Atmospheric Chemistry

Photochemical Pollutants - Ozone

Formation and Degradation
Global Warming
Visibility
Dr. Steven Japar
Ford Motor Co. Retired
March 29, 2005
TROPOSPHERIC CHEMISTRY
John H. Seinfeld, Spyros N. Pandis, Atmospheric Chemistry and Physics (John
Wiley & Sons, 1998)

Photochemical Cycle of NO
2
, NO and O
3

NO
2
+ h (< 424 nm) NO + O (j
NO2
)
O + O
2
+ M O
3
+ M (k
1
)
O
3
+ NO NO
2
+ O
2
(k
2
)
d[NO
2
]/dt = k
2
[O
3
][NO] - j
NO2
[NO
2
]

For O atoms, O
3
(very reactive), invoke pseudo-
steady-state approximation, i.e., rate of
formation = equals rate of loss

d[O
3
]dt = k
1
[O][O
2
][M] - k
2
[O
3
][NO] ~ 0
d[O]/dt = j
NO2
[NO
2
] k
1
[O][O
2
][M] ~ 0
j
NO2
[NO
2
] = k
1
[O][O
2
][M]
d[O
3
]dt = j
NO2
[NO
2
] - k
2
[O
3
][NO] ~ 0

Photostationary state relationship
[O
3
]
ss
= j
NO2
[NO
2
] /k
2
[NO]
Atmospheric Chemistry of Carbon
Monoxide and NO
x
O
3
+ h O + O
2
O(
1
D) + O
2
O(
1
D) + M O + M
O + O
2
+ M O
3
O(
1
D) + H
2
O 2 OH
CO + OH CO
2
+ H

H + O
2
+ M HO
2
+ M
CO + OH + O
2
CO
2
+ HO
2

HO
2
+ NO NO
2
+ OH
Atmospheric Catalytic Oxidation of CO
CO + OH + O
2
CO
2
+ HO
2
HO
2
+ NO NO
2
+ OH
NO
2
+ h NO + O
O + O
2
+ M O
3
+ M
CO + 2O
2
+ h CO
2
+ O
3

HO
2
, OH not consumed in this cycle
Net formation of O
3
: NO NO
2
is
accomplished by HO
2
The chain terminating step:
OH + NO
2
+ M HNO
3
+ M
The Hydroxyl Radical
Most important reactive radical species in
the atmosphere.
Measurements, theoretical estimates --
average tropospheric [OH] =
Daytime (summer) 5-10 x 10
6
molecules cm
-3
Daytime (winter) 1- 5 x 10
6

Nighttime <2 x 10
5

Nighttime reservoir
OH + NO + M HONO + M
Early morning jump start
HONO + h OH + NO
Peroxyacyl Nitrates
CH
3
CHO + OH CH
3
CO + H
2
O
CH
3
CO + O
2
+ M CH
3
C(O)O
2
+ M
CH
3
C(O) O
2
+ NO CH
3
C(O)O + NO
2
CH
3
C(O)O CH
3
+ CO
2

CH
3
C(O)O
2
+ NO
2
<==> CH
3
C(O)OONO
2
Peroxyacetyl nitrate (PAN)
CH
3
C=O

OONO
2
Peroxyacyl Nitrates
Lower troposphere -- relatively
unreactive
Lifetime determined by thermal
dissociation
PAN: ~ 30 minutes at 298 K; 8 hours at
273 K; months in upper troposphere
Upper troposphere lifetime
determined by photolysis, OH
Mechanism for long-range transport of
reactive NOx
Hydrocarbon Oxidation in the
Atmosphere
CH
4
+ 4O
2
+ 2NO + OH HCHO + 2O
3
+
OH + 2NO
2
+ H
2
O

