Modeling Chemistry-

Climate Interactions
Guy P. Brasseur
National Center for Atmospheric Research
Boulder, Colorado
Why Adding Chemistry in AOGCM?

• To assess the effects of changing atmospheric

concentrations of reactive gases on climate.

• To assess the effects of changing climate on the

concentration of reactive gases, and specifically on
air quality, surface deposition, etc.
CLIMATE CHANGE AND AIR QUALITY
FEEDBACK LOOPS

Natural CLIMATE AIR

forcings CHANGE QUALITY

Long-lived Emissions of
greenhouse gases reactive gases
 Where Atmospheric Composition Fits In
Enhanced
 This coupling Greenhouse
Effect
gives rise to major
(H2O), CO2, CFCs, environmental
Ozone-Layer
CH4, ozone, issues
Depletion
aerosols …

 Much of the coupling

between incoming solar
energy and the atmosphere
occurs via trace constituents
 Changes in trace constituents Regional
arise largely from human activities Air Quality
(surface emissions sources)

Bottom line: Understanding atmospheric composition is a key first step in:

• Characterizing the human influence
• Constructing scenarios/predictions for consideration as options
• Identifying “win-win” choices in addressing multiple issues: air quality and climate
 Impacts of trace gases

SO2 NOx NH3 VOC CO 10PM CH4 CO2

Ecosystems
Acidification X X X
Eutrophication X X
O3 X X X X
Health
Direct X X X X X
Via O3, PM X X X X X
Radiative forcing
Direct X X
Via aerosols X X X X X
Via OH X X X X
 Outline

• 1. Impact of change in chemical composition on

climate
• 2. Impact of climate change on chemical composition
• 3. Chemistry-Climate Interactions
• 4. Integrating biogeochemistry in broader and more
comprehensive Earth system models
1. Impact of Change in chemical
composition on Climate
 Impact of Trace Constituents on
Climate
• Trace constituents affect climate directly via radiative
forcing, but also indirectly through changes in the
hydrological cycle and in the circulation.

• The direct effects of trace constituents occur through

• Well mixed greenhouse gases
• Stratospheric and tropospheric ozone
• Aerosol particles (discussed by Phil)
 Well Mixed Greenhouse Gases
and Atmospheric Chemistry
• Carbon dioxide is insensitive to atmospheric
chemistry up to 70 km altitude, above which it is
photolyzed.
• Methane (CH4) is affected by chemistry through its
destruction by the OH radical.
• Nitrous oxide (N2O) is destroyed primarily by
photolysis in the stratosphere. 10% of the loss,
however, results from the reaction with the O(1D)
atom, itself produced by ozone photolysis. The major
source of nitric oxide (NO) in the stratosphere results
from the oxidation of N2O.
• Chlorofluorocarbons are photolyzed above the
tropopause
 The OH Radical

• The hydroxyl radical (OH) is the most important

oxidation agent in the atmosphere. It determines the
lifetime of many chemical species, including
methane.
• It is produced as a result of ozone photolysis
O3 + hv  O(1D) + O2 (< 340 nm)
followed by water vapor oxidation
H2O + hv  2 OH
• Other primary OH production results from the
photolysis of organic compounds, including acetone,
aldehydes, etc.
Primary OH formation

O3 + hv → O(1D) + O2 (_ < 340 nm)

O(1D) + M → O+M 97%

O + O2 + M → O3 + M

O(1D) + H2O → 2OH 3%

OH recycling, formation of HO2

CO + OH → CO2 + H
H + O2 + M → HO2 + M
HO2 + NO → OH + NO2
Modelled zonal OH
 Ozone and Climate

• Ozone interacts with climate through

• Absorption of UV solar radiation (in the stratosphere)
• Greenhouse effect (with the largest contribution in the upper
troposphere)
• Stratospheric ozone decrease has led to a small
cooling
• Tropospheric ozone increase has led to a warming
 Stratospheric
ozone
Stratosphere- Wet removal
troposphere
exchange

Tropospheric Temperature
Ozone humidity
Changes in
tropospheric ozone
production and
destruction Transport:
HOx NOx Interhemispheric&
Synoptic mixing
Weather
ROx Convection patterns
Climate induced changes in emissions:
Lightning NOx NOx, VOC, DMS, halogens, CH4,
emissions mineral dust and seasalt.
SURFACE EMISSIONS DRY DEPOSITION-LAND-USE CHANGES
Ozone and Precursors
O2 + hν → O3
O3 + hν → O(1D)
Ozone
O(1D) + N2O → NO
NO → NO2
→ HNO3

Strato-
sphere
In-situ
Chemistry

E
ST
(NOx) NO
Tropo-
sphere
H2O H2O
CO
NOy
 Destruction of Stratospheric
Ozone
• In addition to the direct Chapman loss process
O + O3  2 O2
• Ozone is catalytically destroyed by fast-reacting
radicals or atoms:
X + O3  XO + O2
XO + O  X + O2

Net: O + O3  2 O2

where X can be NO, H, OH, Cl, Br

 Production of Tropospheric
Ozone
CO + OH → CO2 + H
H + O2 + M → HO2 + M
HO2 + NO → OH + NO2
NO2 + hv → NO + O
O + O2 + M → O3 + M

CO + 2O2 → CO2 + O3 (net)

Net Ozone Production Rate as a
function of N O x levels

HO2+NO OH+NO2

Ocean Urban
Moderately
Polluted areas
HO2+O3

summertime surface conditions

Surface O3 (ppbv) 1990s

Mike Pilling, University of Leeds

 Historical ozone

Very few reliable

measurements until
1960s. Oldest record:
Montssouri, 1760. A few
optical measurements
from early 1900s.

