38

CHAPTER 3

MATERIALS AND METHODS

3.1 STUDY AREA

There have been copious studies in India for air pollution

monitoring of metropolitan cities such as Chennai, Kolkata, Mumbai, Delhi.
The monitoring has also been extended to corporation cities like Maduri,
Salem, Coimbatore etc. But no study in air pollution monitoring was
performed in a medium level city like Karaikudi. Hence Karaikudi has been
chosen in this study for air pollution monitoring in the form of dry deposition.

Karaikudi is a city and a municipality in Sivaganga district in the

Indian state of Tamil Nadu having latitude 10o04’12”N and longitude
78o46’48”E. It is the largest city in Sivaganga district having population about
2 lakhs and is known as the capital of Chettinad region which comprises
Karaikudi and 74 other villages. Karaikudi is located along Trichy
Rameswaram high road at a distance about 90 km from corporation city
Trichy and 140 km from Rameswaram, a pilgrimage centre. Now a day
Karaikudi is termed as tourist centre. Tourists come in large numbers to have
a view on history of Chettinad building (near Karaikudi).

Karaikudi is a great place of religion and learning. It is famous for

its temples which attracts a great amount of devotees and tourists. It is also
adorned with University and colleges. In addition to that Central Electro
Chemical Research Institute (CECRI) is located at Karaikudi. CECRI is one
of the chain of forty national laboratories under the aegis of Council of
 39

Scientific and Industrial Research, New Delhi. In the western part of

Karaikudi, it was adorned with a petrochemical industry.

The important pollutants in and around Karaikudi city are vehicular

pollution, terrestrial dust from commercial places and anthropogenic element
from human activities. Due to presence of above pollutants, based on local
enquiry, people in various part of the city have been experiencing numerous
problems such as allergic response, lung disease, respiratory problem etc. Due
to above facts, pollutants both particulates and gaseous pollutant were
generated. There were so many studies undertaken about Particulate matter.
But little attention was given on gaseous pollutants especially Sulphur
dioxide. Hence this study also focuses on gaseous pollutant namely Sulphur
dioxide.

Sulphur dioxide (SO2) is a major pollutant and is included in almost

all air quality monitoring programmes to define the air quality of a region, and
also in regulatory requirements. Depending upon the expected concnetrtiin
levels in the atmosphere, SO2 can be measured for a sampling duration of
1,2,4,8,12 or 24 hr (Goyal 2001).

Gaseous pollutants can be classified into organic and inorganic type

based on their chemical compositions. The most important oxide emitted by
pollution sourced is Sulphur dioxide. It is a colorless, noninflammable and
non-explosive gas. It causes taste sensation at concentrations ranging from 0.3
to 1.0 ppm in air. At concentrations greater than 3 ppm, SO 2 gas has a
pungent irritating odor. It is partially converted to Sulphur trioxide or
sulphuric acid and its salts by photochemical or catalytic process in the
atmosphere. In a polluted atmosphere, SO 2 reacts photo chemically or
catalytically with other pollutants. Sulphur dioxide gas alone can irritate the
upper respiratory tract and it can be carried deep into lungs (Senthilnathan
2008).
 40

SO2 can be used as a refrigerant as it is being easily condensed and

with a high heat of evaporation, sulfur dioxide is a candidate material for
refrigerants. Prior to the development of freons, sulfur dioxide was used as a
refrigerant in home refrigerators. Sulfur dioxide is a versatile inert solvent that
has been widely used for dissolving highly oxidizing salts. It is also used
occasionally as a source of the sulfonyl group in organic synthesis (Hoffman
1990). Since, Sulphur dioxide is a major pollutant and is included in almost
all air quality monitoring programmes, this study also emphasized on SO 2
monitoring around Karaikudi.

From the above discussions it can be said that important pollutants

in and around Karaikudi city are industrial pollutants, vehicular pollution,
terrestrial dust from commercial places and anthropogenic element from
human activities. Due to presence of above pollutant sources, Karaikudi is
taken as the study area to access Dry deposition.

In the present study, sampling locations were divided into three

categories as follows: i)Zone1( Where the traffic is expected to be higher) ii)
Zone2(mixture of traffic and residential areas) and Zone 3(Consisting of
residential areas). With the classification spatial variation is possible. For the
given location, to analyze temporal variation, data was deliberately divided up
into different months.

