Measurement and Processing of Water Quality Data

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Module 6

Measurement and Processing of Water Quality Data


6.1 Basics of Water Quality
6.1.1 Water Quality Data
6.2 Water quality indicators
6.2.1 Physical Indicators
6.2.2 Chemical Indicators
6.2.3 Biological Indicators
6.3 Types of Pollutants
6.4 Sampling Surface Waters for Quality Tests
6.4.1 Samplers and Sample Containers
6.4.2 Sampling Labelling and Preservation
6.5 Laboratory Analysis of Water Quality Samples
6.5.1 Determination of Biochemical Oxygen Demand
6.5.2 The BOD Changes
6.5.3 Inferences Concerning BOD
6.5.4 Factors Affecting the Oxygen Demand Rate
6.5.5 Chemical Oxygen Demand Test
6.6 Sediment Related Data
6.6.1 Processing of Sediment Data
6.6.2 Sediment Rating Curve
6.6.3 Processing of Bed Material Data
6.7 Water Quality Standards
6.7.1 Water Quality Index
6.8 Water Quality Monitoring in India
6.9 References

Keywords: Water Quality, indicators, Physical, Chemical, Indicators, Sampling, Biochemical


Oxygen Demand, Sediment, Standards, Index

The objectives of this module are:


• to discuss techniques of acquisition, validation, and processing of water quality data;
• to discuss about the processing of sediment related data,
• to describe water quality standards and index in India.

6.1 Basics of Water Quality


Clean water is a clear, colorless, and odorless substance. The term ‘water quality’ denotes the
physical, chemical and biological characteristics of water. Water quality variables show the
status of water vis-à-vis the requirements for needs such as drinking, industrial, agricultural,
energy generation, ecological, etc. This term is most commonly used with reference to a set of
standards; in general “water of good quality” meets the desired standards. The physical
parameters of quality include turbidity, solids, electrical conductance, color, odor, and
temperature.

Pure water rarely occurs in nature. In fact, water commonly contains a variety of
constituents. Quality of water changes due to natural and human actions. Although rain water is
pure, it may interact with the matter present in atmosphere and become polluted. After falling on
the ground, water dissolves and carries impurities present on the ground. Infiltrating water comes
in contact with soil and rocks and some of these are dissolved and transported by water. Natural
waters often interact with organic materials. Human activities produce municipal, agricultural,
mining, and industrial waste. Activities such as recreation, social and religious rituals also cause
pollution.

By the time the precipitation water reaches the surface of the earth, it has already
collected a number of substances. Gases may have been absorbed or dissolved in it and smoke
and dust particles may have been picked up. If the atmospheric water has picked up radioactive
or acidic material, it may not be clean and suitable for some uses.
Precipitation water is subject to further changes of quality after hitting the earth surface
and when it travels on or below the ground, depending upon the place where precipitation falls.
Water reacts with carbon dioxide released by bacterial action on organic matter and acquires
acidic properties. In the acidic conditions, many soil and rock constituents are dissolved in water.
Anthropogenic actions influence the quality of water in significant (and mostly harmful)
ways. Dumping of municipal and industrial waste after little or no treatment in natural waters
results in drastic deterioration of the water quality of natural sources. Agricultural related
activities such as irrigation, use of fertilizer, pesticides, herbicides, etc., may lead to diffuse
pollution of both surface waters and ground water. Irrigation return flows contain chemicals and
also tend to increase salt contents in the receiving water. Construction schemes, such as those
connected with river training, flood control, low flow augmentation, etc., considerably influence
the quality regime. Unscientific mining activities often degrade water quality.
A big range of parameters are used to characterize waters quality. Largely the water
quality management objectives and the previous history of the water body will determine
selection of parameters. Some parameters, however, are of special importance and deserve more
attention. The commonly used parameters are discussed in the following sections. An integral
part of water resources management is that water quality standards are formulated, and
implemented, by doing measurements and monitoring.

Common measurements to estimate the presence of physical impurities and their quantity
in water are turbidity, solids, electrical conductance, color, odor, and temperature. Temperature
measurements help understand the value of density, viscosity, vapor pressure, oxygen saturation
value and rates of biochemical degradation. The test for residue is important in the management
of sewage treatment to indicate the physical state of the principal constituent. The solids present
in the dissolved form impact electrical conductivity of the water.
Monitoring objectives determine which variables are to be measured. Different variables
are measured at different frequencies which depend on the rate of changes in the variable as well
as its intended use. Typically, studies are carried out to collect and define base line or
background information, suitability of water for a designated use, or environmental impact
studies.

6.1.1 Water Quality Data


Water quality variables can be categorized in various groups: organic matter, major and minor
ions, toxic metals, nutrients and sediment data. The biochemical oxygen demand, chemical
oxygen demand and dissolved oxygen show how much organic matter of what type is present in
water. The toxic metals that may be present in water include mercury, lead, arsenic and nickel.
The nutrients, such as nitrogen, phosphorus and potassium, are important from the point of view
of growth of fauna.

Generally water quality variables are not measured continuously because of logistical
reasons. Taking water samples, storing and transporting them to the laboratories, and testing
them are expensive. Therefore, sampling is done at regular (but large) time intervals and
sometimes at irregular intervals. Important water quality variables or those which change rapidly
with time are measured more frequently than those which change slowly. For very few water
quality variables, samples are analysed at the observation station. Most analyses require
sophisticated equipment and are, therefore, carried in a laboratory. A wide range of measurement
techniques have been developed for water quality variables. Here, the discussion is categorized
according to physical, chemical, and biological variables.
After the water quality data have been assembled in a data storage system, the next step is
to interpret the data with respect to specific questions and inputs in management decisions. The
most frequently asked questions are:

• What is the water quality at the location of interest?


