Sampling

UNIT 4 SAMPLING
Structure
4.1 Introduction
4.2 Sampling -An Introduction
4.3 Factors Relevant To Sampling
4.4 Water Sampling
Type of Samples
Sampling Facilities
Sampling Frequency
Sample Containers
Sampling Equipment
Sampling Procedures
Preservation of Samples
Specific Preservation for Individual Parameters
Sampling for Bacteriological Analysis
4.5 Air Sampling
Selection of Sampling Locations
Specific Criteria for Selection of Location
Suspended Particulate Matters
Procedure for Operating Suspended Particulate Sampler
Gaseous Pollutants
4.6 Sampling of Solid Wastes
General Requirement of Sampling
Sampling of Food Materials
4.7 Summary
4.8 Terminal Questions
4.9 Answers

4.1 INTRODUCTION
In the last block you have studied about general perspective of analytical chemistry
and evaluation of analytical data. In this block there are three units. Unit 4 of this
block deals with sampling. The process of sampling consists of drawing a very small
portion of the material as a representative of the bulk of the material. The analysis of
sample begins with the collection of the sample and the result of any test procedure
will depend on the sample. In this we will discuss the sampling methods of water, air
and solid waste. We will also learn about the types of samples, sampling equipments
and preservation of samples.

Objectives
• After studying this unit, you should be able to :

• define sampling,

• explain sampling procedures for water,

• describe preservation methods for water samples,

• select suitable sites for ambient air sampling,

• describe sampling methods for ambient air,

• explain sampling procedures for solid wastes,

• describe methods for volume reduction of solid wastes, and

5
Initiation into • describe methods for sampling of food materials.
Analytical Laboratory

4.2 SAMPLING - AN INTRODUCTION

An analysis is carried out on a sample and it can be no more representative of the
liquid under investigation than that of sample. The analysis of sample begins with the
collection of the sample and the result of any test procedure will depend on the
sample. If the liquid is of relatively uniform composition in both time and space then
any sample should suffice and there is no problem. But if composition varies with time
or is not uniform at place where it is decided to take the sample then no single sample
will be truly representative. It then becomes a question either of taking and analysing a
number of samples or taking a number of sub-samples, combining them suitably to
form one composite sample and analysing that.

The sampling is a process to collect a portion of material small enough in volume to

be conveniently transported to and handled in the laboratory while still accurately
representing the material being sampled. This implies first, that the relative portions of
the concentrations of all pertinent components must be the same in the sample as in
the material being sampled, and second, that the sample must be handled in such a
way that no significant changes in composition occurs before the tests are performed.
The analysis is generally intended to reveal the composition of the environmental
components at the time of or over the period of sampling. Consequently errors are
introduced if changes take place between taking of the sample and analysis. There is
infact a strong likelihood that such changes will occur in most of the environmental
components. The arrangement should be such that these are prevented or atleast
minimised.

Environment mainly comprises of air water and solids. Environmental monitoring is

carried out by collecting a portion of a particular component of the environment. This
practice is known as sampling. Due to this change the chemical composition of an
environmental component may not remain same but may tend to adjust itself
according to its new environment. Constituents of the environmental component,
sample may interact with the surface wall of the container and consequently their
concentration may be altered. This is particularly true for metals. Cases of adsorption
of metals on the container surfaces as well as leaching of metals into sample media
have been observed. These considerations, therefore, are prerequisite of a sampling
programme.

4.3 FACTORS RELEVANT TO SAMPLING

The monitoring of environment quality to give reliable and usable data requires that
analytical and other resources are employed to the best advantage. The first step in the
planning of environmental monitoring is to decide what data is needed and how it is
useful. The type of investigation, purpose of study and anticipated variations are other
points to be considered. The first stage of planning of the sampling programme is the
selection of the most suitable site to provide the required data. A set of samples taken
over a period of time will be valid if they present a true picture of the quality of an
environmental component at a station during the period covered by the results and this
will be determined by the place, time and frequency of sampling and of course by the
representativeness of the samples. In ambient air quality monitoring, the selection of
site meteorological conditions and flowrate of air sampling are most important factors.
Factors for solid wastes and food materials comprise; representativeness of the sample
and methods used for the reduction of the volume of the sample.

Now we will discuss the sampling method of water, air and solid waste.

6
SAQ 1 Sampling

What are requirements for obtaining reliable data on environmental quality?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

4.4 WATER SAMPLING

Water sampling is most important and need lot of care. Let us discuss it point vise.

Site Selection
The objectives of water quality monitoring system are (a) to assess the impact of
activities by man upon the quality of water and its suitability for required uses, (b) to
determine the quality of water in its natural state which might be available to meet the
future needs, and (c) to keep under observations the sources and pathway of specified
hazardous substances. The first objective is met by establishment of impact stations,
the second by the selection of baseline stations and the third by the selection of either
impact or baseline stations. The selection of sampling site is decided by the various
uses of the water and by their location, relative magnitude and importance. The
chances of accidental pollution are also an important factor and should be considered.
The location of a river use downstream of a large urban or industrial area imposes
greater risk and requires more supervision than similar uses located upstream. In a
rapidly developing region there may be expansion of population or industry which
may in relatively short time bring about major changes in the water quality. In case of
such developments, the location of the sampling stations should be reviewed to decide,
if any changes are necessary.

Site Location for Rivers

The possible sampling sites of a river passing through a major city are given below :

Site i: Immediately downstream of an international boundary

Site ii: At a place of abstraction for public supply of large town
Site iii: In an important fishing, recreation and amenity zone
Site iv: At a place of abstraction for large scale agricultural irrigation
Site v: At fresh water tidal limit of major river
Site vi: At a place of abstraction for large industrial supply
Site vii: Downstream of industrial effluent discharges and important tributary
influencing main river
Site viii: Baseline station where water is available in natural state. This may be
undeveloped sparsely populated area

Site Location for Lake

A partially enclosed body of fresh water surrounded by land is called lake. Only four
sampling sites are normally sufficient for monitoring.

Site i: At a place where principal feeder tributary meets the lake

Site ii: At a central place of the lake. The sample from this site gives the general
water quality of the lake

7
Initiation into Site iii: At a place from where water is pumped for water supply for major city
Analytical Laboratory
Site iv: At a place from where water is discharged from the lake

4.4.1 Type of Samples

There are mainly three types of samples
a) Grab or catch samples
b) Composite samples
c) Integrated samples

a) Grab or catch samples

A sample collected at a particular time and place can represent only the
composition of the source at that time and place. However, when a source is
known to be fairly constant in composition over a considerable period of time or
over a substantial distance in all direction, then the sample may be said to
represent a longer time period or larger volume or both, than the specific point at
which it was collected. In such circumstances some source may be quite well
represented by single grab samples. When a source is known to vary with time,
grab samples collected at suitable intervals can be of great value in documenting
the extent, frequency, and duration of these variations. In case the composition
of a source varies in space rather than in time, a set of samples collected from
appropriate locations with less emphasis on timing may provide the most useful
information.

b) Composite samples
The term composite samples refer to a mixture of grab samples collected at the
same sampling point at different times. Sometime the term composite is used
when it is necessary to distinguish this type of sample from others. Time
composite samples are most useful for observing average concentrations, as an
alternative to the separate analysis of a large number of samples, followed by
computation of average and total results. A composite sample of 24 hours period
is considered standard for most determinations. Composite samples cannot be
used for determinations of components or characteristics subject to significant
and unavoidable changes on storage.

c) Integrated samples
Mixture of grab samples collected from different points simultaneously or as
nearly as possible, is called integrated sample. Such samples are useful for river
or stream that varies in composition across its width and depth. The need for
integrated samples also may exist if combined treatment is proposed for several
separate wastewater stream. The preparation of integrated samples requires
special equipment to collect samples from a known depth, without
contamination by over lying water. Prior knowledge about volume, movement
and composition of the various parts of the water being samples is also required.

4.4.2 Sampling Facilities

There are many sampling facilities; however, their availability depends on local
circumstances. They have their own merits and demerits, depending on sampling site.
Some of the sampling facilities commonly used are as under:

i) Bank side: The sample may be collected from the bank of the river or lake. The
sample should preferably be taken where water is turbulent, or from the outside
bank of a bend where the water is usually fast and deep. This is not a preferred
method of sampling and it should only be used when no alternative is available.

8
ii) Boats: Boat is useful for sampling at any point along or across the river or lake. Sampling
It is, however, necessary to identify the sampling point usually by reference to
one or more land marks. Care is necessary to ensure that bottom sediments are
not disturbed, otherwise they will also be included in the sample.

iii) Bridges: Bridges are usually preferred because of their ease of access, the exact
identification of the sampling point, the ability to control the lateral and vertical
positions of sampling and capability to sample safely under all conditions of
flow and weather. Bridge sampling is normally the most expeditious and
economical form of river sampling.

iv) Cable ways: Cable ways used for current velocity measurements can also be
employed, with adaptation for river sampling, quite satisfactorily. However,
their use is restricted to smaller rivers.

v) Helicopter: Sampling by helicopter has the advantage of flexibility. Sample

may be taken at any point on a river or lake speedily. It is also possible to reach
places where access is difficult otherwise.

4.4.3 Sampling Frequency

Water sample should be collected at intervals so that no change in quality could pass
unnoticed. The quality of water in various water bodies is rarely if ever constant in
time but is subjected to change. While there may be some relationship between the
rates of change of different determinands, other alters independently. The larger the
number of samples from which mean is derived, the narrower will be the limits of the
probable difference between observed and true values. However, the sampling
schedule is a compromise between accuracy and the funds, personnel available for the
work.

4.4.4 Sample Containers and Equipment

It is always advantageous to measure the quantity of water in situ by means of sensors
which is lowered into position rather than by withdrawing samples. However, it is not
always possible. Water samples are, therefore, collected in suitable containers. A
sample container must satisfy the following requirements.
• It could easily be freed from contamination
• It should not change the relevant water characteristics on contact
• It should have adequate capacity for storing the samples
• It should be resistant to impact and to internal pressure which is increased by
expansion of water or by release of dissolved gases at elevated temperature on
storage
The sample bottle may be made of either glass or plastic, usually polyethylene. It must
be capable of being tightly sealed either by stopper or cap. The bottles should be
soaked with 10% HCl for 24 hours and then thoroughly cleaned and rinsed with
distilled water.

