Atmospheric Chemistry

C2.4
Lecture 3

Anoop S. Mahajan
anoop@tropmet.res.in

Centre for Advanced Training (CAT) course, Indian Institute of Tropical Meteorology (IITM)
Dr. Homi Bhabha Road, Pashan, Pune 411 008, INDIA
 The main chemicals
Gas Smog Acid Turbidity of Greenhouse Stratospheric Influence on
Rain the effect ozone self cleaning
atmosphere depletion of the
atmosphere

CO2 + +/-
CH4 + +/- +/-
CO + -
N2O + +/-
NOx + + + +/- +/-
SO2 + + + -
VOCs + + +
CFCs + +
O3 + + + +
 Ozone
The many faces of atmospheric ozone:

In stratosphere: 250-350 DU, UV Protection

Stratosphere:
90% of total

In middle/upper troposphere: greenhouse gas

Troposphere
15-40 DU

In lower/middle troposphere: precursor of OH,

main atmospheric oxidant

In surface air: toxic to humans and vegetation

 Earth’s radiative spectrum

TERRESTRIAL RADIATION SPECTRUM FROM SPACE:

composite of blackbody radiation spectra emitted from different altitudes at different temperatures
 Ozone as a GHG

Greenhouse radiative forcing of climate between 1750 and 2005

IPCC,2007
 Ozone as a pollutant

Ozone is a major pollutant. It does

billions of dollars worth of damage to
agricultural crops each year and is the
principal culprit in photochemical
smog.

Ozone, however, exists throughout the

troposphere and, as a major OH source
and a greenhouse gas, plays a central
role in many biogeochemical cycles.

That photochemical processes produce

and destroy stratospheric ozone have
been recognized since the thirties, but
the importance of photochemistry in
tropospheric ozone went unrecognized
until the seventies.
 Ozone as a pollutant

Lungs Eyes

Irritation

Respiration
Plants and vegetation
 Ozone in the troposphere
The classical view of tropospheric ozone was provided by Junge (Tellus, 1962) who
looked at all the available ozone observations from a handful of stations scattered
over the globe.
Free tropospheric concentrations appeared to be fairly uniform, but boundary layer
concentrations were reduced. He also noticed a repeating annual cycle with spring
maxima and fall minima.
Tropospheric ozone maxima lagged stratospheric maxima by about two months. From
this he concluded that ozone is transported from the stratosphere into the troposphere
where it is an essentially inert species, until it contacts the ground and is destroyed.
The implied residence time varies from 0.6 to 6.0 months.

• Source – Stratosphere
• Sink – Surface deposition
• Chemistry – Little or none
• Lifetime 0.6 to 6.0 mo
 Ozone in the troposphere
Levy (Planet. Space Sci., 1972) first suggested that radicals could influence the chemistry of the
troposphere, and Crutzen (Pageoph, 1973), shortly followed by Chameides and Walker (J.
Geophys. Res., 1973), pointed out that these radical reactions could form ozone in the nonurban
troposphere. Chameides and Walker’s model predicted that the oxidation of methane (alone) in
the presence of NOx would account for all the ozone in the troposphere and that ozone has a
lifetime of about 1 day. Chatfield and Harrison (J. Geophys. Res., 1976) countered with data that
show the diurnal variation of ozone in unpolluted sites is inconsistent with a purely photochemical
production mechanism and showed that meteorological arguments could explain most of the
observed ozone trends described by Chameides and Walker.

Radical View
• Source – CH4 + NOx + hn
• Sink – Surface and reaction with HOx
• Lifetime – 1 d
Image from Pasadena, CA 1973
(Finlayson-Pitts and Pitts, 1977).
 Ozone in the troposphere

To summarize, chemists found a possible major anthropogenic perturbation

of a vital natural process.
In their zeal to explain this problem some of the chemists completely
neglected the physics of the atmosphere.
This irritated some meteorologists, who point out that one can equally well
interpret the observations in a purely meteorological context.
With the dust settled, we can see that the physics of the atmosphere controls
the day-to-day variations and the general spatial structure, but chemistry can
perturb the natural state and cause long term trends.

