Chapter III: Water Pollution

Why does the ocean appear blue?

The ocean looks blue because red, orange and yellow (long wavelength light) are absorbed more
strongly by water than is blue (short wavelength light). So when white light from the sun enters the
ocean, it is mostly the blue that gets returned.

Water quality: Water quality is a term usually used to express the suitability of water to sustain
various uses or processes. Parameters in defining water quality can be grouped into three board
categories: physical, chemical, and biological. Physical factors include temperature, sediment and
bed material, suspended sediments, turbidity, color, and odor. Chemical factors consist of the major
and minor elements, and other chemical parameters such as pH, Dissolved Oxygen (DO),
Biological Oxygen Demand (BOD), and Chemical Oxygen Demand (COD). Biological
constituents include Fecal Coli-form and E. coli. Conventionally water quality is expressed in terms
of the measured value(s) of one or more of these parameters in relation to their accepted or implied
limits.

Water quality index: Water quality index (WQI) is a Table: Water quality index
single number which can be calculated and used for overall
description of the quality of water bodies. The six physico- WQI value Water quality
chemical parameters that are routinely measured for water 0 - 25 Excellent
quality index calculation are: pH, turbidity, dissolved 26 - 50 Good
oxygen, biochemical oxygen demand (BOD5), nitrate 51 - 75 Poor
(NO3-) and phosphate (PO43-). 76 - 100 Very poor
> 100 Unfit for drinking

Water pollution: Water pollution is the contamination of water bodies (e.g. lakes, rivers, oceans,
aquifers and groundwater). This form of environmental degradation occurs when pollutants are
directly or indirectly discharged into water bodies without adequate treatment to remove harmful
compounds.

Water pollution affects the entire biosphere - plants and organisms living in these bodies of water.
In almost all cases the effect is damaging not only to individual species and population, but also to
the natural biological communities.

Sources of water pollution: Surface waters and groundwater are the two types of water resources
that pollution affects. Sources of surface water pollution are generally grouped into two categories
based on their origin.
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Point sources: Point source water pollution refers to contaminants that enter a waterway from a
single, identifiable source, such as a pipe or ditch. Examples of sources in this category include
discharges from a sewage treatment plant, a factory, or a city storm drain.
Non-point sources: Nonpoint source pollution is often the cumulative effect of small amounts of
contaminants gathered from a large area. A common example is the leaching out of nitrogen
compounds from fertilized agricultural lands.

Note that groundwater

contamination is not as easily
classified as surface water
pollution. By its very nature,
groundwater aquifers are
susceptible to contamination from
sources that may not directly
affect surface water bodies, and
the distinction of point vs. non-
point source may be irrelevant. A
spill or ongoing release of chemical or radionuclide contaminants into soil may not create point or
non-point source pollution but can contaminate the aquifer below, creating a toxic plume. Analysis
of groundwater contamination may focus on soil characteristics and site geology, hydrogeology,
hydrology, and the nature of the contaminants.

Different types of water pollution: There are many types of water pollution because water comes
from many sources. Below are some types of water pollution:

Biological water pollution: Some viruses and bacteria are water born. These can cause serious
diseases in people in direct contact with this contaminated water. This might include people
drinking, swimming or washing in the contaminated water and extremely serious and contagious
diseases such as cholera and typhoid are spread in this manner.

Oxygen depletion: Oxygen depletion destroys the natural balance of the water and ultimately
bacteria thrive and fish and other wildlife die. Oxygen depletion is caused by the release of
biodegradable matter into the water, such as sewage and the natural process of breaking this down
uses the oxygen in the water.

Nutrients pollution: Nutrients such as phosphorus and nitrogen are essential to plant growth. Too
many nutrients in the water encourage the growth of weeds and algae. This can make the water
highly polluted and result in oxygen depletion.
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Chemical water pollution: This term is used to describe the act of adding unwanted chemicals to
the water and is done through the accidental spillage of substances into water; waste from factories
or industry and through pesticides running off fields into water. Chemicals in water are poisonous
and harmful to wildlife as well as making the water too polluted to drink.

Suspended matter: Not all chemicals and pollutants are water soluble, and those that aren't are
called suspended matter. The tiny particles of matter stay in the water and eventually fall to the
bottom, forming a layer of silt on the floor of the lake or river. This is harmful to wildlife and
causes long term problems due to an imbalance in the natural infrastructure of the water.

Radioactive waste: Radioactive waste is another source of water pollution. Radioactive substances
are used in nuclear power plants, industrial, medical and other scientific processes. If not properly
disposed of, radioactive waste can result in serious water pollution incidents.

