Composition and structure

of the atmosphere
 Atmosphere
• Earth’s atmosphere is a thin layer
of gas held around the surface by
gravity.

• 90% of the atmosphere’s mass is

within 15 km of the earth’s surface
– Earth's radius is about 6400 km
– The atmosphere is like a layer
of paint on a basketball
 Atmosphere
• The atmosphere protects life on Earth by:
 absorbing ultraviolet solar radiation,
 warming the surface through heat retention
(greenhouse effect),
 And reducing temperature extremes
between day and night (the diurnal
temperature variation).

• The Mass of the atmosphere:

It is about 5.15×1018 kg, three quarters of
which is within about 11 km of the surface.
 Atmosphere
 The Earth's atmosphere is characterized by variations of
temperature and pressure with height.

 In fact, the variation of the average temperature profile with

altitude is the basis for distinguishing the layers of the
atmosphere.
 Atmospheric Structure
Troposphere. The lowest layer of the
atmosphere, extending from the Earth's
surface up to the tropopause, which is at
10-15 km altitude depending on latitude
and time of year (Higher near equator
and lower towards poles); characterized
by decreasing temperature with height;
rapid vertical mixing (baring BL).

Stratosphere. Extends from the

tropopause to the stratopause (From ~
45 to 55 km altitude); temperature
increases with altitude.

Mesosphere. Extends from the

stratopause to the mesopause (From ~
80 to 90 km altitude); temperature
decreases with altitude to the
mesopause, which is the coldest point in
the atmosphere.
Composition of the Atmosphere
 Atmosphere
• The very cold temperature of the tropopause layer at the top of
the troposphere serves as a barrier that causes water vapor to
condense to ice so that it cannot reach altitudes at which it
would photodissociate through the action of intense high-
energy ultraviolet radiation. If this happened, the hydrogen
produced would escape the earth’s atmosphere and be lost.

• The atmospheric layer directly above the troposphere is the

stratosphere, in which the temperature rises to a maximum of
about -2˚C with increasing altitude.
 Atmosphere
• The heating effect is caused by the absorption of ultraviolet
radiation energy by ozone.

• Ozone serves as a natural atmospheric filter to prevent this light

from reaching the surface, thereby protecting Earth's life from
damages.

• The upper regions of the mesosphere and higher define a

region, called the exosphere, from which molecules and ions
can completely escape the atmosphere.

• Extending to the far outer reaches of the atmosphere is the

thermosphere, in which the highly rarified gas reaches
temperatures as high as 1200˚C by the absorption of very
energetic radiation of wavelengths less than approximately 200
nm by gas species in this region.
 Atmosphere

In Thermosphere temperatures increase again with altitude due to

absorption of strong UV solar radiation by N2 and O2. The
troposphere and stratosphere account together for 99.9% of total
atmospheric mass and are the domains of main interest from an
environmental perspective.

The fraction of total atmospheric weight located above altitude z is

P(z)/P(0). At 80 km altitude the atmospheric pressure is down to
0.01 hPa, meaning that 99.999% of the atmosphere is below that
altitude.
 Unit Conversion
It has become common use in atmospheric chemistry to describe volume mixing
ratios by the following units:

Volume mixing ratio= 1mL/1m3 =1 mL/106 mL = 10-6

E.g., 1 mL SO2 in 106 mLof Air

parts per million (ppm) 10-6 μmol mol-1

parts per billion (ppb) 10-9 nmol mol-1
parts per trillion (ppt) 10-12 pmol mol-1

These quantities are sometimes distinguished by an added v (for volume) and m

(for mass), that is,
Ppmv parts per million by volume
Ppmm parts per million by mass

Another common unit used to measure the concentration is the

unit of mass per unit volume. The interconversion of these units is
simple as exemplified later.
 Ideal Gas Equation
The ideal gas law is the equation of state of a hypothetical ideal gas. It is a
good approximation to the behavior of many gases. The ideal gas law is often
written as:

P V = nRT

where the letters denote pressure, volume, amount, the ideal gas constant,
and temperature of the gas, respectively.