The figure shows that

ozone has increased
throughout the (lower)
troposphere.

from Staehelin et al., 1994

 Changes in Ozone
from 1750 to Present

January (upper panel)

July (lower panel)

Hauglustaine
Hauglustaineand
andBrasseur
Brasseur(2001)
(2001)
 Global NOx emissions
200.0

160.0
SRES A2

120.0

CLE
80.0

40.0
MFR
0.0
1990 2000 2010 2020 2030

Europe North America

Asia + Oceania Latin America
Africa + Middle East Maximum Feasible Reduction (MFR)
SRES A2 - World Total SRES B2 - World Total

Projected development of IIASA anthropogenic NOx emissions by SRES world region (Tg NO2 yr-1).
 Global CH4 emissions
600 SRES A2
500

CLE
400

300 MFR

200

100

0
1990 2000 2010 2020 2030

Europe North America

Asia + Oceania Latin America
Africa + Middle East Maximum Feasible Reduction (MFR)
SRES A2 - World Total SRES B2 - World Total

Projected development of IIASA anthropogenic CH4 emissions by SRES region (Tg CH4 yr-1).
Differences between scenarios

⌤⌤⌤⌤

From Unger et al.

 CH4, τCH4 & OH trajectories
1990-2030
CLE

CLEcc
 CLE

+2 to 4 ppbv over
N. Atlantic/Pacific
>+10 ppbv
A large fraction is India
due to ship NOx

Change in surface O3, CLE 2020s-1990s

BAU Mike Pilling, University of Leeds
Change in the CO concentration

Change in the concentration

of ozone precursors (%)
From 2000 to 2100
Scenario A2P
July

Change in the NOx concentration

 Changes in Ozone from
Present to 2050

IPCC Scenario IS92a

January (upper panel)

July (lower panel)

Hauglustaine
Hauglustaineand
andBrasseur
Brasseur(2001)
(2001)
O 3 Radiative Forcing 2000 – 2100

Gauss et al., 2002

 Indirect Chemical Effects

• Increase in methane concentrations leads to

enhanced ozone concentrations with additional
radiative forcing
• For example (Shindell)
• CH4 direct forcing: 0.6 Wm-2
• CH4 forcing with ozone contribution: 0.8 Wm-2 (half of the
CO2 forcing!)
• Increase in methane affects OH concentration and
hence conversion of SO2 to sulfate, with radiative
impacts
 Gas Phase Compunds and
Aerosols
• Some gas phase compunds can be converted into
aerosols. The conversion of DMS to SO2 by OH and
of SO2 into sulfate by H2O2 and O3 is an example.
Another example is provided by the oxidation of
biogenic terpenes, which produce organic aerosols.

• Similarly, the presence of aerosols modifies the

photolysis rate of gas phase compounds. Surface
reactions on aerosol particles can also play an
important role (activation of chlorine and ozone hole
formation)
 Effects of air pollutants on climate

Global Hansen and Sato [2001]

Air pollution - related greenhouse forcing: 0.5 (O3) + 0.8 (BC) + 0.7 (CH4)
= 2.0 W m-2…larger than CO2

Cooling from scattering anthropogenic aerosols: -1.3 (direct) – 1.0 (clouds)

= -2.3 W m-2 …would cancel half the warming

Global radiative forcing is not the whole story, pollutants also affect
 regional and surface forcing ε regional climate change
 climate variables not quantified by radiative forcing (effect of aerosols on
precipitation, of ozone on stratospheric temperatures…)
2. Impact of Climate Change on
chemical composition
 Impact of Climate Change on Air
Quality
• More frequent stable meteorological situations
(blockings) and summertime heat waves will lead to
severe degradation of air quality [summer 2003 and
2006(?) in Europe]
• More frequent wildfires in a warmer and dryer
climate will enhance emissions of primary pollutants
and lead to a degradation of air quality
• More frequent precipitation events will improve air
quality
• Many more potential impacts of climate change…..
 Effects of climate
Probability change on air quality
of daily max 8-h O3 > 0.08 ppmv
vs. daily max. T -through perturbations to air
pollution meteorology, chemistry,
d [O3 ] ∂[O3 ] ∂[O3 ] ∂xi scavenging
= +∑
dT ∂T i ∂xi ∂T
- through perturbations to regional
and intercontinental transport

- through perturbations to fires,

dust generation, biogenic emissions

Transpacific transport of Asian aerosol pollution

MODIS AOD Model dust Model sulfate MOPITT CO
 CH4 emissions and global change

Methane emissions:

Natural (wetlands, termites, oceans, hydrates)

= 150-240 Tg CH4/yr
Anthropogenic (energy, landfills, waste, rice paddies, biomass
burning) = 310-350 Tg CH4/year

Temperature dependence of wetland emissions: 20%/K (Walter

and Heimann, 2000)

But: systematic flux measurements lacking, more particularly for

tropical wetland ecosystems

Other large uncertainty: behavior of methane hydrates locked in

oceans and permafrost
 Methane allocation and transport
O2
↑ E M I S S I O N ↑

vascular transport
aerobic horizon oxidation water table level

ebullition
diffusion
micro-aerobic horizon
root
oxidation
root
exudation
entrapped
anaerobic horizon gas bubbles
dissolved CH4
gaseous CH4
acetate, CO2, H2 m e t h a n o -
genesis

decomposition of dead organic matter

Mean annual CH4 fluxes plottet against
annual mean soil temperature
Hestur
25
Zackenberg
Kevo
CH4 flux (mg/m2/hr)

20
Plotnikovo
15 R2 = 0.8379 Abisko

10 Poly. (all)

0
4 6 8 10 12 14 16 18
Soil temp (°C)

Christensen et al. GRL, 2003.

