Water Quality Management

Water Pollutants and their Sources

Groups/Types of Pollutants
 Physical: Temp, Turbidity, Solids (TSS, TDS, VSS, FS,
etc.)
 Chemical: pH, colour, nitrogenous compounds, oxygen
demanding compounds (BOD, COD, TOC, etc.),
metals,
 Organic
 Inorganic
 Degradable (Non-conservative)
 Non-degradable (Conservative)
 Biological: Mainly referring to pathogens and microbes
(bacteria, virus, fungus, etc.)
 Hazardous & Toxic
 Units of the Pollutants: Depends on the Pollutant
Dissolved Oxygen (DO) is NOT a pollutant……
 Major Water Pollutant Categories and
Principal Sources of Pollutants

Pollutant category Point Sources Non-Point Sources

Domestic Industrial Agric. runoff Urban runoff
sewage Wastes
Oxygen-demanding
material X X X X
Nutrients
X X X X
Pathogens
X X X X
Suspended solids
/sediments X X X X
Salts
X X X
Toxic metals
X X
Toxic organic chemicals
X X
Heat
X
 Water Pollution Sources
 Non – point sources : This is made up of pollutants
from Agricultural runoff and urban runoff (stormwater
drainage). This is characterized by multiple discharge
points.

NPS is mainly caused due to precipitation and it varies from

one landuse and landcover to another.

 Point sources : This is made up of pollutants from

domestic sewage and industrial waste collected by a
pipe network or channels and conveyed to a single
point for discharge .

In general point source pollution can be reduced or

eliminated through waste minimization and proper
wastewater treatment prior to discharge to a natural water
source
 Major Water Pollutant Categories and
Principal Sources of Pollutants
• Oxygen – demanding material: Any material that can be oxidized in the
receiving water using dissolved molecular oxygen.
– Sources : Food residue, human waste, food processing, paper industry, farm
inputs e.g. fertilizer, pesticide, herbicides.
– Effects : Threat to aquatic and human life.
• Nutrients :
– Source : Nitrogen and phosphorous fertilizers, food processing wastes,
detergents, etc.
– Effect : Excessive nutrients leads to upset in the food web (chain) e.g. excessive
growth of algae, water hyacinth, etc.
• Pathogenic Organisms : Bacterial, viruses and protozoa excreted by diseased
persons or animals
– Effect : Makes water unsafe for drinking, fishing, swimming. Certain shell fish
become toxic.
• Suspended solids / sedimentation: Organic and inorganic particles in waste
water discharged into a receiving water.
– Effects : Organic suspended solids exert oxygen demand,
• Reduces the usefulness of water
– Sources : Soil erosion due to logging, strip mining, construction activities,
discharge of industrial waste, destruction of aquatic life due to sediment deposits.
 Major Water Pollutant Categories and
Principal Sources of Pollutants
• Salts :
– Make up of the total dissolved solids (TDS) in water .
– Sources : Discharge from industries, excessive use of
fertilizers ( inorganic ) in farming.
– Effects :Damage to aquatic and plant life. Makes water
unsuitable for water supplies,
• Toxic metals and toxic organic compounds :
– Sources : Urban runoff, agricultural runoff – use of farm inputs
e . g pesticides, herbicides etc ,industrial waste water
discharges e . g. electroplating , electronics.
– Effects : Toxicity in the food chain, Toxic to human even in
small quantities.
• Heat :
– Sources : Industrial processes, power plants etc
– Effect : increases rate of oxygen depletion, reduces aquatic life
of fish.
 Water Quality Management in Rivers
• Objective :
– To control the discharge of pollutants so that water
quality is not degraded to an unacceptable level.

