The chemistry of the

troposphere and stratosphere

Prof. M. J. Pilling
The University of Leeds (UK)

helyett
Turányi Tamás

Eredeti Pilling előadások:

2009. február 23-27
A PowerPoint file-ok és a videofelvételek letölthetők:
http://garfield.chem.elte.hu/Turanyi/oktatas/Pilling.html
Textbooks

 R.P.Wayne, “Chemistry of Atmospheres”, Chapter 4

(3rd Edition, OUP, 2000)
 D. J. Jacob, “Introduction to Atmospheric Chemistry”,
Princeton University Press, 1999.
 G.P. Brasseur, J.J. Orlando and G.S. Tyndall,
“Atmospheric Chemistry and Global Change” (OUP,
1999),
 J.H. Seinfeld and S.N. Pandis, “Atmospheric Chemistry
and Physics : From Air Pollution to Climate Change”,
(Wiley, 1998),
Structure of the atmosphere
 Temperature and pressure variations in the
atmosphere

z
Heating by
exothermic
photochemical
reactions

Convective heating
from surface.
Absorption of IR
(and some VIS-UV)
radiation
Barometric equation
p = p0exp(-z/Hs)
 Atmospheric transport
• Random motion – mixing
– Molecular diffusion is slow, diffusion coefficient D ~ 2x10-5 m2 s-1
– Average distance travelled in one dimension in time t is ~(2Dt).
– In the troposphere, eddy diffusion is more important:
– Kz ~ 20 m2 s-1. Molecular diffusion more important at v high
altitudes, low p. Takes ~ month for vertical mixing (~10 km).
Implications for short and long-lived species.
• Directed motion
– Advection – winds, e.g. plume from power station.
– Occurs on
• Local (e.g. offshore winds)
• Regional (weather events)
• Global (Hadley circulation)
 Winds due to weather patterns

As air moves from high to low pressure on the surface of the rotating
Earth, it is deflected by the Coriolis force.
 Global circulation – Hadley Cells

Intertropical conversion
zone (ITCZ) – rapid
vertical transport near the
equator.
Horizontal transport timescales
Stratospheric chemistry
O2  O(3P) + O(3P) Threshold  = 242 nm
O2  O(3P) + O(1D) Threshold  = 176 nm
 UV absorption spectrum of O3 at 298 K

Hartley Small but significant

bands absorption out to 350
Very strong nm (Huggins bands)
absorption

Photolysis mainly yields O(1D) + O2, but as the stratosphere is very dry
(H2O ~ 5 ppm), almost all of the O(1D) is collisionally relaxed to O(3P)
Integrated column - Dobson unit
Timescale
Slow (J is small)
Fast < 100 secs
Fast ~ 1000 s
Slow (activation
barrier)
 J1 k 2 2
Altitude/km [O3 ]  [O2 ] [ M ]
z J 3 k4
J1 J1 = rate of O2 photolysis (s-1)
J3
J3 = rate of O3 photolysis (s-1)

Graph shows the altitude dependence

of the rate of photolysis of O3 and O2.
Note how J1 is very small until higher
altitudes

(1) The ratio J1/J3 increases rapidly with

altitude, z
J1 (2) As pressure  exp (-z) then [O2]2 [M]
decreases rapidly with z
This balance results in a layer of O3
J3
 HOW GOOD IS THE CHAPMAN MECHANSIM?

The Chapman
mechanism
overpredicts O3 by a
Altitude / km

factor of 2.

Something else must

be removing O3

(Or the production is

too high, but this is
very unlikely)
 Catalytic ozone destruction
The loss of odd oxygen can be accelerated through catalytic cycles whose net result is the
same as the (slow) 4th step in the Chapman cycle
Uncatalysed: O + O3  O2 + O2 k4
Catalysed: X + O3  XO + O2 k5
X is a catalyst
XO + O  X + O2 k6
Net rxn: O + O3  O2 + O2
and is reformed

X = OH, Cl, NO, Br (and H at higher altitudes)

Reaction (4) has a significant barrier and so is slow at stratospheric temperatures
Reactions (5) and (6) are fast, and hence the conversion of O and O 3 to 2 molecules of
O2 is much faster, and more ozone is destroyed.
The sources of X
CFC’s are not destroyed in the
troposphere. They are only
removed by photolysis once they
reach the stratosphere.
 Data from NOAA
CMDL
Ozone depleting gases
measured using a gas
chromatograph with an
electron capture
detector (invented by
Jim Lovelock)
These are ground-based
measurements. The maximum
in the stratosphere is reached
about 5 years later
45 years 100 years