VOCs biogenic emissions and climate chan
VOCs emitted in large quantities by vegetation
 Ozone production in high NOx areas
 Ozone destruction in very low NOx areas

Isoprene emissions as a function of temperature

 Isoprene Emissions
Model of Alex Guenther, NCAR

Present-day (2000) Future Climate (2100)

Biomass burning emissions and climate change

Biomass
Biomassburning:
burning:
50%
50%CO
COsurface
surfaceemissions
emissions
21%
21%NOx
NOxsurface
surfaceemissions
emissions
8%
8%CH4
CH4emissions
emissions
•• 15-18%
15-18%ofofglobal
globalsurface
surfaceozone
ozoneresults
resultsfrom
frombiomass
biomassburning
burning
•• Most
Mosttropical
tropicalbiomass
biomassburning
burningisishuman-related
human-related

Impact
Impactof
ofclimate
climatechange:
change:
•• lightning
lightningfrequency
frequency
2xCO2
2xCO2climate
climate44%
44%increase
increasein
inlightning
lightning
(Price
(Priceand
andRind,
Rind,1994;
1994;Flannigan
Flanniganet
etal.
al.2000)
2000)
•• change
changein
inamount
amountof
ofavailable
availablebiomass
biomass

Quantification:
Quantification:Difficult
Difficultas
aslarge
largedependence
dependenceon
onforest
forestmanagement
management
 NOx lightning emissions

Global NOx production: 2-20 TgN/yr

Important for the ozone budget:

- high altitude
- clean environment

- Very large spatial and temporal

variability

Climatic impact: linked to changes in the hydrological cycle

-Use of a climate model: 1oC increase  5-15 % increase in lightning
(Price and Rind, 1994; Stenke and Grewe, 2002)
 NO a n d N2 O emissions by s o i l s

Soil NO surface emissions: 5 – 10 Tg N/year (10-25%

of total emission)
Natural emissions have a significant anthropogenic
component (use of fertilizers)

Emissions depend on soil temperature, moisture,

vegetation cover, etc.:
Assessment of impact of climate change requires the
development of process-based models
 Emissions of d u s t

Mineral dust emissions: depends on wind speed, soil moisture

 increase of 10% in a future climate (IPCC, 2001)
large uncertainty, especially at the regional scale

Oceanic emissions

- ocean temperature change  plankton bloom change

climate change  winspeed change
may lead to a change in DMS emissions of a few %

- emissions of sea salt are strongly dependent on wind speed

future climate : increase of sea-salt by as much as 75% (IPCC, 2001)
 Dry a n d wet deposition
Removal of species at the surface through dry deposition:
- depends on surface cover (most effective over vegetation)
- role of surface wetness not yet quantified
Climate change  change in surface cover
 change in stomatal exchanges (ambient CO2)

wet deposition:

H2O2, HNO3 and CH2O efficiently removed

by wet deposition

Climate change:
- increase of precipitation
- increase in intensity of rainfall events

Climate change could lead to a global

ozone decrease of a few percent mostly in from http://www.ceh.ac.uk/aboutceh

the tropics (Grewe et al. 2001)

Changes in
climate-sensitive
natural gas
emissions from
today to 2030:
•Methane from
wetlands,
•Nox from
lightning
•DMS from the
ocean

From Unger et al.

 Z o n a l mean H2 O increase 2020s-
1990s

IIASA
 Z o n a l mean PAN decrease 2020s
(climate change – fixed climate)

Colder LS

Increased
PAN
thermal
decomposition,
due to
increased T
IIASA

Mike Pilling, University of Leeds

 Z o n a l mean N Ox change 2020s
(climate change – fixed climate)

Less Increased
tropical N mid-lat
convection convection
and and
lightning lightning
Increased
PAN
decomposition

IIASA

Mike Pilling, University of Leeds

 Z o n a l mean OH change 2020s
(climate change – fixed climate)

Complex
function:

f(H2O,
NOx,
O3,
T,…)

IIASA

Mike Pilling, University of Leeds

 _O3 from climate change

Warmer
temperatures &
higher humidities
increase O3
destruction
over the oceans

But also a role

from increases
in isoprene
emissions from
vegetation &
changes in
lightning NOx

2020s CLEcc- IIASA

2020s CLE
Influence of climate change on O3
– 4 IPCC ACCENT models
 Stratospheric feedbacks

•Decreased stratospheric temperature:

•Decreased ozone destruction rates, (but more PSCs) →more
stratospheric ozone → increased ozone flux, decreased UV
flux into troposphere → increase in tropospheric ozone.