Factors affecting surface water pollution: The nature and extent of surface water pollution
depends on the following factors:
(i) Hydrological characteristics of diluting biocides and the extent of self-purification,
(ii) Vegetation, soil type and degree of weathering rocks,
(iii) Waste water disposal systems and techniques for treatment of domestic and urban sewage
including pretreatment of industrial waste waters,
(iv) Physical, chemical and biological characteristics of waste water entering the surface waters,
(v) Hygienic and health situations of the communities residing near surface waters.

Control measures of water pollution: Water pollution can be controlled in the multiple ways:
(i) Public awareness must be initiated regarding adverse effects of water pollution using the media.
(ii) No type of waste (treated, partially treated or untreated) should be discharged into any natural
water body. Industries should develop closed loop water supply schemes and domestic sewage
must be used for irrigation.
(iii) Bathing and washing clothes near water bodies such as lakes, ponds, and rivers should be
avoided.
(iv) Avoid overusing pesticides and fertilizers. Use of eco-friendly fertilizers and herbicides should
be encouraged.
(v) Industrial plants should be based on recycling operations as it helps prevent disposal of wastes
into natural waters but also extraction of products from waste.
(vi) Oxidation ponds can be useful in removing low level of radioactive wastes.
(vii) Qualified and experienced people must be consulted from time to time for effective control of
water pollution.
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(viii) Laws, standards and practices should be established to prevent water pollution and these laws
should be modified from time to time based on current requirements and technological
advancements.
(ix) Basic and applied research in public health engineering should be encouraged.

Dissolve oxygen: Dissolved oxygen (DO) is the amount of free, non-compound oxygen present in
water. It is an important parameter in assessing water quality because of its influence on the
organisms living within a body of water. The amount of oxygen dissolved in water is expressed as a
concentration, in mg/L (ppm) of water.

Non bonded water molecules in water

Oxygen has limited solubility in water, usually ranging from 6 to 14.5 mg L -1. Oxygen solubility
varies directly with partial pressure of oxygen (Remember Henry’s law !) but inversely with water
temperature and salt concentration (salinity).

Temperature, Oxygen solubility, Temp., Salinity,

o
C mg/L
o
C parts per thousand
0 14.6 10 20 30 40 50
10 11.3 0 14.6 13.6 12.7 11.9 11.1
20 9.2 20 9.1 8.6 8.1 7.6 7.2
30 7.5 25 8.2 7.8 7.4 7.0 6.6
40 6.4
50 5.5
100 0.0

Henry's law is one of the gas laws formulated by William Henry in 1803 and states: "At a constant
temperature, the amount of a given gas that dissolves in a given type and volume of liquid is
directly proportional to the partial pressure of that gas in equilibrium with that liquid”.

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Oxygen is absorbed in water by direct diffusion from the atmosphere, which is enhanced by
surface-water agitation. Water also absorbs oxygen released by aquatic plants during
photosynthesis. Note that the dissolved oxygen level in water is constantly changing and represents
a balance between respiration and decomposition that deplete oxygen and photosynthetic activity
(CO2 + H2O + hν → {CH2O} + O2) that increases it.

The DO in water has an important impact on aquatic animals and plants. Most aquatic animals,
such as fish, require oxygen in the water to survive. As dissolved oxygen levels in water drop
below 5.0 mg/L, aquatic life is put under stress. The lower the concentration, the greater is the
stress. Oxygen levels that remain below 1-2 mg/L for a few hours can result in large fish kills.

Without oxygen at the bottom of the water body, anaerobic bacteria produce acids (lactic acids,
etc.). These acids not only increase acidity, but also cause a massive release of phosphorus and
nitrogen, two major fertilizers, from the organic sediment and into the water column. These same
anaerobic bacteria put toxic gases in the water including H2S, NH3, CO2 and CH4. These gases are
all toxic to fish, beneficial bacteria and insects. Lack of bottom oxygen is the cause of odors
produced by anaerobic bacteria.

Determination of DO in water: There are three methods available for measuring dissolved oxygen
concentrations. The most precise and reliable titrimetric procedure for DO analysis is the Winkler
titration method developed by Winkler in 1888. It is an iodometric titration, in which the amount of
oxygen in the sample is determined in directly via iodine. It is the most precise and reliable
titrimetric procedure for DO analysis.