• What are the water quality trends for the station or region; is the quality improving or
getting worse?
• How do certain parameters relate with one another ?
• What is the total mass loading of materials ?

6.2 Water quality indicators


We discuss here three categories of indicators: physical, chemical, and biological.

6.2.1 Physical Indicators


The most important physical properties of water are temperature, density, viscosity, specific
weight, and vapor pressure. Most of the physical properties vary with temperature and such data
are widely available in literature (see McCutcheon et al. 1993). Clear natural water is
transparent. Turbidity is measured by determining light transmission. The test has little meaning
in relatively clear waters but is useful in defining the drinking water quality.

Solids can be classified by their state, chemical characteristics, and size and distribution.
Solids can be either dissolved (including colloidal and small suspended particles) or suspended
(including settleable). Particles passing a membrane filter with a pore size of about 1.2 micron
are considered dissolved and those retained on the filter are considered suspended.

The total solids content is the sum of dissolved and suspended solids. The amount of total
dissolved solids (TDS) in water is an important indicator of its quality for drinking, irrigation and
industrial use. TDS affects dissolved oxygen concentration and also influences the ability of a
water body to assimilate wastes. Dissolved solids affect ionic strength of water and thereby
impact mobility and transformation of metals. TDS also affects the growth and decay of aquatic
life.

To determine TDS, a sample of known volume is dried in an oven and the weight of the
residue divided by the volume of the sample, gives TDS which is normally expressed in mg/L.
Wide variations in the TDS concentration are observed in natural waters. TDS concentration in
rain water is below 10 mg/L; in river water it may be of the order of hundreds of mg/L.

Temperature: Temperature is important in water quality studies. Chemical and biochemical


reaction rates increase with temperature. Gas solubility decreases and mineral solubility
increases with temperature. The growth and respiration rates of aquatic organisms depend on
temperature. Most organisms reproduce only when temperature is in suitable ranges.

Temperature of river water generally follows the long term average ambient temperature
of the area. Temperature of water in a lake varies with depth. Cold-water species reside in deep
waters while warm-water species are found in shallow regions near the edges.

Color: The color of water depends on factors such as the type of dissolved material and the
suspended particles. Colors associated with water are many times the result of colloidal
suspension, e.g., tea. Most colors in natural waters result from dissolved material coming from
decaying plants. Many industrial wastes are colored.

Odor: Pure water has no odor. Odor indicates some toxic pollution of water. Water may smell
due to the presence of decaying organic matter. The decaying organic matter may accumulate in
bottom where conditions are suitable for the anaerobic bacteria. Sources of the organics include
plant debris washed into streams, dead animals, microorganisms, and wastewater.

Hardness: Water is classified as soft when the carbonate concentration is below 50 mg/L and is
called as very hard when it exceeds 180 mg/L. According to the guidelines of the World Health
Organization, the hardness of water should not exceed 500 mg/L.

6.2.2 Chemical Indicators


Two type of chemical matter may be present in water (a) inorganic and (b) organic matter. The
chemical tests of water quality determine the presence of specific ions. Indicators such as
alkalinity and hardness are also used to define water quality.

(a) Inorganic Matter


Natural water contains a variety of dissolved salts in solution. The principal chemical
constituents in most waters are Cations (Calcium, Magnesium, Sodium, and Potassium) and
Anions (Bicarbonate, Sulfate, Chloride, and Nitrate). Potassium is usually present in small
amounts and is derived from soil minerals, decaying organic matter, and ashes of burned plants.
Nitrate may also be present in small amounts. Besides, many minor ionic species, derived from
the contact of water with various mineral deposits, are also present.

Silica (SiO2) is the main non-ionic mineral found in natural surface water. Its presence
creates problems especially in industrial applications, where it causes scaling. A variety of heavy
metals may also be found. Important among these are arsenic, barium, cadmium, chromium,
lead, mercury, selenium, silver, zinc, and cyanide. These constituents are of concern primarily
because of their toxicity to micro-organisms, plants, and animals. Typically these constituents
come from the discharge of improperly processed industrial wastes, and high concentrations are
often found in wastewater sludges.

For a solution, pH varies from 0 (maximum acidic) to 14 (maximum basic); pH of a


neutral solution is 7. All geochemical reactions are affected by pH. Anthropogenic sources of
acidity include acid deposition and acid mine drainage (e.g. from coal mines). In addition, some
sources of acidity arise naturally due to the oxidation of sulfide bearing ores.

(b) Organic Matter


Decomposition of organic matter draws upon the oxygen present in water and may render it
unsuitable for aquatic life. In this way, organic matter is important for the health of a water body.
Organic matter is characterized by BOD (biochemical oxygen demand) and COD (chemical
oxygen demand). BOD is the most important indicator of pollution by organic matter. Similarly,
a direct measurement of dissolved oxygen is an important indicator of the health of a water body.
A low value of DO indicates high pollution by organic matter.
Most organic compounds are combinations of carbon, hydrogen, oxygen, nitrogen,
phosphorous, and sulphur. The principal organic compounds found in natural waters and
wastewater includes proteins, carbohydrates, and lipids. Large presence of organic compounds in
water is harmful from health, treatment, and ecological standpoints. Some organic compounds
may be carcinogenic or may cause mutation in humans and other living forms at extremely low
concentrations, e.g. surfactants, pesticides and agricultural chemicals, organic solvents, etc.

