Anthropogenic Climate Changes

Human production of freons (CFCs) è Ozone Hole Depletion

Human production of CO2 and CH4 è Global Warming

Human change of land use è Deforestation

Measurements of Ozone

(1) Number Density

      Number of molecules per cubic centimeter (molecules/cm³).

      The number density is typically about 5x10¹²molecules/cm³ near 20 to 25 km altitude, near the peak of ozone concentration in the stratosphere.

(2) Layer Thickness

      The thickness of pure ozone would have at 1 atm pressure.

       One atmosphere-centimeter (1 atm-cm) is equal to 2.687x10¹⁹ molecules/cm².

       One Dobson Unit (DU) is equivalent to a layer of pure ozone 0.001 cm thick at 1 atm pressure.

      A typical midlatitude ozone column depth is about 300 DU (0.3 atm-cm).

Why is Ozone Important?

The stratospheric ozone layer reduces the amount of UV-B radiation from the sun reaching Earth’s surface.

UV-B exposure can damage human’s immune system, increase risk of skin cancer, and damage terrestrial plant life, single-cell organisms, and aquatic ecosystem.

How Is Ozone Formed?

Ozone Distribution

The greatest production of ozone occurs in the tropics, where the solar UV flux is the highest.

However, the general circulation in the stratosphere transport ozone-rich air from the tropical upper stratosphere to mid-to-high latitudes.

Ozone column depths are highest during springtime at mid-to-high latitudes.

Ozone column depths are the lowest over the equator.

Polar Vortex

Ozone Production and Destruction

Radiation and Ozone

Ozone Production

      UV photons are required for ozone production:

              O₂ + UV photon à O + O

      Below about 20 km, UV photons are absorbed by ozone. Therefore, O2 can be photolyzed only above 20 km. This is why the ozone layer is located in the stratosphere and not near Earth’s surface.

Ozone Destruction

      O3 can be split by radiation in the visible-light range:

              O₃ + photon à O₂ + O

      Because many more visible photons than UV photons are available, O3 is photolyzed (ozone destruction) much faster than O₂ (ozone production).

       Also, O3 can be photolyzed all the way sown to Earth’s surface.

Other Ozone Destruction Processes

Other atmospheric trace constituents, such as nitrous oxide (N2O), water vapor, and freons, can also be photolyzed. They produce highly reactive radicals that keep ozone abundances lower than they would otherwise be.

These radicals include: nitric oxide (NO), atomic chlorine (Cl), bromine (Br) radicals, and hydroxyl (OH) radicals.

These radicals can destroy stratospheric ozone through “catalytic cycles”.

A catalytic cycle is a set of chemical reactions facilitated by the presence of a catalyst.

A catalyst is a substance that increases the rate of a chemical reaction but is itself unchanged by the reaction.

The Chlorine Catalytic Cycle

The Nitrogen Catalytic Cycle

Where do those ozone-depleting catalysts come from?

(1) Cl – related to natural and man-made substances

(2) Br – related to natural and man-made substances

(3) NO2 reacts with Cl and Br to produce reservoirs for Cl and Br.

The Odd Nitrogen Cycle

N2O: from Earth’s surface, where it is produced by microbial activity in soil and in the ocean.

è In the stratosphere, some of N2O reacts to form NO, the rest is photolyzed back to N2 and O2.

The NO so produced participates in the ozone-destroying nitrogen catalytic cycle.

Once for a while, the resulting NO2 molecule interacts with a hydroxyl radical (OH), producing nitric acid (HNO3).

Nitric Acid (HNO3) then diffuses down into the troposphere and dissolves into rain.

Other Sources of NO

N2O is currently the largest source of stratospheric odd nitrogen (NO and NO2).

How human activity affect NO?

       high-flying, supersonic transport airplanes

       è Jet plane-produced high temperatures from combustion.

       è combine N2 and O2 to form NO.

       è injected NO goes to the stratosphere and destroy ozone

       è This is why jet plans can affect stratospheric ozone layer

             (even though jet plans fly in the upper troposphere).