Numerous types of sampling equipments have been devised. However, the sampler
design is generally immaterial except for dissolved gases or constituents particularly
affected by atmospheric gases. Sampling equipments are briefly described below:

i) Ball-valve type sampler

This sampler is used for the collection of sample at any desirable depth. The
sampler is lowered up to desired depth and then valve is opened by rapidly

9
Initiation into raising and lowering several times in succession, which opens the ball valves at
Analytical Laboratory either end and traps the water.

ii) Dussart Sampler

It is a bottle of convenient size surrounded by lead sheath and closed by a rubber
bung containing two holes. Through one hole passes a glass tube leading nearly
to the bottom of the bottle and through the other a short glass tube. The two
being connected at the top by rubber tubing. The bottle is suspended by a 0.3 m
long stirring whose both ends fastened round the neck of the bottle. This elastic
device and a piece of cord attached to the rubber tube joining the glass tubes are
connected with a metal loop to which also attached the cord used for lowering
the bottle. In taking samples, the bottle is lowered to the required depth and the
suspended cord is given a sharp jerk. This removes the rubber tube and allows
the water to be filled in the bottle.

iii) Freedinger Sampler

The equipment consists of essentially of a hollow tube with hinged flaps at each
end, the lower one including a tap for final withdrawal of the sample. It is
lowered to the required sampling depth with flaps open at the end of the wire
passing over a pulley on a gantry which records, the depth to which the
apparatus has been let down. Sending a 'messenger' down the wire operates an
arrangements which causes the flaps to close tightly thus including in the water
only from the depth to which the tube has been lowered. The apparatus is finally
raised to the surface and water emptied from the bottle using the sampling cock
in the lower flap.

iv) Kemmere and Ruttner type Sampler

The basic equipment consists of an open tube of 1 litre to 3 litres capacity with a
hinged lid at each end. The lids may then be closed down by a messenger (a
weight slide down the suspending cable). The Ruttner tube is made of
polymethyl methacrylate (Perspex, Plexiglass) & Kemmerer of copper. The lids
are open but they do impede water flow through the tube. Once the desired
depth is reached the sampler must be alternatively raised and lowered 25 cm,
several times to flush out contaminant water.

v) Wales (Flask) Sampler

This is similar in principle to the Dussart flask but the flask closure is magnetic
and more complicated. The first jerk opens the flask. The second seals it again.
It is most suitable for bacteriological sampling.

vi) Watt Flask or J.Z. Sampler

Evacuated glass flasks are used for this sampler. These are closed by an
expandable glass seal. The 'messenger' smashes the seal.

4.4.5 Sampling Procedures

The determinands for water quality monitoring may be classified as (i) conservative
which does not change with time (ii) Non-conservative which changes with time but
can be stabilised, for at least 24 hours by appropriate treatment, and (iii) Non-
conservative which changes rapidly with time and cannot be stabilised. The first two
groups can be measured by taking representative samples for subsequent analysis in a
laboratory. The third group including temperature pH and dissolved oxygen, need to
be measured in the field immediately after sampling.

10
The sampling may be carried out either manually or automatically using appropriate Sampling
samplers. The simplest manual sampling is carried out by a plastic bucket or stainless
steel jar fastened by a rope. However, it has got a drawback that the sample is taken at
the surface and undue proportion of floating matters is also collected. An alternative is
to immerse the sample bottle directly in water. Sample from various depths may be
collected by using any of the sampler described above. A variety of ingenious
automatic sampling euipments are also available for taking sample mechanically at
fixed intervals or continuously. Any sampling techniques may be used, however,
adaption of a particular technique depends upon what is being analysed and what
constituents are to be determined. Under this section we will discuss general procedure
for sampling, sample collection and some other important points.

i) General Procedure for Sampling

Obtaining representative samples and then maintaining the integrity of the
constituents is an essential pre-requisite to any analysis. In sampling, the
objective is to remove a small portion of the environment that is representative
of the entire body and the procedure must be capable of providing a valid
sample. It is then obvious that improper sampling will give erroneous results.
Once the sample is taken, the constituents of the samples must stay in the same
conditions as collected. The length of the time that these will remain stable is
related to the preservation method. Effective sample preservation will allow a
sample constituent to be preserved for reasonable periods of time.

ii) Sample Collection

Wherever possible the container should be rinsed out two or three times with the
sample to be examined before being finally filled. If this cannot be done the
container should be well drained. The stopper should not be laid down, but kept
in hand before reinserted. Unless it is absolutely unavoidable, no funnel or jug
should be used in filling the container, and the container should be so held that
the water does not come in contact with hand before entering.

In taking a sample from a tap or pump, the nozzle should be examined to see
that it appears clean. If not, it should be cleaned and water should be allowed to
run to waste before filling the bottle unless it is desired to ascertain whether the
water is affected by standing in the main or pump pipe. If such is the case, it is
better to take the sample first in the morning before anyone has drawn for other
purposes.

In taking samples from springs and rivulets it is often necessary to make

excavation sufficiently large to hold hand and bottle, and allow sufficient time
for all matter disturbed to be washed away before taking the samples. Where the
sample must be taken by immersing the bottle, as in ponds, reservoirs, lakes,
rivers and many wells, it is generally quite satisfactory, if any container is
weighted sunk rapidly to the required depth.

iii) Other Points Requiring Attention

Some other important points which require attention are:
• Samples where water is well mixed. Weirs enhance the settling of solids
upstream and accumulate floating solids and oil downstream, therefore,
such location should be avoided as a sample source.
• Avoid large non-homogeneous matter such as leaves, rags, twigs and
other floating material in the sample
• Sample preferably at 0.6 times of depth in a shallow channel or where
velocity of mixing is sufficient to prevent solids deposits. For depths

11
Initiation into greater than 1m, collect two samples at 0.2 times and 0.8 times of depth
Analytical Laboratory below the surface
• Sample facing upstream to avoid contamination by slowly drawing water
from the source into the container
• Force sampling container through the entire cross-section of the stream,
whenever possible
• Ascertain that the sampler operates at the proper time before the sampling
with a depth sampler. If doubt exists, discard and re-sample
• Provide complete information on the source and conditions under which
the sample was collected
Attach a record tag to the sample container. The tag contains information on sample
number, source of sample, analysis required, temperature and name of person
collecting the sample. The tag should be signed, date and time recorded by the person
collecting the sample.

4.4.6 Preservation of Samples

The physico-chemical determinands of interest are :
i) Nutrient Group
ii) Metal Group
iii) Physical and Mineral Group
iv) Organic Group
Let us discuss each of them briefly.

i) General preservation of Nutrient Group

Use HCl rinsed borosilicate glass bottle (dark coloured bottle should be avoided)
or polyethylene container. Add in the first sample 40 mg/L HgCl2 as
preservative for surface and mildly polluted waters or 400 mg/L HgCl2 for
highly polluted waters. For TOC (Total Organic Carbon) and COD (Chemical
Oxygen Demand) samples, add 0.2 ml of conc. H2SO4 per 100 mL of sample so
that the pH of the sample is around 2.0. For soluble TOC and COD samples,
acid must be added after the samples are filtered using Whatman No.42 or GFC
of 0.45 micron porosity filters. Refrigerate sample at 4°C, if refrigeration
facilities are not available, store the samples in ice box containing salt-ice
mixture, ensure that ice always remains.

For BOD (Bio-chemical Oxygen Demand) estimation, the samples may be

preserved at 4°C and analysed within 24 hours. Problem arises in the
determination of BOD in the river water due to:
• Loss of BOD during interval between sample collection and its processing
in the laboratory
• Loss of DO (Dissolved Oxygen) when its value is in excess of 9.3 mg/L,
the saturation value at 20°C. The DO may escape from the sample and
false BOD value may be recorded. This is corrected by aeration of sample
before setting up the BOD test. The sample should be raised to above
20°C before aeration during winter.
Dissolved determinands: Filter rapidly the sample through Whatman No.42
(membrane filter of 0.45 micron porosity is preferred) and add HNO3 to pH
below 2 and analyse the filtrate within six months.

12
ii) Metals Groups Sampling
Take 200 ml portion of sample into a HNO3 rinsed polyethylene container (pec)
and analyse for chromium (VI) immediately.
Take a second portion of 100 ml sample in a separate polyethylene container for
boron. A third 250 ml sample can be acidified to pH 2 with HNO3 and
refrigerated at 4°C for analysis within six months. A fourth sample is collected
for Hg and preserved as recommended.

iii) General Preservation for Physical and Mineral Group

Collect a 4 litre sample in polyethylene container and then immediately separate
the aliquot for phenolic, cyanide and sulphite and add the appropriate chemical
preservative. If possible in situ of pH determination is recommended.

iv) Container Washing and Preparation

The specific situation will determine the use of borosllicate glass bottle or
polyethylene container. Rinse with chromic acid solution (35 ml of saturated
Na2Cr2O7 in 1 L. Conc. H2SO4) followed with tap and distilled water and then
invert them to dry. If metals are to be analysed, rinse the container with a
solution. Containing 1 part HNO3 in 4 parts of water followed by distilled water.
If phosphorous is to be analysed, rinse the container with a solution with 1 part
HCl to one part water followed by distilled water.

v) Preservation of Samples of Organic Groups

Ideally, analysis of the sample for organic groups should be conducted within a
matter of hours from the time of collection. However, this is impractical in
terms of distance from the sampling site to laboratory and/or the laboratory
workload. Samples for organo-chlorine residues may be held up to a week under
refrigeration at 2 to 4°C and for organo-phosphorus or carbamate, sample should
be frozen immediately after sampling. These samples may be stored for the
maximum period of four days. Samples for PCB's, PAH's and Chlorophenoxys
should also be stored below 4°C. Water samples should be collected and stored
in all glass system. Glass containers must be scrupulously cleaned and rinsed
with some of the solvents to be used for subsequent pesticides extraction. All
bottle caps should be teflon or aluminium foil lined to prevent contamination of
the samples with the trace quantities of impurities which may be present in
laminated paper liners.

