Environmental Chemistry Topic 2:

Ozone

Christoph Koch
 Learning objectives
The students can...

2.1 describe the importance, location, and thickness of the ozone layer.

2.2 explain the chapman reaction sequence.

2.3 explain the depletion of the ozone layer using various ozone-depleting substances.

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 Stratospheric chemistry: Ozone
The stratosphere is the layer above the lowest layer, the troposphere.

The blue beam is the ozone layer

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 Stratospheric chemistry: Ozone
The stratosphere extends from 15 to 50 km in altitude.

Even though the main gases are identical with the troposphere (O2 and N2), the temperature
inversion at the tropopause produces a stable atmosphere with minimal mixing.

In addition, higher-energy radiation leads to different chemical reactions than in the

troposphere: Especially the generation and decomposition of ozone (O3).
Stratosphere

Absorbs high-energy
solar UV radiation

Causes irritation via

its oxidizing potential
and acts as a
greenhouse gas

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 UV radiation
Not all UV radiation is equal.

UV-A: 315-400 nm
7% of total solar flux. Not particularly harmful, but nevertheless problematic
UV-B: 280-315 nm
1.5% of total solar flux. Especially harmful after prolonged exposure
UV-C: 100-280 nm
0.5% of total solar flux. Extremely and rapidly harmful

Approximately 90% of UV-B radiation is absorbed

at an average thickness of the ozone layer
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 UV radiation
The absorption of UV-B radiation by O3 is relatively small and thus requires
a thicker and intact ozone layer

The benefit of UV-B irradiation: The risk of UV-B irradiation:

Allows synthesis of vitamin D 2 types of skin cancer

As a protective mechanism,
our skin produces melanin

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 Sunscreen
We can help our skin against UV irradiation with sunscreen and sunblocks.

Sunscreens contain molecules that strongly absorb in the 250-325 nm range

(almost no UV-A!) and might also contain free radical scavengers.

The sun protective factor (SPF):

A SPF of 15 means, you can stay 15 times longer in the sun.

How effective is the sun absorbed?

100
15 =
100 − &
100
⇔ & = 100 −
15
⇔ & = 93.3

93.3% of the UV-B radiation (of a certain wavelength)

is absorbed.

Sunblocks contain solid particles (most often titanium dioxide or zinc oxide)
that reflect UV radiation (including UV-A).
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 Sunscreen
But there are some issues with sunscreen…

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 Ozone Chemistry
The formation and decomposition of ozone is described by the Chapman reaction sequence:

Formation ∆H°(kJ mol-1)

O2 + hv (λ ≤ 240 nm) ➝ O + O Slow +498.4
M is usually
then: O + O2 + M ➝ O3 + M Fast -106.5 N2 or O2

Decomposition
O3 + hv (λ ∼ 200-315 nm) ➝ O2* + O* Fast +386.5
or: O + O3 ➝ O2 + O2 Slow -391.9

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 Ozone Chemistry
We need O2 and intense radiation to form O3.
Therefore, the ”sweet spot” for the formation of ozone is at app. 23 km

Too little O2, but

sufficient intense
radiation
ozone layer

Sufficient O2, but

too little intense
radiation

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 Ozone Concentration
A sufficiently thick ozone layer is required for a proper protection.
But how to measure the extremely reactive ozone?

“On site” measurement of sun light at 255 nm,

which is the absorbance maximum of ozone.

The number of total ozone molecules is

expressed in Dobson Unit (DU).
It represents an equivalent thickness
of pure ozone.

The global average is app. 300 DU

This equals a 3 mm thick layer of pure ozone

The Dobson ozone spectrophotometer

(invented 1924 by Gordon Dobson)

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 Ozone Concentration
The ozone layer is not equally thick everywhere or at any time.
In contrary, there are significant monthly and seasonal variations:

The thickness ranges from 250 DU in the tropics to 400 DU in the more
northern and southern regions.

And the local weather can influence concentrations by 20-30 DU daily.