CH
3
CH
3
+ 2NO + OH + O
2
CH
3
CHO +
2NO
2
+ OH

C
2
H
4
+ OH + NO + 2O
2
NO
2
+ 1.44
HCHO + 0.28 HOCH
2
CHO + OH
Urban Atmosphere on a Smoggy Day
NO
X
/Hydrocarbon/Ozone
Relationships in the Atmosphere
Urban-Suburban
O
3
: 100-400 ppb
Rural
O
3
: 50-120 ppb
Remote
O
3
: 20-40 ppb
Marine
O
3
: 20-40 ppb
Ozone Isopleths
Graphical representation of the
dependence of O
3
formation on initial
[VOC] and [NOx]
Simple box model representation of the
atmosphere
After initialization, nothing enters or leaves the
box

Implications for Control of O
3

All VOC/NOx regimes are not equal


Ridge line: low
VOC/NOx vs. high
VOC/NOx

Above ridge line
Decreased [NOx]
increased [O
3
]
Decreased [VOC]
decreased [O
3
]

Below ridge line:
Decreased [NOx]
decreased [O
3
]
Decreased [VOC]
no change in [O
3
]
VOC-limited
NOx-limited
Michigan Air Pollution
http://www.deq.state.mi.us/documents/deq-aqd-aqe-ozone-bumpdown-
westmich.pdf
Air quality in Michigan has been improving since
the mid-1980s
Visibility

Extinction Coefficient - b
ext

Measure of atmospheric transparency
Measure of the fraction of light energy lost
from a collimated beam of energy E in
traversing a unit thickness of atmosphere
The extinction coefficient has dimensions
of inverse length (e.g., Mm
-1
)
b
Ray
is light scattering by gas
molecules known as Rayleigh
scattering
Gas scattering is almost entirely attributable
to oxygen and nitrogen molecules in the air.
It is unaffected by pollutant gases and is 12 x
10
-6
m
-1
(Mm
-1
) at the wavelength of 550nm at
sea level. (V
r
~300 km)
b
sp
is light scattering by particles
Dominated by fine particles in the size range
of 0.1~1.0 m
ap ag sp Ray abs scat ext
b b b b b b b
b
ag
is light absorption by gases
NO
2
is the only common atmospheric gas that
significantly absorbs light

b
ap
is light absorption by particles
Absorption arises nearly entirely from
elemental carbon particles
0.1 2 m diameter
particles scatter the
most light per unit
mass.
Sulfates ~ two-thirds
of the visibility
reduction in the
Appalachian Mts.
In southern California,
nitrates are the greatest
contributor to haze,
with organic carbon
also very important.

Dry
Wet
Visual Range Koschmieder
Equation
Distant objects are perceived in terms of
contrast against the background (usually the
sky)
At increasing distances, both bright and
dark objects fade and approach the
horizon of the brightness
Apparent contrast relative to the horizon
decreases
Initial object contrast (C
o
) = ratio of the
object brightness minus the horizon
brightness divided by the horizon
brightness.
For a homogeneous atmosphere (pollutant
concentration, sky brightness), the apparent
contrast decreases with increasing object-
observer distance;
C = C
o
exp(b
ext
x)
b
ext
is the extinction coefficient
x is the observer-object distance.
For a large black object C
o
= -1; assume the
contrast threshold for human perception is
0.02
0.02 = - exp(b
ext
V
r
) and V
r
= 3.912/b
ext
Pristine coastal air: V
r
~ 160-200 km
Remote continental air: V
r
~ 80-120 km
Urban Plume: V
r
~ 5-20 km
Smoke from multiple wildfires in Canada blanketed the eastern U.S.
with a smoke plume nearly 200 miles wide, affecting air quality from
New York to Washington D.C in July 2002. CREDIT: NASA/GSFC.
1981-1985 1986-1990 1991-1995
b
ext
derived from V
r
B. A. Schichtel, et al, Atmospheric Environment 35, 5205-5210 (2001)
Visibility Trends in the Eastern U.S.
Trends in improving visibility in the eastern
U.S. correlate well with the decrease in
SO
2
emissions (precursor to particle
sulfate in the atmosphere) in the U.S.
Air Emissions Trends - Continued Progress Through 2003
http://epa.gov/airtrends/econ-emissions.html
National Air Pollutant Emissions Estimates
for Major Pollutants
This image shows ocean-crossing aerosols as dust from the
Sahara desert is carried over the Atlantic Ocean. Dust and
pollution from Asia floats toward the Pacific Northwest. CREDIT:
NASA/GSFC.
Global Warming
Definitions
Weather: Look out the window
High short-time variability
High, low pressure systems; meandering
jet stream
High spatial variability (E. Lansing vs. Detroit)
Climate
Weather averaged over large areas (sub-
continental global) and long time periods
(decades centuries)
Recent climate change in Michigan?
What Determines Climate?
Physics and Chemistry of the Atmosphere
Greenhouse gases; aerosols
Feedbacks
Water Vapor and Clouds
The Sun
Interactions between Biosphere and
Atmosphere