4.4.7 Specific Preservation for Individual Parameters

Now let us discuss briefly specific preservation for following.

Acidity: Samples should be collected in polyethylene or pyrex bottles and stored at

low temperatures. Determination should be performed as soon as possible after
sampling but preferably within 24 hours.

Alkalinity: Samples should be collected in polyethylene or pyrex bottles and tightly

capped after sample collection and stored at low temperature. Determination should be
carried out as soon as possible and preferably within 24 hours, due to instability of the
constituents.

Aluminium: Losses of aluminium have been reported at pH above 2.5 both in pyrex
and nalgene containers. Samples should be collected in clean acid-rinsed polyethylene
bottles, stored at low temperature and examined as soon as possible after collection. If
storage is unavoidable, the sample should be acidified to pH less than 2.5 with reagent
grade HNO3.

13
Initiation into Arsenic: No special precautions are required other than those cited earlier.
Analytical Laboratory
Boron: Samples should be stored in polyethylene bottles or in alkali resistant, boron
free glasswares.

Calcium: The sample container (glass or plastic) should be tightly capped as soon as
the sample has been collected and calcium determined at the earliest.

Cadmium: Considerable loss of cadmium has been reported at pH 6.0 and pH 8.0
both from pyrex and nalgene containers. Sample should be acidified to pH 2.0. Loss of
cadmium in 20 days at pH<6.0 is also reported. Polypropylene containers were found
to give high blank values.

Chlorine: No special treatment has been recommended, but determination should be

carried out as soon as possible.

Chromium: Loss of chromium from water samples at pH 8.0 has not been reported
yet. However, it is suggested that the sample should be acidified to pH 1.5 with
reagent grade HNO3 and stored at low temperature.

Colour: The colour should be determined as soon as possible after collecting the
sample and after opening the sample container in the laboratory as biological changes
occurring may affect the colour.

Copper: High losses of copper occur in all types of containers viz. Teflon,
polypropylene, polyethylene, flint glass and pyrex. The losses being highest for pyrex
containers at pH 6.0 at room temperature and least for teflon. Storing at 5°C reduced
the losses by 4-11% but acidification to pH 1.0 was found to be most effective. At pH
1.0, at room temperature after ten days storage 2% copper was lost from teflon
container and 10% from pyrex glass and polypropylene containers. In view of this,
acidification of samples with reagent grade HNO3 to pH 1 and storage at low
temperature is advised.

Cyanide: It has been stated that up to 5 days no loss of cyanide ions occurs, while
10% loss occurs in 7 days. The losses increase with increase in storage time at room
temperature. Further it is found that addition of zinc acetate or CHCl3 as preservative
or addition of NaOH to raise the pH to 11, no loss of cyanide ion occurs. Similarly,
storage at 4°C also minimises losses. Consequently, it is advised that the sample
should be collected in a clean 1 litre or larger polyethylene bottle. Add 2 ml of 10 N
NaOH/1 of sample to raise the sample pH to 12 or above. The sample should be
analysed as soon as possible. If storage is required, the samples may be stored in
refrigerator or in ice chest filled with ice and water to maintain the temperature at 4°C.

Oxidising agents like Chlorine decompose most of cyanides. Test a drop of sample
with KI-starch test paper; a blue colour indicates the need for treatment. Add ascrobic
acid, a few crystals at a time, until a drop of the sample reduces no colour on the
indicator paper. Then add on additional 0.6 g of ascorbic acid for each litre of sample
volume.

Fluoride: Studies carried out have shown that up to 30 days no loss of fluoride ions
occurs and as such no special precautions are required in handling and storing water
samples for fluoride analysis. However, polyethylene bottles are generally preferred
for collecting and storing water samples for fluoride analysis. The plastic sample
container should be tightly closed immediately after collection of sample and fluoride
should be determined as soon as possible.

14
Glass bottles are satisfactory provide precautions are taken to prevent use of containers Sampling
which previously contained high fluoride solution. The usual precautions of rinsing
the bottle with portion of sample should be observed.

Hardness: Sample container (Plastic or glass) should be tightly capped as soon as

possible the sample has been collected.

Iodide: The sample container should be tightly capped after collection of the sample.
Store at 4°C and analyse the sample as soon as possible.

Iron: Methods of collecting, storing and pretreating samples for iron determinations
should be planned in advance. The sample container should be cleaned with acid and
rinsed with distilled water. The value of the determination is greatly dependent upon
the care taken to obtain a representative sample. Iron in well water or tap water sample
may vary in concentration and form with the period and degree of flushing before and
during the sampling and considerable pumping of the water to waste should be done,
particularly when relatively unused tube wells are being sampled. Immediately after
sample collection, the container should be tightly capped leaving no air gap in the
container. Iron may also be present as soluble salt or possibly in combination with
organic acid, contributing to the colour of the sample. Ground waters containing more
than 1 mg/L of iron in apparent solution as bicarbonate soon become cloudy and iron
precipitates as red, colloidal ferric hydroxide through oxidation. For precise
determination of total iron, a separate container should be used for collection of
samples. This sample may be treated with reagent grade HCl or HNO3 to prevent
formation of deposits on the container wall.

Ferrous-ferric iron: For study of ferrous-ferric equilibria and also to get an idea of
redox potential, it is sometime desirable to determine the ferrous content of the water
sample. For such determination add 10 mL of 1% o-phenanthroline or
bathophenanthroline and 1 mL glacial acetic acid to the 1 litre sample bottle before
sample collection for iron. Both o-phenanthroline and bathophenanthroline will
complex soluble ferrous iron before it is oxidised to ferric state. The addition of
nitrilotriacetic acid to the system further helps to stabilise the ferrous-ferric system.

Lead: Studies have shown that rapid and almost complete adsorption of lead occurs on
glass and polyethylene containers at pH 6 and above. At pH 2.0 only borosilicate glass
was effective in maintaining lead ion in solution beyond four days aging period. Once
lead is adsorbed on the container walls acidification to pH 2 with HNO3 is ineffective
in desorbing adsorbed lead. In view of this it is desirable to filter the sample in the
field and acidify to pH 1.5 with reagent grade HNO3 for determination of soluble lead.

Manganese: Manganese may exist in soluble form in ground waters, particularly from
confined aquifers but oxidises to higher oxidation state and precipitates from solution
or gets adsorbed onto the surface of container. Even shallow well waters may contain
substantial amounts of manganese 2-3 mg/L in solution. Unlike Iron, precipitation of
manganese hydroxy oxides takes longer time and takes place at higher pH values. It
has been reported as much as 60-80% loss of Mn from pyrex and nalgene containers
within 5 days at pH 6-8 occurred while at pH-1.6 to 2.5 even after 30 days storage no
detectable losses in Mn ion concentration were noticed.

Mn should be determined as soon as possible after collection of water sample.

However, if storage is necessary the sample may be filtered through 0.45 micron
membrane filter and acidified with reagent grade HNO3 to pH 1.5. If total Mn is
required then the filtration may be avoided and the sample should be acidified directly.

Magnesium: The sample bottle should be tightly capped after collection of sample.
Since Mg bicarbonate and magnesium carbonate are relatively more soluble than the

15
Initiation into corresponding calcium salts. Precautions taken for calcium will suffice for magnesium
Analytical Laboratory too.

Mercury: Bacteria is the principal cause of instability of dilute mercury solutions.

Mercury is effectively stabilised in water samples with 0.05% KMnO4 solution with
any acidification. Considerable reduction is found in Hg losses when pH of the sample
was lowered to 1. Teflon is found to be the most suitable container material followed
by flint glass, polypropylene, polyethylene and pyrex glass in that order.

Molybdenum: Sample should be acidified to pH 1.5 immediately after collection (for

total Mo) or filtered through 0.45 micron membrane filter and the filtrate acidified to
pH 1.5 with reagent grade HNO3 for determination of soluble Mo.

Nickel: Investigations carried out show that slow adsorption of nickel occurs on the
walls of the containers even at pH 2, the loss being around 15% on all types of
containers. It is, therefore, suggested that analysis of nickel should be carried out
immediately after collection of water samples. If storage has to be done, then the
sample should be acidified to pH 1.5 with reagent grade HNO3 immediately after
collection (for total Ni) or the sample should be filtered through 0.45 micron
membrane filter (for soluble Ni) immediately after collection and filtrate acidified to
pH 1.5 with reagent grade HNO3 and stored at 4°C.

Ammonia-Nitrogen: The most reliable results are obtained on fresh samples. If this is
not possible, the bottle should be tightly capped and precautions should be taken to
retard biological activity by storing the sample at 4°C. Analysis should however, be
performed on the same day. Where such measure is not possible addition of 0.8 mL of
conc. H2SO4L of sample is recommended. If acid preservation is practised, the sample
acidity should be neutralised with NaOH or KOH to pH 7 immediately before the
analysis is undertaken.

Residual chlorine, if present, should be reduced immediately after the sample is

collected in order to arrest consumption of NH3.

The use of HgCl2 (40 mg/L) for preservation is also possible. However, HgCl2 used as
preservative gives negative interference by complexing with NH3. This is overcome by
adding comparable amount of HgCl2 to the NH3 standards used for preparation of
standard curves.

Nitrate: Analysis should be carried out immediately after collection of samples to

avoid any change in the nitrate content by biological activity. If this is not possible, the
sample may be preserved by addition of 2 mL of conc. H2SO4 per litre of sample or
addition of 40 mg/L of HgCl2 and storage at 4°C. For acid preservative, the sample
may be neutralised to pH 7 by NaOH or KOH, before proceeding further with
analysis.

Nitrite: The determination should be made promptly on fresh samples to prevent

bacterial conversion of nitrite to nitrate or ammonia or vice-versa. No preservative is
recommended.