Toxic metals and other elements may exist naturally in water. These metals include
Copper (Cu), Chromium (Cr), Mercury (Hg), Lead (Pb), Nickel (Ni), Cadmium (Cd), and
Arsenic (As). In many instances, concentrations of these have increased due to human activity.
Arsenic has been detected in many water sources in eastern India.

6.2.3 Biological Indicators


Domestic waste may contain a variety of pathogenic organisms, including viruses, bacteria,
protozoa and helminths. Tests for all these organisms are costly and time consuming. Most
commonly sample is tested for Escherichia coli (E. Coli) whose presence indicates the potential
for other pathogenic organisms. Presence of E coli is expressed as the most probable number
(MPN)/100 ml. Important microorganisms of concern in water and wastewater include bacteria,
fungi, algae, and viruses.

Bacteria are single cell protists. Most bacteria can be grouped into four general categories:
spheroid, rod, curved rod or spiral, and filamentous. Fungi are aerobic, multicellur,
nonphotosynthetic, heterophic, eucaryotic protists. Most fungi obtain food from the dead organic
matter. Fungi play an important role in the breakdown of organic materials in terrestrial and
aquatic environments. Consequent to decomposition of organic materials, carbon dioxide is
released to the atmosphere and nitrogen to the terrestrial environment.
6.3 Types of Pollutants
Pollutants can be categorized in five classes: Pathogenic micro-organisms, Organic matter,
Nutrients, Dissolved solids, and Trace compounds.

Faecal pollution is present in large numbers in faeces of individuals. Coliform bacteria


are indicators of faecal pollution and are expressed as most probable number, MPN/100mL. The
presence of the coliform group of bacteria determines the bacteriological quality of water.
Escherichia coli is the most widely known member of the group and is present in large numbers
in domestic and municipal sewage. Its presence in water indicates sewage contamination and
likely presence of pathogenic micro-organisms of human origin. The presence of coliforms in
water is detected by observing their growth in special culture media and making a statistical
inference about their number is reported as MPN /100 ml.
Although tests are available for specific pathogenic micro-organisms, there is no way of
knowing which pathogenic organism may be present in a sample. The cost of testing for all
pathogenic organisms is large. Furthermore, in an aquatic environment the die-off rate of E. coli
parallels that of pathogenic organisms. Hence, E. coli is frequently used as an indicator for
pathogenic organisms. E. coli is exclusively of faecal origin. Some coliform bacteria are normal
inhabitants of soil and water. Results of bacteriological analysis may be reported as total
coliforms and faecal coliforms.

Organic matter depletes dissolved oxygen (DO) through microbial decomposition. Deficit
of oxygen or anaerobic conditions change ecological regime: fishes may die, water emits foul
odours and unsightly conditions develop. BOD test measures aggregate organic matter in terms
of oxygen equivalence.
Organic matter is classified as that biochemically decomposable and that which cannot be
decomposed. Organic matter is characterized by BOD, COD and volatile solids. BOD test
measures biochemically decomposable or degradable organic matter, the other two measure total
organics. It may be pointed out that the three parameters reflect the aggregate organic
constituents. The BOD test measures oxygen equivalence of organic matter. The equation for
BOD decomposition reaction may be written as:

Micro-organisms + Organic matter + O2 ‹ CO2 + H2O (6.1)

Bacteria utilize various types of waste organic matter as their food to obtain energy. They
decompose the organic matter to carbon dioxide and water in presence of oxygen. The amount of
oxygen consumed is taken as a measure of the quantity of organic matter. The test is carried out
in a laboratory representation of the aquatic environment; a water sample is added to oxygenated
water and the loss of oxygen measured over a period of time.

Dissolved Oxygen: The DO amount in a surface water body is an important indicator of its
‘health’. The presence of oxygen in water is necessary to maintain favourable conditions for
growth and reproduction of a normal population of fish and other aquatic life. The absence of a
low level of DO in surface waters indicates pollution by organic matter. Under such conditions,
organic matter is decomposed by anaerobic bacteria and obnoxious end-products, such as
hydrogen sulphide, ammonia, etc. are produced
Generally, the dissolved oxygen concentration is near saturation in pristine rivers.
However, concentrations of gases change throughout the day. Usual concentration of CO2 in
river water could be up to 10 ppm. BOD is generally 1 to 2 ppm for unpolluted river and. pH
values are generally around 7 (neutral). Turbidity is very high in flood season. Quality of ground
water is superior to that of surface water in some respects. For example ground water is free from
suspended solids and objectionable colour. But at the same time, ground water generally contains
higher dissolved solids.