The value of R can be expressed in a number of units, the most useful in

environmental chemistry relate to litres and atmospheres. Therefore:

It is helpful to estimate the volume of gas at any temperature and Pressure,

The most useful value to remember is at STP
what is the concentration of 1ppm by volume of Ozone expressed in g/m3 at 25
C and 750 mm Hg pressure?
Solution:
We know at STP 1 mol of ozone occupies 22.41 L
Using Ideal gas equation

Where P1 = 760 mm Hg, T1 = 273 K and P2 = 750 mm Hg , T2= 298 K

We get:

V2= 24.79 L

Mol wt of Ozone = 48
Now In these conditions 24.79 L contains 48 g of Ozone
So 1 L (1000 mL) will contain g of Ozone

I ml will contain g of Ozone

This 1 mL of Ozone in 1 m-3 of air can be expressed as

 Atmospheric Scales Of Motion

Four rough categories of

atmospheric scales of
motion:

1. Microscale. Phenomena
occurring on scales of the
order of 0-100 m, such as
the meandering and
dispersion of a chimney
plume
2. Mesoscale. Phenomena
occurring on scales of tens
to hundreds of kilometers,
such as land-sea breezes, Fig: Spatial and temporal scales of
and fronts. variability for atmospheric constituents.

3. Synoptic Scale. Motions of whole weather systems, on scales of

hundreds to thousands of kilometers.

4. Global Scale. Phenomena occurring on scales exceeding 5 000 km.

 Spatial scales characteristic of various atmospheric
chemical phenomena are given in the Table
There is more or less of a
continuum between

(1) urban and regional air

pollution,
(2) the aerosol haze
associated with regional
air pollution and aerosol-
climate interactions,
(3) greenhouse gas increases
and stratospheric ozone
depletion,
(4) tropospheric oxidative
capacity and stratospheric
ozone depletion.
Fate of air pollutants and role of
atmosphere
 Hazardous air pollutants
• Photolysis
• Chemical reaction with OH radical, nitrate radical and O3.
• Reaction with OH radical and O3 is predominant.
• Photolysis is chemical fragmentation or rearrangement of a chemical
upon the adsorption of light of appropriate wavelength. Photolysis is
only important during daytime only for those chemicals that strongly
absorb light.
• Formaldehyde and acetaldehyde form as a result.
• Major removal mechanism is OH abstraction of addition.
• Product of reaction would be CO2 and CO.
• Atmospheric lifetime generally less than 1 day.
Nitrogen Dioxide
Nitrogen Dioxide
 Photochemical oxidants
• Unlike other pollutants the photochemical
oxidants results entirely from atmospheric
reaction. Thus they are called secondary
pollutants.
• O3 is primary photochemical oxidant.
• O3 formation is basically attributed to the
nitrogen dioxide photolytic cycle.
• Hydrocarbon modifies this cycle by reacting
with atomic oxygen to form free radicals
(highly reactive organic species)
 Sulfur oxides
• Sulfur oxides may be both primary and
secondary pollutants.
• Power plants, industries, volcanoes and
ocean emit SO2, SO3, and SO42- directly as
primary pollutants.
• Biological decay process and some industrial
sources emit H2S, which is oxidized to for
SO2.
• 0.125 Pg (Natural sources) and 45 Tg
(anthropogenic sources)
 Problem
An coal power plant burning coal at the rate
of 1.00 kg/s. If the analysis of coal reveals a
sulfur content of 3% what is the annual rate
of emission of SO2. sulfur content of the ash
5% of input sulfur
Fate of SO2 in the atmosphere
IIT Delhi-
2009-10
 Particulate Matter
Particles come in different
shapes and sizes

Particle sizes
• Ultra-fine particles (<0.1 µm)
PM 10

• Fine particles (0.1 to 2.5 µm)

• Coarse particles (2.5 to 10 µm)

Crustal material Carbon chain agglomerates

Section 7 – Chemical Aspects

29
AREP GAW, WMO Report
of Air Pollution
 Particulate Matter
Composition
• Geological Material – suspended dust
consists mainly of oxides of Al, Si, Ca, Ti,
Fe, and other metal oxides
• Ammonium – ammonium bisulfate,
sulfate, and nitrate are most common
• Sulfate – results from conversion of SO2
gas to sulfate-containing particles
• Nitrate – results from a reversible
gas/particle equilibrium between ammonia
(NH3), nitric acid (HNO3), and particulate
ammonium nitrate
31
• NaCl – salt is found in PM near sea coasts
and after de-icing materials are applied
• Organic Carbon (OC) – consists of
hundreds of separate compounds
containing mainly carbon, hydrogen, and
oxygen
• Elemental Carbon (EC) – composed of
carbon without much hydrocarbon or
oxygen. EC is black, often called soot.
• Liquid Water – soluble nitrates, sulfates,
ammonium, sodium, other inorganic ions,
and some organic material absorb water
vapor from the atmosphere
Chow and Watson (1997)
 Particulate Matter Chemistry