The Chlorine Cycle

Natural sources of chlorine:

(1) Methyl chloride (CH3Cl): produced by marine plankton. (2) Hydrogen chloride (HCl): produced by volcanic eruption and by evaporation of sea spray.

These natural-generated chlorine are most removed by precipitation before they reach the stratosphere.

The largest sources of stratospheric chlorine today are freons (CFCs), which are thropogenic compounds.

CFCs do not react in either the troposphere or lower stratosphere

CFCs go all the way to the upper stratosphere and are photolyzed by UV radiation.

è The Cl so produced proceeds to destroy ozone.

è Eventually, Cl react with CH4 and is diffused to the troposphere, where it is precipitated out.

Chlorine Sources

Man-Made Sources for CFCs

There are two kinds of CFCs: freon-11 (CCl3F) and freon-12 (CCl2F2).

Freon-11 has been used:

      (1) as a propellant in spray cans

      (2) as a blowing agent for producing foams

      (3) to clean semiconductor chips.

Freon-12 has been used as

      (1) a refrigerant

      (2) working fluid in most car air conditioners.

The Bromine Cycle

Br is also a ozone-depleting catalyst

The bromine cycle is similar to the chlorine cycle.

The natural source of bromine is Methyl Bromine (Ch3Br), which is a byproduct of biological activity in the ocean. These natural source reacts in the troposphere.

The man-made source of bromine is two chemical compounds: Halon-1211 (CF2ClBr) and Halon-1301 (CF3Br).

These two halons are used in certain types of fire extinguishers.

Halons diffuse up to the stratosphere, where they are photolyzed into bromine atmos. They eventually rain out.

Bromine Sources

Coupling Between Odd Nitrogen and Chlorine Cycles

Throughout most of the lower stratosphere, the nitrogen and chlorine cycles are coupled by the above chemical reaction.

The chlorine nitrate (ClONO2) formed in this reaction does not react directly with either ozone or atomic oxygen. Therefore, this coupling reaction keeps chlorine from being in its reactive forms (Cl and ClO) (which can destroy ozone).

Polar Stratospheric Clouds (PSCs)

In winter the polar stratosphere is so cold (-80°C or below) that certain trace atmospheric constituents can condense.

These clouds are called “polar stratospheric clouds” (PSCs).

The particles that form typically consist of a mixture of water and nitric acid (HNO3).

The PSCs alter the chemistry of the lower stratosphere in two ways:

(1) by slow down the coupling between the odd nitrogen and chlorine cycles

(2) by providing surfaces on which heterogeneous reactions can occur.

How PSCs Affect Chlorine?

In most of the seasons, there are always abundant NO2 in the stratosphere to tie up a significant fraction of the available chlorine in the form of chlorine nitrate.

In the wintertime Antarctic stratosphere, NO2 concentrations are low, because most of the odd nitrogen has been converted into HNO3 and become droplets in PSCs (polar stratospheric clouds).

Therefore, the formation of PSCs allow reactive chlorine concentration to increases.

The PSCs particles also help convert unreactive forms of chlorine into reactive chlorine by providing surfaces on which heterogeneous reaction can occur.

Three Factors for the Ozone Hole

Chemical Reactions – polar stratospheric clouds (PSCs)

Atmospheric Circulation – stratospheric polar vortex

Sunlight – spring season

The Polar Vortex

The wintertime circulation over the South Pole is characterized by a gigantic whirlpool of cold and dense air, called the polar vortex.

The cold and dense cold air in the middle of the vortex is subsiding.

The sinking air carries cloud particles along with it.

Remove odd nitrogen from the stratosphere.

Very little ozone and odd nitrogen can be brought into the south pole.

Antarctic Ozone Hole

The decrease in ozone near the South Pole is most striking near the spring time (October).

During the rest of the year, ozone levels have remained close to normal in the region.

Satellite View of the Ozone Hole

The 1997 Ozone Hole

Ozone Hole Depletion

Long Antarctic winter (May through September)

The stratosphere is cold enough to form PSCs

PSCs deplete odd nitrogen (NO)

Help convert unreactive forms of chlorine (ClONO2 and HCl) into more reactive forms (such as Cl2).

The reactive chlorine remains bound to the surface of clouds particles.

