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SSV 3013




After completing the work associated with this experiment, Im able to:

Understand the implications of water pollution.


Perform a basic experiment to determine the water quality of a given system

based on biochemical oxygen demand (BOD) and chemical oxygen demand


Gain an awareness of water pollution problems from municipal solid waste

landfill leachate.


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 is typically referred to as polluted
when it is impaired by anthropogenic contaminants and either does not support a
human use, such as drinking water, or undergoes a marked shift in its ability to
support its constituent biotic communities, such as fish. Natural phenomena such as
volcanoes, algae blooms, storms, and earthquakes also cause major changes in water
quality and the ecological status of water.
Although interrelated, surface water and groundwater have often been studied
and managed as separate resources. Surface water seeps through the soil and becomes
groundwater. Conversely, groundwater can also feed surface water sources. Sources
of surface water pollution are generally grouped into two categories based on their
origin. 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. The U.S. Clean Water Act (CWA) defines point source for regulatory
enforcement purposes. The CWA definition of point source was amended in 1987 to
include municipal storm sewer systems, as well as industrial storm water, such as

from construction sites. Nonpoint source pollution refers to diffuse contamination that
does not originate from a single discrete source. NPS 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.
Nutrient runoff in storm water from "sheet flow" over an agricultural field or a forest
are also cited as examples of NPS pollution.
Other than that, interactions between groundwater and surface water are
complex. Consequently, groundwater pollution, also referred to as 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 (located away from a surface water body) may not create point or non-point
source pollution but can contaminate the aquifer below, creating a toxic plume. The
movement of the plume, called a plume front, may be analyzed through a
hydrological transport model or groundwater model. Analysis of groundwater
contamination may focus on soil characteristics and site geology, hydrogeology,
hydrology, and the nature of the contaminants.
The rapid growth in population and development has increased the amount of
solid waste generated. Method used for the disposal of wastes in the country such as
by open dumping or controlled tipping tend to cause water pollution due to the
production of landfill leachate. Landfill leachate which is a liquid produced as a result
of water percolation from the process of water infiltration, surface runoff,
precipitation and liquid from the compacted waste not only would pollute the ground
water as it moved into the landfill but also the surface water. Once leachate polluted
the ground water it becomes a threat to the environment and would create potential
hazards to human health because it contains organic and inorganic substances as well
as the toxic heavy metal compounds. Improper management of disposal sites will
cause water pollution and pose short and long-term hazards and risks to the
environment and the public.

Im given water samples from landfill leachate and river water. The organic pollution
levels of the samples were compared by measuring the BOD and COD.
Biological oxygen demand (BOD):
2 BOD bottles
1 air outlet with rubber tubing
3 x 2 ml dropper pipettes
50 ml burette
100 ml measuring cylinder
250 ml conical flask
10 ml measuring cylinder
5 ml pipette
10 ml pipette
Clean container for dilution water
1 litre measuring cylinder
Manganous sulphate solution (50%) MnSO4.4H2O
Alkali-iodide reagent
Sulphuric acid (50%) H2SO4
Thiosulphate solution (0.0125M) Na2S2O3.5H2O
Potassium iodide solution (KI)
Starch solution
Distilled or deionized water
Dilution water reagent
Chemical oxygen demand (COD):
COD reactor
COD Digestion Reagent Vials
Distilled water
Deionized water
5 ml pipette
Test tube and rack


Biological Oxygen Demand (BOD) (Winkler Titration Method):

This lab exercise measures how much oxygen is consumed through respiration
and decomposition of microscopic organisms. Before we can measure the
BOD of a water sample, we must know the dissolved oxygen (DO) content of
the sample. The amount of DO in water affects natural biochemical processes
in two ways: by limiting the amount of oxygen available for respiration and by
affecting the solubility of essential nutrient in the water. The decomposition of
organic matter is the greatest factor in the depletion of available oxygen in a
given body of water. As the organic content of water increases, there is a
corresponding increase in bacterial activity and decrease in the dissolved
oxygen content (Figure 3.1). The dissolved oxygen content of the water is
measured under saturated conditions (the water sample contains maximum
amount of oxygen it can hold) and again after incubating for five days in the
dark at approximately 20oC. The difference between the two values is the
amount used by microorganism decomposition and is known as biochemical
oxygen demand (BOD).

Figure 3.1 Oxygen sag curve


Water samples were obtained from two places that want to test and the organic
pollution levels are compared. Each sample should consist two sets of bottles.
One set of bottles will be tested on day one. The second set of bottles will be
stored for 5 days.


Distilled water saturate with air was prepared and the temperature was brought
to 20 3C.