Also, ozone levels are higher in winter and spring, but fall off during summer and autumn.
These seasonal variations are more pronounced than the daily variations.

“Ozone hole” refers to a thinning of the ozone layer, as it is described since the 1980s for the
Antarctic (October) and more recently for the Arctic (March).

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 Ozone Concentration
Variations in the thickness of the ozone layer.
Northern hemisphere from November 2020 till May 2021

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 Catalytic decomposition of ozone
Ozone is decomposed by naturally occurring species and
species that are of industrial and agricultural origin.

Speciation means the distinction between the different manifestations of an environmental

chemical such as dissolved, complexed or adsorbed forms.

Many follow the same general mechanism:

X + O3 ➝ XO + O2
XO + O ➝ X + O2

O + O3 ➝ O2 + O2

The most important catalysts are radicals of the following groups:

HOX, including ∙H, ∙OH, HOO∙

NOX, including ∙NO, ∙NO2
ClOX, including ∙Cl, ClO∙

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 Catalytic decomposition of ozone: HOX
HOX is a group of species that is mainly naturally occurring.

To form HOX, hydrogen is required in the stratosphere where oxygen is abundant.

Stratosphere -2 ºC
does not
CH4
freeze

-60 ºC
H2O freezes
Troposphere

+17 ºC

Hydrogen is extracted in the stratosphere from methane via photochemical reactions.

∙OH + O3 ➝ HOO∙ + O2
HOO∙ + O ➝ ∙OH + O2
O + O3 ➝ O2 + O2
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 Catalytic decomposition of ozone: NOX
Nitric oxide (NO) and nitrogen dioxide (NO2) are present in the troposphere
because of various combustion processes.
But their atmospheric lifetime is too short for them to reach the stratosphere in large numbers.

Instead, the main source for stratospheric NOX is nitrous oxide (N2O), which is produced by
bacteria in a natural process called “denitrification” as part of the nitrogen cycle.

But the extent of this process depends on the availability of nitrate (NO3-),
which is strongly affected by agriculture.

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 Catalytic decomposition of ozone: NOX
N2O is not water-soluble and does not photolyze, meaning it can reach the stratosphere.

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 Catalytic decomposition of ozone: NOX ???
The pre-industrial era level of nitrous oxide has risen from 275 ppbv to 328 ppbv in 2015.

N2O is today considered as the most important anthropogenically influenced

ozone depleting substance (ODS).
(In addition, it is one of the most important greenhouse gases)

90% of stratospheric N2O is destroyed by photochemically induced reactions:

N2O + hv ➝ N2 + O
N2O + O ➝ N2 + O2

But the reaction with excited oxygen can yield NO:

N2O + O* ➝ 2 NO

NO can also be generated in altitudes greater than 30 km via:

N2 + hv (λ ≤ 126 nm) ➝ 2 N
N + O2 ➝ NO + O

And we now know how NO can deplete ozone:

NO + O3 ➝ NO2 + O2
NO2 + O ➝ NO + O2
O + O3 ➝ O2 + O2
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 Catalytic decomposition of ozone: ClOX
Chlorine and chlorine containing radicals (and their bromine analogues)
can also deplete ozone.

The most important natural precursor of atomic chlorine is methyl chloride (CH3Cl),
which is mainly released by biological reactions in the oceans.

Only small amounts reach the stratosphere, where atomic chlorine radicals can be released:

CH3Cl + hv ➝ ∙CH3 + ∙Cl

And as a consequence, it can react with ozone:

∙Cl + O3 ➝ ClO∙ + O2
ClO∙ + O ➝ ∙Cl + O2
O + O3 ➝ O2 + O2

However, natural source for atomic chlorine are not nearly as important as chlorine derived
from anthropogenically manufactured chlorofluorocarbons (CFC)…

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 Chlorofluorocarbons and related compounds
CFCs were developed in the 1930s and have several advantageous properties:

• Low viscosity
• Low surface tension
• Low boiling point
• Chemical and biological inertness

CFC free?
Yes, the production of CFCs has been
discontinued since the early 1990s.

