Atmospheric Chemistry

SARP: Atmospheric chemistry
Sally Pusede
University of Virginia
Alex Kotsakis
University of Houston
London smog
Los Angeles, California, 1950s.
Los Angeles (photochemical) smog
Ozone (O3) trends: O3 is not emitted but

chemically formed in the atmosphere
D. D. Parrish and W. R. Stockwell, EOS, 2015.
Los Angeles today
Los Angeles, California, present day.
The fundamental chemistry

organic emissions (VOCs): biogenic / anthropogenic
forests, chemical processing, agriculture
organic
molecule
OH
RH
+
sunlight-driven source

organic reactivity: concentration of a given
species weighted by its reaction rate with OH
organic
molecule
OH
RH
+

organic reactivity
organic
molecule
OH
RH
O2
RO2 + H2O

organic reactivity
organic
molecule
OH
RH
RO2
NO
RO
NO is emitted by
combustion processes:
cars, trucks, power
plants, fires
NO + NO2 = NOx
NO2

1. NOx
2. organic reactivity
3. HOx source
organic reactivity
organic
molecule
OH
RH
RO2
NO
RO
NOx is emitted by
cars, trucks, power
plants, fires
NO2
O3
A sense for the complexity

organic reactivity
organic
molecule
NO2
OH
RO2
NO
light
O3
RH
NO
HO2
NO2
O3
RO
oxidized organic
molecules
cars, trucks, power
plants, fires
biogenic / anthropogenic emissions

organic reactivity
aerosol acid rain

HNO3 organic
(PM)
RO2NO2
molecule
NO2
OH
RH
RO2
NO
O3
NO
HO2
RO
oxidized organic
molecules
cars, trucks, power
plants, fires
NO2
NO2
O3
O3
aerosol
RONO2
(PM)
NO2
O3
aerosol (PM)

organic reactivity
aerosol acid rain

HNO3 organic
(PM)
RO2NO2
molecule
NO2
h
O3
OH
OH
RH
1 x 1011%!
HO2
NO
RO2
NO
RO
oxidized organic
molecules
cars, trucks, power
plants, fires
NO2
NO2
O3
O3
aerosol
RONO2
(PM)
NO2
O3
Pollutant lifetime and spatial scale of impacts
Tropospherestratosphere exchange
Inter-hemispheric
mixing
Intra-hemispheric
mixing
Boundary layer
mixing

organic reactivity
aerosol acid rain

HNO3 organic
(PM)
RO2NO2
molecule
NO2
OH
RH
RO2
NO
O3
NO
HO2
RO
oxidized organic
molecules
cars, trucks, power
plants, fires
NO2
NO2
O3
O3
aerosol
RONO2
(PM)
NO2
O3
aerosol (PM)
Ozone (O3) chemistry is a nonlinear function of:
O3 production (ppb h1)
1. NOx
2. organic reactivity
3. HOx source
analytical model
30
30
20
20
10
10
0
0
10
NOx abundance (ppb)
15
0
0
Ozone (O3) chemistry is also a nonlinear function

of organic reactivity
ORGANIC REACTIVITY: concentration of a given
organic compound weighted by how reactive it is.
30
organic reactivity:
15 s1
10 s1
5 s1
30
20
20
10
10
0
0
10
NOx abundance (ppb)
15
0
0
Ozone (O3) chemistry is a nonlinear function of

both NOx and organic reactivity
NOxsensitive
organic reactivitysensitive
30
organic reactivity:
15 s1
10 s1
5 s1
30
20
20
10
10
0
0
10
NOx abundance (ppb)
15
0
0
Nitrogen dioxide (NO2) is a reactive trace gas

0.01100 ppb
NO2 (molecules cm2)
9 10x1015
MayOctober 20052006
weekdays

both NOx and organic reactivity
rural
urban
30
organic reactivity:
15 s1
10 s1
5 s1
30
20
20
10
10
0
0
10
NOx abundance (ppb)
15
0
0

0.01100 ppb
NO2 (molecules cm2)
9 10x1015
MayOctober 20052006
weekdays

0.01100 ppb
NO2 (molecules cm2)
9 10x1015
MayOctober 20122013
weekdays

0.01100 ppb
NO2 (molecules cm2)
9 10x1015
MayOctober 20122013
weekends
Large decreases in nitrogen oxides (NOx) over

the last decade across the U.S.
MayOctober 20122013
In U.S. cities,
urban
rural chemistry.
OMI Berkeley High-resolution Retrieval (BEHR)