Natural Climate Variability
Facts
Since ~1800
Earth has warmed 0.8
o
C (since 1880)
GHG atmospheric concentrations have
increased
CO
2
: 280 ppm 370 ppm
CH
4
: 0.7 ppm 1.75 ppm
N
2
O: 270 ppb 320 ppb
Climate is controlled by the
Greenhouse Effect


The Natural Greenhouse Effect
345 Wm
-2
105 Wm
-2
Atmospheric Absorption
68 Wm
-2
Contribution to the Natural Greenhouse
Water 90-98%
Carbon Dioxide 3-5%
Methane <1%
Nitrous Oxide <1%
Contribution to the Natural Greenhouse
Water 90-95%
Carbon Dioxide 5-7%
Methane <1%
Nitrous Oxide <1%
Physics and Chemistry of the
Atmosphere
Greenhouse gas concentrations
Radiative forcings
Feedbacks
Chemistry, physics, meteorology
Water vapor and clouds
Atmospheric CO
2
Concentrations
Currently ~372 ppm
Aerosols/Particles
Major impact on climate
Atmospherically inhomogeneous, short lifetimes
unlike GHGs
Direct Effects Fairly straight-forward
Particles scatter and absorb solar radiation
Light scattering cools (all particles)
Light absorption warms (primarily BC and iron-
containing dust)
Indirect Effects Very difficult to quantify
Cloud formation (condensation nuclei)
Cloud properties (water droplet size; cloud water
content)
Feedbacks
2x CO
2
Direct warming ~0.5-1.0
o
C
Predictions ~5
o
C require positive
climate system FEEDBACKS that amplify
the direct warming from the extra GHGs.
Water vapor
Clouds
Inherent uncertainties in feedback
mechanisms
Water Vapor and Clouds
ICE CRYSTALS
WATER DROPLETS
CLOUDS
PRECIPITATION
WATER
VAPOR
SEA SURFACE - EVAPORATION
On average, clouds cover 40-45% of the Earths surface
Additional 2-3% cloud cover offsets warming from man-
made GHG (+2.5 Wm
-2
)
Model grid scale requirements make it impossible to
directly model clouds and their climate effects

8-Day Atmospheric Water Cycle
The Sun and Global Warming
Correlation Between Solar Cycle and
Surface Temperature
Courtesy of George Wolff (GM)
Dashed line is length of suns magnetic cycle..
Solar Hypothesis

Excellent correlation between solar activity and
temperature for past 30,000 years
Solar activity greatest in last 8000 years
S. Solanki, et al., Nature (28 Oct. 2004)
Change in direct solar forcing ~ 10% of the
observed temperature variation
Solar/climate theory
High solar activity strengthens magnetic barrier which
deflects cosmic particles away from earth (known)
Cosmic particles enhance cloud formation (limited
recent data)


