1he 1roposphere

1roposphere: ground level Lo abouL 13 kllomeLers aluLude - maln componenLs (lgnorlng

Lhe normally ever-presenL buL varlable waLer vapor) of an unpolluLed verslon of Lhe
LarLh's aLmosphere are dlaLomlc nlLrogen (n
2
, abouL 78 of Lhe molecules), dlaLomlc
oxygen (C
2
, abouL 21), argon (Ar, abouL 1), and carbon dloxlde (CC
2
, presenLly abouL
0.04).

1he 1roposphere
Source: lnLroducuon Lo ALmospherlc ChemlsLry [!acob 1999]
1ropospherlc composluon
Remaining 0.1%
NOTE: Does not include H
2
O
1ropospherlc ChemlsLry:

l. Pydrocarbons
MeLhane (CP
4
)
Vo|an|e Crgan|c Compounds (VCC)

ll. nlLrogen oxldes
nlLrlc oxlde (nC)
nlLrogen dloxlde (nC
2
)
NC
x
= NC + NC
2
Cxldauon producLs (e.g., PnC
3
)


lll. Sulfur compounds
lv. 8adlcals and oxldanLs
Czone (C
3
)
Pydroxyl radlcal (CP)
Scales of varlablllLy
Sources of Lrace gases
Primary pollutant: directly emitted to the atmosphere
Secondary pollutant: created in the atmosphere
Biogenic emissions AND
Anthropogenic emissions
Alr quallLy: London laLe 1800s
Claude MoneL !"#$% "' ()*+,)-%./0 12%3/$ "' $#.+,45/ ,. /5% '"4 1904
Why ls Lropospherlc ozone lmporLanL?
Reference: Aris et al., Am. Rev. of Respiratory Diseases 1993
After 4hr exposure at 200ppb
Healthy Lung Tissue
Production of tropospheric ozone = F(hydrocarbons, nitrogen oxides, sunlight)

1. At the surface, ozone is a powerful oxidant having detrimental effects on human health and
crop yields.

2. O
3
is formed in the atmosphere, not directly emitted

1ropospherlc ozone
GOAL: Describe and predict how changes in emissions of VOC and NOx will alter
the concentration of ozone on a regional scale.






Questions:

1. What are the sources and magnitude of primary emissions?

2. What chemical reactions occur in the atmosphere that process these emissions
and lead to secondary pollutant production?

3. How are chemicals transported within the atmosphere?

4. What are the removal mechanisms (sinks) for trace gases, radicals, and particles?

Production of tropospheric ozone = F(hydrocarbons, nitrogen oxides, sunlight)

Background Material: Ozone
Stratospheric Ozone:

Protective shield against high energy UV light
Source of O in formation is O
2






Tropospheric Ozone:

Powerful oxidant and respiratory irritant
Source of O is NOT O
2

M O M O O + ! + +
3 2
Where is the O atom from?
Data Courtesy: Dr. Anne Thompson, PSU
Tropospheric Ozone Production
Photolysis of nitrogen dioxide (NO
2
) provides atomic oxygen
Tropospheric Ozone Production
If ozone is the only oxidant, this is a Null Cycle
Tropospheric Ozone Production
Ozone production continues until the chain is terminated
NO
x
! NO + NO
2

Partitioning of Global NO
x
Sources
Source Tg N year
-1

Fuel Consumption
25.6
Biomass Burning
5.8
Soil Emission
8.9
Total
1

40.3
Jaegle et al. Faraday Discussions, 130, 407-423, DOI: 10.1039/b502128f, 2005
NO
x
! NO + NO
2

Satellite Observations of Tropospheric Column NO
2

Tropospheric Column Nitrogen Dioxide (NO
2
)
Color scale in molecules NO
2
cm
-2

Data source: NASA/KMNI OMI Instrument AURA Satellite
Satellite Observations of Tropospheric Column NO
2

Anthropogenic Pollution
Satellite Observations of Tropospheric Column NO
2

Biomass Burning
Satellite Observations of Tropospheric Column NO
2

Why does this image look so nice?
Reactive Nitrogen Cycle: NO
x
Reservoirs
NO
y
! NO
x
+ "PNs + "ANs + HNO
3
+ "
Teaser: Reactive Nitrogen (NO
y
) Partitioning
A
8
150 km
B. Aged Air
NO
x

"PNs
"ANs
HNO
3

A
8
Reactive Nitrogen (NO
y
) Partitioning
150 km
"PNs
HNO
3

"ANs
NO
x

A. Near Source
Aircraft Observations of NO
y
Partitioning
INTEX-B Spring 2006
MILAGRO Spring 2006
INTEX-A Summer 2004
PAVE Winter 2005
TC
4
Summer 2007
NO
x
(NO + NO
2
) "PNs (Total Peroxynitrates) "ANs (Total Alkylnitrates) HNO
3
(Nitric Acid)
In order to accurately describe P
ozone
need to understand:
I. NO
x
and HO
x
sources
II. NO
y
partitioning
III. Transport of NO
x

Ozone Production
Constraints on Global Ozone Production Rates
Chemical
Transport
Model
Inflow Outflow
[x]
Emission
Deposition
Chemical
production
Chemical
loss
In each box:
Model Data Courtesy: Dr. Shiliang Wu, Harvard University
Constraints on Global Ozone Production Rates
Chemical
Transport
Model
Inflow Outflow
[x]
Emission
Deposition
Chemical
production
Chemical
loss
In each box:
Model Data Courtesy: Dr. Shiliang Wu, Harvard University
Czone ln Lhe Lroposphere? ConLrol sLraLegles?
Ar|e Ian naagen-Sm|t (CalLech)
C
3
producuon