Why are values in

the N hemisphere
slightly higher?
 Removal of the catalyst X. Reservoir is
“Do nothing” cycles unreactive and relatively stable to
photolysis. X can be regenerated from
Ox is not destroyed
the reservoir, but only slowly. [X] is
reduced by these cycles.
Reduces efficiency
of O3 destruction For Cl atom, destroys 100,000 molecules
of O3 before being removed to form HCl
Interactions between different catalytic cycles
Reservoir species limit the destruction of ozone
ClONO2 stores two catalytic agents – ClO and NO2
Effects of catalytic cycles are not additive due to coupling

Mechanism Ozone Column

(Dobson units)
Chapman only (C) 644
C + NOx 332
C + HOx 392
C + ClOx 300
C + NO x+ HOx + ClOx 376
Coupling to NO leads to null cycles for HOx and ClOx cycles
Increase of Cl and NO concentrations in the atmosphere has less effect
than if Cl or NO concentrations were increased separately
(because ClOx and NOx cycles couple, hence lowering [X])
 Bromine cycle
Br + O3  BrO + O2
Cl + O3  ClO + O2 Bromine is very
important for O3
BrO + ClO  Br + ClOO
destruction in the
ClOO  Cl + O2 Antarctic stratosphere
where [O] is low
Net 2O3  3 O2
Br and Cl are regenerated, and cycle does not require O atoms, so can
occur at lower altitude
Source of bromine : CH3Br (natural emissions from soil and used as a
soil fumigant)
Halons (fire retardants)
Catalytic cycles are more efficient as HBr and BrONO2 (reservoirs for
active Br) are more easily photolysed than HCl or ClONO2
 Total Ozone Mapping Spectrometer (TOMS)
Monthly October averages for ozone, 1979, 1982, 1984,
1989, 1997, 2001

Dobson units (total O3 column)

 October 2000 “For the Second time in less than a week dangerous
levels of UV rays bombard Chile and Argentina, The public should
avoid going outside during the peak hours of 11:00 a.m. and 3:00
p.m. to avoid exposure to the UV rays”

Ushaia, Argentina
The most southerly city
in the world
At 15 km, all
the ozone
disappears
in less than
2 months
This cannot
be explained
using gas-
phase
chemistry
alone
US Base in
Antarctica
Steps leading to ozone depletion within the Antarctic vortex

ClO+BrOCl+Br+O2
Simultaneous measurements of ClO and O3 on the ER-2
Late August 1987 September 16th 1987
Still dark over Antarctica Daylight returns

The “smoking gun” experiment – proved the theory was OK

 Ozone loss does appear in the Arctic, but not as dramatic

Above Some years see

significant
Spitzbergen
depletion, some
years not, and
always much
less than over
Antarctica
Tropospheric chemistry
 Global tropospheric chemistry
Questions to be addressed:
1. Many organic compounds emitted to the atmosphere
are oxidised, eventually forming CO2 and H2O. What
determines the oxidising capacity of the atmosphere?
2. Methane is a greenhouse gas, whose atmospheric
concentration has more than doubled since the
industrial revolution. What governs it concentration?
3. Tropospheric oxidation is strongly influenced by NOx,
whose lifetime is ~ 1 day. How is NOx transported to
regions with no NOx emissions?
4. Ozone is a secondary pollutant. In the boundary layer it
affects human health, growth of vegetation and
materials. It is also a greenhouse gas. What governs its
concentration?
Methane oxidation

CH4 + OH (+O2)  CH3O2 + H2O

CH3O2 + NO  CH3O + NO2
CH3O + O2  HO2 + HCHO
HO2 + NO  OH + NO2

HCHO + OH (+O2)  HO2 + CO + H2O

HCHO + h  H2 + CO
HCHO + h (+2O2)  2HO2 + CO

Note:
2 x(NO  NO2) conversions
HCHO formation provides a route to radical formation.
 General oxidation scheme for VOCs
O3 + h  O1D + O2
O1D + H2O  2OH
OH + RH (+O2)  RO2 + H2O
RO2 + NO  NO2 + RO
RO  HO2 (+R’CHO)
HO2 + NO  OH + NO2