3.2 DRY DEPOSITION FLUX MEASUREMENT

Dry depositions of atmospheric particles are collected based on

“Standard operating procedure for preparation, handling of dry deposition
plates: Dry deposition of atmospheric particle”. Dry deposition plates are used
to measure the mass flux. This standard operation procedure (SOP) address
the protocol for preparation, handling. The SOP also discusses the quality
 41

assurance and quality control measures (Rajendra Paode and Thomas Holsen
1996).

A schematic of dry deposition plate is presented in Figure 3.1. The

plate is made of Poly Vinyl Chloride and is 21.6 cm long, 7.6 cm wide 0.65
cm thick with a sharp leading edge (<10 degree angle) to ensure laminar flow.
Each plate is covered with four mylar strips (5.7 cm x 1.8 cm) coated with
grease to collect impacted particles (Rajendra Paode and Thomas Holsen 1996).

Figure 3.1 Top and side view of dry deposition plate

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The dry deposition flux was measured at six different location

using Eagle II dry deposition collectors. This sampler contains two-deposition
plate mounted on arms that are pointed into the wind with a wind vane .These
arrangements are made to allow the plates swing freely into the wind
(Usamalin Shahin et al 2000). Eagle II arrangements are shown in Figure 3.2.
Dry deposition plates were exposed in the field with the help of Eagle II
arrangements. Atmospheric particles were deposited onto the strips. The strips
were weighed before and after exposure to determine the total mass of particle
collected. The mass flux is determined by dividing the collected mass by the
exposure time and the exposed surface area. As per Equation 3.1 (Puji Lestari
et al 2003), dry deposition flux is calculated.

m
f (3.1)
at

where f = dry deposition flux (mg/m2/hr); m = mass collected on greased strip

(mg); a = exposed collected surface area over number of strips (m2);
t = duration of sampling ( hr).
 43

Figure 3.2 Eagle II arrangement of Dry deposition plate

3.3 ATMOSPHERIC PARTICLE CONCENTRATION

Particle concentration was collected on 20.3 x 25.4 cm2 glass fiber

filter using a high volume sampler (Mustafa odabassi et al 2002). Sampling
time was kept as 12 hours and sampling volume for air samples was 612 m 3.
Flow rate in high volume sampler was kept as 850 litre per minute (lpm).
Sampling duration was 12 hours. Therefore, sampling volume of air samples
was 850 x 12 x 60 = 612000 litre = 612m3. Figure 3.3 shows the inner
arrangement of high volume sampler.
 44

Figure 3.3 Inner arrangement of high volume sampler

Air borne particulate matter is an ensemble of solid particles

suspended and dispersed in air. The properties of these particles vary in terms
of chemical composition, morphology (size/shape), optical parameters
(colour/light scattering) and electrical characteristics (charge, resistance).
Particles, which in general are non spherical are classified in terms of their
aerodynamic diameter. This is defined as diameter of a sphere of density
(1 g/cc) having a settling velocity equal to that of particle in question.

The sampler uses continuous duty blower to suck in an air stream.

When fitted with a particle size classifier, it separates particle greater than
 45

10 m size from the air stream. The air stream is then passed through a filter
paper to collect particles lesser than 10 m size (PM10). Gravimetric
measurements yield values of suspended particulate matter (SPM), as the sum
of two fractions and PM10, the material retained on the filter paper.

The filter assembly consists of two parts, a top cover connected to

the outlet port of the cyclone and a filter adaptor with a backing screen for the
filter paper. A rectangular 20.3 cm x 25.4 cm glass fibre filter is placed on the
backing screen and the top cover is bolted. Suitable gasket connection is used
to obtain an air tight connection. The collected matter on the filter paper is
classified as PM10.

3.3.1 Flow Measurement

The blower is capable of maintaining a flow rate in the range of 0.9

to 1.4 m3/min through the assembly. For correct flow rate, zero level of red oil
in the manometer was ensured. Airflow is measured from the difference in
manometer reading which can be adjusted. The reading is then graduated
in terms of flow rate in m3/min by using calibration curve as shown in
Figure 3.4.
 46

Figure 3.4 Calibration curve to choose flow rate

3.3.2 Gaseous Sampling Attachment

High volume Sampler can also be used to sample gases with the
help of gaseous sampling attachment. It consists of set of four impingers
(bubblers). The impingers can be operated either in series or parallel
 47

according to requirement. The impingers can be filed up to 35ml of reacting

reagent. Gaseous sampling requires only 0.2 to 2 L/min of airflow through
individual impingers. The impingers have a common outlet for the air after it
passes through reacting reagent. The outlet is connected to a tapping on the
suction side of the blower for drawing the air. The flow through the impingers
is regulated by means of individual needle valves, for each of four impingers ,
and one common outlet. The airflow rate is adjusted /measured with a
rotameter provided with the attachment.