= l (nC
x
, vCC, h#)
Czone ln LA: ln Lhe 1970s
Czone ln Lhe Lroposphere: Pow much ls Lhere?
Czone sLandards
0 20 40 60 80 100 120 ppb
Lurope ACS
(seasonal)
u.S. ACS
(8-h avg.)
relndusLrlal
ozone
background
resenL-day ozone
background aL norLhern
mld-lauLudes
Lurope ACS
(8-h avg.)
Mexlcan ACS
(1-h avg.)
2008
ACS = Alr CuallLy SLandard
CLD SLandard [80ppb 8hrs] 2008 SLandard [73ppb 8hrs]
Czone sLandards
need Lo undersLand whaL drlves C
3
producuon ln order Lo conLrol lL!
Speclc Lxamples
C
3
producuon ln nC
x
llmlLed and vCC llmlLed reglmes
C
3
producuon ln nC
x
llmlLed and vCC llmlLed reglmes
keduce |eve| of reactants |.e. NC
x
, VCCs (hydrocarbons)
Most common -reduce hydrocarbons but |n many urban areas,
NC
x
determ|nes rate of reacnon
Caveat: n|gh hydrocarbons from natura| sources, dec|duous trees
em|t h|gh|y reacnve terpenes [e.g., |soprene]
Lower temp of combusnon ( NC
x
)
Cata|ync converters eecnve |n remov|ng 80-90 of
hydrocarbons+CC + NC
x
from auto exhaust
Correct a|r fue| m|xture
SLraLegles Lo reduce C
3
levels
Lxample: WhaL ls mlsslng from Lhls plcLure?
keduce |eve| of reactants |.e. NC
x
, VCCs (hydrocarbons)
Most common -reduce hydrocarbons but |n many urban areas,
NC
x
determ|nes rate of reacnon
Caveat: n|gh hydrocarbons from natura| sources, dec|duous trees
em|t h|gh|y reacnve terpenes [e.g., |soprene]
Lower temp of combusnon ( NC
x
)
Cata|ync converters eecnve |n remov|ng 80-90 of
hydrocarbons+CC + NC
x
from auto exhaust
Correct a|r fue| m|xture
SLraLegles Lo reduce C
3
levels
Lxample: WhaL ls mlsslng from Lhls plcLure?
Answer: vapor recovery sysLem

CaLalyuc ConverLers
1wo-way cata|ync converter:

ConverL CC and unburned hydrocarbons lnLo CC
2

used on gasollne englnes unul ~1980

unable Lo conLrol nC
x
emlsslons

CaLalysL: launum (oxldlzlng caLalysL)

Mechanlsm:


CaLalysL lowers L
a
(Lhus
lncreaslng Lhe raLe of Lhe
reacuon, buL has no eecL on
Lhe Lhermodynamlcs of Lhe
overall reacuon.
Cx|danon chamber (|annum cata|yst)
2CC + C
2
2CC
2
C
n
P
m
+ (n + m/4) C
2
nCC
2
+ m/2 P
2
C


CaLalyuc ConverLers
Alr polluuon regulauons
C|ean A|r Act - uS lederal Law. Lnforced by Lhe LA Lo develop and enforce regulauons
Lo proLecL Lhe general publlc from exposure Lo alrborne conLamlnanLs"

llrsL passed ln 1963, amended many umes

LsLabllshes Lhe nauonal AmblenL Alr CuallLy SLandards (nAACS)

o||utant 1ype Averag|ng
1|me
Standard
SC
2
rlmary 24-hour 140 ppb
CC rlmary 1-hour 33 ppm
CC rlmary 8-hour 9 ppm
C
3
Secondary 1-hour 120 ppb
C
3
Secondary 8-hour 73 ppb
nCx rlmary / Secondary annual 33 ppb
M (2.3) rlmary / Secondary 24-hour 13 g m
-3

Alr quallLy - have regulauons been successful?
Alr quallLy - have regulauons been successful?
Alr quallLy - have regulauons been successful?
CZCnL 18LnuS ln u.S.
hup://www.epa.gov/alrLrends/
8osLon Lrend
nauonal Lrend
Confoundlng facLors - changlng global background
0 20 40 60 80 100 120 ppb
u.S. ACS
(8-h avg.)
relndusLrlal
ozone
background
resenL-day ozone
background aL norLhern
mld-lauLudes
2008
1996 - 2002
$ 1ropospher|c Co|umn
4.0 x 10
16
mo|. cm
2



~13 ppbv lncrease ln nC
2


8lchLer eL al., 6)/#*% 2003
Changlng nC
x
Lmlsslons
Where ls Lhls lmporLanL?
Clobal changes ln nlLrogen emlsslons
Lmlsslons lnvenLory
SaLelllLe observauons
1ropospherlc C
3
ls a global problem
eroxynlLraLes
eroxynlLraLes
Intercontinental Transport of NO
y
Wind Speed [m sec
-1
] x [NO
y
] [molecules cm
-3
]
Intercontinental Transport of NO
y
Comparison to NO
x
Emission Estimates:
1,2
East Asia Top Down 2004-2005 [Martin et al., 2006] 0.039 Tg N day
-1


2
China Bottom Up 2004 [Zhang et al., 2007] 0.051 Tg N day
-1

1
Sample Region [70E 150E, 11N 55N]
2
Based on annual average emission rate
Fraction carried by: NO
x
= 0.10 "PNs = 0.62 "ANs = 0.05 HNO
3
= 0.23


NO
y
Flux 0.007 0.002 Tg N day
-1

Cuesuons?