Chapter 6.

Chemical forcing of climate change

https://data.giss.nasa.gov/gistemp
 Emission of radiation
• Radiation is energy transmitted by electromagnetic waves
• All objects at T > 0 K emit radiation by oscillation of electric charges in object
emitting object

oscillating
charge

receptor object
emitting object
loses energy oscillating
(heat) charge
speed of light c

• Hotter objects have higher

oscillation frequencies and so Electric field excites charge in receptor object;
shorter emission wavelengths; object absorbs radiation, gains energy (heat)
frequency ν = c/λ
• Radiation emitted within an object can be reabsorbed by object; actual
radiation emitted by object to outside is proportional to area of object
• An object can absorb radiation of a given wavelength only if it can have
oscillating charges for that wavelength
 Measuring the radiation flux emitted by an object
• A spectrometer measures the radiation flux DF emitted by an object in discrete
wavelength bins [l, l+Dl]

We normalize DF by Dl
because DF can be expected
to be proportional to Dl

• Consider now an ideal spectrometer with infinite resolution dl:


( )  lim is the radiation flux distribution function characteristic of the object
 0 

Total radiation emitted by object:  ()d 

0
 Blackbody radiation
• Objects that absorb 100% of incoming radiation are called blackbodies
• For blackbodies,  is given by the Planck function:
2hc 2 h = Planck constant
(, T )  c = speed of light
 hc 
 5  exp( )  1 k = Boltzmann constant
 kT   T = temperature

• Integrate over all λ to get total radiation flux:

F =
wheresT
4
s = 2p 5k 4/15c2h3 = 5.67x10-8 W m-2 K-4
is the Stefan-Boltzmann constant

• Solve d/d = 0 for λ of max emission:

lmax = hc/5kT = 2900/T Wien’s law
 Kirchhoff’s law: emissivity = absorptivity
e(, T ) a (, T )
Emissivity = ratio of emitted radiation flux to that of a blackbody at same T

Absorptivity = fraction of incoming radiation that is absorbed

The absorption spectrum

of an object can be measured
in the lab:

The emission spectrum of

that object is then solely
determined by its absorption
spectrum and its temperature
Solar radiation spectrum: blackbody at 5800 K

lmax = 0.5 mm (green)

0.4 0.7
 Terrestrial radiation spectrum measured from satellite:
composite of blackbody radiation spectra for different T

lmax ≈ 10 mm (IR)

Most terrestrial radiation is emitted in the 5-50 μm range (thermal IR)

 Radiative equilibrium for the Earth
assuming uniform-T blackbody radiation for Sun and Earth

Sun sees Earth disk

at any given time

Energy emitted by Sun per unit time: ES = 4pRS2sTS4

Solar radiation flux intercepted by Earth (solar constant):
FS = ES /(4pd2) = sTS4(RS/d)2 = 1360 W m-2
Average solar radiation flux received by the Earth: FSpRE2/(4pRE2) = FS/4
Radiative equilibrium for the Earth:
flux in = flux out
(1-A)FS /4 = sTE4 = 255 K

where A is the albedo (reflectivity) of the Earth COLD!

 TE = 255 K is called the effective temperature of the Earth

It’s the mean temperature that would be inferred by an observer in space

measuring the radiation flux emitted by the Earth

Earth seen by Voyager-1 4 billion miles away

That object has a temperature

of 255 K!

• But maybe the observer is not seeing the surface of the Earth but its
atmosphere?
• It depends on whether the atmosphere can emit radiation in the 5-50 μm
range where most of Earth’s radiation is emitted
• …and thus on whether the atmosphere can absorb radiation in that range
 Absoption of radiation by gas molecules
…requires quantum transitions in internal energy of molecule.