3.4 WIND SPEED MEASUREMENT

Wind speed (U) and Temperature (T) were also recorded during
sampling. Wind speeds were recorded by using digital anemometer (make:
Lutron AM-4201) as shown in Figure 3.5. This can be hold either by hand or
attach to it something stationary with the tripod connector. The large LCD
display will make us for easy reading. This has four scales to choose from:
feet per minute, knots per hour, kilometer per hour, miles per hour.

Figure 3.5 photo view of digital Anemometer

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3.5 SULPHUR DIOXIDE SAMPLING

Sulphur dioxide sampling was performed as per Indian standard

Methods for measurement of air pollution IS 5182(Part 2):2001.

3.5.1 Range and Sensitivity

Concentrations of sulphur dioxide in the range of 25 to 1050 g/m3

can be measured under given conditions. Concentration below 25 g/m3 can
be measured by sampling large volumes of air, but only if the absorption
efficiency of the particular system is first determined and found to be
satisfactory. Higher concentrations can be analyzed by using smaller gas
samples, or a suitable aliquot of the collected sample. Beer’s law is followed
through the working range from 0.03 to 1.0 absorbance unit. This corresponds
to 0.8 to 27 g of sulphite ion in 25 ml of final solution calculated as sulphur
dioxide. The lower limit of detection of sulphur dioxide in 10 ml absorbing
reagent is 0.75g based on twice the standard deviation which represents a
concentration of 25 g/m3 in an air sample of 30 l.

3.5.2 Interferences

The effects of the principle known interferences have been

minimized or eliminated. Interferences by oxides of nitrogen are eliminated
by 1 ml of 0.06 percent sulphamic acid. Ozone is made to decompose by
allowing the solution to stand for sometime prior to analysis. The interference
of trace metals may be eliminated by the addition of 1 drop of 0.01 percent
ethylene diamine tetra acetic acid (EDTA) to the absorbing solution prior to
sampling. Atleast 60 g iron(III), 10 g manganese (II) and 10 g chromium
(III) in 10 ml absorbing reagent may be tolerated in the procedure. No
significance interference was found from 10 g copper(II) and 22 g
vanadium (V). Ammonia, sulphides and aldehydes do not interfere.
 49

3.5.3 Principle

Sulphur dioxide is absorbed from air in a solution of potassium

tetrachloromercurate(TCM). A dichlorosulphitomercurate complex which
resists oxidation by the oxygen in the air, is formed. This complex is stable to
strong oxidants such as ozone and oxides of nitrogen and therefore absorber
solution may be stored for some time prior to analysis. The complex is made
to react with para rosaniline and methylsulphonic acid. The absorbance of the
solution is measured by means of a suitable spectrophotometer.

3.5.4 Potassium Tetrachloromercurate (TCM) – 0.04M

10.86 g mercuric chloride, 0.066g EDTA and 6.0 g potassium

chloride was dissolved in distilled water and brought to the mark in a 1 litre
volumetric flask. The pH of this reagent shall be approximately 4.0 but it has
been shown that there is no appreciable difference in collection efficiency
over the range of pH 5 to 3. The absorbing reagent is normally stable for six
months. If a precipitate forms, after removing mercury, the reagent was
discarded.

3.5.5 Stock sodium thiosulphate solution – 0.1 N

To prepare a stoke solution, 25 g of sodium thiosulphate

pentahydrate was taken in a beaker and 0.1 g of sodium carbonate was added
and dissolved using boiled and cooled distilled water making solution up to a
final volume of 1 litre. This solution was allowed to stand one day before
standardizing.

To standardize, 1.5 g of primary standard potassium iodate dried at

180oC, was accurately weighed to the nearest 0.1mg and diluted to 500 ml in
a volumetric flask. 50 ml of iodate solution was taken by pipette into a 500 ml
 50

iodine flask abd 2 g of potassium iodide and 10 ml (1:10) hydrochloric acid

were added and flask was stoppered. After 5 min stock thiosulphate solution
was titrated to pale yellow colour. 5 ml of starch indicator solution was added
and titration was continued till the blue colour disappeared.

