ENVR 2020 Urban Air Pollution Gaseous Pollutants: Based On Lecture Notes From Dr. Meike Sauerwein

ENVR 2020
Urban Air Pollution
Gaseous Pollutants
Based on lecture notes from Dr. Meike Sauerwein

Urban Air Pollution - ENVR 2020 1
Your Questions
What compositions are in the air right now?
Gases Particles

Gases in the
atmosphere
Major gases
total ~99.9%
Argon 1% Other Gases <0.1%
Trace Gases Oxygen 21%

(each << 0.001 %)
At elevated concentration these gases Nitrogen 78%

have adverse effect on
• Human health e.g. O3
• Climate e.g. CO2, CH4, N2O
• …
Jacob (1999) Introduction to Atmospheric Chemistry, (modified)

What else
is in the air? (more trace gases)
A huge variety of
Volatile Organic
Compounds (VOC)
and several inorganic gases
such as
• Sulfur Dioxide (SO2)
• Nitrogen Oxides (NOx)
• Carbon Monoxide (CO)
_ • AND WATER VAPOR (H2O) Ho et al. 2013, Volatile Organic Compounds in Roadside Environment of Hong Kong;
Aerosol and Air Quality Research

Air Pollutants - Classification Scheme
Ozone depletion
Green House Gas effect
Air Quality / Smog Acid Rain

Ozone
Particle
formation
(formation)

Objectives
• Clearly differentiate different gas pollutants

• Sources – where do they come from
• Impacts - ozone depletion, green house effects or local air pollution
• Describe how Urban air pollutants
• react in the atmosphere
• can be removed from the atmosphere

Ozone Depletion
The thinning ozone layer
/ozone hole
Jacobs, 1999: Introduction to Atmospheric

Chemistry - CHAPTER 10. Stratospheric Ozone

Stratospheric Ozone (O3) - The “good” ozone
Ozone layer protects earth inhabitants from UV-C and UV-B radiation
The Ozone layer
- high
energy .
• absorbs UV-C (via Ozone formation) and partially
¥4
absorbs UV-B radiation (via Ozone photolysis) UV-C 180-280nm
UV-B 280-320nm
UV
Like that it filters UV radiation UV-A 320-400nm
Ozone layer depletion ,

• would increase the UV-B radiation that reaches the ¥*¥x
earth surface, and lead to
Eye cataracts Weakened Damage to

Energy
skin-cancers
(clouding of the lens immune eco-systems http://www.theozonehole.com/cfc.htm
in the eye) systems
http://www.who.int/uv/faq/whatisuv/en/index2.html

Formation of the “Ozone layer” (simplified)
Photolysis:
• Ozone layer forms from photolysis of atmospheric oxygen the separation of molecules
• only UV-C radiation can photolyze the oxygen molecule by the action of light
UV-C Chiqh energy) Bonds in the Ozone

molecule weaker than
in oxygen molecule!
+
Oxygen 2 Oxygen Oxygen Oxygen
molecule (O2) atoms (O) atom (O) molecule (O2) Ozone molecule
(O3)
• Photolysis of ozone needs less energy (UV-B radiation sufficient)
UV-B UV-C 180-280nm

Ozone does not get destroyed, O UV-B 280-320nm Energy
+ and O2 can react back to Ozone UV-A 320-400nm
(OZONE-Cycling)
Ozone molecule Oxygen Oxygen
(O3) atom (O) molecule (O2)
Natural removal of Ozone
+ Oxygen atom 2 Oxygen molecules
Other mechanisms possible where Ozone reacts with Hydrogen oxide or N2O
Ozone formation and natural removal are slow

But OZONE-Cycling is fast
OZONE-Cycling

Ozone Depletion (Loss of Polar Ozone)
The role of Chlorofluorocarbons (CFC)
Diatomic Oxygen
released to atmosphere
70% by
Chlorine radical
breaks bond in
+
Chlorine
Ozone molecule Chlorine containing gases
monoxide
Chlorine Catalytic Cycle

+ 30% involves
radical
Chlorine &
UV-B
Produces free Bromide
chlorine radical containing gases
+ Solar radiation breaks

bond in Chlorine
UV B radiation removes monoxide dimer
chlorine from CFC ClOO molecule will
molecule release another Cl radical
& Oxygen to atmosphere

all harmful
Ozone depleting Gases
Where do they come from?
Chloro fluoro carbons (CFCs)*

odorless, non-flammable, non-corrosive
Bromo fluoro carbons (BFCs)*
Tetra chloro methane (CCl4)*
Hydro chloro fluoro carbons (HCFCs)*

The Montreal Protocol is estimated to have prevented:
• 19 million more cases of non-melanoma cancer
Nitrous oxide (N2O) • 1.5 million more cases of melanoma cancer
• 130 million more cases of eye cataracts
*Restricted by Montreal protocol http://www.theozonehole.com/cfc.htm