0
NO2 (molecules cm2)
10x1015
Thinking globally
Globally, air pollution is a growing problem.
Anthropogenic emissions are increasing.
NO2 (molecules cm2)
OMI image courtesy of NASA GES DICS
2011
9 10x1015
In high NOx cities, chemistry is strongly coupled to temperature.
Anthropogenic drivers of atmospheric

composition
Oildale, California

composition
Wasco County, California

both NOx and a diverse array of organic reactivity
rural
urban
30
15
temperature:
hot
moderate
cool
20
10
0
0
10
NOx abundance (ppb)
15
Ozone (O3) trends: O3 is not emitted but

chemically formed in the atmosphere
D. D. Parrish and W. R. Stockwell, EOS, 2015.
How do we do an experiment in the atmosphere?

On chemistry in a past atmosphere?
NOx sensitive
30
30
organic reactivity:
15 s1
10 s1
5 s1
20
10
0
0
20
10
10
NOx abundance (ppb)
15
0
0
10
15

Day of week and interannual trends in NOx
taken together
are a constraint on trends in nonlinear chemistry,
especially when combined with temperature.
NOx sensitive
30
30
organic reactivity:
15 s1
10 s1
5 s1
20
10
0
0
20
10
10
NOx abundance (ppb)
15
Pusede, S. E. and Cohen, R. C.: Atmos. Chem. Phys., 2012.

0
0
5Pusede, 10
15 Atmos. Chem. Phys., 2014.
S. E. et al.:
Pusede, S. E. et al.: Atmos. Chem. Phys., 2016.

taken together
How has urban O3 chemistry changed?


taken together
How has urban O3 chemistry changed?

How will O3 chemistry change due to future?
altered emissions and weather

Study area: San Joaquin Valley, California

Severe O3 air pollution
San
Francisco
History of emission controls

Highly regular meteorology
e.g., cloudless skies,
regular winds
50 mi
100 km
Los Angeles

San
Francisco
50 mi
100 km
Northern Valley
Northern Valley
San
Francisco
Southern Valley
Southern Valley
Los Angeles
Los Angeles

NO2 (molecules cm2)
x1015
9 10
Temperaturecombined with NOxgives insight

into trends in O3
analytical model
ozone production
1
0.75
0.75
0.5
0.5
0.25
0.25
0
0
12 15 18
0
0
1
0.75
0.5
0.25
0
0
12 15 18
NO2
12 15 18
0.75
0.75
0.75
0.5
0.5
0.5
0.25
0.25
0.25
0
0
12 15 18
0
0
12 15
12 15

into trends in O3
O3 exceedance
probability
1
0.75
0.5
0.25
0
0
12 15 18
1
0.75
0.5
0.25
0
0
12 15 18
12 15
12 15
NO2 (ppb)
1
0.75
0.5
0.25
0
0
12 15 18
0.75
0.75
0.75
0.5
0.5
0.5
0.25
0.25
0.25
0
0
12 15 18
0
0

into trends in O3
observations
O3 exceedance
probability
1
0.75
0.5
0.25
1
0.75
0.75
0.5
0.5
0.25
0
0
20032006
3
12 15 18
NO2 (ppb)
0.75
0.5
0.25
0
0
weekends
0.25
weekdays
12 15 18
0.75
0.75
0.5
0.5
0.25
0.25
0
0
12 15 18
0
0
12 15

into trends in O3
O3 exceedance
probability
Northern Valley: urban core
plume center
1
0.75
0.5
0.25
0
0
20032006
3
12 15 18 0
12 15 18 0
weekdays
weekends
3
12 15 18
NO2 (ppb)
1
0.75
0.5
0.25
0
0
downwind
12 15 18
0.75
0.75
0.75
0.5
0.5
0.5
0.25
0.25
0.25
0
0
12 15 18
0
0
12 15

into trends in O3
plume center
downwind
O3 exceedance probability
high T: 3445oC
0.75 48 days year1
0.5
0.25
20032006
weekdays
weekends
moderate T: 2833oC
0.75 79 days year1
0.5
0.25
0
0
12 15 18 0
12 15 18 0
12 15 18
NO2 (ppb)