• Impact of pollution on water :

– Factors :
• Volume and speed of the flowing water .
• The depth of water in the channel
• Type of bottom, surrounding vegetation etc
• Climate of the region.
• Land use patterns.
• Mineral content of the watershed.
• Type of aquatic life in the river.
Effects of Nutrients on Water Quality in Rivers

• Effects of Nitrogen :
– In high concentrations, NH3-N is toxic to fish.
– NH3, in low concentrations, and NO3- serve
as nutrients for excessive growth of algae.
– The conversion of NH4+ to NO3- consumes
large quantities of dissolved oxygen.

• Effects of Phosphorus :
– Serves as a vital nutrient for algae growth.
– Increase in oxygen demand by dead algae
(made up of organic matter).
– Over taxing of the Dissolved oxygen (DO)
supply of the water leading to fish death.
 Management Strategy for Control of
Excessive Nutrients
• Removal of nitrogen and / or phosphorus from waste
water before discharge using tertiary treatment.
• Reduction in the use of substances or industrial
process or producing nitrogen and phosphorus
containing materials.
• Waste minimization through recycling, conversion ,
technology modification etc.
 Receiving Water Quality Standards (from NWQS)
parameter units CLASSES
I IIA IIB III IV V
DO mg/L 7 5-7 5-7 3-5 <3 <1
COD mg/L 10 25 25 50 100 >100

BOD mg/L 1 3 3 6 12 >12

Total mg/L 500 1000 - - 4000 -

dissolved
solids

Total mg/L 25 50 50 150 300 >300

suspended
solids

Faecal counts/ 10 100 400 5000 5000 -

coliform 100ml
Total counts/ 100 5000 5000 5000 5000 >50000
coliform 100ml
 Receiving Water Quality Standards (from NWQS)
Class USES
Represents water bodies of excellent quality. Standards sets for the conservation of natural
I environment in its undisturbed state. Water bodies such as those in the national park areas,
fountain heads, inland and in undisturbed areas come under this category where strictly no
discharges of any kind is permitted. Water bodies in this category meets the most stringent
requirements for human health and aquatic life protection.
Represents water bodies of good quality. Most existing raw water supply sources come under
II this category. In practice, no body contact activity is allowed in this water for the prevention of
probable human pathogens. There is a need to introduce another class for water bodies not
used for water supply but similar quality which may be referred to as Class IIB. The
determination of Class IIB standards is based on criteria for recreational use and protection of
sensitive aquatic species
Is defined with the primary objectives of protecting common and moderately tolerant aquatic
III species of economic value. Water under this classification may be used for water supply with
extensive/advanced treatment. This class of water is also defined to suit livestock drinking
needs.

Defined water required for major agricultural activities which may not cover minor application to
IV sensitive crops

Represent other water which do not meet any of the above uses
V
 Environmental quality Regulations, 1979
(Sewage and Industrial Effluents)
Maximum Effluent Parameter Limits Standards A and B
 Biochemical Oxygen Demand (BOD)
• Definition: The amount of oxygen required to oxidize a substance to
carbon dioxide and water by microorganisms.
• When a water sample is placed in a closed container and inoculated
with bacteria, the oxygen consumption follows the pattern shown
below:
 Biochemical Oxygen Demand (BOD) contd.
BOD can be described mathematically as a first order reaction as follows:

dL
 kL
dt
L  oxygen equivalent of the organic chemicals remaining
k  reaction rate constant(i n days -1 )
dL
 kdt
L
Lt t
dL
Lo L  k 0 dt
Lt
ln  kt
Lo
or
Lt  L0 e  kt
Lo  oxygen equivalent of organics at time , t  o(mg/L)
Lt  oxygen equivalent of the organic chemicals remaining at time , t (mg/L)
BOD t  Lo  Lt
 Lo  Lo e  kt
BOD t  amount of oxygen used in the consumptio n of organics
Lo  ultimate BOD i.e. the maximum oxygen consumptio n possible when the waste has been completely degraded
 Biochemical Oxygen Demand (BOD) contd.