Sunlight returns in springtime (September)

The sunlight releases reactive chlorine from the particle surface.

The chlorine destroy ozone in October.

Ozone hole appears.

At the end of winter, the polar vortex breaks down.

Allow fresh ozone and odd nitrogen to be brought in from low latitudes.

The ozone hole recovers (disappears) until next October.

Global Total Ozone Change

Why No Ozone Hole in Artic?


	Human production of freons (CFCs) è Ozone Hole Depletion
	Human production of CO2 and CH4 è Global Warming
	Human change of land use è Deforestation


	(1) Number Density
	Number of molecules per cubic centimeter (molecules/cm³).
	The number density is typically about 5x10¹²molecules/cm³ near 20 to 25 km altitude, near the peak of ozone concentration in the stratosphere.
	(2) Layer Thickness
	The thickness of pure ozone would have at 1 atm pressure.
	One atmosphere-centimeter (1 atm-cm) is equal to 2.687x10¹⁹ molecules/cm².
	One Dobson Unit (DU) is equivalent to a layer of pure ozone 0.001 cm thick at 1 atm pressure.
	A typical midlatitude ozone column depth is about 300 DU (0.3 atm-cm).


	The stratospheric ozone layer reduces the amount of UV-B radiation from the sun reaching Earth’s surface.
	UV-B exposure can damage human’s immune system, increase risk of skin cancer, and damage terrestrial plant life, single-cell organisms, and aquatic ecosystem.


	The greatest production of ozone occurs in the tropics, where the solar UV flux is the highest.
	However, the general circulation in the stratosphere transport ozone-rich air from the tropical upper stratosphere to mid-to-high latitudes.
	Ozone column depths are highest during springtime at mid-to-high latitudes.
	Ozone column depths are the lowest over the equator.


	Ozone Production
	UV photons are required for ozone production:
	O₂ + UV photon à O + O
	Below about 20 km, UV photons are absorbed by ozone. Therefore, O2 can be photolyzed only above 20 km. This is why the ozone layer is located in the stratosphere and not near Earth’s surface.

	Ozone Destruction
	O3 can be split by radiation in the visible-light range:
	O₃ + photon à O₂ + O
	Because many more visible photons than UV photons are available, O3 is photolyzed (ozone destruction) much faster than O₂ (ozone production).

	Also, O3 can be photolyzed all the way sown to Earth’s surface.


	Other atmospheric trace constituents, such as nitrous oxide (N2O), water vapor, and freons, can also be photolyzed. They produce highly reactive radicals that keep ozone abundances lower than they would otherwise be.
	These radicals include: nitric oxide (NO), atomic chlorine (Cl), bromine (Br) radicals, and hydroxyl (OH) radicals.
	These radicals can destroy stratospheric ozone through “catalytic cycles”.
	A catalytic cycle is a set of chemical reactions facilitated by the presence of a catalyst.
	A catalyst is a substance that increases the rate of a chemical reaction but is itself unchanged by the reaction.


	(1) Cl – related to natural and man-made substances
	(2) Br – related to natural and man-made substances
	(3) NO2 reacts with Cl and Br to produce reservoirs for Cl and Br.


	N2O: from Earth’s surface, where it is produced by microbial activity in soil and in the ocean.
	è In the stratosphere, some of N2O reacts to form NO, the rest is photolyzed back to N2 and O2.
	The NO so produced participates in the ozone-destroying nitrogen catalytic cycle.
	Once for a while, the resulting NO2 molecule interacts with a hydroxyl radical (OH), producing nitric acid (HNO3).
	Nitric Acid (HNO3) then diffuses down into the troposphere and dissolves into rain.


	N2O is currently the largest source of stratospheric odd nitrogen (NO and NO2).

	How human activity affect NO?
	high-flying, supersonic transport airplanes
	è Jet plane-produced high temperatures from combustion.
	è combine N2 and O2 to form NO.
	è injected NO goes to the stratosphere and destroy ozone
	è This is why jet plans can affect stratospheric ozone layer
	(even though jet plans fly in the upper troposphere).