into trends in O3
plume center
downwind
high T: 3445oC
0.75 48 days year1
0.5
weekdays
weekends
0.25
1
moderate T: 2833oC
0.75 79 days year1
19992002
20032006
20072010
0.5
0.25
0
0
12 15 18 0
12 15 18 0
12 15 18
NO2 (ppb)

into trends in O3
plume center
downwind
high T: 3445oC
0.75 48 days year1
0.5
weekdays
weekends
0.25
1
moderate T: 2833oC
0.75 79 days year1
19992002
20032006
20072010
0.5
0.25
0
0
12 15 18 0
12 15 18 0
12 15 18
NO2 (ppb)
Decreases in organic emissions have greatly impacted the

number of violations. NOx effects are location and year specific.

into trends in O3
Northern Valley: plume center
15
6 18
9
0.75
0.75
0.75
0.75
0.5
0.5
0.5
0.25
0.25
0.25
high T: 3445oC
moderate T: 2833oC
0.75
0.75
0.5
0.5
0.25
0.25
0
12 150 183
0
9
0
weekdays
weekends
0.75
0.5
0.25
12
3 15
6 18
9
NO2 (ppb)
Southern Valley:
0.5
0.25
1
plume center
19992002
20032006
20072010
0.75
0.5
0.25
0
12 015 318 6
0
90
12
3 15
6 18
9
120 153 186
NO2 (ppb)
Evidence for 2 distinct kinds of organic sources, dominate at

different temperatures, that exhibit different inter-annual trends.

CALifornia at the NEXus of Air Quality and
Climate Change (CALNEX) experiment
18 May29 June 2010
San
Francisco
Northern Valley
Southern Valley
CALNEX-SJV
50 mi
100 km
Los Angeles

A wide suite of nitrogen oxides, +120 organic
compounds, OH, total OH reactivity, O3, HOx
source molecules, and many other parameters.

e.g., cloudless skies,
regular winds
Observed organic reactivity is either temperature

independent or temperature dependent
mixing ratio (ppb)
0.6
o-xylene
daily average
(10 am2 pm)
0.06
0.4
0.04
0.2
0.02
0
6.0
0
6.0
formic acid
4.0
4.0
2.0
2.0
162
164
166
168
170
172
174
day of year (10 June28 June 2010)
176
178
0
15
20
25
30
35
daily maximum
temperature (oC)
Organic compounds arise from multiple sources: Some are independent of

temperature, others are known to be temperature dependent.
40
Observed organic reactivity is either temperature

independent or temperature dependent
12
T-independent speciated reactivity:
organic reactivity (s1)
reactivity
T-independent
T-dependent reactivity
10
Molecules associated with light-duty

vehicle tailpipe emissions
T-dependent measured reactivity:

6
Molecules are mostly small aldehydes,

small alcohols, or are unidentified.
4
2
0
2
15
20
25
30
35
40
daily maximum temperature (oC)
Reactivity: concentration of a given species weighted by its OH reaction rate.

Pusede S. E. et al.: Atmos. Chem. Phys., 2014.
Temperature-reactivity relationships give insight

into decadal trends in organic reactivity
12
T-independent speciated reactivity:

Controlled reactivity
organic reactivity (s1)
reactivity
controlled
uncontrolled reactivity
10
Well-documented controls on light-duty

vehicle emissions over the last decade.
higher
reactivity a
6 decade ago
8
T-dependent measured reactivity:

Uncontrolled reactivity
Know of no deliberate effort to control

this reactivity.
2
0
2
15
20
25
30
35
40
Reactivity: concentration of a given species weighted by its OH reaction rate.