What makes them
Ozone depleting gases?
Bromine
Chlorine radical
transported all the way radical
to the stratosphere
release radicals
And N2O?
• non-reactive in the troposphere
• reacts in the Stratosphere with
Oxygen atoms (from the ozone cycle)

Green House
Effect
Jacobs, 1999: Introduction to Atmospheric
Chemistry - CHAPTER 7. The Green House Effect

Radiation
Incoming solar radiation
• main source of heat to the Earth is solar

energy (solar radiation, short wave)
• Earth itself emits radiation back to space
(terrestrial radiation, long wave)
• Some of terrestrial radiation is trapped by

Outgoing greenhouse gases (e.g. water vapor, CO2) &
terrestrial radiated back to the Earth
radiation
• This warming effect makes the earth
temperature liveable for humans

Anthropogenic emissions of Greenhouse Gases
E-
… adding on the natural Greenhouse Effect
• Carbon Dioxide (CO2)
• Methane (CH4)
• Nitrous oxide (N2O)
• Hydro fluoro carbons (HFCs)

electrical
• Sulfur Hexafluoride (SF6) insulator
• CFCs, HCFCs*
*exclusively anthropogenic emissions

What makes them Greenhouse Gases?
ability to absorb & re-emit

longwave radiation (heat)
https://www.acs.org/content/acs/en/climatescience/greenhousegases/properties.html

Global An effective H 2O
greenhouse gas: CO2
warming absorption compared strength of
wavelength lifetime concentration
potential to water & CO2
molecules
absorbed absorption
Global warming potential ~100

Measure of how much energy the
emissions of 1 kg of a gas will absorb
over a given period of time, relative
to the emissions of 1 kg of carbon
dioxide (CO2).
Replacing CFCs with HFCs helped to stop

the stratospheric Ozone depletion, but
made the greenhouse effect even worse…
https://www.epa.gov/ghgemissions/understanding-global-warming-potentials;
https://www.acs.org/content/acs/en/climatescience/greenhousegases/properties.html

Air quality
Jacobs, 1999: Introduction to Atmospheric Chemistry
- CHAPTER 11. Oxidizing Power of the Troposphere
- CHAPTER 12. Ozone Air Pollution
- CHAPTER 13. Acid Rain

Primary and Secondary pollutants
Secondary pollutants Secondary pollutants

e.g. HNO3 SO3 H2SO4 Formed through reaction
Chemical reactions H2O2 O3 Nitrate sulfate of primary pollutants and
⇐
the compounds of the
unpolluted atmosphere
Gas emissions Primary pollutants (precursor gases) Primary pollutants

e.g. CO2 SO2 NO NO2 CH4 N2O Released directly from
CFC volatile organic compounds emission sources
(also primary aerosols)

Chemical reactions in atmosphere
What is a reactive gas?
During transport through the atmosphere, all except the most non-reactive substances
participate in chemical reactions in two ways.
1. Photochemical reaction
• Gas molecule absorbs0 light (photon) and
“breaks apart” (photolysis), changes its structure,
or reacts further with another molecule
2. Thermal reaction Reaction of 2 gases

• Two substances collide and react
Reaction of a gas
with a solid particle
Reaction of a gas
with a droplet

Free radicals
“Detergents of the atmosphere”
How are they formed?

• in the atmosphere from photochemical reaction
• Common radical species in the atmosphere:

• Hydroxyl radicals (•OH) (formed from Ozone and H2O)
• Hydroperoxy radical (HO2•) (formed from volatile organic compounds)
Radicals can be regarded as “detergents of the atmosphere”

• they are very reactive
• these reactions remove pollutants from the atmosphere

Removal of pollutant gases from the atmosphere
1. Gas pollutants react
IT
• Photochemical or
• with Radicals or Ozone 03
2. Reactions transform gases into gases with
• lower volatility
• higher water solubility
Gases can then react with particles and cloud droplets and be removed to the surface by
Dry deposition Washout (Scavenging) Interception Rainout

Chemical reactions in atmosphere –
Ozone formation

Tropospheric Ozone – The “Bad” Ozone
a Secondary pollutant
① Zone
• ~10% of the atmospheric ozone is naturally
occurring in the troposphere (10’s of ppb) To Ozone (O3)
Meteorological conditions that
• Most is produced from photochemical reaction favour Ozone formation
involving • High temperatures
=
• Nitrogen oxides (NOx) and • Light winds
• Volatile organic compounds VOCs • Stable conditions
• Temperature inversion

Ozone Formation: The Role of NOx
joint
'
Photochemical oxidation of Nitrogen dioxide (NO2)
Noz → No -14
Nitrogen dioxide (NO2) + light Nitrogen oxide (NO) + Oxygen atom