Sample was diluted with distilled water saturate with air and 1 ml of
phosphate buffer, 1 ml of MgSO4, 1ml of CaCl2 and 1 ml of FeCl3 solutions
were added to the required dilution factor with 1 L final volume using
volumetric flask.


The diluted sample was mixed and poured into three clean BOD bottles so that
they overflow.


A stopper was inserted into the bottle and make sure there are no air bubbles
adhering to the inside of the bottles by tapping the sides and then the stoppers
were inserted firmly.


One set of the bottles was incubated at 20 3C for five days.


To the other set of bottles 1ml of manganous sulphate (MnSO 4) solution was
added followed by 1 ml of alkali-iodide solution. The purpose was to fix the
sample so that oxygen exchange will not occur during testing.


The stopper was placed firmly to exclude air bubbles and any overflow of
water was mopped up with tissue. This could be alkaline so TAKE CARE.


The bottle was held with a finger on the lid, the bottle was shook vigorously.


When precipitate has settled sufficiently (to approximately half the bottle
volume) to leave clear supernate above the manganese hydroxide floc,1 ml of
concentrated H2SO4 was added using a dropper pipette with the tip below the
water surface.


The stopper was placed and mixed thoroughly (the precipitate has now
dissolved and iodine has been release to give a clear reddish brown color).


A volume corresponding to 200 ml original sample was titrated after

correction for sample loss by displacement with reagents. Thus for a total of 2
ml (1 ml each) of MnSO4 and alkali-iodide-azide reagents in 300 ml bottle,
200 x 300/(300-2) = 201 ml was titrated.


0.025M Na2S2O3 solution was titrated to a pale straw colour.


A few drops of starch solution were added and a deep blue color is formed.


The titration was continued until the blue color disappears and the burette
reading was noted down.


For titration of 200 ml sample, 1 ml of 0.025M Na2S2O3 = 1 mg/l DO.


The DO of incubated samples (5 days) is tested using the same procedure.


The BOD of a blank was determined by filling two set of bottles with
dilution water and its DO was measured before and after five days (One set
BOD blank can be performed for each batch of samples)


BOD value was determined by the following formula:

BOD value in mg/l = [(D1-D2) (B1-B2)] /P

D1= initial DO in a sample
D2= final DO in a sample
B1= initial DO in blank
B2= final DO in blank
P= fraction of the BOD bottle that is represented by the sample or mL pipetted
divided by 300mL when a 300mL bottle is used.

Chemical Oxygen Demand (COD) (Reactor Digestion Method)

Chemical oxygen demand (COD) refers to chemicals present in water that are
not biodegradable or are at least slowly degraded by microbes. It measures the
amount of oxygen required to stabilize organic matter using a strong chemical
oxidant, which is typically potassium dichromate (K 2Cr2O7) that reacts with
the sample under controlled conditions. The reaction that takes place in the
sample is the chromate reduction of Cr 6

Cr3+. This reaction may be

represented as follows:
Organic + Cr2O2-7 + H+

CO2 + H2O + 2Cr3+

The dichromate-sample solution is then titrated with a standard ferrous

ammonium sulfate solution using ferroin as an indicator. The ferrous ion will
react with the dichromate ions and the mixture would eventually change in
color from bluish green to reddish brown via the following reaction.
6Fe2+ + Cr2O2-7 + 14H+

6Fe3+ + 2Cr3+ + 7H2O

The change in color of the solution will be recorded using spectrophotometer.

The quantity of oxidant consumed is reported in terms of its oxygen
equivalence of mg/L.

Sample was diluted with distilled or deionized water.


The COD reactor was turned on. It was preheated to 150 oC.
CAREFULL the reactor is hot.


The caps were removed from two COD Digestion Reagent Vials. (Be
sure to use vials for the appropriate range)


One vial was held at a 45-degree angle. A volumetric pipette was used
to add 2 ml of sample to the vial prepared sample.


Another vial was held at a 45-degree angle. A clean volumetric pipette

was used to add 2ml of deionized water to the vial (blank).


Cap the vial tightly. Rinse them with deionized water and wipe with a
clean paper towel.


Hold the vials by the cap over a sink. Invert gently several times to
mix. Place the vials in the preheated COD reactor. The sample vials
will become very hot during mixing.


Heat the vials for two hours.


Turn the reactor off. Wait about 20 minutes for the vials to cool to
120oC or less.


Invert each vial several times while still warm. Place the vials into a
rack and cool to room temperature.


Measure the COD at 420 nm (low range) or 620nm (high range). COD
is measured in a unit of mg/L


Compare the COD and BOD readings in both samples. Do you think that the
landfill leachate has polluted the nearby river? Discuss.


List the differences between BOD and COD measurements.