Understanding the past to predict the future:

15
Effects
of controls are temperature dependent
% change in O3 production
10
5
50
50%
NOx
25
weekday
Large impacts at the highest

temperatures.
0
25
weekend
50
15
20
25
30
35
40
50 maximum temperature (oC)

daily
25
0
25
50
15
20
25
30
35
40
Effects of controls are temperature dependent

15
10
5
50
50%
NOx
% change in O3 production
25
weekday

temperatures.
0
25
weekend
50
50
50%
T-independent
25
organic reactivity
0
25
50
15
20
25
30
35
Large impacts at low temperatures;

no impact at high temperatures:
Controllable organics are a small fraction of
the total.
Chemistry is not very sensitive to changing
organics.
40

8-h O3 exceedances
exceedances in 2010
in 2010:
93 total 27
50
25
0
0
% change
in Oin3 PO
production
change
(%)
3
0
0
50%
NOx
weekday
weekend
NOx reductions are effective when

high O3 is most frequent.
25
25
50
50
20
15
10
5
0

temperatures.
50
50%
T-independent
25
organic reactivity
0
25
0
15
64
15
15
10
10
55
00
50
15 30
20
25
30
25
20 35
25 40
30 35
35 40
40
Large impacts at low temperatures;

no impact at high temperatures:
Controllable organics are a small fraction of
the total.
Chemistry is not very sensitive to changing
organics and will be even less so in the next
decade.
temperature
( C)
daily maximum
temperature
(oC)

8-h O3 exceedances
exceedances in 2010
in 2010:
93 total 27
50
25
0
0
% change
in Oin3 PO
production
change
(%)
3
0
0
50%
NOx
NOx reductions are effective when

high O3 is most frequent.
25
25
50
50
20
15
10
5
0
weekday
weekend
50
50%
T-independent
25
organic reactivity
0
25
0
15
64
15
15
10
10
55
00
Without the temperature

context we emphasize
the wrong controls!
50
15 30
20
25
30
25
20 35
25 40
30 35
35 40
40
o
temperature
( C)
daily maximum
temperature
(oC)
Outstanding questions:
What sources/molecules drive organic reactivity

in California? What is the resulting chemistry?
Clues:
emissions are temperature driven
unaccounted for by previous measurements
form alkyl nitrate (RONO2) in very low rates
1
NO + RO2
NO2 + RO
RONO2
O3
Perring, A. E., Pusede S.E., and Cohen, R. C.: Chem. Rev., 2013.

1
NO + RO2
O3
NO2 + RO
RONO2
Suppressed RONO2 formation enhances O3 production:

35
15
10
5
0
w observed = 2%
w Los Angeles = 7%
30
20
organic reactivity:
3.06.0 s1
0
10
NOx (ppb)
15
PO3 (ppb h1)
PO3 (ppb h1)
25
25
20
15
10
organic reactivity:
7.012.0 s1
5
0
10
15
NOx (ppb)
20

Clues:
1
NO + RO2
NO2 + RO
RONO2
O3
Tools: new measurements, spatially resolved in

the region during SARP
Fresno
Fresno
Bakersfield
0 1
3 4
NO2 (molecules
7 8
9 10
cm2)
Bakersfield

composition
Oildale, California

composition
Harris Ranch, California

composition
Almond trees, San Joaquin Valley, California
2015 USDA crop data

Fresno
Fallow
Cotton
Almonds
Grapes
Oranges
Winter wheat
Urban
Alfalfa
Bakersfield
2011 USDA crop data

Fresno
Fallow
Cotton
Almonds
Grapes
Oranges
Winter wheat
Urban
Alfalfa
Bakersfield

Clues:
1
NO + RO2
NO2 + RO
RONO2
O3
How have this chemistry and these sources

been affected by the drought?

Clues:
1
NO + RO2
NO2 + RO
RONO2
O3

What about Los Angeles?
Atmospheric composition: greenhouse gases

N2O is long-lived greenhouse gas and stratospheric O3 destroyer;
trending upward.
Sources are poorly constrained. In the San Joaquin Valley, agricultural
activities large emissions.
Free-troposphere N2O
328
326
Increasing at ~0.8 ppb N2O year1
N
N22O (ppb)
324
322
320
318
316
annual means
Mauna Loa Observatory (NOAA ESRL)
314
2000 2002 2004 2006 2008 2010 2012 2014
year
year
Horizontal variability in N2O: spatial patterns

match those of other agricultural emissions
N2O matches patterns in agricultural emissions
Fresno
Fresno
3
328
4
329
5
330
6
331
N2O (ppb)
Bakersfield
350
550 2600
750
2200 2400
20 40 60 80
CH4 (ppb)
Bakersfield
N2O and CH4 measured by the DACOM in the afternoon within the
boundary layer (determined by individual profiles)
Horizontal variability in N2O: spatial patterns