Global Average Radiative Forcing
Baseline: Pre-Industrial Revolution
TAR (IPCC, 2001)
Major Forcing Uncertainties
Black carbon
Very short-lived, strong solar energy absorber
As important as CO
2
?
Aerosol indirect forcing
Aerosols impact cloud formation, cloud characteristics
Offset much of the GHG warming?
Land use changes
Changes planetary surface albedo
Solar influence
An important warming component?
Natural Climate Variability
Natural Climate Variability
What do we know?
140 years of real data, paleo-data, GCM
predictions: +0.2-0.3
o
C
100 Years of Consensus
Example: Sargasso Sea Temperatures
Medieval Warm Epoch
Little Ice Age
Natural Climate Variability
Consensus challenged in 1998 (IPCC 2001) by the
Hockeystick
Minimized the importance of Medieval Warm Epoch;
Little Ice Age regional rather than global event
Regional Climate Cycles
El Nino
-40
-30
-20
-10
0
10
20
30
Jan-81 Jan-86 Jan-91 Jan-96 Jan-01 Jan-06
Date
S
O
I
Australian Bureau of Meteorology
El Nino hot
and dry on
west coast of
Americas
La Nina cold
and rainy on
west coast of
Americas;
intense
drought in
Australia
Global
connections
Existing Issues
Radiative forcing clouds, aerosols
Natural climate variability
Cycles within Cycles within Cycles
Ocean response - Instantaneous climate
shifts freezing in the greenhouse?
Sea level ice melt, thermal expansion; will the
glaciers grow?
Carbon cycle - terrestrial sinks; deforestation
Land use
Extreme weather floods, droughts, hurricanes
Regional climate change - winners and losers
Global Average Surface
Temperatures
GISS Annual Average Surface Temperatures
[Relative to the 1951-1980 Average Annual Temperature]
-60
-40
-20
0
20
40
60
80
1880 1900 1920 1940 1960 1980 2000
Year
T
e
m
p
e
r
a
t
u
r
e

A
n
o
m
a
l
y

(
D
e
g
.

C

x

1
0
0
)
GISS Annual Average Surface Temperatures
[Relative to the 1951-1980 Average Annual Temperature]
-40
-20
0
20
40
60
80
1940 1950 1960 1970 1980 1990 2000 2010
Year
T
e
m
p
e
r
a
t
u
r
e

A
n
o
m
a
l
y

(
D
e
g
.

C

x

1
0
0
)
Great Pacific Climate Shift
1975-1980 - 0.23 deg. C
Since 1976, temperature
has increased 0.17
deg./decade
25-Year Temperature Trends
http://www.junkscience.com/MSU_Temps/CD-Trends.GIF
Arctic Temperature Trends
Graph from JunkScience.com

Arctic Paleoclimate
Overpeck, et al., Science 278, 1251 (1997)
-1.5
-1
-0.5
0
0.5
1
1600 1725 1850 1975
Year
T
e
m
p
e
r
a
t
u
r
e

(
d
e
g
.

C
)
Summer-weighted, Arctic-wide (29 sites)
Annual Temperatures: Proxy Data
T = -0.942 + 0.00313(Year-1600)
For 1600-1800
~0.016 deg./yr for
1880-1950
Commentary
On the Basis of the Facts:
Anthropogenic impacts on climate are occurring
We cannot accurately quantify those impacts
Prediction of future climate is very difficult
Significant issues involving the representation
of climate science, including feedbacks, in
global climate models
Unverifiable assumptions about societal
actions and technological evolution
Linear extrapolations from non-linear
systems

Kyoto Protocol Requirements
2008-2012 Timeframe
(vs. 1990 CO
2
Emissions)
EU
Goal: -8%
Chance of success: uncertain, even with major
emissions cuts associated with UK conversion to
natural gas and the shutdown of East German
industry after 1990
Population trends (UN, 1998): -3% (2010); -5%
(2020)
US
Goal: -7%
Current status: +32% projected for 2010
Population trends: +14% (2010); +21% (2020)
Developing Countries (China, India, Indonesia, S.
Korea) -- NO REQUIREMENTS
Growth In Developed/ Developing
Nations
Billion Metric Tons C/yr
(IPCC Scenario IS92a)
0
2
4
6
8
10
12
14
16
18
20
1990 1992 2000 2005 2010 2025 2100
Rest of World
Former Soviet Bloc
Other OECD
United States
Accumulated CO
2
emissions 1990 to 2100 is
1,500 bmt C.
Results of the Kyoto Protocol