A divalent manganese solution is added followed by strong alkali to a water sample in a glass
stoppered bottle. Any DO present in the sample rapidly oxidizes an equivalent amount of the
dispersed divalent manganous hydroxide precipitate to hydroxides. The sample is then acidified
with H2SO4. In the presence of iodide ions in an acidic solution, the oxidized manganese reverts to
the divalent state, with the liberation of iodine equivalent to the original DO content. The iodine is
then titrated with sodium thiosulfate and starch as an indicator. The equations are as follows:

(i) Manganous sulfate reacts with hydroxide (potassium or sodium) to give a white precipitate of
manganous hydroxide. In the presence of oxygen, brown manganic basic oxide is formed.
MnSO4 + 2KOH → Mn(OH)2 + K2SO4
2Mn(OH)2 + O2 (from DO) → 2 MnO(OH)2

(ii) Addition of sulfuric acid dissolves the brown manganic sulfate which reacts instantly with
iodide to yield iodine.
2MnO(OH)2 + 4 H2SO4 → 2Mn(SO4)2 + 6H2O
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2Mn(SO4)2 + 4 KI → 2MnSO4 + 2K2SO4 + 2I2

(iii) In effect, oxygen oxidizes Mn2+ to Mn4+ and the Mn4+ oxidizes I- to I2. Iodine is then determined
titrimetrically via titration with sodium thiosulfate (Na 2S2O3) with starch as an end point indicator
(deep blue).

(iv) Thiosulfate solution (made up as Na2S2O3) is used, with a starch indicator, to titrate the iodine.
4Na2S2O3 + 2I2 → 2Na2S4O6 + 4NaI

From the above stoichiometric equations it is apparent that four moles of thiosulfate are titrated for
each mole of molecular oxygen (O2).

Thus 1 mL of 0.025 M sodium thiosulfate is equivalent to 0.025 meq of oxygen. This value is
commonly multiplied by 8 mg/meq to convert to mg O2. When 200 mL of the original sample is
titrated, then 1 mL 0.025 M Na2S2O3 ≡ 1 mg dissolve oxygen/L.

+ I3- ⇄
n

S2O32- ion S4O62- ion Reaction of I3- with starch indicator

Some oxidizing agents liberate iodine from iodide (+ interference) while some reducing agents
reduce iodine to iodide (- interference). Organic matter is oxidized partially when the manganese
precipitate is acidified, causing negative errors. The azide modification removes interference
caused by nitrate, common in biologically treated effluents. The permanganate modification is used
to remove iron interference of > 5 mg ferric iron salts/L. Ferrous interference can be removed by
adding H3PO4 for acidification (only if Fe3+ is < 20 mg/L). With suspended solids the alum
flocculation modification works well, while for activated-sludge mixed liquor the copper sulfate-
sulfamic acid flocculation modification can be used. In many cases, these interferences can be
overcome by using the dissolved oxygen probe method.

Biological oxygen demand (BOD): Biological oxygen demand (also called biochemical oxygen
demand) is the amount of dissolved oxygen demanded by aerobic microorganisms to break down
organic material present in a given water sample at certain temperature over a specific time period.
Microorganisms
{CH2O} + O2 → CO2 + H2O
Biomass

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Sources of BOD include topsoil, leaves and woody debris, animal manure, effluents from pulp and
paper mills, wastewater treatment plants, feedlots, and food-processing plants, failing septic
systems, and urban storm-water runoff.

Thus BOD indicates the amount of putrescible organic matter present in water. The higher the BOD
value, the greater is the amount of organic matter or food available for oxygen consuming bacteria.
If the rate of DO consumption by bacteria exceeds the supply of DO from aquatic plants, algae
photosynthesis or diffusing from air, unfavorable conditions occur. Depletion of DO causes stress
on aquatic organisms, making the environment unsuitable for life. Further, dramatic depletion can
lead to hypoxia or anoxic environments.

The biochemical oxygen demand (BOD) is one of the most widely used criteria for water quality
assessment. A low BOD is an indicator of good quality water, while a high BOD indicates polluted
water. Note that Regulations for BOD will vary by country and region.

BOD level in mg/L Water quality

1-2 Clean water with little organic matter.
3-5 Moderately clean water with some organic waste.
6-9 Poor. Lots of organic material and many bacteria.
> 10 Very poor water quality. Large amounts of organic material in the water.

The BOD level is determined by comparing the DO level of an aerated water taken immediately
with the DO level of a water sample that has been incubated in a dark location at 20 oC for 5 or 7
days. The BOD after five or seven days incubation (BOD 5/BOD7) is expressed in ppm or mg O2/L
of water. However, the selection of microorganisms is crucial and the results are obviously not
reproducible.