But why? And how do CFCs look like?

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 Chlorofluorocarbons and related compounds
CFCs are normally named according to the following scheme:

number of H-atoms + 1

CFC – xyz number of F-atoms

number of C-atoms - 1 (omitted if x = 0)

The balance of atoms required for a saturation is then made up of chlorine

Example:
CFC-115
2 carbon, 0 hydrogen, 5 fluorine, 1 chlorine

Or:
CFC-11
1 carbon, 0 hydrogen, 1 fluorine, 3 chlorine

(Add 90 to each number to get a quicker answer)

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 Chlorofluorocarbons and related compounds
As mentioned before, CFCs are very inert and thus distribute well in the troposphere.
But when they reach the stratosphere, they can undergo photolytic decomposition.

For instance for CFC-11:

CFCl3 + hv (λ ≤ 290 nm) ➝ ∙CFCl2 + ∙Cl

From there on, the first Cl can deplete ozone.

The different CFCs have various ozone depleting potential.

The ODP is expressed in relation to CFC-11 and varies with reactivity, lifetime, molar mass
and the number of chlorine atoms.

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 Moving away from CFCs
A small number of scientists already suggested in the 1960s that human activities might be
damaging the ozone layer.

One of their main concerns at the time was the use of CFCs, but it took several years more
before the first substantial hypothesis on how CFCs might actually deplete the ozone layer
was published.

20 years later, the ozone hole was discovered, leading to further action.

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 Moving away from CFCs
Eventually, 27 states signed the “Montreal Protocol on Substances that deplete the Ozone
Layer” in 1984. Originally only stating that the use of certain CFCs should be reduced to 50%
until 1999, the treaty was updated several time.
The last time in 2016 in Kigali.

What are HFCs?

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 Moving away from CFCs
Knowing that the long tropospheric lifetime and number of chlorine atoms are an issue…
Why not substitute (some) chlorine to solve both issues?

Group Name Structure Tropospheric lifetime ODP GWP

CFC CFC-11 52 y 1 5160

HCFC HCFC-22 12 y 0.05 1780

H

HFC HFC-32 5.4 y 0.0 704

F
H
H
HCFCs and HFCs are more expensive, more flammable, not suitable for all applications
(and still greenhouse gases)
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 Concentrations of CFCs and related compounds
How are the concentrations behaving after amendments to the Montreal Protocol?

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Concentrations of CFCs and related compounds
So far so good? Yes, somehow…

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Concentrations of CFCs and related compounds
Annual changes in atmospheric concentrations of CFC-11

CFC-11 emissions are now declining faster again

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 The “ozone hole”
When the ozone hole was discovered in 1985, the question was raised:
Why is the Antarctic so susceptible to ozone depletion?

The ozone hole shows a clear seasonal trend:

Summer

Spring

Winter

Autumn

Summer

After the long “polar night”, the first sunlight in spring starts a cascade that results in
a relative sudden depletion of ozone.

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 The “ozone hole”
Due to the the Earth’s rotation and intense cold (-80 ºC) during the antarctic winter,
air is drawn towards the South Pole. This creates the so-called polar vortex.

Under these conditions, two types of polar stratospheric clouds (PSC) are formed:

Type I Type II
(nitric acid 1:3 water) (only water)

Type I clouds play an essential role in

the formation of the ozone hole.

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 The “ozone hole”
In addition to PSC, so-called reservoir species are also present in the vortex.

These reservoir species are formed when two radicals – which would otherwise
deplete ozone – react with each other:

For instance:

∙NO2 + ∙OH + M ➝ HNO3 + M

∙Cl + CH4 ➝ HCl + CH3
ClO∙ + ∙NO2 + M ➝ ClONO2 + M

During the polar winter, these species react on the surface of the PSC and generate HNO3:

HCl + ClONO2 ➝ Cl2 + HNO3

H2O + ClONO2 ➝ HOCl + HNO3

This situation is more or less stable until the first sunlight can cause a relative rapid
release of chlorine which then depletes ozone causing the Antarctic ozone hole.