PM Sample
Sources Emissions Formation PM Transport/Loss Collection
Chemical Processes
Mechanic Particles
al • NaCl
• Sea • Crust gases condense onto
Measurement
salt al particles cloud/fog
• Dust Issues
Combusti Particles processes
• Inlet cut points
on• Motor • Soot transpo
vehicles • Metals • Vaporization of nitrate
rt
• Industrial • OC sedimentation H2O, VOCs
• Fires (dry • Adsorption of VOCs
Gases condensation and
• NOx deposition) • Absorption of H2O
coagulation wet
• SO2
• VOCs photochemical deposition
• NH3 production cloud/fog
Other gaseous Gases processes
• Biogenic • VOCs
• Anthropoge • NH3
nic • NO
Meteorological Processes
x

Winds Temperature Clouds, fog Winds Temperature

Solar radiation Temperature Precipitation Relative humidity
Vertical mixing Relative humidity Winds
Solar32radiation

AREP GAW, WMO Report

 Comparison of CPCB (India) and WHO Standards for Particulate Air Pollution

R. Gopalaswami et al. A Study on Effects of Weather, Vehicular Traffic and Other Sources of Particulate Air Pollution on the City
of Delhi for the Year 2015. Journal of Environment Pollution and Human Health, 2016, Vol. 4, No. 2, 24-41. doi:10.12691/jephh-
4-2-1

Component of Particulate Air 24-Hr Annual

Pollution
CPCB (India) WHO CPCB WHO

50 µg/m3
100 µg/m3 AQI 137 60 µg/m3 20 µg/m3
Particulate matter (PM10),
AQI 174 Unhealthy to AQI = 153, AQI =68
µg/m3
Unhealthy Sensitive Unhealthy Moderate
Groups

60 µg/m3 25 µg/m3 AQI =112, 10 µg/m3

Particulate matter (PM2.5), Unhealthy to
AQI 153 AQI =78, AQI = 42,
µg/m3 sensitive groups
Unhealthy moderate Good
Table . Monthly Average Particulate Air Pollution (PM 2.5) over a 3-year period in Delhi and Beijing

Measured Values of Particulate Air Pollution (PM 2.5) In

Micrograms/ cubic-metre
2013 2014 2015
Season Month
Site at
Site Not Specified Site Not Specified
Chanak
yap uri
Delhi Beijing Delhi Beijing Delhi
Winter and Early Jan 230 100 200 120 184
Summer Feb 120 120 150 150 139
Mar 115 115 100 105 71
Apr 100 70 100 100 62
Summer
May 130 80 110 80 74
Jun 100 100 100 80 55
Jul 60 70 90 85 33
Monsoon (Rainy) Season
Aug 60 70 90 60 33
in India
Sep 70 70 70 70 50
Oct 100 100 130 130 105
Winter Nov 270 110 240 100 236
Dec 240 90 230 100 249
R. Gopalaswami et al. A Study on Effects of Weather, Vehicular Traffic and Other Sources of Particulate Air Pollution on the City
of Delhi for the Year 2015. Journal of Environment Pollution and Human Health, 2016, Vol. 4, No. 2, 24-41. doi:10.12691/jephh-
4-2-1
Venkataraman et al. Atmos. Chem. Phys., 18, 8017–8039, 2018 https://doi.org/10.5194/acp-18-8017-2018
 Ozone
• Presence of O3 in the upper atmosphere
20-40 km and up provides a barrier to UV
radiation.
• Small amount that do seep through
provide you with your summer tan.
• To much UV will cause skin cancer.
• O2 also serves as barrier to UV radiation,
it absorbs only over a narrow band centred
at a wave length of 0.2 m.
 Ozone destruction
• Photoreaction of O3 and O3 destruction
by chlorofluorocarbon
Ozone destruction
 Helsinki Declaration
• Eight countries met in Helsinki, Finland in the spring of 1989 and Helsinki
declaration took place as follows.
• All joint the 1985 Vienna Convention for the protection of O3 layerand the
follow up Montreal protocol.
• Phase out production and consumption of O3 depleting CFCs no later than
2000.
• Phase out production and consumption as soon as feasible of halons and
such chemicals as carbon tetrachloride and methyl chloroform that also
contribute to O3 depletion.
• Commit themselves to accelerated development of environmentally
acceptable alternative chemical and technology.
• Make relevant scientific information, research results and training available
to developing countries.
 Alternative to CFCs
• Hydrofluorocarbons (HFCs)
• Hydrochlorofluorocarbons (HCFCs)
• In contrast to CFCs HFCs and HCFCs contain one or more C-H
bonds. This makes them susceptible to attack by OH radicals in the
lower atmosphere.
• HFCs do not contain chlorine they do not have the O3 depletion
potential.
• HCFCs contains chlorine, this chlorine is not transported to the
stratosphere because of OH scavenging in the troposphere is
relatively efficient.