match those of other agricultural emissions
near-surface N2O
agricultureassociated N2O
emissions
Fresno
Visalia
3 329
4 330
5 331
6
328
ppb
10
20
30
tons y1
Bakersfield
Horizontal variability in N2O: spatial patterns are

poorly represented
agricultureassociated N2O
emissions
near-surface N2O
all N2O
emissions
Fresno
Visalia
3 329
4 330
5 331
6
328
ppb
50
100
50
100
tons y1
Bakersfield
50
100
50
100
tons y1
EDGAR 2010
Summertime aircraft study (2010) found large differences in spatial

patterns and estimated agricultural emissions to be 34 times greater
than annual means strong N2O seasonality.
Xiang et al., GRL, 2013
Quantifying atmospheric composition

Exploiting a physical property of a gas or particle
Ideally a unique property because the atmosphere is a
complicated matrix.
Some qualities of a good measurement: Ask how these are
achieved!
accuracy
precision
sensitivity
selectivity
sampling efficiency
response time
data coverage
DACOM-Differential absorption CO measurement
NASA Langley
(Glenn Diskin)
DACOM-Differential absorption CO measurement
DLH-Diode laser hygrometer

NASA Langley
(Glenn Diskin)

Exploiting a physical property of a gas or particle
Ideally a unique property because the atmosphere is a
complicated matrix.
Some qualities of a good measurement: Ask how these are
achieved!
accuracy
precision
sensitivity
selectivity
sampling efficiency
response time
data coverage

Clues:
1
NO + RO2
NO2 + RO
RONO2
O3

What about Los Angeles?

Atmospheric Chemistry

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SARP: Atmospheric chemistry

Los Angeles, California, 1950s.

Los Angeles (photochemical) smog

Ozone (O3) trends: O3 is not emitted but

D. D. Parrish and W. R. Stockwell, EOS, 2015.

Los Angeles today

Los Angeles, California, present day.

The fundamental chemistry

The fundamental chemistry

The fundamental chemistry

The fundamental chemistry

The fundamental chemistry

A sense for the complexity

biogenic / anthropogenic emissions

A sense for the complexity

aerosol acid rain

biogenic / anthropogenic emissions

A sense for the complexity

aerosol acid rain

biogenic / anthropogenic emissions

Pollutant lifetime and spatial scale of impacts

A sense for the complexity

aerosol acid rain

biogenic / anthropogenic emissions

Ozone (O3) chemistry is a nonlinear function of:

O3 production (ppb h1)

NOx abundance (ppb)

Ozone (O3) chemistry is also a nonlinear function

O3 production (ppb h1)

NOx abundance (ppb)

Ozone (O3) chemistry is a nonlinear function of

O3 production (ppb h1)

NOx abundance (ppb)

Nitrogen dioxide (NO2) is a reactive trace gas

NO2 (molecules cm2)

Ozone (O3) chemistry is a nonlinear function of

O3 production (ppb h1)

NOx abundance (ppb)

Nitrogen dioxide (NO2) is a reactive trace gas

NO2 (molecules cm2)

Nitrogen dioxide (NO2) is a reactive trace gas

NO2 (molecules cm2)

Nitrogen dioxide (NO2) is a reactive trace gas

NO2 (molecules cm2)

Large decreases in nitrogen oxides (NOx) over

OMI Berkeley High-resolution Retrieval (BEHR)

NO2 (molecules cm2)

NO2 (molecules cm2)

OMI image courtesy of NASA GES DICS

In high NOx cities, chemistry is strongly coupled to temperature.

Anthropogenic drivers of atmospheric

Anthropogenic drivers of atmospheric

Wasco County, California

Ozone (O3) chemistry is a nonlinear function of

O3 production (ppb h1)

NOx abundance (ppb)

Ozone (O3) trends: O3 is not emitted but

D. D. Parrish and W. R. Stockwell, EOS, 2015.

How do we do an experiment in the atmosphere?

O3 production (ppb h1)

NOx abundance (ppb)

How do we do an experiment in the atmosphere?

O3 production (ppb h1)

NOx abundance (ppb)

Pusede, S. E. and Cohen, R. C.: Atmos. Chem. Phys., 2012.

How do we do an experiment in the atmosphere?

How has urban O3 chemistry changed?