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Measurement and Processing of Water Quality Data
Measurement and Processing of Water Quality Data
Measurement and Processing of Water Quality Data
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.
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:
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 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.
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.
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.
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.
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:
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).
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.
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.
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
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.
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.
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.
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
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.
i
(6.3)
i=1
where N = number of subindices, k = a positive constant, and si is ith subindex.
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.