NO2 + h  NO + O; O + O2  O3

OVERALL
NOx + VOC + sunlight  ozone
The same reactions can also lead to formation of secondary
organic aerosol (SOA)
THE OH RADICAL: MAIN TROPOSPHERIC OXIDANT
Primary source:

O3 + hO2 + O(1D) (1)

O(1D) + M O + M (2)

O(1D) + H2O 2OH (3)

Sink: oxidation of reduced species

CO + OH CO2 + H Major
OH sinks
CH4 + OH CH3 + H2O

HCFC + OH H2O + …

GLOBAL MEAN [OH] ~ 1.0x106 molecules cm-3

Other oxidising species

NO3
NO2 + O3  NO3 + O2
NO2 + NO3 + M  N2O5 + M
NO3 is rapidly lost in the day by photolysis and reaction with NO
( NO2), so that its daytime concentration is low. It is an
important night time oxidant. It adds to alkenes to form
nitroalkyl radicals which form peroxy radicals in the usual way.

O3
Ozone reacts with alkenes to form a carbonyl + an energised
Criegee biradical. The latter can be stabilised or decompose.
One important reaction product is OH: O3 reactions with alkenes
can act as a source of OH, even at night.
 Global budget for methane (Tg CH4 yr-1)
• Sources:
Natural 160 • Sinks:
Anthropogenic 375 – Trop. oxidation 445
Total 535 by OH
Natural Sources: – Transfer to 40
wetlands, termites, oceans… stratosphere
Anthropogenic Sources: – Uptake by soils 30
natural gas, coal mines, Total 515
enteric fermentation, rice
paddies,

Notes:
1. The rate of oxidation is k5[CH4][OH], where the concentrations
are averaged over the troposphere
2. Concentrations of CH4 have increased from 800 to 1700 ppb since pre-
industrial times
3. Methane is a greenhouse gas.
 HISTORICAL TRENDS IN METHANE

Historical methane trend

Recent methane trend

1260
Northern hemisphere background CH4, µg m -3

Recent measurements at Mace

1240
Head in W Ireland.
Baseline
1g m-3 = 0.65 ppb
1220
12 month mean

NB – seasonal variation –
1200
higher in winter
1180
Jan 1995

Jan 1996

Jan 1997

Jan 1998

Jan 1999

Jan 2000

Jan 2001

Jan 2002

Jan 2003

Jan 2004

Jan 2005

Jan 2006

Jan 2007

Jan 2008
 GLOBAL DISTRIBUTION OF METHANE

NOAA/CMDL surface air measurements

• Seasonal dependence – higher in winter than summer (maximum in NH correlates

with minimum in SH).
• NH concentrations > SH – main sources are in NH; slow transport across ITCZ.
GLOBAL BUDGET OF CO
 GLOBAL DISTRIBUTION OF CO
NOAA/CMDL surface air measurements

• Compare CH4. What are the differences and why?

(Rate coefficients at 298 K/10-12 cm3 molecule-1 s-1: CH4: 7x10-3;
CO: 0.24)
Global VOC emissions (Tg yr-1)
Anthropogenic:
fuel production and distribution 17; fuel consumption 49; road
transport 36; chemical industry 2; solvents 20; waste burning 8,
other 10. Total 142 Tg yr-1

Biogenic:
isoprene 503; monoterpenes 127; other reactive VOCs 260,
unreactive VOCs 260; Total 1150 Tg yr-1

Typical atmospheric lifetimes (for [OH] = 1x106 molecule cm-3)

 = 1/k[OH]
CH4 6 yr isoprene 2.7 h
CO 48 days ethane 46 days
benzene 6 days ethene 30 h
 Global budget for NOx
• Global sources (Tg N yr-1):
Fossil fuel combustion 21; Biomass burning: 12
Soils 6 Lightning 3
Ammonia oxidation3 Aircraft 0.5
Transport from strat 0.1
• Coupling (rapid - ~ 1 minute in the day)
NO + O3 → NO2 + O2
NO2 + Light → NO + O; O + O2 + M → O3 + M
Also HO2 + NO → NO2 + OH
• Loss
OH + NO2 + M → HNO3 + M
Rainout of HNO3
• Lifetime of NOx is about 1 day. NOx is a key component in ozone
formation. Can it be transported to regions where it is not strongly
emitted?
PEROXYACETYLNITRATE (PAN) AS RESERVOIR FOR
LONG-RANGE TRANSPORT OF NOx
 3000