•Increased stratospheric Brewer-Dobson circulation:

•Increase in strat-trop exchange of ozone → increase in
tropospheric ozone. More rapid ozone recovery
3. Chemistry-Climate Feedbacks
Feedbacks in tropospheric
chemistry
Stratospheric
Ozone
aerosol Lightning
(NOx)
Chemistry
VOC OH NO2 Tropospheric Transport
RO2 HO2 NO
Ozone

Emissions Winds,Temperature
(NOx, VOC, CO, CH4) Humidity

Deposition
(O3, HNO3, NOx, ...)

Climate Change
Changes in the zonally averaged monthly mean (July)
T
temperature (K) and water vapor concentration (percent)
resulting from climate change (doubling of CO2 level)

Temperature (K) Water vapor (%)

ECHAM-5 and OM-1

Atmosphere-Ocean model
Global production of NOx (TgN/yr) by lightning
calculated for conditions representative of
years 2000 and 2100

Price and Rind (1993)

parameterization.
 %-change Year 2100 (A2),
climate as in year 2000

Climate – Chemistry
Feedbacks

%-change Year 2100 (A2)

Climate of year 2100
No climate change

Surface ozone changes

2000-2100 (A2)

With climate
change
 Change in the Zonal Mean Ozone Concentration (%)
due to Climate Change expected from 2000 to 2100

ECHAM-5 MOZART-2
 Summary and evaluation of impacts

Process/activity Impact on global tropospheric ozone

resulting from climate change
human activity-fossil fuel related emissions Small ?
biomass burning Medium to large +/-
soil NOx Medium ?
lightning NOxl Medium-to-large +
natural CH4 emissions Medium-to-Large +
natural VOC emissions Medium-to-large +
Oceanic emissions of sulfur containing gases Small ?
Heterogeneous chemistry on seasalt Medium -
Heterogeneous chemistry on mineral dust Small-medium -
Organohalogens Unknown -
Changes in dry deposition Medium ?
Changes in wet deposition Small-medium -
Effect of meteorology on O3 production and loss Large -
Cloudiness Small -
Climate induced changes in stratosphere- Large +
troposphere exchange
Changes in weather patterns Unknown ?
Feedbacks through the Biosphere

• The role of the biosphere could be important in the

climate-chemistry feedbacks since the biosphere
controls emissions of several chemical species and
has a strong impact on the carbon cycle.
• For ex., fertilization of the biosphere by iron
deposition on the ocean or surface nitrogen and
ozone deposition could affect the carbon cycle, with
impacts on future climate.
Fertilization Atmospheric Distribution of Dust
of the Ocean
by Iron

• Models of dust
mobilisation and
atmospheric
transport are Ocean primary Production
coupled with
models of the
ocean
biogeochemistry
and of the
carbon cycle.
 Nitrogen Fixation

• Process in which atmospheric N2 reacts to form any other

nitrogen compound:
• Examples: Biological fixation by enzyme-catalyzed reduction of
N2 to NH3 or NH4+
• Combustion, lightning, industrial production of ammonia,
fertilizers.etc
• Once fixed, nitrogen is assimilated into biomass (plants,
microbes)
• Nitrification: oxidation to NO2- (nitrites) and NO3- (nitrates).
• Denitrification: reduction of NO3- to N2, N2O, NO)
From 1860 to 1995

Grain
Production

Meat
Production

Energy
Production
From 1860 to 1995

Grain
Production

Meat
Production

Energy
Production
Perturbation to the Global Nitrogen Fixation

GCTE 1997
 The Global Nitrogen Budget in 1860 and mid-1990s, TgN/yr

5
NOy N2
8
1860

120
6 7
0.3

Galloway et al., 2002b

 The Global Nitrogen Budget in 1860 and mid-1990s, TgN/yr

5
NOy N2
8
1860

120
6 7
0.3

5
N2
mid-1990s

NOy
16
21 25 110
25

Galloway et al., 2002b

 The Global Nitrogen Budget in 1860 and mid-1990s, TgN/yr

5 6
NOy N2 NHx
8 6 9
1860

120
6 7 15 11 8
0.3

27

5
N2
mid-1990s

NOy
16
21 25 110
25

Galloway et al., 2002b

 The Global Nitrogen Budget in 1860 and mid-1990s, TgN/yr

5 6
NOy N2 NHx
8 6 9
1860

120
6 7 15 11 8
0.3

27

5 6
N2
mid-1990s

NOy NHx
16 33 23 26 18
21 25 110 100 39
25
N2 + 3H2
54
2NH3

Galloway et al., 2002b

 Nitrogen Deposition
Past and Present
mg N/m2 / y r

5000
2000
1000
750
500
250
100
50
25
5

1860 1993

Galloway and Cowling, 2002; Galloway et al., 2002b

 Challenges for the
Future Based on P. Cox, 2004

CLIMATE

Direct and Indirect Effects /

Feedbacks on natural sources Greenhouse Effect

Heat island effect

Human
Emissions AEROSOLS GREENHOUSE GASES

Fires: soot CH4, O3,

Oxidants: Mineral dust N2O, CFC
OH, H2O2
CO2 Human
HO2,O3 Emissions
N deposition
03, UV radiation
(Gas-phase)
CHEMISTRY ECOSYSTEMS
Biogenic Emissions:CH4,DMS,VOC’s
Dry deposition: stomatal conductance

Human Land-use
Emissions
LAND Damming / Change, Fires
WATER / CITIES Irrigation /
Emission of heat