• Oxygen Depletion:
– Related to the ultimate BOD and the rate constant (k)
– The ultimate BOD increase in direct proportion to the
concentration of degradable organic matter.
– The rate constant is dependent on the following:
• The nature of the waste
• The ability of the organisms in the system to use
the waste
• The temperature
 Biochemical Oxygen Demand(BOD) contd.
Nature of the Waste:
• There are thousands of naturally occurring organic compounds, and not all of
them can be degraded;
• Simple sugars and starches are rapidly degraded and will therefore have a
very large BOD rate constant.
• Cellulose (for example, toilet paper) degrades much more slowly
• Compounds such as the higher molecular weight polycyclic aromatic
hydrocarbons, highly chlorinated compounds such as DDT, PCBs, caffeine, or
many of the estrogenic compounds used 'in birth control pills are almost
undegradable in the BOD test or in conventional wastewater treatment. In
some cases,
• Many of the phenolic compounds are actually toxic to the microorganisms,
killing them so that little or no degradation of the waste can occur.
• The BOD rate constant for a complex waste depends very much on the
relative proportions of the various components.
• The lower rate constants for treated sewage compared with raw sewage
result from the fact that easily degradable organics are more completely
removed than less readily degradable organics during wastewater treatment.
 Biochemical Oxygen Demand (BOD) contd.
Ability of Organisms to Use Waste:
• Any given microorganism is limited in its ability to use organic compounds.
• Many organic compounds can be degraded by only a small group of
microorganisms.
• In a natural environment receiving a continuous discharge of organic
waste, that population of organisms that can most efficiently use this waste
will predominate.
• However, the culture used to inoculate the sample used in the BOD test
may contain only a very small number of organisms that can degrade the
particular organic compounds in the waste.
• This problem is especially common when analyzing industrial wastes.
• The result is that the BOD rate constant would be lower in the laboratory
test than in the natural water.
• To avoid this undesirable outcome the BOD test should be conducted with
organisms that have been acclimated to the waste so that the rate
constant determined in the laboratory is comparable to that in the river.
• Acclimated means that the organisms have had time to adapt their
metabolisms to the waste or that organisms that can use the waste have
been given the chance to predominate in the culture.
 Biochemical Oxygen Demand (BOD) contd.

Temperature.
• Most biological processes speed up as the temperature increases
and slows down as the temperature drops.
• Because oxygen use is caused by the metabolism of microorganisms,
the rate of its use is similarly affected by temperature.
• Ideally, the BOD rate constant should be experimentally determined
for the temperature of the receiving water.
• There are two difficulties with this ideal.
– Often the temperature of the receiving water changes throughout
the year. -a large number of tests would be required to define k.
– An additional difficulty is the task of comparing data from various
locations having different temperatures.
• Laboratory testing is therefore done at a standard temperature of 200
C, and the BOD rate constant is adjusted to the temperature of the
receiving water using the following expression:.
Biochemical Oxygen Demand (BOD) contd.

• The temperature
– T= temperature of interest , oC
– kT= BOD rate constant at the

