• Promote cloud formation  increases cloud reflectivity and cloud lifetime  increases albedo
(cooling)
• Carbonaceous particles (termed black carbon (BC), e.g., soot) increase atmospheric absorption of solar
energy (heating)
• Direct absorption of solar energy;
• Indirect effect: promote snow melting  reduces albedo effect

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Figure 8.25, textbook

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Cumulative radiative forcing (RF), 1750-2005, in W/m2

IPCC 2007 26

Dangerous effects of global warming

• Shorter term
• More frequent heat waves
• More frequent intense storms  extreme flooding
• Drier summers  increased risk of severe droughts
• Less snow and reduced glacial extent  affect snowmelt for water supply (e.g.,
China and India)
• Sea-level rise and increased risk of coastal flooding
• Increased ocean acidity (caused by CO2 absorption by the ocean  ocean
acidification)
• Longer term
• Large-scale, potentially rapid and nonlinear climate responses
• Deglaciation of polar ice sheets  several meters of sea level rise
• Change in ocean circulation
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Oceans and climate change

• Ocean
• High heat capacity
• Ocean current, distributing heat around the globe
• Stores 50 times as much carbon as the atmosphere  a major carbon sink
• Major effects of climate change on ocean
• Ocean acidification
• Rising sea level
• Change in ocean circulation

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Ocean acidification
Air-water equilibrium
CO2 (g) + H2O = H2CO3 (aq) [H2CO3] = KHPCO2 (KH = 0.0334 mol/[Link])

Acid-base equilibrium
H2CO3 = H+ + HCO3- K1 = [H+][HCO3-]/[H2CO3] = 4.47 x 10-7 (pK1 = 6.35)
HCO3- = H+ + CO32- K2 = [H+][CO32-]/[HCO3-] = 4.68 x 10-11 (pK2 = 10.33)

Liquid-solid equilibrium
CaCO3 (s) = Ca2+ + CO32- Ksp = [Ca2+][CO32-] = 4.57 x 10-9

Ocean water has a pH ~ 8 – 8.3 (slightly alkaline)

Increase CO2 concentration  more carbonic acid  greater
[H+]  lower pH
Lower pH  lower [CO32-]  more difficult to form CaCO3
(material in shells and other hard parts of marine organisms)
• Increased potential for dissolving shells
• Affect coral reef
• Affect food marine chain

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National Geography Feature Story

More interesting photos at National Geography

[Link]
acidification/liittschwager-photography

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[Link]

Rising sea level

• Thermal expansion  3 mm / yr rise in
sea levels
• Melting of glaciers and ice caps
• Antarctic ice sheet (29 x 106 km3  73 m sea
level equivalent)
• The Greenland ice sheet (2.95 x 106 km3 
7.4 m sea level equivalent)
• Glaciers and ice caps (0.1 x 106 km3  0.3 m
sea level equivalent) [Link]

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Ocean circulation
• The Atlantic thermohaline circulation
• Warm surface flow transport heat to northern Atlantic ocean

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[Link]

Ozone depletion
• Ozone (O3)
• A greenhouse gas, with strong absorption band at 9 µm
• Strong variation of concentration over time, location

• In troposphere (ground-level ozone)

• An air pollutant
• A principle component of photochemical smog
• High concentration in Northern Hemisphere
• Seasonable variation, higher concentration in summer

• In stratosphere (stratospheric ozone)

• Ozone absorbs UV light, protecting human health
• Decreasing ozone concentrations due to attacks by
chlorine and bromine released by UV-exposed CFCs and
halons
• Ozone depletion led to ozone hole over Antarctica

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Increasing energy of photon

UV light
E = hv = hc/ (h = 6.6 x 10-34 J-s)
(Read ex. 8.13)

Over exposure to UV
 skin burning, skin cancer

O2 + hv  O + O
(absorbing over 130-180 nm)
Absorption by O2
O + O2  O3 and O3
O3 + hv  O2 + O
(absorbing over 200-320 nm)

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Ozone destruction
CFCs, HCFCs, halons + UV-C  Cl and Br radicals

X + O3  XO + O2
X is a free radical (e.g., Cl, Br, NO, …)
XO + O  X + O2
Net: O + O3  2 O2

Cl + O3  ClO + O2 Cl radical serves as catalyst (not

ClO + O  Cl + O2 consumed in the reaction)
 Catalytic destruction of ozone
Net: O + O3  2 O2
(first discovered in 1974  1995
Nobel Prize in Chemistry)

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Ozone depletion potential and response

Montreal Protocol and other following actions

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Readings and practice questions

• Readings
• Essential reading: pp501-561, 568-587

• Practice questions
• Q8.10, 8.13

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