Nutrients are those chemicals which contain elements, such as nitrogen (N), phosphorus
(P), carbon (C), sulphur (S), calcium (Ca), potassium (K), iron (Fe), manganese (Mn), boron (B),
and cobalt (Co). These elements are essential for the growth of living beings. Some of these are
required only in very small quantities and are called micro-nutrients. Plants require relatively
large amounts of C, N, and P. They obtain C from carbon dioxide and N and P from soil or
water. N and P may be limiting in the aquatic or land environment; that is the concentration of
one or other of these species may dictate the biomass of plant species which can survive in a
particular water body.
Nutrients such as nitrogen and phosphorus are essential elements for growth of plants and
animals. Both organic and inorganic forms of these are important. In water quality studies, the
nitrogen-containing compounds of interest are organic nitrogen, ammonia, nitrite and nitrate.
Phosphorus is of importance in aquatic environments. Phosphorous enters into water bodies
through fertilizer, industrial waste and rocks. Phosphorous is vital for all organisms and in many
cases it is the nutrient that limits productivity. Municipal and some industrial wastewaters
contain N and P. When such wastes are added to water bodies, it may result in accelerated
growth of algae (algal blooms or eutrophication). When the algal cells die, it increases the
decomposable organic matter in the water body resulting in consumption of oxygen and the
quality of water degrades.

Nitrogen accounts for about 80% of the gases present in the atmosphere and maintains
equilibrium of nitrogen concentration in open water bodies. Human activities influence nitrogen
in surface water in several ways: A) Nitrogen may be present in wastes discharged into surface
water bodies; B) Runoff from agriculture areas contains nitrogen; C) Nitrogen is also present in
the exhaust of automobiles and industries. The nitrogen solubility in water is very less; of the
order of 15 mg/L. Nitrogen is frequently present as nitrate and ammonia. The usual concentration
of nitrate in streams is 0.5 to 3 mg N/L and of ammonia about 3mg N/L. Runoff from
agricultural areas may have considerably higher concentration of nitrates. Domestic sewage
contains about 15-100 mg/L of the total nitrogen. Nitrification, which is oxidation of ammonia
and nitrite to nitrate, consumes dissolved oxygen in water. Excessive presence of nitrogen in
water can lead to eutrophication.

A large variety of substances exist in water in their ionic form. The major cations are
(positively charged ions) comprise calcium (Ca++), magnesium (Mg++), sodium (Na++) and
potassium (K+) and the associated anions include sulphate (SO4--), bicarbonate (HCO3-) and
chloride (Cl-). The cations having two positive charges are responsible for the hardness of water.
The aggregate salts are measured as total dissolved solids (TDS). Waters having less than 1500
mg/L TDS can be considered fresh waters.

A number of toxic metals and organic compounds may be added to water through
anthropogenic activity. Some metals which are toxic even in small concentrations are cadmium
(Cd), copper (Cu), chromium (Cr), mercury (Hg), lead (Pb), nickel (Ni) and zinc (Zn).

6.4 Sampling Surface Waters for Quality Tests


Sampling is performed to collect a small volume of water to determine the parameter(s) of
interest. Samples should be small enough in volume so that they can be transported conveniently
but should represent the whole water body. The concentration of all pertinent constituents in the
sample should be the same as in the source.
The sampling sites should be clearly located and easily accessible if periodic sampling is
necessary. Only if the samples are taken frequently from the same location, changes in water
quality with time can be determined with confidence. The sampling site should be representative
of the water body. Samples of water taken from the banks are not likely to be representative.
Bridges are good places to collect river water samples since the sample can be taken from the
main current. If there is no bridge in the vicinity of the location, boats are the next best
alternatives. The sample should be stored such that the parameter(s) of interest do no
significantly change before the sample is analysed.

6.4.1 Samplers and Sample Containers


To cover the range of parameters which need to be sampled and analysed a variety of sample
containers are required. Bottles used for collecting microbiological samples must be thoroughly
washed and sterilised before taking the samples. About two to three litres of sample would be
sufficient for most physical and chemical analyses. The simplest water sampler is a bottle
attached to a string. To lower a plastic or glass bottle in a body of water it is necessary to use a
sufficiently heavy holder so that the bottle may drop rapidly to the required depth. Such a holder
designed to carry a bottle to collect samples for dissolved oxygen measurement is shown in
Figure 6.1.
Figure 6.1 Dissolved oxygen sampler

When water from a particular depth is to be collected an arrangement like Meyer’s sample bottle
may be used, Figure 6.2. After the bottle is lowered to the desired depth a slight tug removes the
stopper.

Figure 6.2 Meyer’s sample bottle

Alternatively, if the DO sampler is lowered quickly to the desired depth, it will collect sample
which would be representative of the water at that depth. Small amount of water which gets in
the bottle from other depths while the sampler is being lowered is likely to flow out when water
overflows into the sampler.

6.4.2 Sampling Labeling and Preservation


When collecting the samples weather conditions and the state of water body, etc. at the
sampling site at the time of sampling should be noted. This information will be useful in
analysis and interpretation of data.
Immediately after sampling, the sample bottles should be labeled and given a unique
code number. Information on the label should include:
• Sample code number, location and the person who has collected the sample,
• Date and time of sampling,
• Pre-treatment or preservation carried out on the sample.
• The location of the sampling point should be recorded in terms of district, tehsil
and village, as well as geographical co-ordinates (latitude and longitude). If the
station has a unique identification number, it adequately identifies the sampling
point.
Samples for BOD and bacteriological analyses should be stored at a temperature below
4C and in the dark. In the field this usually means placing them in an insulated cool box
together with ice or cold packs. In the laboratory, samples should be kept in a refrigerator.
Samples for DO measurement should be chemically fixed.
If samples collected for COD analysis cannot be determined on the day of collection
they should be preserved below pH 2 by adding concentrated Sulphuric acid. Samples which
are to be analysed for the presence of metals should be acidified to below pH 2 with
concentrated nitric acid.