• THREE TYPES OF TRANSITION

– Electronic transition: UV radiation (<0.4 mm)
• Jump of electron from valence shell to higher-energy shell,
may result in photolysis (example: O3+hn gO2+O)
– Vibrational transition: near-IR (0.7-20 mm)
• Increase in vibrational frequency of a given bond
requires change in dipole moment of molecule
– Rotational transition: far-IR (20-100 mm)
• Increase in angular momentum around rotation axis

• Very little absorption takes place at visible wavelengths (VIS: 0.4-0.7 mm)
• Gases that absorb radiation in the 5-50 μm range where the Earth emits are
called greenhouse gases; this requires vibrational-rotational transitions
 Normal vibrational modes of CO2

Δp 0 forbidden

Δp 0 allowed

Δp 0 allowed

Infrared spectrum asymmetric

of CO2 stretch
bend

15 μm 4 μm
 Major greenhouse gases

N2, O2, Ar are not greenhouse gases because they cannot acquire a dipole moment
 Radiative transfer and optical depth
Propagation of radiation
for a given wavelength extinction coefficient from species X [m -1]:
absorption+scattering

F ( z  dz )  F ( z )  X ( z )F ( z )dz
Z Integration yields Beer’s law:
Z
F ( Z ) F (0) exp[   X ]  X  X ( z )dz
0
optical depth over [0, Z]

Extinction is proportional to[X]: X ( z )  X nX ( z )

extinction cross-section [cm2 molecule-1]

Atmospheric optical depth integrates to top of atmosphere:

 
F (TOA) F (0) exp[   X ] with  X   X ( z ) dz X  nX ( z ) dz X X
0 0

column concentration [molecules cm-2]

 Greenhouse effect:
absorption of terrestrial radiation by the atmosphere
absorptivity

“atmospheric window”
(8-12 μm)
 Simple model of greenhouse effect
Solar radiation Terrestrial radiation
VIS IR Energy balance equations:
• Earth system
FS (1  A) / 4 (1  f ) To4  f  T14
Incoming Reflected Transmitted
solar flux • Atmospheric layer
Solar flux Surface emission
f  To4 2 f  T14
FS / 4 FS A / 4 (1  f ) To4 1
Solution:   To=288 K
4

 F (1  A) 
To  S
f  e f=0.77
 4(1  )  T1 = 241 K
Atmospheric  2 
f  T14 emission
Atmospheric layer (T1)
f  T14 Atmospheric
emission
absorptivity 0 in VIS
f in IR

Surface emission
FS / 4
FS A / 4  To4
Earth surface (To)
absorptivity 1-A in VIS
1 in IR
 Increasing albedo from aerosols
Aerosols cool the Earth by reflecting solar radiation

solar radiation
relative humidity
>100%

combustion
industry aerosol particles cloud droplets condense on particles
dust (0.01-10 μm)

Aerosol Optical Depth (nasa.gov)

 Climate change arises from disruption of radiative equilibrium

Climate equilibrium: Fin = Fout Radiative forcing: ΔF = Fin – Fout > 0

Fin Fout Fin Fout

increase greenhouse gas by ΔG

Terrestrial
ΔG
Solar

positive radiative forcing

[ warming
visible infrared visible infrared
radiative fluxes
Radiative forcing: ΔF = Fin – Fout < 0
Fin Fout

increase albedo by ΔA ΔA

negative radiative forcing

[ cooling
visible infrared
 Computing radiative forcing
• Start from climate equilibrium: Fin = Fout
Energy flux in Energy flux out
Fin = FS(1-A)/4 Fout = (1-f/2)σTo4

Earth surface
• Now apply an instantaneous greenhouse gas increase df (not allowing To to change):

ΔFout = - σTo4 Δf/2 < 0 → Fin > Fout ; the Earth heats

ΔF = Δ(Fin – Fout) is called the radiative forcing (ΔF > 0 warms, ΔF < 0 cools);

Here Δ F= - Δ Fout an increase of greenhouse gases causes positive radiative forcing

• Or apply an instantaneous increase in albedo: Δ A > 0 → Δ Fin = -Fs ΔA/4 < 0

Fin < Fout and Δ F < 0 ; negative radiative forcing, the Earth cools
 Radiative forcing drives temperature response to restore equilibrium

At equilibrium, ΔTo = λΔF

where λ =(4(1-f/2)σTo3)-1 = 0.3 K m2 W-1 is the climate sensitivity parameter

Earth system models give λ in range 0.6-1.3 K m2 W-1 (best estimate 0.8 K m2 W-1)
Radiative forcing of climate change drives cascade of impacts and feedbacks
Radiative forcing ΔF
Natural: Human:
• solar activity • emissions
• volcanoes • land use

Temperature response ΔTo ΔTo  ΔF

Surface temperature response
climate is proportional to radiative forcing
feedbacks Physical impacts
drive ΔTox3 • sea level rise …until tipping point
• ice loss
• precipitation changes
• ecosystem changes…
transition to new climate