BOD is typically divided into two parts - carbonaceous biochemical oxygen demand (CBOD) and
nitrogenous biochemical oxygen demand (NBOD). Carbonaceous BOD is the result of the
breakdown of carbonaceous materials (cellulose and sugars) present in water into carbon dioxide
and water.
Hydrolysis Hydrolysis Oxidation Oxidation

Cellulose → Cellobiose → Glucose → Organic acids → CO2 + H2O

Cellulase Cellobiase

Nitrogenous BOD is the result of the breakdown of proteins in water. Proteins contain sugars linked
to nitrogen. After the nitrogen is broken off a sugar molecule, it is usually in the form of ammonia,
which is readily converted to nitrate in the environment.

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 Hydrolysis Hydrolysis Oxidation

Proteins → polypeptides → Amino acids → Ammonia or ammonium salts → Nitrates

The short incubation, usually 5 days, is sufficient to detect only the microbial utilization of carbon
compounds. A longer incubation (15 to 20 days) would also detect the oxidation of inorganic
nitrogenous compounds (ammonia and nitrite) and the subsequent demand for molecular oxygen by
chemoautotrophic bacteria.

Problem 1: Calculate the BOD of a water sample which contains 1 g of urea for every 100 L of
water. The reaction between urea and oxygen is,
NH2CONH2 + 4O2 → CO2 + 2NO3- + 2H+ + H2O

Solution: From the balanced equation it is clear that 4 moles of O2 are required to react with 1 mole
of urea. One mole of O2 weighs 32.0 g and one mole of urea weighs 60.0 g. We have
4(32.0 g O2) ≡ 1(60.0 g urea)
or 4×32.0 g O2 ≡ 60.0 g urea
or 128.0 g O2 ≡ 60.0 g urea
To react with 1.0 g urea, we need
1.0 g urea × 128.0 g O2
------------------------------ = 2.13 g O2 = 2.13 × 103 mg O2
60.0 g urea

2.13 × 103 mg O2
Thus BOD = ------------------------ = 21.3 mg/L
100 L

Chemical oxygen demand (COD): Chemical oxygen demand is a measurement of the oxygen
required to oxidize soluble and particulate organic matter in water. The COD values are expressed
in ppm or mg O2/L of water.

The principle involved in the determination of COD is that when the waste water sample is refluxed
(approx. 2 hrs at 150oC) with a known excess of K2Cr2O7 (0.25 N) in a 50% H2SO4 solution in
presence of AgSO4 (as catalyst) and HgSO4 (to eliminate interference due to chloride), the organic
matter of the sample is oxidized to water, CO2 and ammonia.
a + 8d – 3c
CnHaObNc + dCr2O72- + (8d + c)H+ → nCO2 + -------------- H2O + cNH4+ + 2dCr3+
2

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where d = 2n/3 + a/6 - b/3 - c/2. The excess Cr2O72- remaining unreacted in the solution is treated
with a standard solution of ferrous ammonium sulphate. The COD of the sample is calculated as
follows:

(V1 – V2 ) × N × 8 × 1000
COD in mg/L = ----------------------------------
X
where V1 and V2 are the volumes of ferrous ammonium sulphate (of normality, N) run down in the
blank and test experiments respectively and X is the volume of the sample taken for the test.

Chemical oxygen demand is an important water quality parameter because, similar to BOD, it
provides an index to assess the effect of discharged wastewater will have on the receiving
environment. Higher COD levels mean a greater amount of oxidizable organic material in the
sample, which will reduce dissolved oxygen (DO) levels. A reduction in DO can lead to anaerobic
conditions, which is deleterious to higher aquatic life forms. The COD test is often used as an
alternate to BOD due to shorter length of testing time.

Since in the COD test, both the biologically oxidizable and the biologically inert matter are
oxidized, the COD value for a sample is always higher than BOD value.

Difference between biochemical oxygen demand (BOD) and chemical oxygen demand (COD):
Biochemical oxygen demand (BOD) Chemical oxygen demand (COD)
1. Measures biodegradable organics. 1. Measures biodegradable and non-
biodegradable organics.
2. Uses oxidizing microorganism. 2. Uses a strong chemical agent.
3. Five days required for BOD studies. 3. Takes just two hours to complete.
4. Affected by toxic substance. 4. Not affected.
5. Affected by temperature. 5. Not affected.
6. Accuracy ± 10% 6. Accuracy ± 2%

Wastewater treatment methods and disposal: Wastewater treatment is a process to improve and
purify the water, removing some or all of the contaminants, making it fit for reuse or discharge
back to the environment. Treatment technology includes physical, biological, and chemical
methods. A by-product of sewage treatment is usually a semi-solid waste or slurry, called sewage
sludge that has to undergo further treatment before being suitable for disposal or land application.
Widely used terminology refers to three levels of wastewater treatment: primary, secondary, and
tertiary.