2500

Other
NO2 as an air pollutant.
NOx emission (ktonnes)

2000 Other transport &

machinery
Road transport
UK NOx emissions,
1500
Domestic 1970 - 2000
Industry
1000
Public power

500

0
1975

1985

1998
1970

1980

1990

1991

1992

1993
1994

1995

1996

1997

1999

2000

Recent road transport

data for the UK
Spatial distribution
of NOx emissions
Maps of annual mean background NO2 concentrations

UK 2001 UK 2010
Key AQ objective is annual mean of
40 g m-3 to be achieved by
2010 (EU Directive)
Annual mean NO2 concentrations, London

London 1999 London 2010

1407 road links out of 1888 670 road links out of 1888
exceed 40 g m-3 exceed 40 g m-3
 Hungarian air quality network
http://www.kvvm.hu/olm/index.php
NO2 in Budapest
and Hungary in
2005
 MAPPING OF TROPOSPHERIC NO2
FROM THE GOME SATELLITE INSTRUMENT (July 1996)

Martin et al. [2002]

 Global budget for ozone (Tg O3 yr-1)
• Ozone is a secondary pollutant and is not directly omitted.

• Chemical production 3000 – 4600

HO2 + NO 70%
CH3O2 + NO 20%
RO2 + NO 10%
• Transport from stratosphere 400 – 1100

• Chemical loss 3000 – 4200

O1D + H2O 40%
HO2 + O3 40%
OH + O3 10%
others 10%
• Dry deposition 500 - 1500

• Ozone is a greenhouse gas. It affects human health, plant growth and

materials
Regional ozone formation
 Regional air quality – ozone formation

• Ozone is a greenhouse gas. It affects human health,

plant growth and materials
• Ozone is a secondary pollutant and is not directly
emitted.
• Emission of VOCs and NOx, coupled with sunlight leads
to the formation of photochemical smog.
• Major component is ozone. Also aerosols, nitrates …
• Need to understand chemical mechanism for formation
in order to develop strategies and legislation for
reduction of ozone concentrations.
• The European limit values are linked to these aims
• Is it better to control NOx or VOCs – or both?
 Chemical mechanism
• Initiation: OH formed from ozone photolysis at a rate POH (=
2k3[H2O]J1[O3]/{k2[M] + k3[H2O]} )
• Propagation
OH + RH (+O2) → RO2 + H2O (R4)
RO2 + NO → RO + NO2 (R5)
RO + O2 → R’CHO + HO2 (R6)
HO2 + NO → OH + NO2 (R7)
• Termination
HO2 + HO2 → H2O2 (R8)
OH + NO2 + M → HNO3 + M (R9)
• Ozone formation
O3 is formed by NO2 photolysis with a rate equal to the sum of the
rates of reactions 5 and 7 (= v5 + v7)
 DEPENDENCE OF OZONE PRODUCTION
ON NOx AND HYDROCARBONS

O3
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 ] k8
“NOx- saturated” or “NOx-limited” regime
“hydrocarbon-limited” regime
OZONE CONCENTRATIONS vs. NOx AND VOC EMISSIONS
Air pollution model calculation for a typical urban airshed

Ridge
NOx-limited

NOx-
saturated
Air quality and climate change
 Impact of air pollution
UK Air Quality Strategy, 2007
• “Air pollution is currently estimated to reduce the life
expectancy of every person in the UK by an average of 7-
8 months. The measures outlined in the strategy could
help to reduce the impact on average life expectancy to
five months by 2020, and provide a significant step
forward in protecting our environment.”

• Defra estimate the health impact of air pollution in 2005

cost £9.1–21.4 billion pa.
 Timescales of ozone chemistry
1. Global chemistry. Dominated by NOx + CH4 + sunlight.
Timescales are long as are transport distances.

2. Regional chemistry. Many VOCs are emitted, e.g. over

Europe. Each has its own lifetime governed by its rate
constant for reaction with OH. The timescales of ozone
production takes from hours to days. The transport
distance for a wind speed of 5 m s-1 and a lifetime of 1
day is ~500 km.

