An investigation of Ozone formation (NOx,

VOC, CO)
&
its sinks at a sub-urban site of IndoGangetic Plain

Nidhi Verma

Atmospheric Ozone

50km

Good or Bad ozone

Good Ozone, filters out

20km
harmful UV radiations
Stratosphere:

------------------------------------------------------------------------------------------------------------------------

Upper Troposphere: Bad Ozone, acts as a green house

gas.

Mid Troposphere:
of hydroxyl radicals

Good Ozone, , it is the major source

(OH) which acts as detergent.

Lower Troposphere: Bad Ozone, makes photochemical smog

Effects of Ozone
In Stratosphere: Filters out harmful ultra-violet
radiation from the sun, protecting life on earth.
In Troposphere:
Being a key constituent of Photochemical
Smog it is responsible for
i. Increased susceptibility to diseases.
ii. In plants ozone is responsible for impaired
photosynthesis, protein and chlorophyll
degradation, and changes in metabolic
activity
(Booker and Fuhrer et. al., 2009)

Brown spots in Grape

Ozone in Troposphere
Stratosphere
Chapman cycle

--------------------------------------------------------------Stratosphere- troposphere
exchange----------------

Troposphere:

Formation and destruction pathways of O3

Ozone Precursors

NOx
Natural Sources:
Bacterial activity
Volcano
Lightening
Anthropogenic:
Industries
Fuel burning
Electric utilities

CO
VOCs
BVOCs
AVOCs
OVOCs
NMHCs

Incomplete combustion
of fossil fuel
Biomass burning

Ozone sinks:

Loss by Black Carbon (BC)

Black carbon (BC) is a heat absorbing aerosol, is a product of

incomplete combustion of fossil fuel, biomass, agricultural waste and
forest fire. BC has been found to have a large effect on
photochemistry derived pollutants such as ozone (Li et al., 2005)

I.

Loss by alkenes to form Organic Acids

Initial step

II. Formation of Criegee intermediate

III. Criegee intermediate contains excess energy and either

can be stabilized or decompose in a variety of ways. For ex.
For criegee intermediate produced in O3- propene reaction
following pathways are possible:(Atkison et.al., 1997 a)

Other possible sources of organic acids:

Direct emissions from the vegetation (Kesselmeier et. al.,
2001)
Ants (Chebbi et. al., 1996)
Biomass burning (Goode et al., 2000; Christian et al., 2003;
Yokelson et al., 2009)
Biofuel (Yevich et. al., 2003)
Anthropogenic combustion sources like vehicles and
stationary sources (Perola et. al., 2011; Freitas et. al., 2012;

Objecti
ves
To study the diurnal and seasonal trends of Ozone and its
precursors (NOx and CO).
To determine the levels of some representative VOCs
and study their seasonal trends.
To explore the ozone loss processes through:
Organic acids
Black Carbon
Modeling Ozone levels through PCA & ANN.

O3, NOx and CO measurement

O3 Analyzer: Principle
ozone (O3) molecules absorb UV light at a wavelength of 254 nm.
The degree to which the UV light is absorbed is directly related to
the ozone concentration as described by the Beer-Lambert Law:

where:
K = molecular absorption coefficient, 308 cm-1 (at 0C and 1 atmosphere)
L = length of cell, 38 cm
C = ozone concentration
I = UV light intensity of sample with ozone (sample gas)
Io = UV light intensity of sample without ozone (reference gas)

Schematic diagram of O3 analyzer

NOx analyzer
Principle
NO and O3 react to produce a characteristic
luminescence with an intensity linearly proportional to
the NO concentration. Infrared light emission results
when electronically excited NO2 molecules decay to
lower energy states. Specifically,
Nitrogen dioxide (NO2) must first be transformed into
NO before it can be measured using the
chemiluminescent reaction.
NO2 is converted to NO by a molybdenum NO2-to-NO
converter heated to about 325 C.

Schematic diagram of NOx analyzer

CO Analyzer
Principal: It works on Beer-Lamberts Law.
It uses a high-energy heated element to
generate a beam of broad-band IR light.
This beam is directed through multi-pass
cell filled with sample gas.

What are VOCs

VOCs are chemical compounds containing carbon

and hydrogen that vaporize easily and enter the
atmosphere
VOCs are compounds that lead to the formation of
ground level Ozone smog
VOCs can be found in anything from paints to
deodorant

ampling and Analysis

Samples of VOC
(BTX) will be
collected
by
sampling ambient
air
through
activated charcoal
tubes (SKC) for 4
hrs using SKC
personal sampler
@ 2 LPM.

 Exposed
tubes will be
extracted in
CS2 by
ultrasonicatio
n

Extractio
n

Analysis
Analysis will
be done by
GC-FID using
N2 as carrier
gas

 Black carbon or elemental carbon analysis will

be done by OC-EC analyzer (Sunset aboratory,
USA, model 2000).
1.5 cm2 punch will be cut from the
loaded 47 mm quartz fibre filter paper
In first stage, OC is volatilized from in a non
oxidizing atmosphere (100% He) through a stepwise heating (340, 500 and 615 C maintained for
60s and at 870 C for 90s)

In the second stage, the oven is cooled

to below 550 C for 60s.
A mixture of oxygen and helium gas
(2% +98, by volume) is introduced
Temperature is increased up to 900 C, then
thermograph is produced to give different
fraction and we calculate OC and EC

Organic acid: Sampling and Analysis

Samples are collected using HVS
Envirotech APM 550 Respirable Dust
Sampler operating at flow rate of
16.6 l/min for 24 hrs on 47 mm
quartz fiber filter paper

Extraction was done in

water and add few
drops of CHCl3 to
avoid bacteria
development

Cut of filter
paper for
organic acids
analysis

Analysis is done by ion chromatograph

(Dionex ICS 1100) using AS11
analytical column and 0.03 mM NaOH
as eluent

Before
sampling filter
paper is
treated for 4
hrs at 900C

Stored at 4
C

Thanks