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Primary treatment is usually the first stage of wastewater treatment. It is designed to remove gross,
suspended and floating solids from raw sewage. The process employed includes sedimentation,
mechanical flocculation and chemical coagulation. After this treatment, about 60% of the
suspended solids, 35% BOD, 30% COD, 10% phosphorus and 20% total nitrogen, are generally
reduced.

Secondary treatment removes the dissolved and colloidal organic matter that escapes primary
treatment. This is achieved by biological processes involving bacteria and other micro-organisms.
These processes may be aerobic or anaerobic. They bring about the following sequential changes:
(i) Coagulation and flocculation of colloidal matter, (ii) Oxidation of dissolved organic matter to
CO2, (iii) Degradation of nitrogenous organic matter to ammonia, which is then converted into
nitrite and eventually to nitrate, and (iv) Reduction of BOD.

Secondary treatment technologies include the activated sludge processes, trickling filters or
biofilters, oxidation ditches, and rotating biological contactors (RBC). About 85% of the suspended
solids, 90% BOD, 80% COD, 30% phosphorus, and 50% total nitrogen can be removed by a well
running plant with secondary treatment.

Tertiary treatment is any practice beyond secondary treatment and is designed to remove non-
biodegradable organic pollutants and mineral nutrients such as nitrogen and phosphorus salts. The
main objectives of tertiary treatment processes are: (i) Removal of fine suspended solids, (ii)
Removal of dissolved inorganic solids, (iii) Removal of final traces of organics, as desired,
(iv) Removal of bacteria, (v) Decrease the load of nitrogen and phosphorus in the effluents, and (vi)
Further purification of wastewater to enable its reuse.

This advanced treatment can be accomplished by a variety of methods such as coagulation

sedimentation, filtration, reverse osmosis, and extending secondary biological treatment to further
stabilize oxygen-demanding substances or remove nutrients. Tertiary treatment can remove more
than 99% of all the impurities from sewage, producing an effluent of almost drinking-water quality.

Physical-chemical treatment of municipal wastewater: Municipal waste water includes domestic

discharges and commercial and industrial waste water collected in public sewerage system. The
sewage contains human and industrial waste water collected in public sewerage system. The
sewage contains human and animal excreta, food residue, detergents, and other wastes. It always
contains organic matter, bacteria, and other biological pollutants.

The main goal of treating municipal wastewater was simply to reduce its content of suspended
solids, oxygen-demanding materials, dissolved inorganic compounds, and harmful bacteria. Such a

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treatment uses a combination of mechanical, biological and chemical processes, typically
comprises (i) preliminary treatment; (ii) primary treatment including grit removal, screening,
grinding, and sedimentation; (iii) secondary treatment, which entails oxidation of dissolved organic
matter by means of using biologically active sludge, which is then filtered off; and (iv) tertiary
treatment in which advanced biological methods of nitrogen removal and chemical and physical
methods such as granular filtration, activated carbon absorption and disinfection are employed.

The basic steps of a municipal wastewater treatment facility are shown below:

Schematics of a complete physical-chemical treatment facility for municipal wastewater.

Drinking water: The water that is fit for drinking purposes is called drinking or potable water.
Potable water has the following characteristics:
(i) It should be colourless, odorless and tasteless.
(ii) It should be free from turbidity and other suspended impurities.
(iii) It should be free from germs, bacteria and other pathogenic organisms.
(iv) It should not contain toxic dissolved impurities, such as heavy metals, pesticides, etc.
(v) It should have a pH in the range 7 - 8.5.
(vi) It should contain high enough oxygen.
(vii) It should be moderately soft, having hardness preferably in the range 50-100 ppm.
(viii) It should be aesthetically pleasant.

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Reverse osmosis: Reverse osmosis is a water purification technology that uses a semipermeable
membrane to remove ions, molecules, and larger particles from drinking water. In reverse osmosis,
an applied pressure is used to overcome osmotic pressure, a colligative property that is driven by
chemical potential differences of the solvent, a thermodynamic parameter. Reverse osmosis can
remove many types of dissolved and suspended species from water, including bacteria, and is used
in both industrial processes and the production of potable water. The result is that the solute is
retained on the pressurized side of the membrane and the pure solvent is allowed to pass to the
other side. To be selective, this membrane should not allow large molecules or ions through the
pores, but should allow smaller components of the solution (such as the solvent) to pass freely.

Phenomenon of reverse osmosis.

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