6.5 Laboratory Analysis of Water Quality Samples


Variations of parameters over a period of time are studied and trends are obtained for each
parameter at various locations. The results of the tests carried out are compared with the trends
obtained. The classification of the river waters of the station is carried out based on the results of
various water quality parameters using the classification chart of U.S. Salinity diagram for
classification of irrigation waters. The results are also compared with the various tolerance limits
for each parameter prescribed by the BIS codes, before publishing Water Quality Books.

6.5.1 Determination of Biochemical Oxygen Demand


When organic matter is deposited in the aquatic environment, it degrades through the action of
micro-organisms. To degrade the organic matter, micro-organisms take up the oxygen dissolved
in water. Consequently, the amount of dissolved oxygen (DO) in water is depleted at a rate
which depends on the temperature and the properties of material discharged. Generally, simple,
non-toxic organic chemicals are degraded faster than complex molecules and thus can exert their
oxygen demand more quickly. As more and more oxygen is depleted, it leads to degradation of
water quality since aquatic plants and animals need oxygen to survive and grow and will die if
adequate quantity of oxygen is not available. Shortage of DO also produces foul odours. The
term oxidation originates from a reaction with oxygen (where the substance that was oxidised
loses electrons to oxygen).
The biochemical oxygen demand (BOD) is the most frequently reported indicator to
assess the state of water bodies affected by organic pollution and depletion of oxygen. The rate
of BOD reaction depends on the temperature, the population of bacteria, and the amount of
organic matter present in the sample. The BOD test measures aggregate polluting organic matter
in a water sample and uptake of oxygen by recreating in the laboratory the same environment
that prevails in nature. Of course, not all environmental conditions can be recreated and so the
BOD test merely gives an indication of the likely pollution.
The standard BOD test is conducted over a 5 day period at 20 C. In India, the test may
also be conducted over a 3 day period at 27 C (IS 3025, Part 44, 1993) because the average
ambient indoor temperature in India is around 27 C. This temperature is higher than 20 C
which is the case for the UK where the test was originally developed. Besides, the 27 C 3-day
BOD value is comparable to the 20 C 5-day BOD value. Another reason behind adopting the 27
 C test in India is that in the event of power failure during the test the impact will be less
pronounced as the incubator containing the samples will be at nearly the same temperature as the
laboratory. As a result, heat exchange will be small and the desired sample temperature will be
maintained for longer periods.
Often the test is carried out over five days at 20 ˚C and is designated as ‘BOD5’. The
Indian Standard BOD test involves assessing the loss of dissolved oxygen in a sample incubated
for three days at 27 ˚C. This is done by comparing the DO concentration of a sample which has
been incubated for three days with the DO concentration of the sample before incubation. The
loss of DO over the three day period is taken as the BOD (or BOD3) of the sample. Clearly, the
three day test will normally yield lower BOD values than a five day test. When the temperature
is increased from 20 ˚C to 27 ˚C, the reaction proceeds at a faster rate and hence the difference
between the 3 day and 5 day tests is small.

As an example, Table 6.1 gives DO values in BOD bottles, containing identical samples
when incubated at 20 and 27 ˚C over a period of 5 days. It also gives the cumulative oxygen
uptake values. Note that the BOD3 27 ˚C and BOD 5 20 ˚C values are nearly the same.

Table 6.1 DO values in BOD bottles, containing identical samples when incubated at 20 and 27
˚C over a period of 5 days.
Day DO, mg/L 20 Cumulative DO DO, mg/L 27 ˚C Cumulative DO
˚C consumed, mg/L, 20 ˚C consumed, mg/L, 27 ˚C
0 8.1 0 8.1 0
1 6.5 1.6 5.5 2.6
2 5.0 3.1 3.8 4.3
3 3.9 4.2 2.5 5.5
4 3.3 4.8 1.7 6.4
5 2.5 5.6 1.4 6.7

6.5.2 The BOD Changes


Figure 6.3 shows change in BOD over a number of days for two samples. Here sample 1
represents a water body which exerts the oxygen demand rapidly as seen from steep slope of the
curve in initial stages. The sample 2 exerts oxygen demand slowly as seen by the flatter slope of
the curve. Sample 1 could be containing organic material, untreated sewage effluent, or some
material which can be easily oxidised. Sample 2 represents a behavior which is typical of
effluents containing complex organic materials such as industrial chemicals, solvents, or fats
which are difficult to oxidise. The point where the curve asymptotically becomes horizontal and
the BOD value stabilizes is also known as the ‘ultimate BOD’ of the sample. Depending upon
the organic material content of sample, it may take 10 days or even more to arrive at this point.
Twenty-day BOD (BOD20) is frequently considered to be the ultimate BOD.
BOD (mg/I)

Sam

Figure 6.3 BOD curves for two samples: Sample 1 – easily degradable organics, Sample 2 –
difficult to degrade organics.

After a sample of water containing organic material is taken from a water body, the
oxidation reactions in the sample will continue thereby altering its BOD. To avoid this, the
samples should be analyzed as soon as possible after collection. If a delay in the analysis is
expected, samples should be stored around 4 to 5 ˚C which greatly reduces the rate of oxidation
reactions and the BOD does not change significantly.
6.5.3 Inferences Concerning BOD
The BOD test relies on growth of the micro-organisms degrading the organic matter in the
sample. Hence, right conditions to allow the microorganisms to grow without undue
environmental stress should be created. If the pH of the sample is too low (below 6.5) or too high
(above 7.5), the BOD analysis may be affected by the ability of bacteria to grow. Therefore, if
the pH of the samples is below 6.5 or above 7.5, it should be modified by the addition of acid or
alkali so that a pH is within the range 6.5 to 7.5.