The future: a full treatment of climate-chemistry-ecosystem-land surface feedbacks

Do we need chemistry in climate
models?
• In the long-term, the CO2 forcing will dominate.
• However…..
• Impact of methane is uncertain: Future methane trend is a
major unknown. Release of methane from permafrost regions
could be huge. Treatment of methane requires wetland model,
ice sheet model, and must account for trends in OH.
• Changes in air quality in response to climate change are
societally important. During recent heat waves, many deaths
were due to air quality issues
• Stratospheric ozone recovery will be affected by future
climate change.
 Do we need chemistry in climate
models?
• Computational costs of chemistry (typically 50-100
species) are high.
• Balance in the Earth system modeling system can be
achieved by
• reducing the number of species (simple chemical
mechanism)
• considering time slices at 10-20 year intervals
 Do we need chemistry in climate
models?
• Even if many of he chemical processes do play play a
first-order role in determining the future state of the
physical climate, there are a lot of intersting
questions related to chemistry-climate-ecosystem
interactions that will have to be addressed by
comprehensive earth system models.
• Many of these questions may have a regional
dimension with important social aspects (e.g., the
evolution of the Arctic, the fate of the Amazon) but
with global links.
4. Integrating biogeochemistry in
broader and more comprehensive
Earth system models
From GCMs to Earth System Models

IPCC 2001
Towards Operational Earth System Monitoring,
Assimilation and Prediction Systems

Atmosphere
Models The Earth System
Unifying the Models

Climate / Weather

and Biogeochemistry
Models

Carbon Cycle
Water Cycle
The Predictive
Hydrology Earth System
Process
Ocean Models
Models

Land
Surface Natural Hazard
Models Prediction
Terrestrial
dels
Biosphere Mo
Models rth
Ea
lid
So

Megaflops Gigaflops Teraflops Petaflops

2000 2010
The Human Dimensions?
Global Biogeochemistry Socioeconomic Metabolism
Climate Change

Geologic Substitution
Sequestration
CO2
CO2
coupled
H 2O
Wood Products
Irrigation
Bioenergy
Evaporation
Harvest
Demography
Land
Agriculture Economy
Use
Life Styles
Change
Technology
(Non-Climatic) Global Change Trade
Solar
Energy

Natural Capital Human-made

Capital
Atmosphere 11 Biomes (includes Built Capital
Human Capital,
and Social Capital

Ecosystem
Services
Anthropo-
Hydrosphere Biosphere Human sphere
Impacts

Lithosphere Human welfare

and health
Ecosystem function & health

From R. Costanza; Boumans et al. 2002

 A first step: Introducing mechanistic agriculture into
dynamic vegetation model and assessing the impacts on chemical
emissions and climate
fractional land fully mechanistic harvesting, computed sowing
use shares “crop functional types” residues & harvesting dates

multiple
mosaics of natural cropping
and agricultural lands
grazing
mechanistic vegetation
and soil processes
irrigation

LPJ Land use

change
Climate and
CO2 change

LPJ
Human Dynamics in Global Models

Focus on economics and land-use change?

Agent-based models? Game theory? Network

approaches? Hybrid integrated models?

How can we model contingent events?

Should we focus on modelling or scenario

development to inform the future?
 Challenges for the Future

• Earth system science should contribute to the themes

that will drive fundamental research in the 21st
century:

• Interfaces between the micro- and the macro-worlds

• Interfaces between the living and the dead nature
• Interfaces between nature and culture
The End
CH4 global trend
How much of the relatively rapid changes in the CH4 trend
is related to

- changes in meteorological/climatic variability?

- changes in surface emissions

From the NOAA/CMDL GLOBALVIEW network

⌤⌤⌤⌤
⌤⌤⌤⌤
⌤⌤⌤⌤
⌤⌤⌤⌤
 Regional Global phenomena
Question 3: What are the effects of regional pollution on the global
atmosphere and the effects of global climate and chemical change on
regional air quality and atmospheric chemical inputs to ecosystems?

1. Characterize the contributions of regional pollution, for example that of North

America and of Asia, on global ozone and aerosol levels. Characterize the
influence of global changes on regional levels of ozone and aerosol.

Will provide an estimate of the contributions of regional and sub-regional

(e.g., mega cities) production of pollutants and their precursors on global
levels of ozone and aerosols.

Will provide a measure of the contribution of the global "background" levels

on regional scale air quality and show what levels of pollutions are beyond
national/regional control.

2. Carry out the first global survey of vertically resolved distribution of

tropospheric ozone and its key precursors.

Will provide an observationally vetted data for climate modeling of the

radiative forcing by ozone.
 Ozone Layer Recovery
Question 4: What are the time scale and other characteristics of the recovery
of the stratospheric ozone layer in response to declining abundances of
ozone-depleting gases and increasing abundances of greenhouse gases?

1. Continue monitoring of stratospheric ozone, ozone-depleting substances,

stratospheric sulfate aerosol loading, and UV radiation. Continue studies of
chemical and transport processes that control stratospheric ozone and evaluate
new substances for their "ozone and climate friendliness."

Will provide decision makers an updated assessment of the state of the

ozone layer, its recovery, and effectiveness of policy decisions.

2. Carry out observational, modeling, and laboratory studies to understand the

cross-tropopause processes.