3.5.6 Standardized Sulphite Solution for Preparation of Working

Sulphite TCM Solution

0.30 g of sodium metabisulphite (NaHSO3) or 0.40 g of sodium

sulphite (Na2SO3) was dissolved in 500 ml of fresh boiled and cooled distilled
water. Sulphite solution is unstable; it is therefore important to use water of
the highest purity to minimize this instability. This solution contains the
equivalent of 320-400 g/ml of SO2. The actual concentration of the solution
is determined by adding excess iodine and back-titrating with standard
sodium thiosulphate solution. To back titrate, 50 ml of the 0.01N iodine
solution was pipetted out in each of two 500 ml iodine flasks A (blank) and B
(sample). To flask A (blank) 25 ml of distilled water was added and into flask
B (sample) 25 ml of sulphite solution was measured. Flasks were stoppered
and they were allowed to react for 5 min. By means of a burette containing
standardized 0.01N thiosulpahte, each flask in turn was titrated to a pale
yellow color. Then 5 ml of starch solution was added and titration was
continued until the blue color disappears.

3.5.7 Working Sulphite – TCM Solution

2 ml of standard sulphite solution was measured into 100 ml

volumetric falsk by pipette and brought to mark with 0.04 M TCM.
Concentration of sulphur dioxide in the working solution was calculated in g
of sulphur dioxide per milliliter as per Equation 3.2. This solution is stable for
30 days if kept in the refrigerator at 50C. Otherwise freshly prepared when it
is needed.
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Calculation

V1 V2 x N x 32000 x 0.02
Cs (3.2)
25

where Cs = concentration of SO2 solution in g/ml

V1 = volume in ml of thiosulphate used for blank
V2 = volume in ml of thiosulphate used for sample
N = normality of thiosulphate
32000 = milli equivalent weight SO2, g
25 = volume of standard sulphite solution in ml
0.02 = dilution factor

3.6 PREPARATION OF STANDARD CALIBRATION GRAPH

This graph was prepared from standard sodium sulphite solution.

Working sodium sulphite tetra mercurate(TCM) solution were taken in
different dosage (0,1,2,3 and 4 ml)into a series of 25 ml volumetric flasks.
Then these solutions were to be added with sulphamic acid, formaldehyde
solutuion and pararosaniline solution. After 20 minutes the absorbance values
for each dosage were found out by spectrophotometer.

The graph was plotted between the mass of sulphur dioxide in g

versus absorbance values. The plot between absorbance and mass of SO2 in
calibration curve should be a linear relationship as per IS 5182(Part 2):2001.
However, the observations of absorbance taken for blank and 1ml are much
deviating from the remaining data and hence they have not been considered
while obtaining the line of best fit using the regression analysis. For
maximum precision, the line of best fit using regression analysis by the
method of least squares should be determined. The mass of sulphur dioxide
was determined by multiplying the concentration standard (got as 310 g/ml
from titration) with the amount of sulphite solution added (ml). A linear
 52

relationship should be obtained. Among five different dose of TCM, first and
second dose (0ml and 1ml) did not cop up with the linear relationship. Hence
it was omitted. Correlation coefficient for the remaining data points were
obtained as 0.9897 as shown in Figure 3.6. The slope of the line of best fit
was also determined and reciprocal of this slope is denoted as B, the
calibration factor.

Figure 3.6 Standard calibration graph (for the best linear relationship)

3.7 CALCULATION OF VOLUME OF AIR SAMPLES AND

CONCENTRATION OF SO2

Volume of air samples for sulphur dioxide concentration was

calculated from product of flow rate and time at which sampling was
performed. It is given in Equation 3.3.

3
F1 F2 * t * 10
Volume of air sampled (Va) = (3.3)
2
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where F1 = initial flow rate at start of sampling (lpm)

F2 = final flow rate at end of sampling (lpm)
t = duration of sampling (min)
10-3 = Conversion factor from litre to m3

Calculation of sulphur dioxide was determined from the Equation (3.4)

A A0 * B
Concentration of SO2 = (3.4)
Va

where A = sample Absorbance

A0 = Reagent blank absorbance
B = Calibration factor ( g/absorbance)
Va = Volume of air sampled (m3)

Calibration factor (B) was obtained from standard calibration

graph.