Toxic material present in the BOD sample also inhibits the analysis and hence the sample
must be ‘seeded’ with bacteria so that the analysis proceeds normally. Organic compounds are
not the only materials which, when discharged to the aquatic environment, have an oxygen
demand. Ammonia, either free or when released from nitrogen containing organic compounds, is
also oxidised in rivers resulting in depletion of dissolved oxygen. The oxidation of nitrogen
compounds, carried out by nitrifying bacteria (a process known as nitrification) in the BOD
sample can be suppressed by the addition of an inhibitory chemical so that only the BOD
resulting from the oxidation of carbon compounds is determined. If such a chemical is not added,
the resulting BOD may be a combination of the oxygen demand caused by both carbonaceous
matter and ammonia based material in the sample.

Algae have the ability to produce oxygen by photosynthesis. Hence, if the sample
contains algae, they must be stored in the dark.

Example 6.1: Calculate the oxygen demand exerted by a sample of industrial waste whose
ultimate BOD is 256 mg/L, in 1, 2, 3 and 4 days. Assume that 25% of remaining demand is
exerted each day.

Solution: Table below shows the computations of BOD. First column shows the day number and
the second the BOD remaining in the sample. Column 3 gives the BOD exerted for the day and
the last column is the cumulative BOD. The BOD at the end of day t is the BOD at the beginning
of a day t less the BOD exerted on day t.

Time Remaining BOD mg/L BOD exerted for the day Cumulative BOD exerted
day mg/L mg/L
0 256 0 0
1 192 64 64
2 144 48 112
3 108 36 148
4 81 27 175
6.5.4 Factors Affecting the Oxygen Demand Rate
A number of factors control the rate of oxidization of organic matter in the aquatic environment.
These are the composition of the material, water temperature and the concentration of micro-
organisms. Generally the rate of the BOD reaction increases with temperature.

The concentration of micro-organisms present in the water body also affects the rate of
the BOD reaction. Normally there are sufficient numbers of suitable micro-organisms in a
natural water body to allow the BOD reaction to proceed. In some cases, for example, when
water contains chemicals which are toxic to bacteria, a few micro-organisms may be there to
carry out the oxygen demand reaction. If the BOD of such a sample were to be determined, it
would give a value much lower than that given the concentration of organic matter in the sample.
To get the correct results, the sample must be ‘seeded’ with suitable bacteria. Usually a small
amount of settled raw sewage is used as a source of seed. In case the waste is toxic, an
acclimated seed must be developed.

6.5.5 Chemical Oxygen Demand Test


When organic polluting matter is discharged in the aquatic environment, it normally takes up
dissolved oxygen during its degradation thus reducing the oxygen available for the respiration of
fish and other aquatic life. The chemical oxygen demand (COD) analysis measures the maximum
amount of oxygen that can be consumed by the organic matter in a sample of water. The test is
based upon the fact that all organic compounds, with a few exceptions, can be oxidised by the
action of strong oxidising agents under acidic conditions.
However unlike BOD, in the COD test the oxygen demand is determined by means of a
chemical test. A strong chemical oxidizing agent is added and it is ensured that virtually all
organic matter within the sample is oxidized during the analysis, some of which may not be
susceptible to bacterial decomposition. The amount of oxygen used during the test is then
calculated. Some naturally occurring organic compounds such as celluloses, or many synthetic
petrochemicals, are either non-decomposable or are degraded very slowly by bacteria.
A limitation of the COD test is its inability to differentiate between biologically
oxidisable and biologically inert organic matter. Further, COD does not provide any evidence of
the rate at which the biologically active material would be stabilised under the existing
conditions. Hence, COD values are greater than BOD values and may be much greater when
significant amounts of biologically resistant organic matter is present. Nevertheless, the COD
test gives a rapid indication of the amount of oxygen a sample will demand when released to the
aquatic environment.

After a sample of water containing organic matter has been collected, it is possible that
natural biochemical reactions within the sample will act to reduce the COD. Therefore, samples
should be tested without delay. If delay in analysing the sample is unavoidable, the sample
should be preserved by acidification to pH = 2 or below.
Since the COD test measures both the biologically degradable and biologically non-
degradable organic matter, the COD value of a sample is always higher than its BOD value.
Further, COD test measures the total oxygen equivalents of the organic matter while the BOD
test measures oxygen equivalents of organic matter which is degraded in 3 days. This 3 day
value is about 70 % of the ultimate BOD. For domestic wastewaters and many decomposable
industrial wastes, COD is about 2.5 times the BOD. For unpolluted surface and ground waters
this ratio is even higher.

The Total Organic Carbon (TOC) content of a water sample is a measure of all the
carbon, which is bound up in the organic matter in the water sample. TOC is related to BOD and
COD as most of the oxygen demand measured during these analyses is due to organic carbon.

Since the BOD of a sample can be related to both the COD and the TOC, it is possible to
estimate the BOD from either the COD or the TOC. For this purpose, it is necessary to establish
a relationship between these variables for a particular sampling point. This is best done by
carrying out BOD and COD or TOC analyses on the sampling point under various conditions to
establish a reliable relationship.