Will provide information needed to assess the impact of short-lived gases on

stratospheric ozone and of water vapor (and other greenhouse gases) on the
climate of the stratosphere, now and in the future.
 Multiple Environmental Issues
Question 5: What are the couplings among climate change, air pollution, and
ozone layer depletion, which were once considered as separate issues?

1. Build and evaluate diagnostic/prognostic models of the coupled climate,

chemistry, transport, and ecological systems (in collaboration with other
elements of the program).

Will help determine how actions taken or considered with regard to one issue
influence other issues, positively or negatively.

2. Carry out multiple issue state-of-understanding assessments, in partnership

with the spectrum of stakeholders, with the aim of characterizing integrated
“If…, then…” options.

Will synthesize the understanding of the impacts of multiple stresses on

humans (e.g., heat and air quality) and ecosystems (e.g., soil moisture and
chemical exposure).

3. Undertake a policy-relevant assessment of the issues related to

intercontinental transport and the climatic effects of air pollutants.

Will provide scientifically sound information to policymakers for consideration

in developing integrated control strategies to benefit both regional air quality
From the NOAA/CMDL GLOBALVIEW network
 John Plane, UEA, co-chair
Iodine Chemistry in Implementation Group 1, with
Maurice Levasseur Chair,
the MBL Canadian SOLAS
 A Chemical Instability: The "Bromine Explosion"

Inversion
Well mixed Boundary Layer (up to
≈1000m)
Br2 + hν → 2 Br
Br + O3 → BrO + O2
BrO + HO2 → HOBr + O2
net: BrO --> 2 BrO
(Bromine – Explosion Mechanism)

Snow Surface or Aerosol: HOBr + Br- + H+ → Br2 + H2O

• Polar Boundary Layer Frost

flowers
• Salt Lakes
• Coastal Areas Tang & McConnel 1996,
Vogt et al. 1996
• ... Platt & Lehrer 1997
Wennberg 1999
Polar Tropospheric Ozone Depletion

Alert 2000,
Bottenheim
et al., 2002
 Tropopause Location

Holton et al., Reviews of Geophysics, 33, 4, 403, 1995 (figure courtesy of C. Appenzeller)

Sue Schauffler
 Tropopause Folding Event

Tropopause fold observed during

TOPSE: Browell et al., NASA Langley.

J. Atmos. Sci., 37, 994, 1980 Shapiro, M.A.

Sue Schauffler
 Stratosphere-Troposphere
Stratosphere-TroposphereExchanges
Exchanges
Lidar
LidarMeasurements
MeasurementsininGarmisch
Garmisch––Partenkirchen
Partenkirchen(D)
(D)

Stohl
Stohland
andTrickl,
Trickl,1999
1999
 The NOx -free atmosphere

1. OH formation (ozone → HOx conversion)

O3+hν → O(1D)+O2 (majority yields O(3P), which does not react with H2O!)

O(1D)+H2O → 2*OH (a large fraction is quenched by collision with N2 or O2:

O(1D)+M → O(3P)+M)

2. HOx (and ozone) loss

OH+OH → H2O2 or H2O+O
OH+O3 → HO2+O2 (peroxy radical formation - a minor channel)

HO2+O3 → OH+2*O2
HO2+HO2 → H2O2+O2
HO2+OH → H2O+O2
 CO and hydrocarbon oxidation

3. CO oxidation
OH+CO+O2 → HO2+CO2

4. Methane oxidation
OH+CH4+O2 → CH3O2+H2O (the methyl peroxy radical is born)

CH3O2+HO2 → CH3O2H+O2
CH3O2+CH3O2 → ... (e.g. methanol: CH3OH)

5. HOx regeneration
H2O2+hν → 2*OH (also reaction with OH possible, i.e. HOx
loss)

CH3O2H+hν +O2 → OH+HO2+HCHO (formaldehyde)

 CO and hydrocarbon oxidation (2)

5. HOx regeneration (continued)

HCHO+hν → H2+CO (ca. 60%)

HCHO +hν+O2 → 2*HO2+CO (ca. 40%)

HCHO+OH+O2 → HO2+CO+H2O

6. Simplified NMHC scheme

OH+RH+O2 → RO2+H2O (R=C2H5, C3H7, ...)

RO2+HO2 or RO2+CH3O2 or RO2+RO2 → peroxide

peroxide+hν+O2 → HOx+aldehyde
aldehyde+hν+O2 → HOx and RO2
aldehyde+OH → other stuff
 The crucial role of NOx

7. The catalytic ozone formation cycle

NO+O3 → NO2+O2
NO2+hν+O2 → NO+O3
NO+HO2 → NO2+OH (this is the key reaction!)

NO+CH3O2→ NO2+CH3O (CH3O immediately reacts with O2 to form HO2+HCHO)

NO+RO2 → NO2+RO

8. The end of the story

OH+NO2 → HNO3

Note: in the stratosphere catalytic ozone destruction, in

the troposphere catalytic ozone formation!
 The NOx cycle

Nighttime NOx losses

NO2+O3 → NO3+O2 (nighttime reaction)

NO2+NO3 ↔ N2O5 (nighttime reaction)

NO3+hν → NO2+O or NO+O2 (daytime reaction)

PAN (an important reservoir for NOx)

RCHO+OH → CH3COO2+... (aldehyde oxidation → peroxy acetyl radical)
NO2+CH3COO2 → CH3CONO2+O2 (PAN formation)

PAN → NO2+CH3COO2 (thermal decomposition)