2020 vs 1990
US, OECD CO
2
emissions: 3 GT to 2.8 Gt
RoW CO
2
emissions: 1.8 Gt to 3.0 Gt
Net Effect: Global CO
2
emissions increase from 6
to 8 Gt (vs. 8.2 Gt) -- no measurable progress
2100 vs 1990
US, OECD CO
2
emissions 0 Gt
RoW - emissions increase from about 1.8 to 13.2
Gt
Net Effect: Global emissions increase from 6 to
15.5 Gt (vs. 20 Gt)
CO
2
emissions are 2.5 times 1990 levels
Temperature rises about 1.8
o
C vs. 2.1
o
C for no
reductions T.M.L. Wigley, Geophys. Res. Lett., 25, 2285
(1998)

2300 2200 2100 2000
-1
16
14
12
10
8
6
4
2
0
550 ppm
350 ppm
Emission Pathways
(Fossil Fuels, Deforestation, & Cement Calcination Included)
M
a
n

s

E
m
i
s
s
i
o
n
s

(
B
i
l
l
i
o
n

M

T
o
n
s

C
a
r
b
o
n
/
Y
e
a
r
)
No Controls Assumed
300 Years
Kyoto Commitment Period
2008 TO 2012
Emission
Paths to
Achieve:
Constant 1990 Emissions
T. Wigley, R. Richels, and J. Edmonds, Nature 379, 240 (1996)

Stabilization of Atmospheric CO
2
Stabilization of Atmospheric CO
2

Levels
Massive controls on CO
2
emissions are needed
for stabilization as far as 300 years into the
future.
Stabilization at 550 ppm emissions reduced
~70% from current levels
Stabilization at 350 ppm 85-90% reduction in
emissions (with a period of zero CO
2

emissions around the year 2100).
The specifics of the short-term (25-50 years)
emissions control scenarios have very little
impact on long-term stabilization.

It is certain that society is on a path that will lead
us to atmospheric CO
2
concentrations of at least
550 ppm.
Regional Climate Cycles
NAO: Dominates winter climate variability in the N.
Atlantic region from central North America to Europe and
into Northern Asia.
Positive Phase: N. Atlantic intense winter storms; warm, wet
winters in Europe, eastern US
AO: Controlled by sea level pressure in the Arctic
High index or warm phase: Below normal Arctic SLP,
enhanced upper level westerlies in the N. Atlantic; warm US
winters; warm, wet winters in N. Europe; thinning Arctic sea ice.
PDO: Long-term ocean fluctuation of the Pacific Ocean
Major impacts in the N. Pacific, especially along N. America
Positive (warm) phase: SSTs cool in central, north Pacific, warm
along N. America coast

NAO: Controlled by Icelandic low pressure vs. subtropical high
pressure
Dominates winter climate variability in the N. Atlantic region central North
America to Europe and into Northern Asia.
Positive Phase: N. Atlantic intense winter storms; warm, wet winters in
Europe, eastern US
Negative Phase: Fewer N. Atlantic storms; cold winters (snow) in Europe,
eastern US.
http://www.ldeo.columbia.edu/NAO/
AO: Controlled by sea level pressure in the Arctic
High index or warm phase: Below normal Arctic SLP, enhanced upper
level westerlies in the N. Atlantic; warm US winters; warm, wet winters in
N. Europe; thinning Arctic sea ice.
Low index or cool phase: Above normal Arctic SLP, weak upper level
westerlies; cold US, N. Europe winters; robust Arctic sea ice.
http://jisao.washington.edu/wallace/natgeo/ArcticSubart.pdf
PDO: Long-term ocean fluctuation of the Pacific Ocean
Major impacts in the N. Pacific, especially along N. America
Negative (cool) phase: SSTs warm in central, north Pacific, cool along N.
America coast
Positive (warm) phase: SSTs cool in central, north Pacific, warm along N.
America coast
http://sealevel.jpl.nasa.gov/science/pdo.html