Primary pollutant
0+0 , -7 0]
Oxygen atom + Oxygen molecule (O2) Ozone molecule (O3)
Secondary pollutant 03-1 NO -702-1 Nor
O3 + NO O2 + NO2

Ozone Formation: The Role of VOCs
Free radicals formed from VOC
• Free radicals such as HO2• are produced from the degradation (oxidation) of volatile
organic compounds (VOCs)
-
VOC HO2• Radical
→ V02 t.at
NQ 1- two
• The key role of HO2• Radicals is
+ +
Nitrogen oxide + HO2• Radical Nitrogen dioxide + •OH Radical

auto
Free radicals recycle NO2
polit
.

Primary pollutant

Secondary pollutant
0-102-7 03
Ost NO → Norton
Free radicals recycle NO2
HO2• Radical
• Radicals produced from VOC recycle NO2

• More NO2 means more Ozone

Primary pollutant

Secondary pollutant

Ozone Formation
The tricky part is
• Degradation of VOC produces free radicals (e.g., HO2•)

• VOCs also consume free
-
radicals e.g. •OH
• NO2 is removed from the atmosphere by reaction with

the •OH free radical, too Nbz -1 OH →
-
• thus, VOCs and NO2 “compete” for •OH

Your Questions
How to reduce the ozone concentration?

Ozone Isopleth Plot ☒ jane
NOx -limited
• In “NOx -limited” case

• Reducing NOx emissions will lower Ozone
• Reducing VOC emissions will have no effect v0
VOC -limited
• In “VOC-limited” case Go
• Reducing NOx emissions will increase Ozone

• Reducing VOC emissions will lower Ozone = VUL

How about Hong Kong and
the Pearl River Delta Region?
VOC-limited?

Hong Kong and the Pearl River Delta Region
• In most of the PRD region, the formation regime is

• VOC-limited in the morning
• NOx-limited during peak ozone hours
• some areas are always VOC-limited, but

• their ozone concentrations are relatively low
• ozone increases caused by NOx reduction generally do not cause
higher ozone levels than the region's original ozone maxima

Ozone control in the Pearl
River Delta (PRD) region
• NOx regulation
• reduces ozone levels over the long term
• increases short-term ozone levels in metropolitan regions (VOC-limited)
such as the PRD region
• NOx reduction in the PRD region
• may raise the mean ozone concentration
• it can also decrease peak ozone levels
Modelling results show that in addition to VOC control, NOx control can
be effective for reducing peak ozone concentrations in the PRD region.

Chemical reactions in atmosphere –
Acid Rain

Acid Deposition/Rain
Precipitation with acidic components
• Wet or dry deposition incl.

• Rain, snow, fog, hail
or acidic particles
• Once deposited to surfaces

• water bodies, vegetation, buildings
• And harm plants, wildlife, materials
https://www.epa.gov/acidrain/what-acid-rain

Acid Rain
• Normal rain has a pH of about 5.6

• due to the naturally occurring CO2 that reacts with water to
form small amounts of carbonic acid (H2CO3)
• Acid rain usually has a pH
between 4.2 and 4.4
• Sulfuric or nitric acid are
significantly stronger acids
than H2CO3
https://www.epa.gov/acidrain/what-acid-rain

Acid Rain Formation
Example sulfuric acid (H2SO4)
• SO2 emitted to the atmosphere

• Oxidation reaction with OH radical and Oxygen SO3
• SO3 can via reaction with water form sulfuric acid (H2SO4)
• In the atmosphere H2SO4 plays a crucial role for

• Acid rain phenomena
• And New particle formation (Secondary aerosols, see next lecture)

Does Hong Kong suffer from acidic rain?
Rain water in Hong Kong in the past years slightly less acidic
80000
(annual average)
4.9
Rain water pH
70000
4.7
60000
4.5
50000
Central/Western
Total annual rain fall
Kwun Tong 4.3

40000 Yuen Long
4.1
30000
[t/ha]
20000 3.9
10000 3.7
0 3.5
Air Quality in Hong Kong, EPA, Reports 1996 - 2015

Atmospheric life time
• Average time that gas

molecules of one
substance remain in the
atmosphere before they
are removed by reaction
or deposition.
Gas
Particle
SO2 oxidation into sulfuric acid & sulfate containing particles may proceed during long-range transport
acid rain may fall far away from where SO2 is emitted

Spatial and temporal
scales
• Gases that are non-reactive
have a long life time and can
• accumulate (if they keep being
emitted)
• be transported over long
distances
• Most gases are reactive, yet
their lifetime can vary from
hours to weeks

Scales of Air Pollution
Urban Air Pollution
30 km
20 km
10 km
Seinfeld, Pandis (2006), Atmospheric chemistry and physics : From air pollution to
climate change, Table 1.1
http://www.spatioepi.com/images/map_lib/index%20map/indexmap.jpg

Regional
Air Pollution
200 km
100 km
Seinfeld, Pandis (2006), Table 1.1
http://www.d-maps.com/carte.php?num_car=20982&lang=en

Regional & Global
Atmospheric 40,000 km
Phenomena
2000 km
1000 km
Seinfeld, Pandis (2006), Table 1.1

Your Questions
Can the air pollution problem actually be

solved? Because it’s such a global problem
with many factors to consider, which has
existed for so long.