PH: The pH determination on water sample must be carried out in the field itself at
site, as it is liable to change rapidly. If this cannot be done, the sample should be
collected in a plastic container, tightly capped and sealed immediately after collection.
A minimum of air gap should be given in the bottle and the same preserved at 4°C. It
is then brought to the laboratory and pH determination is carried out. There should be
no delay in pH measurement after the sample container has been opened and sample
reached room temperature.

16
Phosphate: Since phosphate is present both in soluble and particulate and Sampling
biodegradation of organic phosphate and hydrolysis of polyphosphate occurs, the
water sample should be filtered immediately at the time of collection. This is
particularly important if suspended matter is present as adsorption and/or desorption of
phosphate may occur during storage. The filter paper should be carefully chosen, as
the certain filter papers and filter aids contain appreciable amounts of phosphate and
hence should not be used. Other material such as asbestos can adsorb phosphate from
solution. And should be used, only after thoroughly seasoning. It is, therefore,
desirable to analyse the sample for phosphate as soon as possible preferably the same
day on which it is collected. If this can not be done, the sample may be preserved by
addition of 2 mL conc. H2SO4 or 40 mg HgCl2 /L of sample and storing at 4°C. The
HgCl2 interferes in phosphate determination if the chloride level of the water sample is
less than 50 mg/L. This interference is overcome by spiking samples with 50 mg/L of
NaCl. An alternative procedure is to transfer 100 mL aliquot of sample to 125 mL
glass Erlenmeyar flask and acidified with mL 30% H2SO4 acid. The sample should be
cooled to 4°C as soon as it is collected.

Silica: Samples should be collected in polyethylene bottles and glass containers

avoided.

Silver: Considerable loss of Ag occurs through adsorption on the container walls, the
losses being as high as 50% on pyrex glass after 10 days storage; the taflon containers
loss being 17% only. Lowering the temperature to 5°C results in lowering of Ag loss
but lowering of pH of sample to 1 is found to be more effective; the losses with teflon
being only 6% after thousand hours of storage. It has also been reported that losses of
Ag at pH 4.5 on borosilicate and polyethylene container occurs and no Ag is adsorbed
at pH 2 by container even after 36 days storage.

The sample bottle should be washed with 1:1 HNO3 and then rinsed with silver free
water. The sample should be acidified immediately after collection with reagent grad
HNO3 to pH 1.5. Alternatively disodium of EDTA should be added to the sample
container before collection. The sample should be in any case analysed within 10 days
of collection. Further if the sample is to be analysed by atomic absorption directly (by
conc. of sample) the same amount of EDTA must be added to the standard and the
standard processed in the same way as the sample.

Selenium: Since losses of selenium from aqueous solution. at higher pH have been
reported, the sample should be acidified to pH 1.5 with HNO3 immediately after
collection.

Strontium: Polyethylene bottles are preferably for storage, although pyrex container
may also be used. Sample should be tightly capped after sample collection for Ca and
Mg.

Sulphate: In the presence of organic matter, certain bacteria may reduce sulphate to
sulphite or vice-versa. To avoid, this heavily polluted waters should be stored at lower
temperature or treated with formaldehyde. Sulphite may be oxidised to sulphate by
dissolved oxygen at pH 8 and above. Samples containing sulphite should have their
pH adjusted below this level.

Sulphide: Since sulphide may be lost from solution. by oxidation, special treatment is
required and a separate sample should be collected. The following procedure is
advised.

Pipette 1 mL of 1M zinc acetate in the bottle in which the sample is to be collected.

Immediately after the sample has been collected, add 1 mL of 1 M NaOH. Mix well,
cap the bottle tightly. Analyse sulphide content of the sample, either by taking the

17
Initiation into entire sample or shaking well to have a uniform suspension or than pipetting on
Analytical Laboratory aliquot of the same. Cadmium acetate may also be used instead of zinc acetate.

Specific Conductance: The plastic container should be tightly sealed immediately

after collection of the sample and the specific conductance determined as soon as the
bottle is opened.

Turbidity: Equilibrium conditions may change sufficiently to alter the suspension

characteristic of a water sample with time. The measurement should thus be made as
rapidly as possible after sample collection. If storage is unavoidable, samples may be
stored in the dark up to 24 hrs. For even longer storage, treat 1 L of sample with 1 g of
HgCl2. All samples should be vigorously shaken before examination.

Zinc: A loss of 20% of zinc from water sample in borosilicate glass container at pH 5
after 60 days storage has been reported. Hence samples should be analysed preferably
within six hours after collection. The addition of reagent grade HCl or HNO3 to bring
the sample pH to 1.5 will preserve the zinc ion for quite some time in the sample.

4.4.8 Sampling for Bacteriological Analysis

Sampling Bottles: Sterilized glass bottles provided with ground glass stopper having
an overlapping rim should be used. The stopper and the neck of the bottle should be
protected by brown paper. Some important point we will discuss under separate
heads.

Dechlorination of Samples
Sodium thiosulphate should be added to the clean, dry sampling bottles before
sterilization in an amount to provide an approximate concentration of 100 mg per litre
in the samle. This can be done by adding 0.2 mL of 10 per cent thiosulphate solution
to a 250 mL capacity bottle. The bottle is then stoppered and sterilized by either dry
heat at 180°C for 1 hour or steam sterilization at 15 lb pressure for 15 minutes.

Sampling Procedures
The sample should be representative of the water to be tested and they should be
collected with utmost care to assure that no contamination occurs at the time of
collection or prior to examination. The sample bottle should not be opened till the time
of filling. The stopper should be removed with care to eliminate soiling. During
sampling, the stopper and the neck of the bottle should not be handled and they should
be protected from contamination. The bottle should be held near the base, filled
without rinsing, and the stopper replaced immediately. Then the brown paper
wrapping should be tied to protect the samples from contamination.

Sampling Direct from a Source

When the sample is to be collected directly from a stream, river, lake, reservoir,
spring, or a shallow well, it should be representative of the water that will be taken
from a point which is too near the bank or too far from the point of draw off, or at a
depth above or below the point of draw off. Areas of relative stagnation in a stream
should be avoided.

Samples are to be taken by holding the bottle in the hand near its base and plunging its
neck downwards below the surface. The bottle should then be turned until the neck
points slightly upwards, the mouth being directed against the current. If no current
exists, as in a reservoir, a current should be artificially created by pushing the bottle
horizontally forward in a direction away from the hand. If it is not possible to collect
samples from this situation in this way, a weight may be attached to the base of the

18
bottle which can then be lowered into the water. In any case, damage to the bank must Sampling
be guarded against, otherwise fouling of the water can occur.

Special apparatus which permits mechanical removal of the stopper of the bottle below
the surface is required to collect samples from the depths of a lake or a reservoir. If the
sample is to be taken from a well, fitted with a hand pump, water should be pumped to
waste for four to five minutes before the sample is collected. If the well is fitted with a
mechanical pump, the sample should be collected from a tap on the discharge.

If there is no pumping machinery, the sample can be collected directly from the well
by means of a sterilized bottle fitted with a weight at the base. In this case, care should
be taken to avoid contribution of the sample by any surface scum. Where it is not
possible to collect the sample directly into the bottle as for example where there is a
high bank the sample may be obtained by means of suitable metal jug. The jug is
sterilized by pouring into it a teaspoonful of methylated spirit and tilting the jug in
such a way that the spirit comes in contact with the entire inner surface of the jug and
in igniting. The jug should be lowered into the required depth and then drawn up and
down two or three times before it is brought to the surface. It should be rinsed out at
least twice before the sample is taken. Should the jug come in contact with the bottom
or skid along the surface so that it may have collected the surface film, the sample
should be discarded, the jug resterilized and another sample drawn. The water from
the jug should be poured into the bottle and the glass stopper of the bottle be replaced,
care bing taken to avoid the cover being caught between the stopper and the neck of
the bottle.

Size of the Sample

The volume of the sample should be sufficient for carrying out all the tests required,
and in no case, it should be less than 250 mL (aproximately 8 oz).

Preservation and Storage: Water samples should be examined immediately after

collection. However, this is seldom practical and hence it is recommended that the
samples should be preferably analysed within one hour after collection, and in no case,
this time should exceed 24 hours. After collection, the samples should be stored in ice
box. During transit also the samples should be carried in ice box. Care must be taken
to avoid the entry of water from the ice box into the sample bottle.

SAQ 2
What are objectives for water quality monitoring?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

SAQ 3
Classify determinants for water quality monitoring.

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

19
Initiation into SAQ 4
Analytical Laboratory
Describe problems arising in the sampling of water for the determination of BOD.

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

4.5 AIR SAMPLING

The substances which alter the natural composition of ambient air are regarded as air
pollutants. The term "air pollutant" referes to wide variety of substances ranging from
natural compounds like CO2 or CH4 to purely anthropogenic compounds like
chlorofluorocarbons (CFCs). The concentration ranges of pollutants may be from part
per hundred (percent) to less than parts per billion (ppb). The air pollutants may be in
particulate state (aerools) or gaseous state. Air pollutants may be either of natural
origin (wind blown dusts, forest fires, volcanoes) or of anthropogenic origin. In urban
air pollution, anthrapogenic sources are predominant. The anthrapogenic (produced
due to human activities) sources comprise; industrial processes, power plants, waste
disposal, mobile or stationary combustion processes and agricultural practices.

Airborne particulate matter is an ensemble of solid and liquid particles suspended and
dispersed in air and known as suspended particulate matter (SPM). Usually SPM
consists of particles less than 20 um. The SPM is heterogeneous in character and
therefore, have limited value with reference to its impact on health. The monitoring
objectives have, therefore, been narrowed down to determine particulate matter whose
size is less than 10 um. These particulates are known as Respirable Suspended
Particulate Matter (RSPM) or PM10.

Primary gaseous pollutants which are directly emitted from combustion processes and
which have been known for many years to be major urban/industrial pollutants
include; carbon monoxide (CO), sulphur dioxide (SO2) and oxide of nitrogen (NOx).

General sampling methods for particulate matters and gaseous pollutants have been
described in foregoing sections.