PAN+hν → products

Terminal loss of NOx occurs through deposition of HNO3, aldehydes, peroxides, …

 Global Concerns about Air Quality

 Regional and global air quality

• Human health
• Impacts on agriculture and natural ecosystems
• Deteriorating visibility

 Climate change
• Increases in tropospheric O3
• Direct radiative effects of aerosols
• Indirect aerosol effects on clouds and precipitation

 Tropospheric self-cleaning (oxidizing) capacity

• Changes in atmospheric residence times of other climatically important
gases (CH4, HCFC’s…)
• Changes in spatial distributions (SO2, NOx, …)
Tropospheric Ozone
and Oxidants

•What are the effects of ozone and its

precursors on climate?
•How does climate change affect the
oxidizing power of the atmosphere?
The Tropical Reactor
 Impact of Climate Change on
Meteorology

• Higher temperatures
• Larger concentrations in water vapor
• Change in precipitation and in rainout
• Change in transport and convective activity
Past, present, and future ozone

1890 2000

2100
 Climate change vs. emission changes

+
(2*CO2-1*CO2)/1*CO2 , emis. 2000 [%] (emis.2100 – emis.2000)/emis.2000 , 1*CO2 [%]

≈
(2100-2000)/2000 [%]
 Non linearities in tropospheric ozone

surface
ozone
[ppb]

(Δclimate + Δemissions) - Δ(climate+emissions)

 Impact of climate change on production and loss rates of ozone

Difference in % change from 2000 to 2100 (A2 scenario) when climate

change is included, relative to a current climate

Flux Stevenson et al. Johnson et al. Zeng and Pyle

(2000) (2001) (2002)

O3 chem. prod. +6% 0% +20%

O(1D)+H2O +21% +15% +40%
O3 chem. destr. +10% +4% +37%
Net Chem. Prod. -31% -35% -50%

Models: chemistry-transport models + UK Met Office Hadley Centre Model

Global mean surface temperature: increase of 3.5 K from 2000 to 2100
Increase in humidity: 15 to 85%
 Conclusions
•We have to recognize the complexity of the issues related to
chemistry, aerosols, clouds, biosphere, climate interactions,
and their importance for future climate predictions at the global
and regional scales.

•Atmospheric oxidants and aerosols introduce strong regional

components in the climate forcing. Timescales much shorter than
in the case of well-mixed GHG, but with global effects.

•Only comprehensive global Earth system models with regional

capabilities, together with appropriate observations and process
Studies, will lead to more reliable predictions of the future patterns
in the Earth’s climate.
Stratospheric Ozone

•What is the impact of stratospheric ozone changes

on climate?
•How will climate change affect ozone recovery?
•Increase in stratospheric water vapor?
 Well-mixed
Greenhouse Gases
 Impact of emission changes on surface ozone
over Europe

all emissions changes changes in Europe only

ppb

MOZART-2.1, monthly mean, winds of May 1997

Impact of meteorological variability on surface
ozone over Europe
Mai 1993 - Mai 1996 1995 - 1990

Meteorology Emissions ppb

MOZART-2.1, monthly mean, winds of May 1997

CH4 from space Frankenberg
in August through
et al., Nov.
Science, 2005 2003.
(Science Express 17th March)

From J. Burrows, Univ.

of Bremen
 Dynamic Global Nitrogen Scheme
Plant N Pool
Natural N
N fix Deposition N2
Litter Up N2O NO
Fall take N2O
NO
NH3
Litter N Pool
Volatilization Denitrification
Mineralization NH3
Nitrification
NH4+ NO3- NO2-
Soil Inorganic N Pool

Mineralization

Soil Organic N Pool Mineralization Assimilation

Leaching

XuRi et al., MPI, 2005

 Climate (K)

Response to
Potential
Improvement in
Air Quality
• In blue: GHG unchanged
after year 2000
(commitment (%)
experiment).

• In Red: GHG unchanged

and anthropogenic
sulfate aerosols removed
after year 2000
(sensitivity experiment).
 Response in
Temperature
and
Precipitation
• (30 year
Temperature average)
increase larger
than 1K over the continents,
larger than 4K in the Arctic.
• Temperature and precipitation
changes bear some resemblance
with greenhouse warming
experiments
• A significant increase in
precipitation is found in Eastern
Pacific, suggesting an El-Nino
like change in the mean climate
state.
 Challenges for the Future
• Address fundamental uncertainties in our
understanding of aerosol microphysics, chemical
composition of aerosols, aerosol-cloud interactions,
indirect climate effects, etc.
• Assess in particular the role of organic aerosols.
• Develop appropriate field campaigns, laboratory
experiments, and physical models to provide the
basic knowledge required to study the aerosol
climate interactions.
• Investigate the role of aerosols in the earth system:
impact on the biosphere, on the ocean, the carbon
cycle, etc.
 Challenges for the Future

• Better quantify the role of the changing oxidizing

power of the atmosphere on the climate system.
• Better determine through which processes climate
change could affect air quality.
• Better assess the role of the biosphere and of the
UTLS region in the chemistry-climate interactions.
• Make full use of space observations to better
understand the processes affecting chemical
compounds in the atmosphere, and to better quantify
their budget.
Thank You
Modelling
Modelling the dynamics of
the Earth System is often
centred around the
dynamics of the
atmosphere. But is that the
best approach for
simulation the long-term
dynamics of the Earth
System as a whole - the
biosphere and chemistry as
well as the climate? And
how do we deal with
humans - the new global
geophysical force of the
Anthropocene?
 Dynamics of the Earth System:
“Tyranny of the Atmosphere”
Compartment of the Earth System