Your Questions
If the air pollution keeps getting worse.

[In] How many years will the earth be
totally polluted and people cannot live in?

Greenhouse gases vs other air pollutants
Greenhouse Gases
Gases that affect air quality
/ Ozone depleting Gases
Reactivity • Reactive (oxidative processes, particle
• Inert, not chemically reactive
formation, gas-particle reactions)
• Long lived species, can take years / • Are removed from the atmosphere
decades to be removed from Lifetime within days by reaction with aerosols
atmosphere and deposition and/or washing out
• ODG: UV light breaks and activates
molecules to react with Ozone (UV)-light • Reaction of gases triggered by light
• GHG: absorb & emit longwave
radiation (heat)
• Ambient concentrations generally Health • Ambient concentrations can harm
not harmful to humans threats human health, animals, vegetation, etc.

Take aways
The special and temporal scale of air pollution problems are closely linked
• Short lived pollutants are associated with localized impacts
• Long lived pollutants are associated with regional and global impacts
Compare pollutant lifetime to transport time

ENVR 2020 Urban Air Pollution Gaseous Pollutants: Based On Lecture Notes From Dr. Meike Sauerwein

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ENVR 2020

Urban Air Pollution

Based on lecture notes from Dr. Meike Sauerwein

What compositions are in the air right now?

Urban Air Pollution - ENVR 2020 2

Argon 1% Other Gases <0.1%

Trace Gases Oxygen 21%

At elevated concentration these gases Nitrogen 78%

Jacob (1999) Introduction to Atmospheric Chemistry, (modified)

Urban Air Pollution - ENVR 2020 3

Urban Air Pollution - ENVR 2020 4

Green House Gas effect

Air Quality / Smog Acid Rain

Urban Air Pollution - ENVR 2020 5

• Clearly differentiate different gas pollutants

Urban Air Pollution - ENVR 2020 6

Jacobs, 1999: Introduction to Atmospheric

Urban Air Pollution - ENVR 2020 7

• absorbs UV-C (via Ozone formation) and partially

Ozone layer depletion ,

Eye cataracts Weakened Damage to

Urban Air Pollution - ENVR 2020 8

UV-C Chiqh energy) Bonds in the Ozone

• Photolysis of ozone needs less energy (UV-B radiation sufficient)

UV-B UV-C 180-280nm

+ Oxygen atom 2 Oxygen molecules

Ozone formation and natural removal are slow

Urban Air Pollution - ENVR 2020 10

Chlorine Catalytic Cycle

+ Solar radiation breaks

Urban Air Pollution - ENVR 2020 11

Chloro fluoro carbons (CFCs)*

Bromo fluoro carbons (BFCs)*

Tetra chloro methane (CCl4)*

Hydro chloro fluoro carbons (HCFCs)*

*Restricted by Montreal protocol http://www.theozonehole.com/cfc.htm

Urban Air Pollution - ENVR 2020 12

Urban Air Pollution - ENVR 2020 13

Urban Air Pollution - ENVR 2020 14

• main source of heat to the Earth is solar

• Some of terrestrial radiation is trapped by

Urban Air Pollution - ENVR 2020 15

• Carbon Dioxide (CO2)

• Nitrous oxide (N2O)

• Hydro fluoro carbons (HFCs)

*exclusively anthropogenic emissions

Urban Air Pollution - ENVR 2020 16

ability to absorb & re-emit

Urban Air Pollution - ENVR 2020 17

Global warming potential ~100

Replacing CFCs with HFCs helped to stop

Urban Air Pollution - ENVR 2020 18

Urban Air Pollution - ENVR 2020 19

Secondary pollutants Secondary pollutants

Gas emissions Primary pollutants (precursor gases) Primary pollutants

Urban Air Pollution - ENVR 2020 20

2. Thermal reaction Reaction of 2 gases

Urban Air Pollution - ENVR 2020 21

How are they formed?

• Common radical species in the atmosphere:

• Hydroperoxy radical (HO2•) (formed from volatile organic compounds)

Radicals can be regarded as “detergents of the atmosphere”

Urban Air Pollution - ENVR 2020 22