3. Urban chemistry: high concentrations of NO from

transport sources. Ozone is depressed by the reaction:
NO + O3  NO2 + O2
 Radiative Forcing

• Radiative forcing: the change in the net radiation balance at the

tropopause caused by a particular external factor in the absence of
any climate feedbacks.
• These forcing mechanisms can be caused by:
– change in the atmospheric constituents such as the increase in
greenhouse gases (GHGs)
– aerosols due to anthropogenic activity,
– changes in other components of the Earth/atmosphere system
such as changes in the surface albedo (the fraction of incoming
radiation that is reflected). Albedo changes are caused, e.g., by
changesin vegetation (e.g. burn scars or agriculture).
 Mechanisms of the radiative forcing
due to greenhouse gases and of the direct
radiative forcings due to aerosols
Global-average radiative forcing (RF) estimates
and ranges in 2005
(relative to 1750) for anthropogenic GHGs and
other important agents and mechanisms
Carbon dioxide and methane mixing ratios versus time
(NOAA Climate Monitoring and Diagnostics Laboratory
http://www.cmdl.noaa.gov/ccgg/insitu.html)
Climate System
Evolution of models
 SRES (IPCC Special Report on Emission
Scenarios) scenarios
• The A1 storyline is for a future world with very rapid economic
growth, global population that peaks in mid-century and declines
thereafter, the rapid introduction of new and more efficient
technologies and with a substantial reduction in regional differences
in per capita income. Within this family are three sub-scenarios with
different technological emphasis:
• A1FI – A1, fossil fuel intensive
• A1T – A1, with non-fossil energy source emphasis
• A1B – A1, with a balance across energy sources.
• The A2 storyline is a more pessimistic scenario, describing a very
heterogeneous world based on self-reliance, regional differences in
economic and technological development and continuous increase in
global population.
• The B1 storyline describes a convergent world like A1, with global
population peaking in mid-century, but with rapid changes in
economic structures, introduction of clean and resource-efficient
technologies, emphasis on global solutions to social and
environmental sustainability.
• The B2 storyline describes a world with emphasis on local solutions
to social and environmental sustainability, less rapid and more
diverse than in B1 and A1, with continuously increasing global
population, but at a lower rate than A2.
Royal Society Report on ozone over next 100 years
Level of automobile emission limits in Asian
countries, compared with the EuropeanUnion.
Source: Clean Air Initiative for Asian cities
 Impact of improved technologies in Asian
countries on assessment of NOx emissions
New estimates of CO emissions
New estimates of CH4 emissions
Predicted lobal temperature rise for different
scenarios
 Future summer temperatures

Using a climate model

simulation with
greenhouse gas emissions
that follow an IPCC SRES
A2 emissions scenario,
Hadley Centre predict that
more than half of all
European summers are
likely to be warmer than
that of 2003 by the 2040s,
and by the 2060s a 2003-
type summer would be
unusually cool
Stott et al. Nature, December 2004
2003: hottest on record (1860)
Probably hottest since 1500.
15 000 excess deaths in Europe
Impact of climate change on air quality - ozone
 2020s CLEcc-
ΔO3 from climate change 2020s CLE

Warmer temperatures
&higher humidities
increase O3destruction
over the oceans

O3 + h O1D + O2
O1D + H2O  2OH
O1D + N2, O2  O3P

But also a role from

increases in isoprene
emissions from
vegetation &changes in
lightning NOx

OH+RH(+O2)
 RO2 + H2O
RO2 + NO RO + NO2
NO2+ h(+O2)NO+O3
 PAN – peroxy acetyl nitrate
PAN is formed from reactions of the acetyl peroxy radical and NO2:
e.g. CH3CHO + OH (+O2)  CH3COO2 + H2O
CH3COO2 + NO2 CH3COO2NO2 (PAN)

PAN is a reservoir compound

for nitrogen oxides and provides
a mechanism for their transport,
especially in the upper
troposphere. It provides a means
of carrying nitrogen oxides from
polluted to less polluted regions.
It is a major player in the
intercontinental transport of
pollutants
Heat wave in Europe, August 2003

• Monitoring stations in
Europe reporting high
band concentrations of
ozone
• >15 000 ‘excess deaths’
in France; 2000 in UK,
~30% from air pollution.
• Temperatures exceeded
350C in SE England.
• What about Hungary?
• How frequent will such
summers be in the
future?
Köszönöm a figyelmet!