Societal impacts
• water resources
• agriculture
• fires
• disease…
 Global warming since pre-industrial time

+1.2oC

https://data.giss.nasa.gov/gistemp
 Contributions to radiative forcing since pre-industrial times
and temperature response

• Temperature response to ΔF is similar for all radiative forcing agents, so total effect
on temperature can be obtained by summing the radiative forcings
• Aerosols offset 30% of greenhouse warming, drive uncertainty in radiative forcing
• Total radiative forcing ΔF = 2.7 W m-2 is only 1% of equilibrium Fin = 245 W m-2 but
drives ΔTo = 1.3 K IPCC [2022]
 Air quality imperatives will drive decrease of aerosol (PM2.5)
What kills people around the world?
Dietary Risks
All Cancer
Tobacco
All Air Pollution
Ambient PM2.5
Indoor Air Pollution
Water Sanitation
Lung Cancer
action
Unsafe Sex
Breast Cancer
Ambient Ozone
Annual mean PM2.5 in China
2013 2018

Future decrease in PM2.5 must be compensated

by more aggressive action on greenhouse gases

HEI, 2019; Zhai et al., 2019

 Global warming potential

How does emitting ΔmX = 1 kg of X compare to emitting 1 kg of CO2?

GWP-H of gas X for time horizon H:

to  H

GWP-H 
 to
FX (t )dt
to  H
 to
FCO2 (t )dt

FX
where  X  is the radiative forcing efficiency
mX
Table 7-1. Global warming potentials (GWPs) of selected greenhouse gasesa

Gas Atmospheric GWP-20 GWP-100

lifetime, years
CO2 ~100b 1 1
CH4 12 81 28
N2O 110 270 270
CFC-11 52 8300 6200
HFC-134a 14 4100 1500
a
From IPCC AR6. GWP-20 and GWP-100 are for 20-year and 100-year time horizons respectively.
b
The lifetime of a CO2 perturbation involves multiple time scales as discussed in chapter 5.
 General design of climate metrics

climate metric =  (impact) (discount rate) dt
to

Figure 6-18. Design of a climate metric convolving an emission pulse, an impact function, and a discount
rate.
https://www.cnn.com/2024/03/18/climate/air-pollution-report-2023-asia-climate-intl-hnk
 The agents of climate change

Observed rise in global mean surface temperature

aerosol others
particles (~100 years)
(1 week)
methane
(9 years)

+1.2oC CO2
(100+years)

Warming from methane includes additional contributions from ozone, water, and CO 2
when methane is oxidized in atmosphere
 PM2.5 air quality may be major driver of decarbonization in global South

action to
decrease PM2.5

Annual mean PM2.5 in China

2013 2018
…but this will offset the near-term benefit
of CO2 decreases

State of the Air, 2020; Zhai et al., 2019

Projected temperature responses from aggressive 1.5oC decarbonization scenarios
relative to constant emissions

Decreasing aerosol delays improvement until 2050

No improvement until 2050

relative to constant emission scenario

Shindell and Smith [2019]

 Increasing attention to methane in climate policy
Biden at COP26 announcing Global Methane Pledge, now signed by 150 countries
Why the importance of methane for staying below 1.5oC of danger?

Observed rise in global mean surface temperature

aerosol others
particles (~100 years)
(1 week)
methane
(9 years)

+1.2oC CO2
(100+years)
 Effect of zeroing out methane emissions

Observed rise in global mean surface temperature

others
(~100 years)
aerosols
(1 week)
CO2
+0.7 C
o
(100+years)

Warming decreases by 40%

buys us time as we work to decarbonize the economy

Decreasing methane would also improve ozone air quality
with benefits for public health, crops, natural vegetation … and CO 2
 Methane has been growing rapidly and its sources are complicated

Methane is a major greenhouse gas…

but where does it come from?

Wetlands: 100-220 Tg a-1 Oil/gas: 40-100 Coal mines: 20-60

Pre-industrial: 650 ppb

Present: 1930 ppb
Rice: 20-40

Waste: 50-80

Livestock: 90-140
 Decreasing methane emissions should be easy
Simple measures can go a long way, there is no stockage problem like for CO 2

fix leaks, venting practices flare excess gas recover gas from landfills
…or use it

digest gas from manure ponds, change cattle feed change rice practices
wastewater plants
 …but problem is that methane comes from a zillion
of individually small point sources with highly variable
emissions
My flare
went out! I’m
venting!