4.5.1 Selection of Sampling Locations

It would be desirable to collect samples at more than one location in each city, but for
the number of cities in the net-work such a program would be economically
unfeasible. Establishment of only one sampling site in each urban area wherever
possible, and located in a central business district is generally adequate. For nonurban
stations location is not critical since immediate sources of high emission are not a
problem. An average of measurements obtained at a station in the central business
district and a nonurban station provides a reasonably good estimate of the mean of the
entire city.

Even though precautions are taken to ensure that the sampling site is as representative
as possible of the urban area as a whole, it is impossible to be ascertain that the
measurements obtained at a specific size are not unduly influenced by local factors.
Such factors might include topography, structures, and sources of pollution in the
immediate vicinity of the site, and other variables the effect of which cannot always be
accurately anticipated. It must be kept in mind then, that when comparisons are made
among pollution levels for various cities, they are valid only insofar as the sites are
comparable.

20
SAQ 5 Sampling

What do you understand by the word SPM?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

4.5.2 Specific Criteria for Selection of Location

The first requirement of the sampling location is the site which must be representative
of the area under study. The sampling site must be located in such a way that the
collected samples represent air that is actually breathed by the exposed population
group. The sampling sites would therefore be ideal if located on the ground at the
breathing level. However, this may lead to flaw in the sampling procedure because of
some local activity, for example, the passing of a smoking vehicle across the sampler
or any other such similar activity would lead the sample to the wrong estimate of the
average conditions.

It is, therefore, considered advisable to locate the sampler at least 5 to 10 meters above
ground level depending upon the average building structures in the city. This
proposition is quite sound in locating the sampling stations with a little difficulty. It
not only gives representativeness but also helps to select the site at the choice of the
investigator from technical considerations. The flat roof of the building is a secure
place, and the sample can run without any disturbance. However special attention has
to be given to see that the selected site is not overshadow by taller buildings which
would obstruct the free flow of air movement. Certain public or government offices,
such good places to locate sampling stations the entry to the roof of these buildings
can be restricted for security reasons.

SAQ 6
Describe criteria for the selection of location of sampling site for ambient air quality
monitoring.

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

4.5.3 Suspended Particulate Matters

Particulate matter present in the atmosphere may be organic or inorganic; in liquid or
solid state. Particulate matter, in the suspended form if present in atmosphere is known
to have adverse effects upon health and welfare. Carbon or soot particles, acid
droplets, metalic oxides and salts, silicates and other dust including metallic fumes are
the common forms of particulate matter. The types of particulate matter and sources of
emission are given below:

21
Initiation into Types and Sources of Particulate Matter
Analytical Laboratory
Types Sources
Carbon or soot Automobiles, power generation space
heating aircraft, refuse incineration
Metallic oxides and salts Catalyst from refinery; metal
industries, coal and oil combustion,
auto exhaust combustion of black
liquor, drying and calcination operation
Oily orotarry droplets Motor vehicles, exhaust emission from
gasoline and diesel powered vehicles,
incomplete combustion and refuse
incieneration
Acid droplets Power plants, metal working and
plating operations, storage battery
reclamation, waste rendering and
incineration, acid plants
Silicates and other inorganic dusts Quarring operations, sand and gravel
crushing plants and cement kilns
Metallic fumes Metal industry and printing press

Suspended particulates are a composite group of substances, liquid or solid dispersed

in the atmosphere. Which range in diameter from a fraction of a micron to several
hundred microns. Suspended particulate matter required careful definition since its
effects are determined not only by its chemical composition, but also by its physical
characteristics.

The most significant fraction of suspended particulate matter is the respirable size, i.e.,
larger than about 0.1 microns and smaller than about 5 microns. Particles in this size
range persist in the atmosphere longer than other sizes. This size range is significant
not only is respect of health, but also in causing reduced visibility and entering into
atmospheric reactions. Further more, the proportion of suspended particulate matter in
the fine particulate's size range will increase.

4.5.4 Procedure for Operating Suspended Particulate Sampler

There are nine procedures for this. We will discuss each of them separately

A. Filter preparation
The procedure for filer preparation is given below:
i) Expose glass fibre filter to the light source and inspect for pinholes,
particles or any other imperfection. Discard the filter if these are visible.
ii) Weigh the filter accurately into the fourth decimal of a gram. In order to
facilitate weighting, it may be necessary to fold the filter loosely without
producing any cramps over it. Record its weight and serial number and
note its identification number in the field book or on the field data sheet.
iii) Unfold the filter-paper after weighing and place it in a plastic folder to any
man handling.
iv) Carry the plastic folder with filter to the site of sampling in sample kit.
v) If there is dusty atmosphere, carry additional preweighted filter paper for
likely changing of filter in the course of 24 hr. run.

22
B. Sample collection Sampling
i) Before mounting the Fibre-filter on the sampler, dust sampler carefully by
wiping it with a duster-cloth. All the surface area of the equipment should
be properly wiped out and kept clean before starting the sampler.
ii) Check carbon-brushes and cleaning armature. Confirm the life of carbon
brushes fixed in the sampler from the record-book and if necessary,
replace them with new one.
iii) Open the shelter-Hood and loose the wing-nuts of the face-plate. Remove
faceplate from the filter frame and mount the pre-weighed filter in
position over the frame with right surface upward. (Note : The glass fibre
filter two sides, the rough surface is right surface whereas the plain
surface is the reverse side of the filter). Replace the faceplate over the
frame without disturbing the filter and fasten it securely with wing-nuts.
Loose tightening of wing-nuts may develop air leakage, on the other hand,
over-tightening may damage the sponge rubber gasket of the face-place.
Therefore, tightening of wing-nuts should be optimum.
iv) A very light application of talcum powder may be used casually over the
rubber gasket of the face-plate to prevent the filter from sticking. Care
must be taken that talcum application should not add to the weight of the
filter.

C. Sampler Operation
i) Close the shelter hood and start the sampler for about 5 minutes. Check if
there is any air leaking out through the neck of the blower. If so, tighten
the hopper adequately.
ii) While on run, connect manometer tube to the nipple of the exhaust pipe
(bent pipe) and - note the manometer reading. Observe the flow rate from
the calibrated graph, if observed rate flow of the sample is very high than
a normally expected flow, there is every possibility of defective mounting
of the filter paper, giving way to air leaking. Confirm the expected normal
flow rate by remounting the filter paper and running the sampler for a
minute.

D. Recording the Data

Record the time and date of sampling on field data sheet and start the sampler
for its operation. Check the manometer level (flow-rate) again and record the
same in field data sheet. Disconnect the manometer from the exhaust pipe.

E. Flow Rate
Keep on checking the flow are rate of the sampler (after every one hour interval)
by connecting manometer to the exhaust pipe and record the corresponding flow
in the data sheet. The manometer should never be kept connected to the sampler
except when the flow is being measured.

F. Corrective Measures
i) In a dusty atmosphere, there is every possibility that the flow rate may go
down rapidly with sampling time and sometimes the manometer level
difference may be zero due to cloggi of the filter paper. In order to avoid
such an event, the sampler should be stopped when the flow rate is
reduced to a minimum of 6 mm manometer level. If such untimely closure
of the sampler is warranted, stop the sampler when the flow rate has come
down close to 6 mm manometer level and record the time and the flow
rate before closing the sampler.

23
Initiation into ii) Normally samples are to be collected over a 24 hour run. In the event of
Analytical Laboratory closure of the sampler in the middle, take out the sample filter from the
samples, remount another filter paper and restart sampling for remaining
period of completing 24 hours run. For example, if the sampler is started
at 10.00 a.m. and required to be stopped at 8.00 p.m. (i.e. after 10 hrs. Run
of the sample) due to falling of manometer level to a mark of 6 mm or
below. Mount a fresh filter paper at 8.00 p.m. and restart sampling and
continue until 10.00 a.m. next day. (This sample shall have 14 hr. Run). In
case the 24-hour run of the previous sampling is short of six hours or
more, sampling is continued with fresh filter for shorter interval, i.e. less
than 6 hours, there is no need for restarting of the sampler in such cases.

G. Closing of Sampler
i) Observe the manometer reading and record the corresponding flow rate,
time of closure and date in the data sheet.
ii) Switch off the sampler.
iii) Open the shelter-hood loose the wing nuts and remove the faceplate
carefully without disturbing filter sample protect the filter sample from
flying out due to blow of a wind.
iv) Observe the outer edge of sample paper which should be spotlessly clean
and white. In case, there is a black streak impression over the edge, this
indicates the possible leakage of air, making the sampler defective. Make
a note in the data sheet if such a defect is noticed.
v) Take out the filter sample carefully from the sampler holding only outer
edges. Fold the filter lengthwise such that only the dust surface of the
filter coincides with one another, then refold widthwise in the middle and
place the same in a sample cover and carry the same to laboratory for
analysis.
vi) Confirm that the field data sheet is completely filled with respect to filter
number, location, data and time of sampling, initial & final flow rates and
any other factors such as meteorological conditions or certain human
activity relating to dust generation in the neighbourhood which might
affect the result.

H. Analysis at the Laboratory

i) Take out the filter sample from the cover and keep on a clean large petry
disc for drying in an oven (105°C) for an hour without unfolding the filter.
ii) Remove the sample filter from the oven after 1 hr. And cool it in a
dessicator of suitable size for 15 minutes.
iii) Cary the dessicator with sample to the balance and weight the filter
sample accurately, nearest to the fourth decimal of a gm. Record the
weight of the filter in the data sheet.
iv) Preserve the filter sample by replacing it back into the same sample cover
for detailed chemical analysis for future study.