Copyright © 2010 R.R. Dickerson 10

 Chemistry in the troposphere

THE TROPOSPHERE WAS VIEWED AS CHEMICALLY INERT UNTIL 1970

• “The chemistry of the troposphere is mainly that of a large number

of atmospheric constituents and of their reactions with molecular
oxygen…Methane and CO are chemically quite inert in the
troposphere” [Cadle and Allen, Atmospheric Photochemistry,
Science, 1970]
• Lifetime of CO estimated at 2.7 years (removal by soil) leads to
concern about global CO pollution from increasing car emissions
[Robbins and Robbins, Sources, Abundance, and Fate of Gaseous
Atmospheric Pollutants, SRI report, 1967]
 Oxidation in the troposphere

FIRST BREAKTHROUGH:
• Measurements of cosmogenic 14CO place a constraint of ~ 0.1 yr on the
tropospheric lifetime of CO [Weinstock, Science, 1969]

SECOND BREAKTHROUGH:
• Tropospheric OH ~1x106 cm-3 predicted from O(1D)+H2O, results in
tropospheric lifetimes of ~0.1 yr for CO and ~2 yr for CH4 [Levy, J.
Geophys. Res. 1973]

THIRD BREAKTHROUGH:
• Methylchlroform observations provide indirect evidence for OH at levels
of 2-5x105 cm-3 [Singh, Geophys. Res. Lett. 1977]

…but direct measurements of tropospheric OH had to wait until the 1990s

 Ozone – stratosphere - troposphere

O2  h  O  O
O  O2  M  O3  M
O3  h  O2  O (1 D )
O(1 D )  M  O  M
XO  O  X  O2
By contrast, in troposphere:

• no photons < 240 nm

 no oxygen photolysis;

• nelgible O atom conc. O2+hv

g no XO + O loss O3+hv
So what is driving tropospheric ozone?
 Ozone – stratosphere - troposphere

CONSTRAINT ON CROSS-TROPOPAUSE OZONE FLUX

FROM OBSERVED OZONE-NOy CORRELATION
IN LOWER STRATOSPHERE
NOy / N 2O  0.073 (  14%)

N 2O  O(1 D)  2 NO NOy chemical family

Oxidation products (HNO3, etc.)

FN2O = EN2O in lower strat.: NOy / O3  0.0033 (  12%)

tropopause
FN 2O (NOy / N 2O)
FO 3   540  140 Tg O3 yr -1
NOy / O3

EN2O = 13 Tg N yr-1 (±17%)

 Ozone – stratosphere - troposphere

tropopause
FO 3  540  140 Tg O3 yr -1
Chemical loss:
O(1 D)  H 2O  2OH
OH  O3  HO2  O2 LO 3  4600  700 Tg O3 yr -1
DO 3  1000  200 Tg O3 yr -1

HO2  O3  OH  2O2
deposition

Ozone chemical loss is driven by photolysis

frequency J(O3 gO(1D)) at 300-320 nm:

J   q ( ) ( ) I ( )d 
0

dJ/dl, 10-6 s-1 nm-1

Closing the tropospheric ozone budget requires
a tropospheric chemical source >> FO3
Tropospheric ozone production

CLEAN AIR
(1) O3 + h  O2 + O(1D)
 
(2) O(1D) + H2O  2OH
 
(3) OH + O3  HO2 + O2
 
(4) HO2 + O3  2O2 + OH
-----------------------------------------
(3+4) 2O3  3O2 NET
Tropospheric ozone production

DIRTY AIR
(3') OH + CO  H + CO2
 
(4') H + O2 + M  HO2 + M
 
(5') HO2 + NO  NO2 + OH
 
(6') NO2 + h  NO + O
 
(7') O + O2 + M  O3 + M
-------------------------------------------------
(3'-7') CO + 2 O2  CO2 + O3 NET
 Tropospheric ozone production

SIMILAR REACTION SEQUENCE FOR METHANE

CH4 + OH® CH3 + H2O

CH3 + O2 + M® CH3O2 + M
CH3O2 + NO® NO2 + CH3O
CH3O + O2 ® H2CO + HO2
HO2 + NO® NO2 + OH
NO2 + hn ® NO + O
O + O2 + M® O3 + M
--------------------------------
CH4 + 4O2 + hn ® 2O3 + H2CO + H2O NET
 Tropospheric ozone production

What is the fate of formaldehyde?

2H2CO + hn ® H2 + CO
® HCO + H
H + O2 + M® HO2 + M
HCO + O2 ® HO2 + CO
------------------------------
2H2CO + 2O2 ® 2CO + 2HO2 + H2

The grand total is 4 O3 per CH4 oxidized!

 Tropospheric ozone production

What constitutes sufficient NO to make ozone photochemically?

HO2 + O3  2O2 + OH (4)

HO2 + NO → NO2 + OH (5)

When R4 = R5 then k4[O3] = k5[NO] and production matches loss.