6.6 Sediment Related Data


The data of amount of sediment transported by a river is need in design and management of
water resources projects, flood control structures, bridges, canals etc. The movement of solids
transported in anyway by the flowing water is termed as sediment transport. The measurement of
sediment is an expensive process and hence sediment rating curves are widely used to indirectly
assess the sediment concentration as a function of river stage or discharge.

Sediment being carried away by river flow originates from various sources, including the
watershed, agriculture field river bed and banks. The sediment data collected includes the
particle size distribution for the sediment and the sediment transport as bed and suspended load.
Sediment transport rates depend on many factors, and it may less than the sediment transport
capacity because of sediment availability. The total sediment transport by a river is the sum of
the suspended load and bed load. The sediment might originate as the bed material load and the
wash load. Fig. 6.4 shows the classification of sediment as suggested by ISO (ISO 4363: 1993).
Along Bed
Bed the bed load
material
Total
In load
Total load suspension Suspended
(origin)
load
Wash load in
suspension

Fig. 6.4 Definition of sediment load and transport (Source ISO 4363: 1993).

Sediment samplers are used to determine the concentration of sediment. The type of
sampler depends upon the need and the purpose. The suspended sediment samplers collect
samples of water and sediment mixture in a river. The sampler is lowered to the desired depth
and is filled with a sample. The sampler should be big enough such that an adequate amount of
sample, say at least 0.5 liter, is filled. A special class of samplers, known as the depth integrating
samplers, is used to obtain the vertical profile. The samplers are filled as they are lowered from
surface to bed and then raised up. The rate of lowering or raising should be constant in both
directions.
In flowing channel, samples are collected using scoop material sampler in shallow rivers
and low velocities. Dredge type bed material samplers are useful for higher depths and velocities.
In dry beds the samples are collected by scrappers after digging a pit of about 1 foot depth in
river bed. The samples collected are dried. Normally 3 to 5 samples are collected during pre-
monsoons monsoon and post-monsoon period. These samples are brought to laboratory for
analysis.

When doing the sampling, the width of the cross-section is divided into sub-areas,
depending on the variability of sediment concentration in the lateral direction. Specially designed
samplers are used to measure bed load sediments. Bed load samplers are lowered to the bottom
and are allowed to be filled up for 5-10 minutes. It is necessary to do sampling a wide range of
discharges so that a representative rating curve relating sediment and water discharge can be
established.
The concentration of sediments is commonly expressed in g/cm3 or kg/m3. The
international standards ISO 3716 and 4363 provide details of sediment sampling. The samples
are usually analyzed in laboratories. After allowing the sediments to settle down, water is
carefully removed from the container and the remaining sediments are oven-dried. The particle
size analysis is first carried out by sieving and then the finer sediments are analyzed using
hydrometer. The sediment transported as suspended load is classified in three categories,
depending on the particle size:
• The coarse fraction (particles above 0.2 mm diameter),
• The medium fraction (particles between 0.075 and 0.2 mm diameter), and
• The fine fraction (particles below 0.075 mm diameter).

Acoustic Doppler Current Profilers (ADCPs) are being increasingly used for streamflow
and suspended sediment measurements. These instruments measure either the attenuation of an
acoustic pulse due to suspended particles or the backscatter of the pulse by the particles. Remote
sensing data are also now being used to estimate suspended sediments in water. The reflectance
properties of water change depend on the concentration and the properties of suspended
sediments and these form the basis to estimate suspended sediments.

6.6.1 Processing of Sediment Data


The sediment data collected at each site is checked thoroughly and processed. An important
analysis is derivation of sediment rating curve.
6.6.2 Sediment Rating Curve
A sediment rating curve relates the suspended sediment concentration in a river with water
discharge . Commonly, the relation is of the following form:
C = a Qb (6.2)

where C is the suspended sediment concentration (mg/l), Q is the discharge (m3/s), and a and b
are constants. A typical sediment rating curve is shown in Fig. 6.5. Conventionally, discharge
and sediment concentration are plotted on a log-log graph paper and a straight line is drawn.
Usually, the power equation is log transformed, and linear regression is applied to estimate the
parameters. A least squares method can be used to obtain the values of parameters a and b.
Typically, exponent b in eq. (6.2) lies in the range between 2 and 3.

In a plot between, discharge and sediment concentration there will be a large scatter in
points. One reason behind this scatter is that soil erosion rates in a watershed are not the same
during different seasons of the year. If the scatter is large, it might be necessary to develop
separate rating curves for different seasons or according to streamflow generation mechanisms,
such as rainfall, snowmelt, etc. The data pertaining to rising and falling limbs of the hydrograph
may also be separated to improve the relationship.

A sediment rating curve is mainly applied to obtain the value of sediment concentration
for a given discharge. Along with the flow duration curve at a given location, the sediment rating
curve can also be used to estimate the amount of sediment transport over a period of time, say a
year. Another important use of sediment rating curve is in estimation of the impact of land use
changes and watershed management on sediment yield.

y = 0.1236x - 264.83
R² = 0.5833
Sediment Conc.

Discharge

Fig. 6.5 A typical sediment rating relationship.

6.6.3 Processing of Bed Material Data


Data pertaining to mean diameter, type and grade of sediment are helpful for correct appraisal of
the behavior of rivers such as braiding, scouring, sedimentation etc. This behavior depends on
flow velocity, slope of river bed, type of catchment, and quantum and type of bed material.
6.7 Water Quality Standards
Water quality standards may be classified as ambient water quality standards, specific water use
related standards and effluent water quality standards.
The Central Pollution Control Board has classified the inland surface waters into 5 categories - A
to E on the basis of the best possible use of the water as shown in Table 6.2. The classification
has been made in such a manner that the water quality requirement becomes progressively lower
from class A to class E.
A water body may be subjected to more than one organised use. The use demanding the
highest quality is the designated best use. A water body or stretch of river whose existing water
quality does not meet the designated best use criteria requires action to mitigate the situation.
Based on such analysis river action plans are formulated.