I. Maintenance
i) The blower motor of the sample has carbon brushes which run only for a
limited number of hours. Normally the life of carbon brushes is observed
as 150 running hours. If the blowers are run beyond 150 hours, the motor
of the blower is likely to be damaged. Therefore, a constant watch has to
be maintained by recording the run of the sampler on the data sheet and

24
 replacing carbon brushes promptly when the carbon brush life is Sampling
accounted for nearly 150 running hours. It is advised that carbon brush
should be changed when the total run is accounted in between 125-150
hours.
ii) During the carbon brush changing operation, it is required to clean-up the
surface of the armature with small piece of cloth soaked in carbon
tetrachloride for removal of dust.
iii) It is observed that rubber gasket fixed to the face-plate is likely to get
worm out resulting in air-leakage and defective sampling. Therefore,
replacement of rubber gasket should be promptly carried out as soon as
the gasket is found defective.
iv) The manometer and the nipple at the exhaust pipe are to be kept clean
regularly.

4.5.5 Gaseous Pollutants

Air pollutants occur in the form of gases, vapours, solid particles and liquid droplets.
These forms can exist either separately or in combinations. Due to the heteroceous
nature of air pollutants and the variability of these ambient concentrations, no
universal collection choice is available. There is a need to adapt different sampling
procedures from them for particulate matter, though a few may be common. For air
sampling purposes, it is not necessary to have distinction between gases and vapours,
because both gases and vapours diffuse and are fixed with surrounding air upon their
release in the atmosphere. Vapours are gaseous state of liquids or solids at ordinary
ambient temperatures and pressures while the gases are far away from their critical
states. Therefore, vapours on condensation can be converted to the original solid or
liquid state. Thus a vapour may frequently be collected by simple condensation
methods under which conditions gas would remain unaffected.

Based on the above fundamentals, the sampling methods are classified as under :
a) Sampling of atmosphere without concentration of gases and vapours by
collecting a known volume of air; and
b) Sampling of atmosphere with concentration of gases and vapours by removing
the contaminants from a measured sample of air.

A. Sampling of Atmospheres without Concentrations

For relatively high pollutant concentrations in the air, methods without concentration
are satisfactory since they provide a sufficiently large sample for analysis. Air samples
collected, without concentrations are grab samples.

Evacuated Containers: Almost any type of evacuated container can be used for
sample collection provided; (i) it is vacuum-tight; and (ii) container material does not
interact with the pollutants to be analysed in the sample.

Capacities of glass vary from 200-2500 mL. Stainless steel tanks of a few litres to
several litres are commonly used for sampling. Other metals (unless lined with inert
plastics) are unsuitable for air samples. The containers should be equipped with some
mean for sealing the evacuated vessel inducting the sample and releasing the container
after sample collection for leak-proof transport and/or storage.

Plastic Bags: Plastic bags are widely used in recent years for collecting storing and
shipping of gas and vapour samples. The bags are easily fabricated and are light in
weight, unbreakable for ordinary use. When empty it can be folded and rolled up for
storage. The plastic material used for the bags should be free of any reactions with the

25
Initiation into constituents of the sample and gas permeation through the plastic film should be
Analytical Laboratory negligible. Saran, Scotchpak, Koroseal Mylar, Teflon films have been used as bag
materials and found to be conditionally satisfactory depending upon the kind of gas or
vapour to be sampled. The sample volume in the plastic bag can be determined during
inflation, by placing a small rotameter in the sampling line and timing the sampling
period.

Liquid or Gas Displacement Methods: To fill a container with an air sample by

liquid displacement, a glass jar or aspirator is used. The rate of sampling can be
adjusted within limits to a desired time period. The nature of the displacement liquid
must be such that it will not react, absorb or dissolve the pollutant being samples.
Water, organic solvent and mercury have been used as the liquids for this method of
sample collection. The volume of the air sample collected by displacement method is
assumed to be that of container or of the measured displaced liquid at the ambient
pressure and temperature.

Syringes: Syringes of appropriate volumes are also used for the collection of small air
samples without concentrations. This technique is widely applied in the field of odour
measurement.

B. Sampling of Atmosphere with Concentration

The pollutants occur only in trace quantities and, therefore, collection of large samples
of air a concentrations method may be required to match the sensitivity ranges of
analytical methods. For this, relatively large size samples representing an integrated or
average composition of the atmosphere over that time interval at the sampling site are
collected. Optimum sampling rates and duration of sampling period depend largely on
the particular method used and the type of collector and its collection efficiency. In
quantitative sampling with pollutant concentration, the required equipment consists of
common component of sampling trains, i.e. the collectors, air meter and air mover.

The sampling methods are grouped in the following heads:

a) Absorption in liquids
b) Adsorption on solids
c) Condensation or ‘freeze out’ of the pollutant
d) Miscellaneous techniques
In absorption sampling technique, the pollutants absorbed in an absorbing solution
wherein it is chemically / physically retained in the bulk. Whereas in adsorption
technique, the material is retained on chemically active surfaces of the system. Often,
when the true process is unknown the term ‘sorption’ is applied.

a) Absorption in Liquids
Absorption of gaseous pollutants in a liquid solution has probably been used most
widely for environmental sampling. This popularity is primarily due to the availability
of analytical techniques for analysing the resulting solution, reproducibility of the
results and comparative ease of obtaining data. In gas liquid absorption sampling, two
types of absorption have been recognized. These are physical absorption and chemical
absorption.

Physical or Dissolution Absorption: This involves physical solution of the pollutant

in a liquid. The process is usually reversible. The solubility of the pollutant in a given
absorbant is dependent on the partial pressure of the pollutant in the atmosphere, the
temperature and the purity of the absorbant. An ideal solvent would be relatively non-
volatile, inexpensive, non-corrosive, stable, nonviscous and nonflammable. In any

26
case distilled water fulfils most of these characteristics and is used as the solvent for Sampling
collecting some gases. In general, low efficiency will be obtained for physical
absorption unless the pollutant is very soluble and the ratio of dissolved gas to liquid
volume is small.

Chemical Absorption: In this process a liquid absorbant reacts with the pollutant to
yield a non-volatile product. The solvent selected is one that reacts with the pollutant
in an irreversible fashion, for example, the reaction of ammonia and carbon dioxide
with acidic and basic solvents respectively. Primary factors affecting the choice of an
absorbent in chemical absorption are the solubility of the pollutant, reactive properties
of pollutant and absorbant, and the subsequent analytical method to be used. Care
should be taken to avoid an absorbant which will interfere with subsequent analysis.
Sample procedures using chemical absorption are the determination of sulfur dioxide
by absorbing the pollutant in hydrogen peroxide and titrating the resulting sulfuric
acid with standard sodium hydroxide. In assembly for sampling gases by absorption
usually consists of a short probe or sampling line of glass, non-reactive plastic tubiing,
a filter for removal of particulate matter, an impinger or some other type of absorption
apparatus, a gas meter, a pressure gauge or manometer, appropriate valves and a
pump.

SAQ 7
Describe in short methods of collection of gaseous pollutants with concentration.

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

Collection Efficiency: The extent to which the gas is absorbed in liquid is governed in
general by the volume of the sample and by the following factors:
i) The degree of contact between the gas and the liquid, as determined by bubble
sizes
ii) The duration of contact between the gas and the liquid, as measured by the rate
of gas flow and the length of the gas path through the liquid
iii) The transfer coefficients or rates of diffusion between gas-liquid phases
iv) The degree of solubility of gas in liquid
v) The rate of chemical reaction
vi) The concentration of the reactant in absorbing solution; and
vii) The temperature
With the exception of temperature, the proportionality between the effectiveness of
absorption and each of the above factors is direct. Several of the above factors are
influenced by the design of the collection equipment, i.e., the absorbers. Efficiency of
the absorber can be calculated from theoretical considerations. In practice, the
collection may be far from complete. As a rule, a collection efficiency of 90% or
greater has been considered acceptable for ambient air sampling.

Absorber Characterisation: The characterization is done on the following

consideration

27
Initiation into a) Rate of flow : One of the major determining factors in
Analytical Laboratory collection efficiency of absorber. Absorption
collection efficiency varies immensely with the
flow rate. More the flow, less is the contact
period and thus efficiency is lowered
b) Size of bubble : The collection efficiency of this process depends
upon the probability of successful collisions of
reagent or solvent molecules with gas or vapour
molecules smaller the bubble of gas, larger is the
surface area to react with absorbent and greater is
the efficiency. Hence fritted bubblers have more
efficiency
c) Length of the : The length of the column of the liquid in the
absorbent column absorber is another prime factor. The longer the
gas bubbles in contact with the liquid the more is
the absorption capacity. Bubble rise time is a
function of bubble size and adsorbent height

Chemical Characteristics: For the greatest collection efficiency one has to choose the
absorbent which has a very large capacity for absorbing pollutant without building up
an appreciable vapour pressure. This can be accomplished by choosing a chemical
reagent which reacts with the pollutant in an irreversible fashion. An excess of the
reactant in the absorbing solution is preferable in order to ensure that all the pollutant
is collected and that the reaction rate is at a maximum. Ideally, the reaction should be
instantaneous since the period of contact between the pollutant and the absorbent is
short.

Physical Characteristics: Pressure, temperature and pollutant solubility in the

absorbing medium are the major physical characteristics affecting collecting
efficiency, in many sampling situations. Relative humidity, when it goes down to
values less than 50% plays dominant role on evaporation of the water-based collection
medium. An increase in temperature enhances chemical reactions but decreases
pollutant solubility in the absorbent and its evaporation. In most cases the net effect is
a decrease in collection efficiency with increasing temperature.

b) Adsorption on Solids
Adsorption is the phenomenon in which gas or vapour molecules are attracted,
concentrated and retained at the boundary surface of solid substances. The boundary
surface may be the interface between a gas and liquid, gas and solid, and solid and
solid. With reference to air, adsorption techniques are commonly used for collecting a
specific gas or combination of gases. A typical process consists of passing a gas
stream through a container filled with an adsorbent such as activated charcoal, alumina
or silica gel. The gas is bound to the adsorbent by molecular forces and if
condensation does not occur gas remains physically and chemically unchanged.
Following collection, gas may be the removed from the adsorbent for analysis or
ultimate deposition by application of heat, passing inert carrier gas through the system
or chemical treatment. Two types of adsorption have been recognised, namely, i)
physical or vander Wall's adsorption; and ii) chemical or activated adsorption.