I’m
leaking!

oil field in California

This translates into order-of-magnitude uncertainties in national oil/gas emissions
National methane emission inventories for oil/gas sector (Tg a-1)

UN
reports
Bottom-up
inventories

…and little credibility in emissions reported by individual countries under Paris agreement
Scarpelli et al., 2022
 Lack of confidence in bottom-up methane emission inventories
reported by individual countries to the UNFCCC

• These emission inventories set the basis for Global Stocktake (how the world is doing)

• They set the basis for Nationally Determined Contributions to reduce emissions

• But they are not very good!

Satellites enable global continuous observations of atmospheric methane

Regional/global mapping
0.1-10 km pixels
high precision

in space
scheduled
canceled

Individual plumes
< 60 m pixels

Jacob et al., ACP 2022

TROPOMI (2018-): global daily mapping
with 5.5x7 km2 pixels, 0.6% precision

Over 100 million

Annual mean TROPOMI observations, 2021 observations per year

oil/gas
livestock
landfills coal
livestock
oil/gas landfills
livestock oil/gas
rice livestock rice
wetlands landfills

Balasus et al.,AMT 2023

Inferring methane emissions from satellite observations
by inversion of an atmospheric transport model

Observed methane
concentrations

transport

Emissions
Inferring methane emissions from satellite observations
by inversion of an atmospheric transport model

Observed methane
concentrations

inversion

Emissions
 Top ten methane emitting countries [Tg a-1]
70
from inversions of GOSAT and TROPOMI satellite data
*
60

50
Livestock Rice Waste Oil Gas Coal
40

30

20

10

0
i *
na d *
ia U
S
ra
z il
s ia pia s ia t an ela
nm
ar
C
h In B us th
io
one k is
ezu a
R E d a n iy
I n P e M
V

did not sign the Global Methane Pledge Qu et al., ACP 2021
* Chen et al., ACP 2022
Nesser et al., ACP 2024
 Attributing the 2010-2021 global emission trend

Where are methane emissions increasing and decreasing

• The rise is mainly from tropical wetlands, livestock, rice;

• The sink (OH concentrations) has been flat
Qu et al., in prep.
 TROPOMI observations over the US
Mean methane concentrations, March 2018 – March 2019

Zhang et al., Sci Adv 2020

Quantifying US emissions at 25-km resolution using TROPOMI
Correction to 2023 US EPA inventory by inversion of TROPOMI data

Correction factor
livestock +11%
oil and gas +12%
EPA is low
by 13% coal -29%
landfills +51%
wastewater
other
wetlands

Methane emission, Tg a-1

• EPA emission estimates for individual landfills have large errors:

o Overestimated gas recovery
o Overestimated decay rate of emission
o Inadequate accounting of site-specific operating practices

Nesser et al., ACP 2023

 Geostationary observation of methane plumes
from NOAA GOES weather satellite
geostationary orbit

EELL pipeline from Chihuaha to Durango

supplying Permian
Pipeline gasvalve
blocking to Mexico
in Mexico

Pi
p
el

blocking valve
in
e

Q = 300 tons h-1, 3-h duration

Watine-Guiu, Varon, et al., PNAS 2023

 Targeting methane emissions cannot be a substitute for CO 2…
because it does not do much for long-term climate change

Warming response after 1-year pulse of present-day emissions (IPCC AR6)

CO2 CH4
Response after 10 years

Response after 100 years

• Over 10-year horizon, methane is more important than CO2

• But over 100-year horizon, methane is long gone while CO2 is still there
• Methane and CO2 emissions should not be viewed as “equivalent” in climate policy
(which they unfortunately are)
 Methane is still a powerful lever for near-term climate action
…while we decrease CO2 emissions and develop carbon capture technologies

Business as usual
Climate risks

CO2 emission decrease to near zero

Start of climate
action
CO2 emission decrease
+ carbon capture
CO2 emission decrease
+ carbon capture
+ methane emission decrease
(+solar geoengineering?)

Time
 Solar geoengineering

Stratospheric aerosol injection could work technically but raises serious policy, political,
and ethical issues