	Natural sources of chlorine:
	(1) Methyl chloride (CH3Cl): produced by marine plankton. (2) Hydrogen chloride (HCl): produced by volcanic eruption and by evaporation of sea spray.
	These natural-generated chlorine are most removed by precipitation before they reach the stratosphere.
	The largest sources of stratospheric chlorine today are freons (CFCs), which are thropogenic compounds.
	CFCs do not react in either the troposphere or lower stratosphere
	CFCs go all the way to the upper stratosphere and are photolyzed by UV radiation.
	è The Cl so produced proceeds to destroy ozone.
	è Eventually, Cl react with CH4 and is diffused to the troposphere, where it is precipitated out.


	There are two kinds of CFCs: freon-11 (CCl3F) and freon-12 (CCl2F2).

	Freon-11 has been used:
	(1) as a propellant in spray cans
	(2) as a blowing agent for producing foams
	(3) to clean semiconductor chips.

	Freon-12 has been used as
	(1) a refrigerant
	(2) working fluid in most car air conditioners.


	Br is also a ozone-depleting catalyst
	The bromine cycle is similar to the chlorine cycle.
	The natural source of bromine is Methyl Bromine (Ch3Br), which is a byproduct of biological activity in the ocean. These natural source reacts in the troposphere.
	The man-made source of bromine is two chemical compounds: Halon-1211 (CF2ClBr) and Halon-1301 (CF3Br).
	These two halons are used in certain types of fire extinguishers.
	Halons diffuse up to the stratosphere, where they are photolyzed into bromine atmos. They eventually rain out.


	Throughout most of the lower stratosphere, the nitrogen and chlorine cycles are coupled by the above chemical reaction.
	The chlorine nitrate (ClONO2) formed in this reaction does not react directly with either ozone or atomic oxygen. Therefore, this coupling reaction keeps chlorine from being in its reactive forms (Cl and ClO) (which can destroy ozone).


	In winter the polar stratosphere is so cold (-80°C or below) that certain trace atmospheric constituents can condense.
	These clouds are called “polar stratospheric clouds” (PSCs).
	The particles that form typically consist of a mixture of water and nitric acid (HNO3).
	The PSCs alter the chemistry of the lower stratosphere in two ways:
	(1) by slow down the coupling between the odd nitrogen and chlorine cycles
	(2) by providing surfaces on which heterogeneous reactions can occur.


	In most of the seasons, there are always abundant NO2 in the stratosphere to tie up a significant fraction of the available chlorine in the form of chlorine nitrate.
	In the wintertime Antarctic stratosphere, NO2 concentrations are low, because most of the odd nitrogen has been converted into HNO3 and become droplets in PSCs (polar stratospheric clouds).
	Therefore, the formation of PSCs allow reactive chlorine concentration to increases.
	The PSCs particles also help convert unreactive forms of chlorine into reactive chlorine by providing surfaces on which heterogeneous reaction can occur.


	Chemical Reactions – polar stratospheric clouds (PSCs)
	Atmospheric Circulation – stratospheric polar vortex
	Sunlight – spring season


	The wintertime circulation over the South Pole is characterized by a gigantic whirlpool of cold and dense air, called the polar vortex.
	The cold and dense cold air in the middle of the vortex is subsiding.
	The sinking air carries cloud particles along with it.
	Remove odd nitrogen from the stratosphere.
	Very little ozone and odd nitrogen can be brought into the south pole.


	The decrease in ozone near the South Pole is most striking near the spring time (October).
	During the rest of the year, ozone levels have remained close to normal in the region.


	Long Antarctic winter (May through September)
	The stratosphere is cold enough to form PSCs
	PSCs deplete odd nitrogen (NO)
	Help convert unreactive forms of chlorine (ClONO2 and HCl) into more reactive forms (such as Cl2).
	The reactive chlorine remains bound to the surface of clouds particles.
	Sunlight returns in springtime (September)
	The sunlight releases reactive chlorine from the particle surface.
	The chlorine destroy ozone in October.
	Ozone hole appears.
	At the end of winter, the polar vortex breaks down.
	Allow fresh ozone and odd nitrogen to be brought in from low latitudes.
	The ozone hole recovers (disappears) until next October.