Physical Adsorption: Physical adsorption is a generally occurring process. This type

of adsorption occurs when various gases are adsorbed on charcoal. If the temperature
is low enough any gas will be physically adsorbed to a limited extent. The quantity of
various gases adsorbed under the same conditions is roughly a function of the case of
condensation of the gases. The higher the boiling point or critical temperature of the
gas, the greater is the amount adsorbed.

28
Chemical Adsorption: In contrast to physical adsorption, chemical or activated Sampling
adsorption is characterised by high heat of adsorption of the order to 20-100 kilo
calories per mole of adsorbate and it leads to a much stronger binding of the gas
molecules to the surface. Heats of adsorption are of the same order of magnitudes as
chemical reactions of gas molecules with the adsorbent to form a surface compound.
This type of adsorption resembles chemical bonding and is thus called chemical
adsorption, activated adsorption or chemisorption. Generally, physical adsorpt on
phenomenon is used in air pollution control work. Physical adsorption is also used to a
great extent in the collection of radio-active gases.

Characteristics of Adsorbents: The best solid adsorbents are those with a vast
interior network of pores, cracks and channels, yet hard enough to resist crushing,
breakage and structural deterioration. They should offer minimum possible resistance
to air flow and should be capable of being readily activated and reactivated - a process
in which the adsorbents capacity is increased by appropriate heating in vacuum air or
steam, which distills out various impurities from the adsorbent. The adsorptive
capacity of a given adsorbent for various gases and vapours closely parallels their
critical temperature; but the quantity of a particular gas or vapour that can be adsorbed
by a given amount of adsorbent depends upon several factors outlined below.

Factors Influencing Adsorption: Following factors influence the adsorption

• Concentration of gas in the immediate vicinity of the adsorbent
• The total surface area of the adsorbent
• The temperature of the system
• The presence of other molecules, which may compete for sites on the adsorbent
• The temperature of the system
• The presence of other molecules, which may compete for sites on the adsorbent
• The characteristic of adsorbate, e.g., weight, electrical polarity, chemical
reactivity, size and shape of the molecules
• The characteristics of the adsorbent surface, e.g. electrical polarity and chemical
reactivity.
• The size & shape of the pore of the adsorbent
Ideal physical adsorption of a Gas would be favoured by a high concentration of the
adsorbate freedom from competing molecules, low temperature and by aggregation of
the adsorbate into a form, which conforms with the pore sizes of the adsorbent. From
the stand point of electrical characteristics, solid adsorbents are classified as non-polar
or polar. The most widely used and the only important nonpolar solid is carbon.
Activated carbon (or charcoal, if the source is wood) is very effective in adsorbing non
polar organic molecules in preference to atmospheric moisture. Polar adsorbents are
the oxides of silicon or of metals. The siliceous materials are silica gel, Fuller's earth
and the diatomaceous oarths. The metallic oxides include activated alumina
(aluminium oxide) and activated bauxite. Activated carbon is considered the adsorbent
of choice for sampling odourous gases and vapours due to its high adsorptive capacity
and non-selective adsorption characteristics.

Desorption from activated carbon may be accomplished by using super-heated steam,

or by heating the carbon in vaccum and distilling the desorbed material in a cooled
trap. To desorb substances from silica gel or activated, alumina, an inert carrier gases,
e.g., nitrogen may be passed through the adsorbent either at ordinary temperatures or
heated upto 250°C. Extraction with solvent may also be used.

29
Initiation into SAQ 8
Analytical Laboratory
Describe chemical sorption.

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

c) Condensation or ‘Freeze out’ of the Pollutant

Condensation of ‘Freeze out’ sample are collected by drawing the air sample through a
single but usually a series of intensely cooled collectors or ‘traps’ immersed in
refrigerant bath of progressively lower temperatures.

The collection traps are of double-wall construction with the air flow passing through
the space between the walls. The sampling assembly is usually of all glass
construction with the traps placed in wide mouth Dewar flasks or other insulating
vessels which contain the refrigerents.

Freeze out methods have the advantage of concentrating contaminant gases or vapours
and preserving them in their natural state, without chemical reaction. The method is
particularly useful when the concentration of a given gas in the atmosphere is
extremely low and when highly concentrated samples are required for subsequent
analysis.

d) Miscellaneous Techniques
This category of methods for collection and evaluation of atmospheric gases and
vapours include:
i) Impregnated substrate technique – example lead candle method for measuring
sulfation rate
ii) Direct reading instruments
iii) Static devices – for example, the effect of air pollution on vegetation suggest the
use of plants as static device for the assay of air pollution. A static method for
the detection of hydrogen sulfide gas by lead acetate impregnated tiles and filter
papers. The degree of darkening of the exposed surface is compared with
prepared calibration standards, to obtain indications of hydrogen sulfide levels
in the air.

4.6 SAMPLING OF SOLID WASTES

The term ‘solid waste’ includes raw refuse originating from domestic, commercial,
official, institutional and street sources. It also includes residues of the incineration
process.

4.6.1 General Requirement of Sampling

It is of utmost importance for all analyses that the samples be representative. Cursory
samplings reveal very little about the true composition of the material and may lead to
erroneous conclusions.

Refuse: A mobile hammermill shall be used to take a crude sample of refuse so that
the refuse to be examined may be ground and homogenized on the spot. Crude refuse
100 to 200 kg may be taken as the basic unit for a sample which may be taken at
variable intervals depending on the amount of waste. In accordance with the purpose

30
of the analysis 2 to 4 individual samples may be ground together in order to reduce the Sampling
number of samples during more lengthy tests. The ground refuse has to be mixed
intensively. During mixing, about 10 to 20 small individual portions are taken and
filled into air-tight plastic bags in quantities of 1 to 2 kg, to be stored as samples. This
heterogeneous mixture is the crude sample. Refuse characteristics depend on a number
of factors such as food habits, cultural traditions, socio-economic and climatic
conditions. Refuse characteristic vary not only from city to city but even within the
same city itself and also seasonally. Quality of refuse should be assessed taking into
account seasonal variation, zonal characteristics, etc. Sampling points should be truly
representative of the given occupation sub-group. In residential area, the sampling
point should represent waste coming from at least 100 families. If an average value of
refuse characteristics for the full city is to be given, weightage factors are calculated.
The weightage factor for a specific occupation category will be the ratio of weight of
refuse produced from that occupation group divided by the total weight produced from
the city. The average values of characteristics from different occupation sub-groups
are then multiplied by the weightage factor to compute the average value for the city.

Compost: Grab samples (1 to 2 kg) shall be taken from as many parts of the windrow
as possible and well mixed. It shall be ensured that equal amounts are taken from all
parts. The actual sample of 1 to 2 kg shall be taken from this mixture. In the same way
compost samples shall be taken from the test material in plastic baskets and small
windrows. The mixture obtained in this way is the crude sample.

Sewage sludge: Before a sample is taken, the sewage sludge shall be well
homogenized. However, too intensive mixing with a high speed agitator should be
avoided if the sample is to be used in dehydration tests (flocculation and filtration
tests). The sewage sludge obtained in this way is the crude sample.

Residue after Incineration: The crude sample shall be taken directly from the
conveying system under examination if possible. Fly ash and riddlings shall be taken
from the corresponding areas.

The Sample Size: The size of the sample shall depend on the kind of information
sought and the structure of the material. In the case of single samplings (which may
have a random composition), a large quantity should be taken and prepared. For longer
examination periods, in which several single samples are taken at smaller intervals, the
quantity may be fixed at 100 kg per sampling. Considerable deviations may occur with
smaller quantities. Depending on the information sought, 2 to 4 single samplings may
be ground and mixed in order to limit the number of samplings for lengthier tests.

Preparation of Samples: Crude samples are not ready for examination. They should
be ground and homogenized further after drying. The moisture content of the crude
sample is determined during drying. It is essential that this moisture content of sample
is measured as soon as possible after the sample is collected.

Segregation and Grinding: Waste material may contain glass, ferrous and non-
ferrous metals, plastics, etc. Glass and ceramics may be separated by judicious
sieving, plastics and non-ferrous metals may be hand-picked and ferrous metals may
be removed by a strong magnet. The remaining material may be ground with an
appropriate pulverizing equipment (crushing mill, hammermill, ball mill, knife mill)
until it becomes a farinaceous, homogeneous powder which is sifted through a 0.5 mm
screen. The screening residue should be ground thoroughly to particles of the smallest
size possible. The material in the form of sample is now ready for analysis. The
separated material may further be segregated into organic and inorganic portion. The
organic portion consists mainly of paper, rubber, plastics, wood, textiles and cork. A
part of these materials may be pulverized even further with a knife mill and mixed
with the sample. This is of importance if it is desired to determine the carbon content

31
Initiation into of fermentable organic substance and volatile substance. The mass of the remaining
Analytical Laboratory material shall be determined and expressed as a percentage of the dry substance and
referred to as the organic screening residue. The inorganic screening residue consists
almost exclusively of metals. They shall be cleaned with air pressure and their mass
determined and expressed as a percentage of the dry substance. The screening residue
should be taken into account when calculating the results of analysis of the crude
sample. The inorganic screening residue shall b considered inert while calculating the
calorific value. An approximate value shall be used for the organic part, if necessary.