This happens around [NO] = 10 pptv

Copyright © 2010 R.R. Dickerson 21

 Tropospheric ozone production

Chain terminating steps:

NO2 + OH + M → HNO3 + M
HO2 + HO2 → H2O2 + O2

These reactions remove radicals and stop the catalytic cycle of ozone
production.

Definitions: NOx = NO + NO2

NOy = NOx + HNO3, + HNO2 + HO2NO2 + PAN + N2O5 +
RONO2 + NO3- + …
NOz ≡ NOy - NOx

Copyright © 2010 R.R. Dickerson 22

 Tropospheric ozone production
Photochemical oxidation of CO and volatile organic compounds (VOCs)
catalyzed by hydrogen oxide radicals (HOx)
in the presence of nitrogen oxide radicals (NOx)
HOx = H + OH + HO2 + RO + RO2
NOx = NO + NO2 OH can also add to
Oxidation of CO: Oxidation of VOC: double bonds of
unsaturated VOCs
CO  OH  CO2  H RH  OH  R  H 2O
H  O2  M  HO2  M R  O2  M  RO2  M RO can also
decompose or
HO2  NO  OH  NO2 RO2  NO  RO  NO2 isomerize; range of
NO2  h  NO  O NO2  h 
O2
 NO  O3 carbonyl products

O  O2  M  O3  M RO  O2  R ' CHO  HO2

Net: CO  2O2  CO2  O3 HO2  NO  OH  NO2
Net: RH  4O2  R ' CHO  2O3  H 2O
Carbonyl products can react with OH to produce
additional ozone, or photolyze to generate more HOx
radicals (branching reaction)
 Dependence of ozone production
on nox and volatile organic compounds (VOCs)

Take hydrocarbon RH O3
as example of VOC HOxfamily

NO
RO2 RO
5
RH O2
4 6
PHOx 7
O3 OH HO2
NO
NO2 9 8

HNO3 O3 H2O2

2k4 PHOx [ RH ] PHOx 1/ 2

P (O3 )  P (O3 )  2k7 ( ) [ NO ]
k9 [ NO2 ][ M ] 2k8
“NOx- saturated” or “NOx-limited” regime
“VOC-limited” regime
 Dependence of ozone production
on NOx and volatile organic compounds (VOCs)
India emissions

ECHAM emissions and concentrations

Suvarna Fadnavis, 2013
India emissions
Monthly mean afternoon (1 to 4 PM) surface
ozone concentrations calculated for July
using Harvard GEOS-CHEM model.
Copyright © 2010 R.R. Dickerson
Ozone as a GHG

IPCC,2007
 GLOBAL BUDGET OF TROPOSPHERIC OZONE (Tg O3 yr-1)
IPCC (2007) average of 12 models
Chemical 4700 Chemical loss in 4200
production in troposphere
troposphere ±700 ±500
O2 Transport from 500 Deposition 1000
hn stratosphere
±100 ±200
O3
STRATOSPHERE Ozone lifetime: 24 ± 4 days
8-18 km
TROPOSPHERE

hn
NO2 NO
O3 hn, H2O

OH HO2 H2O2
Deposition
CO, VOC
 Ozone – only GEOS Chem
Chem prod in 4300 Chem loss in 4000
Present-day troposphere, troposphere,
Preindustrial Tg y-1 1600 Tg y-1 1600
Transport from 400 Deposition, 700
O2 stratosphere, Tg y-1
hn Tg y-1 400 400
Burden, Tg 360 Lifetime, days 28
O3
STRATOSPHERE 230 42
8-18 km
TROPOSPHERE

hn
NO2 NO
O3 hn, H2O

OH HO2 H2O2
Deposition
CO, VOC
IPCC radiative forcing estimate for tropospheric ozone (0.35 W m-2) relies
on global models

…but these underestimate the observed rise in ozone over the 20th century

Preindustrial
ozone models

}
Observations at mountain
sites in Europe
[Marenco et al., 1994]
 Ozone
RADIATIVE FORCING BY TROPOSPHERIC OZONE COULD BE MUCH
LARGER THAN IPCC VALUE

Global simulation of late 19th century

ozone observations [Mickley et al., 2001]

Standard model:

DF = 0.44 W m-2

“Adjusted” model
(lightning and soil NOx decreased,
biogenic hydrocarbons increased):

DF = 0.80 W m-2
 INTERCONTINENTAL OZONE POLLUTION INFLUENCES
GEOS-Chem model results for 2006
Surface O3
enhancements from
North American
anthropogenic
emissions

from European
anthropogenic
emissions

from Asian
anthropogenic
emissions

Lin Zhang, Harvard