100
Relative Importance:

ATMOSPHERE
OCEAN

ICE
LAND
0
Min Hour Day Year Decade Century Millennia

Time
Interacting Scales in Biogeochemistry
global biogeochemistry
Biosphere
disturbance and succession
storms, fire
evolution
Ecosystems carbon allocation geographical
and growth distribution of
vegetation types
Plants plant seasonality

plant competition for resources

metabolism and ecological strategies
Leaves

water- and
Cells nutrient budget

photosynthesis
Molecules

Seconds Minutes Hours Years Decades Centuries

Tropical Forest (0.25S, 69.75E) Temperate Forest (50.25N, 10.25E)

Boreal Forest (62.25N, 15.75E) Savannah (14.75N, 20.25E)

Grassland (32.75N, 120.25E)

LPJ-DGVM:
PFT Competition
at Spin-Up
From: Lucht 2005
 Biomass
Distribution of
Vegetation Types
Sitch et al., GCB, 2003

Net Primary
Production

Runoff
LPJ Simulation Results

Gerten et al., J. Hydrol., 2004

Soil Carbon

Fire Frequency
Thonicke et al., GCB, 2001

Soil
Carbon
Change
Sitch et al.,
GCB, 2003
Petoukhov et al. 2000
 Optimize Intertemporal welfare Constraint
Guardrail
function

Per capita Global mean temperature change

consumption
Total radiative forcing

Budget

CO2
concentration Rad. forcing of
Industrial other GHG (exog.)
production
Fossil fuel
Land use CO2
Labour efficiency Energy efficiency
units units change emissions
Capital CO2 emission
SO2 emissions
Labour Energy
Energy
knowledge knowledge
capital capital Desulphurization
(exog.)
Labour
Leakage
Secondary
Renewable fossil Captured CO2
energy Traditional energy and SO2
non-fossil energy
(exog.)
Learning by doing Fossil carbon Fossil fuel
intensity (exog.) Energy
primary extraction
Capital stock energy
Capital stock
fossil energy sequestration
Capital stock Resource scarcity Learning by doing
sector sector
ren. energy
sector
Capital stock
extraction
 Emissions Radiative Forcing
Mitigation Atmospheric
Composition
Geo-engineering
Climate
Emissions
Dynamics
Adaptation
Impacts Impacts Mitigation
Conservation

Risks
Risks
Strategic Industrial
Natural & Metabolism
Managed Disaster Decision Education
Ecoystems Management Making Demand

Demand Perceptions
Compensation
Investment
Costs & Costs &
Benefits Benefits
Human Behaviour
& Well-Being Adaptation

From: H.-J. Schellnhuber

Impacts
 © Sebastião Salgado

…The future will depend on the

nature of human aspirations, values,
preferences and choices…
 Increasing trend in the free troposphere

Data from 9 ozone sonde stations, following Logan, 1999, Figure from IPCC, 2001
 Increasing trend in the free troposphere?

Maximum Maximum
8-hour 8-hour
mean mean
Ozone background concentrations
ozoneatconcentrations
Zugspitze
ozone concentrations
at
English at
surface
Britishstations
stations
from Eurotrac S&I, 2002
70 O3 Zugspitze
Ozone (ppb)

60
50 EU threshold

40
30
20
1980 1985 1990 1995 2000

from Scheel et al., 2002

 Tropospheric O3 Formation

 Initiation by UV radiation
O3 + hν (λ < 330 nm)  O(1D) + O2
O(1D) + H2O  OH + OH

 Hydrocarbon consumption
OH + RH  R⋅ + H2O
R⋅ + O2 + M  ROO⋅ + M

 Catalysis by NOx
ROO⋅ + NO  RO⋅ + NO2
NO2 + hν (λ < 420 nm)  NO + O(3P)
O(3P) + O2 + M  O3 + M
 Feedback from climate
change to AQ

• More O3 destruction from H2O

• More stratospheric input of ozone
• More isoprene emissions from vegetation
• Changes in lightning NOx
• Changes in surface PAN and NOx
• Increases in sulphate from OH and H2O2
• Changes in stomatal uptake.
These are quite poorly constrained – different models show
quite a wide range of response: large uncertainties
 QUANTITIES RELEVANT TO AQ
• Temperature (reaction rates, natural emissions)
• Precipitation (rainout)
• Dynamics (winds, strat-trop exchange, BL)
• Insolation (photolysis)
• Cloud amount (in-cloud reactions, washout)
• Water vapour (supply of H2O)
• Data on all these output by the climate model
Longer-Term Timeline: Key Characteristics

• Maintain and build monitoring capability

> satellite instruments
> integrated (and persisting!) observing sites

• Development of new measurement capability

• Construction of science-quality datasets for atmospheric

change parameters

• Expanded international partnerships

 The Shape of the Future

How to …
• balance of near-term goals/products and investments in
research whose payoffs lie further down the road?

• foster/organize research the elucidates multiple issues?

• craft decision tools that are timely and fully vetted?

• persue information for both national and international needs?

• play our role in integrated atmospheric science, impacts,

technology, and economic assessments?

• commit to near-term understanding, without overcommitting?