SAQ 9
What are the factors which determine the characteristics of refuses?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

4.6.2 Sampling of Food Materials

The collection of representative samples is carried out with the objective that a small
portion from a large bulk is taken in such a way so that analysis results of the sample
is true representative of the bulk of the material. The validity of analytical results,
therefore, purely depends on the sampling. Food materials are in general hetrogeneous.
If proper sampling is not done then one portion will differ from another portion. The
analysis of sample collected without proper precaution will consequently give erratic
results. Some time sampling errors contribute more variation than analytical errors.
There are two main procedures of sampling of food materials. These are known as
random sampling and representative sampling.
i) Random Sampling: In this procedure some portions of the bulk are taken in
such a way that every part of the product has an equal chance of appearing in the
sample.
ii) Representative sampling: The sample is taken in such a way that each portion
taken represents corresponding part of the bulk. The bulk load sampling often
provides a sample too large for analysis. It is, therefore, reduced to a more
convenient size by repeated quartering. In this procedure the sample is initially
arranged as a flat heap. Two opposite quarters are rejected and remaining two
are saved and thoroughly mixed. The operation is repeated as shown in Fig. 4.1
until a suitable size is achieved. In homogenity of tea is an example of erratic
sampling. Replicate analysis of packed tea leave for lead content showed a wide
variation. Subsequent examination established that this variation was due to the
presence of dust admixed with tea. The dust was having lead many times greater
than tea leaves. A sample taken from the bottom with higher dusts showed
elevated levels of lead in comparison to those found in the top portion of tea
leaves.
Mix Mix Mix
A B B+C A B A+D A B B+C Continue upto
a suitable size
thoroughly C D remains
C D thoroughly C D thoroughly

Reject A + D Reject B + C Reject A + D

Fig. 4.1: Sampling by quartering

32
SAQ 10 Sampling

Describe in short representative sampling for food materials

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

4.7 SUMMARY
The main points described in this unit are summarised below:
• The sampling is a process to collect a portion of material small enough in
volume to be conveniently transported to be handled in the laboratory while still
accurately representing the material being sampled. There is infact strong likely
hood that some changes may occur between taking of the sample and analysis.
The arrangement should, however, be such that these changes are prevented or
atleast minimised.
• The first stage of planning of the sampling programme is the selection of the
most suitable site to provide required data. The sampling of water depends on
the selection of place, time, frequency of sampling and representativeness of the
samples. In case of ambient air the selection of site, meteorological conditions
and flow rate of air sampling are most important factors. Factors for solid wastes
and food materials comprise representativeness of the sample and methods used
for the reduction of the volume of sample.
• Water samples comprise grab or catch samples, composite samples and
integrated samples. Water sample should be collected at intervals so that no
change in quality could pass unnoticed. Sampling schedule is, however, a
compromise between accuring and funds and personnel available for the
sampling. When the number of samples that can be handled is limited, it is,
preferable to reduce the number of sampling sites rather than curtail the
frequency of sampling.
• The methods of preservation of samples for nutrient metal, physical & mineral
and organic groups are selected based on their physico-chemical qualities.
Specific preservation methods are required for individual parameters.
• The substances which alter the natural composition of ambient air are regarded
as air pollutants. The term air pollutant refers to wide variety of substances
ranging from natural compounds like CO2 or CH4 to purely anthropogenic
compounds like chlorofluoro carbons. Air borne particulate matter is an
ensemble of solid and liquid particles suspended and dispersed in air and known
as suspended particulate matter (SPM). Particles whose size is less than 10 µ m
are known as respirable suspended particulate matter (RSPM). Primary gaseous
pollutants include carbon monoxide (CO), sulfer dioxide (SO2 ) and oxides of
nitrogen (NOx).
• Establishment of only one sampling site and located in a central business district
is generally adequate. The location is not important for non urban centres since
in these places immediate sources of high emission are not a problem. The
sampling site must be located in such a way that the collected samples represent
air that is actually breathed by the exposed population group. The sampler must
be located 5-10 metres above the ground level.
• Some of the methods most commonly used for the sampling and determination
of suspended particulate matter comprise; gravimetric method, OECD

33
Initiation into gravimetric method, OECD filter soiling method and ASTM filter soiling
Analytical Laboratory method. Each method has got its advantages and limitations. Gravimetric high
volume method is most commonly used.
• The sampling methods for gaseous pollutants comprise; sampling without
concentration of gases and vapour by collecting a known volume of air and
sample of atmosphere with concentration of gases and vapours by removing the
contaminants from a measured sample of air. Any type of evacuated container
can be used provided container material does not interact with the pollutants and
it is vacuum tight.
• The term solid wastes include raw refuse originating from domestic,
commercial, official, institutional and street sources. It also includes residues of
the incineration process. Sample should be representative as cursary sampling
reveal very little about the true composition of the material. The sample size and
sampling methods for composite, sewage sludge and residue after incineration
differ. The sample should be ground and homogenised further after drying.
• The collection of representative samples of food materials is carried out with the
objectives that a small portion from the large bulk is taken in such a way so that
the analysis results of the food samples are the true representative of the bulk of
the material. There are two main procedures of sampling of food materials
which are known as random sampling and representative sampling.

4.8 TERMINAL QUESTIONS

1. Desirable sampling process.

2. What are various kinds of water sample?

3. Write a note on the requirement of sample container for water sampling.

4. Describe preservation and storage method for water samples for bacteriological
analysis.

5. What do you understand by respirable suspended particulate matter?

6. Describe in short the gravimetric method for the determination of suspended

particulate matter.

7. Write a note on the advantages and limitations of ASTM filter soiling method.

8. Classify the methods of sampling of gaseous pollutants.

9. Describe the method for segregating and grinding of solid waste samples.

10. How inhomogenity of food samples can cause errors in the analysis?

4.9 ANSWERS

Self Assessment Questions

1. The requirements for obtaining reliable data include; selection of an appropriate

sampling site, time and frequency of sampling for the water sample. The
selection of site, meteorological conditions and flow rate of sampling are
important factors for air. Most important factors for solid wastes and food
materials comprise; representativeness of the sample and volume reduction
method.

34
2. The objectives of water quality monitoring are; (i) to assess the impact of Sampling
activities by man upon the quality of water and its suitability for required uses,
(ii) to determine the quality of water in its natural state which might be available
to meet the future needs and (iii) to keep under observations the sources and
pathway of specified hazardous substances.

3. The physico-chemical determinands of water are classified as; nutrient, metal,

physical and mineral and organics

4. Problem arises in the determination of BOD in water due to; (i) loss of BOD
during interval between sample collection and its processing in the laboratory.
The problem may also arise due to loss of DO when its value is in excess of 9.3
mg/L, the saturation value at 20°C. The DO may escape from the sample and
false BOD value may be recorded.

5. Airborne particulate matter is an ensemble of solid and liquid particles

suspended and dispersed in air and known as suspended particulate (SPM). The
SPM is heterogeneous in character and consists of particles with size less than
20 µ m.

6. The most important criteria for the selection of location of sampling site for
ambient air quality monitoring is that the selected site should be representative
of the area under study. The site is to be located in such a way that the collected
samples represent air that is actually breathed by the exposed population group

7. The gaseous pollutants occur in trace quantities in ambient. The pollutants are,
therefore, concentrated by passing large volume of air through some sorption
media. This system is known as collection of gaseous pollutants with
concentration. These methods include; absorption in liquids, adsorption on
solids, condensation or freezing out of the pollutant and some miscellaneous
techniques.

8. Chemical adsorption which is also called activated adsorption is characterised

by high heat of adsorption and it leads to stronger binding of the gas molecules
to the surface. This type of adsorption resembles chemical bonding and is,
therefore, called chemical adsorption, activated adsorption or chemisorption

9. Refuse characteristics depend on food habits, cultural traditions, socio-economic

and climatic conditions.

10. The sample of food materials is taken in such a way that each portion taken
represents corresponding part of the bulk. The bulk load of sampling often
provides a sample too large for analysis. It is, therefore, reduced to a more
convenient size by repeated quartering.

Terminal Questions
1. The sampling is a process to collect a portion of material small enough in
volume to be conveniently transported to and handled in the laboratory while
still accurately representing the material being sampled. This implies that the
relative portions of the concentration of all pertinent components must be the
same in the sample as in the material being sampled. In addition, the sample
must be handled in such a way that no significant changes in composition occurs
before the tests are performed.

2. There are three kinds of water samples. These are known as; (i) grab or catch
samples, (ii) composite samples and (iii) integrated samples.

35
Initiation into 3. A water sample container must satisfy the following requirements
Analytical Laboratory
• It could easily be freed from contamination
• It should not change the relevant water characteristics on contact
• It should have adequate facility for storing the samples
• It should be resistant to impact and internal pressure which may increase
due to expansion of water or by the release of dissolved gases at elevated
temperature on storage
• The sample container must have facility for scaling it tightly

4. Waste samples should normally be analysed for bacteriological count

immediately after collection. However, this is seldom practical and as a routine
the sample should be analysed within 24 hours of the sampling. The sample is to
be collected in sterilised glass bottles with ground glass stopper. The sample
should be stored in ice box and care is to be taken to avoid the entry of water
from the ice box into the sample bottle.

5. The suspended particulate matter whose size is less then 10 µ m can enter the
lungs of human being and cause damage. These particulates are known as
Respirable Suspended Particulate Matter (RSPM) or PM10.

6. The concentration of suspended particulate matter is determined gravimetrically.

A known volume of air is drawn through a glass filter paper. The difference
weight of filter paper before and after sampling under controlled conditions
gives a direct measurement of particulate mass.

7. In ASTM filter soiling method the darkness of the stain produced by drawing air
through the filter paper is measured photometrically. The method produces
integrated values by setting the integration period at predetermined values. The
sampling period for each is relatively short and, therefore, the information from
each can be correlated with average wind direction for that period, permitting a
more in-depth analysis of the results. The material on the spot is, however, very
small and does not permit chemical characterization of the dust. Moreover, the
smoke shade measurement is predominantly an indication of dark materials in
air and this may not be proportional to the total weight of the suspended
particulate matter.

8. The sampling methods for the gaseous air pollutants are classified into two
types. These are :
• Sampling of atmosphere without concentration of gases and vapours by
collecting a known volume of air.
• Sampling of atmosphere with concentration of gases and vapours by
removing the contaminants from a measured sample of air.

9. Solid wastes generally contain glass, ferrous and non-ferrous metals, plastics,
etc. Glass and ceramics may be separated by judicious sieving, plastics and non-
ferrous metals may be hand picked and ferrous metals may be removed by a
strong magnet. The remaining materials may be ground with an appropriate
pulverizing equipment.

10. Food materials are in general heterogeneous. If proper sampling is not done then
one portion will differ from the other portion. The analysis of sample collected
without proper precaution will consequently give erratic results.

36