3.8 SAMPLING PROGRAM AND SAMPLING LOCATIONS

As per the CPCB guidelines the night time limit is between 22:00
hours to 07.00 hours as outlined in Ministry of Environment and Forest
Notification S.O. 123 (E) dated 14/02/2000. But in this study, day and night
dry deposition samples and particle concentration were collected from 08:00
to 20:00 and 20:00 to 08:00 respectively as suggested by Holsen et al (1991).
They mentioned that the collection of day and night samples as per the above
time limits will be covering a wide range of atmospheric conditions to be
evaluated. Also, equal time of sampling for day and night may lead to proper
interpretation of the data for day and night samples. 92 samples were
collected in Karaikudi during period of no rain or threat of rain. Wind speeds
were also recorded during the sampling period.
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Sampling locations were classified into three categories as follows:

i) Zone1 (where the traffic is expected to be higher order) ii) Zone2 (mixture
of traffic and residential areas) and iii) Zone3 (consisting of residential areas).
After benchmarking the categories, the samplings were conducted at six
different places such as: i) Police colony ii) Burma colony iii) Ram Nagar
iv) Old Bus Stand v) New bus stand and vi) Tower junction. Eight sets of
sampling at six different places with different time emphasize the examination
of Spatial and Temporal variation of dry deposition flux, concentration of
particles and concentration of SO2. Figure 3.7 shows Map of Karaikudi
showing all sampling locations.

3.8.1 Sampling of Sulphur dioxide

Daytime and Nighttime SO2 Concentration samples were collected

from 08:00 to 20:00 and 20:00 to 08:00 respectively as discussed in section
3.2. The measurements were done by using high volume sampler. In High
volume sampler (HVS), an acrylic rotameter of 3 litre per minute (lpm)
capacity is provided to check the flow rate through the impinger tubes for
gaseous sampling. High volume sampler consists of four impingers. The
impingers can be operated either in series or parallel according to the
requirement. The impingers can be filed up to 35ml of reacting reagent.
Gaseous sampling requires only 0.2 to 2 L/min of airflow through individual
impingers. The impingers have a common outlet for the air after it passes
through reacting reagent. The outlet is connected to a tapping on the suction
side of the blower for drawing the air. The flow through the impingers is
regulated by means of individual needle valves, for each of four impingers ,
and one common outlet. The airflow rate is adjusted /measured with a
rotameter provided with the attachment.

Tetra Chloro Mercurate (TCM) solution is used to absorb sulphur

di oxide from the atmosphere. TCM was taken in an impinger having 35ml
 55

capacity. After collecting SO2 sample, it was brought to laboratory for

analysis.

The collected samples were to be added with Sulphamic acid,

Formaldehyde solution and pararosaline solution and then by using
spectrophotometer to find out the absorbance values of this solution at 560 nm
wavelength.

Figure 3.7 Map of Karaikudi showing the sampling stations

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3.9 MEASUREMENT OF PARTICLE SIZE

Particle size was measured by using X ray diffractometer (XRD).

Brief description of XRD was illustrated as follows:

Company : PAnalytical
Product name : X’Pert Pro
Scan type : continuous
Divergent slit type : fixed
Anode material : Copper
Generator setting : 30mA, 40KV
Configuration : Flat sample stage

XRD consists of coolidge tube to produce X rays, sample stage and

detector. X rays falls on sample which is placed in sample stage. In this study,
strip was placed on the flat sample stage. Scattered rays from the sample
strikes on semi conductor detector. The glancing angle (2 ) which is the angle
between the plane of reflection in the sample to the incident rays. 2 value
varies from 5o to 100o. This is the best operation range for the betterment of
the detector. At the detector, scattered X rays produces current pulses. This
was measured in terms of counts/sec. This count/sec was plotted against 2
value. For particular values of 2 , count/sec is maximum. This shows that
reflection from these planes gives constructive interference of scattered X
rays from these planes. From these peaks particle size was determined.
Particles collected on the strip were usually irregular. Most common form to
describe particle size is through geometric mean and geometric standard
deviation. These kinds of description of particle sizes were possible only if
microscopic count data generated for various ranges of size of particles. In
table 4.1 to 4.8, particle size mentioned were average size of particle collected
on strip. Scherror calculation is used to evaluate particle size from obtained
 57

peak from XRD. (Elements of X ray diffraction by B.D.Cullity , Addison-

Wesley publishing company, INC)

Particle size = 0.9 /Bcos

Where = wavelength of source

B = full width half maximum
= incident angle

In the present study wavelength source of 1.6Ao and incident angle

of 10o to 100o were used. For example Burma colony night sample on
06/06/07, particle size is calculated as follows.

Particle size = 0.9x1.6x10 -10/ 10x /180 x cos(89.9976) o

Paticle size = 20µm

B = full width half maximum should be converted in radians (10 o)

= incident angle (89.9976) (angle at which maximum peak attained)