Cl2 + hv ➝ 2 ∙Cl
HOCl + hv ➝ ∙Cl + ∙OH

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 The “ozone hole”
And where does the stratospheric chlorine come from in the first place?

But the situation should be improving since the Montreal Protocol…

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 The “ozone hole”
Fortunately, the ozone hole seems to recover and protect us from UV-B radiation again.

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 The “ozone hole”
But the last two years were less positive

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 The “ozone hole”
It should not be forgotten, that there is also an ozone thinning above the Arctic.

But even though the “northern vortex” is less pronounced, ozone depletion can start in March
– the northern spring.

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 End

Let us move to the troposphere

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 Picture credits

Slide 3: https://en.wikipedia.org/wiki/Stratosphere
Slides 4, 5: G.W. vanLoon and S.J. Duffy: Environmental Chemistry, a global perspective, 4. Edition, 2017, Oxford University Press, Oxford, UK
Slides 5, 6: https://en.wikipedia.org/wiki/Ultraviolet
Slide 6: https://en.wikipedia.org/wiki/Melanin
Slide 6: G.W. vanLoon and S.J. Duffy: Environmental Chemistry, a global perspective, 4. Edition, 2017, Oxford University Press, Oxford, UK
Slide 7: https://en.wikipedia.org/wiki/Sunscreen
Slide 8: https://oceanservice.noaa.gov/news/sunscreen-corals.html
Slide 11: https://www2.physics.ox.ac.uk/sites/default/files/images/DobsonPhotoelectricSpectrometer.jpg
Slide 11: https://www.theozonehole.com/images/maintomsLO.jpg
Slide 11: https://airbornescience.nasa.gov/sites/default/files/images/Balloon%20FPH%20Launch_0.png
Slide 12: https://ozonewatch.gsfc.nasa.gov/facts/dobson_SH.html
Slide 13: https://ozonewatch.gsfc.nasa.gov/multimedia/index.html
Slide 16: https://de.wikipedia.org/wiki/Dünger
Slide 16: https://en.wikipedia.org/wiki/Nitrous_oxide
Slide 17: https://www.globalcarbonproject.org/nitrousoxidebudget/index.htm
Slide 20: https://ogtstore.com/wp-content/uploads/2017/02/K193506.jpg
Slide 20: https://assets.mitre10.co.nz/sys-master/productimages/h91/hbc/9037881933854/428243xlg.jpg
Slide 20: https://cdn3.volusion.com/xaglw.shdau/v/vspfiles/photos/03116-2.jpg
Slides 22, 23: G.W. vanLoon and S.J. Duffy: Environmental Chemistry, a global perspective, 4. Edition, 2017, Oxford University Press, Oxford, UK
Slide 23: https://en.wikipedia.org/wiki/United_Nations_Environment_Programme
Slide 24: https://www.unep.org/ozonaction/who-we-are/about-montreal-protocol
Slide 26: https://gml.noaa.gov/aggi/aggi.html
Slide 27: https://www.nature.com
Slide 28: https://research.noaa.gov/article/ArtMID/587/ArticleID/2713/Emissions-of-a-banned-ozone-depleting-gas-are-back-on-the-decline
Slide 29: https://en.wikipedia.org/wiki/Polar_night
Slide 29: G.W. vanLoon and S.J. Duffy: Environmental Chemistry, a global perspective, 4. Edition, 2017, Oxford University Press, Oxford, UK
Slide 30: https://en.wikipedia.org/wiki/Polar_stratospheric_cloud
Slide 32: https://en.wikipedia.org/wiki/Ozone_depletion
Slide 33: https://svs.gsfc.nasa.gov/30602
Slide 34: https://atmosphere.copernicus.eu/monitoring-ozone-healthier-world
Slide 35: https://earthobservatory.nasa.gov/images/1771/nasa-confirms-arctic-ozone-depletion-trigger

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