Table 6.2 Primary water quality criteria for various uses of fresh water
Designated best use Class Criteria
Drinking water source A 1. Total coliform organisms MPN/100mL shall be 50 or less.
without conventional 2. pH between 6.5 and 8.5
treatment but after 3. Dissolved oxygen 6 mg/L or more
disinfection 4. Biochemical oxygen demand 2 mg/L or less
Outdoor bathing B 1. Total coliform organisms MPN/100mL shall be 500 or less
(organised) 2. pH between 6.5 and 8.5
3. Dissolved oxygen 5 mg/L or more
4. Biochemical oxygen demand 3 mg/L or less
Drinking water source C 1. Total coliform organisms MPN/ 100mL shall be 5000 or
with conventional less
treatment followed by 2. pH between 6 and 9
disinfection 3. Dissolved oxygen 4 mg/L or more
4. Biochemical oxygen demand 3 mg/L or less
Propagation of wild life, D 1. pH between 6.5 and 8.5
fisheries 2. Dissolved oxygen 4 mg/L or more
3. Free ammonia (as N) 1.2 mg/L or less
Irrigation, industrial E 1. pH between 6.0 and 8.5
cooling, controlled waste 2. Electrical conductivity less than 2250 micro mhos/cm
disposal 3. Sodium absorption ratio less than 26
4. Boron less than 2mg/L
Source: Central Pollution Control Board, Govt. of India.

6.7.1 Water Quality Index


A number of attempts have been made to develop an aggregate index to denote quality of water
based on broad categories (physical, chemical, and biological). Within each category, a number
of quality variables may be employed and the suitability of a given water source for an intended
use depends on the magnitude of these quality variables. To describe water quality, it is useful to
employ a subindex of a quality variable to indicate the quality of the water on a zero (worst
quality) to unity (best quality) scale. In this context, a variety of subindices have been proposed
over the last two decades. Swamee and Tyagi (2000) conceived the following general
aggregation form:
−k
I = 1 − N +  s −1/ k
N

i
(6.3)
 i=1 
where N = number of subindices, k = a positive constant, and si is ith subindex.

6.8 Water Quality Monitoring in India


India has 14 major rivers basins (each with a catchment area exceeding 20,000 sq. km) and these
account for 85% of the total surface runoff. Over the time, most of the rivers in India have
become grossly polluted in various stretches. Regular monitoring networks started coming up in
the seventies. Central Pollution Control Board (CPCB) is now operating water quality
monitoring networks on major rivers under Global Environmental Monitoring System (GEMS)
and Monitoring of National Aquatic Resources (MINARS) programmes either directly or
through State Pollution Control Boards (SPCB). Some state pollution control boards have their
own monitoring stations. In addition, the Central Water Commission (CWC) is monitoring water
quality at a number of stations on almost all the major rivers. The National River Conservation
Directorate (NRCD) has also started monitoring river water quality under its action plans.
The Central Ground Water Board (CGWB) is maintaining a countrywide network of
groundwater level and quality stations. Details are given at their web-site: www.gov.in.
Groundwater data are also collected by various state agencies and some pollution control boards.
It can be noted that a number of agencies are collecting water quality data. As maintenance of
water quality networks is expensive, there is a need to clearly state the objectives
of the programmes and optimize the effort where possible

6.9 Closure
Monitoring, modeling, and management of water quality of various sources of water has become
very important for India because many of our rivers and lakes are highly polluted. In fact, some
rivers are so polluted that they resemble a dirty water drain. A disturbing recent trend is that the
aquifers are also being polluted by seepage of polluted water from surface and rivers; some
industries are pumping polluted water in the aquifers to avoid treatment and escape detection by
enforcement agencies. Urgent actions are needed to restore water quality of the sources so that
the ecosystems remain in healthy conditions and provide sustainable benefits to the society.

6.10 REFERENCES
McCutcheon, S.C., Martin, J.L, and Barnwell, T.O. (1993). Water Quality. In Handbook of
Hydrology, Edited by D.R. Maidment. McGraw-Hill Inc., New York.
Reichel, G. (1998). Suspended sediment monitoring: Use of Acoustic Doppler Current
Profiler. In Encyclopedia of Hydrology and Water Resources, edited by Herchy,
R.W., and Fairbridge,
R.W. Kluwer Academic Publishers, Dordrecht.
Swamee, Prabhata K. and Aditya Tyagi (2000). Describing water quality with aggregate
index.
Journal of Environmental Engineering, ASCE, 126(5), 451-455.
WMO(1988). Manual on water quality monitoring -- planning and implementation of
sampling and field testing. Operational Hydrology Report No. 27, WMO No. 680.
World Meteorological Organization, Geneva.
WMO(1989). Management of ground water observation programmes. Operational
Hydrology Report No. 31, WMO No. 705. World Meteorological Organization,
Geneva.
WMO (2008). Guide to Hydrological Practices. Volume I: Hydrology – From
Measurement to Hydrological Information. WMO No. 168. World Meteorological
Organization, Geneva.

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