kT  k 20 ( ) T  20
temperature of interest ( in days-1)
– K20= BOD rate constant determined
at 20 oC ( in days-1)
– Θ = Temperature coefficient. For
typical domestic wastewater this
varies from 1.135 for 4 oC to 20 oC
And 1.056 for 20 oC to 30 oC
 Types of BOD
Oxidation
• Oxygen consumption due to oxidation of carbon is called carbonaceous BOD
(CBOD), and that due to nitrogen oxidation is called nitrogenous BOD (NBOD).
• The organisms that oxidize the carbon in organic compounds to obtain energy
cannot oxidize the nitrogen in these compounds.
• Many organic compounds, such as proteins, also contain nitrogen that can be
oxidized with the consumption of molecular oxygen.
• Because the mechanisms and rates of nitrogen are distinctly different from those
of carbon oxidation, the two processes must be considered separately.
• The nitrogen is released into the surrounding water as ammonia (NH3).
• At normal pH values, this ammonia is actually in the form of the ammonium.
cation (NH4+).
• The ammonia released from organic compounds, plus that from other source such
as industrial wastes and agricultural runoff (i.e., fertilizers), is oxidized to nitrate
(NO3-) by a special group of nitrifying bacteria as their source of energy in a
process called nitrification.
• The rate at which the NBOD is exerted depends heavily on the number of
nitrifying organisms present.
• Few of these organisms occur in untreated sewage, but the concentration is high
in a well-treated effluent.
 CBOD and NBOD
• When samples of untreated and treated
sewage are subjected to the BOD test, oxygen
consumption follows the pattern shown in
Figure
• In the case of untreated sewage, the NBOD is
exerted after much of the CBOD has been
exerted.
• The lag is due to the time it takes for the
nitrifying bacteria to reach a sufficient
population for the amount of NBOD exertion to
be significant compared with that of the
CBOD.
• In the case of the treated sewage, a higher
population of nitrifying organisms in the
sample reduces the lag time. Once nitrification
begins, however, the NBOD can be described
by Equation with a BOD rate constant
comparable to that for the CBOD of a
well-treated effluent (k = 0.80 to 0.20 day').
• Because the lag before the nitrogenous BOD
is highly variable, BOD5 values are often
difficult to interpret.
• When measurement of only carbonaceous
BOD is desired, chemical inhibitors are added
to stop the nitrification process.
 NBOD

• Total Kjeldahl Nitrogen (TKN) is a measure of the total

organic and ammonia nitrogen in wastewater.
• TKN gives a measure of the availability of nitrogen for
building cells, as well as the potential nitrogenous oxygen
demand that will have to be satisfied.
• The overall reaction for ammonia oxidation is:

NH 4  2O2 nitrificat ion

microorgan isms
 NO3  H 2O  2 H 
grams of oxygen used (2 moles)(32 g O 2 .mol1 )
NBOD  
grams of nitrogen utilized (1 mole)(14g N.mol-1 )
 Chemical Oxygen Demand (COD)
– This is used to determine the oxygen equivalent of the
organic matter that can be oxidized by a strong
chemical oxidizing agent e.g. Potassium dichromate in
an acid medium.
– In general the COD of a waste will be greater than the
BOD5 because more compounds can be oxidized
chemically than can be oxidized biologically.
– BOD5 is typically less than ultimate BOD (which is less
than COD) except for totally biodegradable waste.
– The COD test can be conducted in about and hour
– The result can be correlated with BOD5 which can be
used to aid in the operation and control of the
wastewater treatment plant.
 Effects of BOD on the River Water
DO Sag Curve

• The concentration of dissolved oxygen in a river

is an indicator of the general health of the river.
• All rivers have some capacity for
self-purification.
• As long as the discharge of oxygen-demanding
wastes is well within the self-purification
capacity, the DO level will remain high, and a
diverse population of plants and animals,
including game fish, can be found.
• As the amount of waste increases, the
self-purification capacity can be exceeded,
causing detrimental changes in plant and animal
life.
• The stream loses its ability to cleanse itself, and
the DO level decrease,
• When the DO drops below about 4 to 5 mg/L
most game fish will have been driven out.
• If the DO is completely removed, fish and other
higher animals are killed or driven out, and,
extremely noxious conditions result.
• The water becomes blackish and foul-smelling
as the sewage and dead animal life decompose
under anaerobic conditions (i.e., without
oxygen).
 Effects of BOD on the River Water (contd.)
• One of the major tools of water
quality management in rivers is
assessing the capability of stream to
absorb a waste load.
• This is done by determining the
profile of DO concentration
downstream from a waste
discharge.
• This profile is called the DO sag
curve because the DO
concentration dips as
oxygen-demanding materials are
oxidized and then rises again further
downstream as the oxygen, is
replenished from the atmosphere
and photosynthesis.
• The biota of the stream are often a
reflection of the dissolved oxygen
conditions in the stream.
 Effects of BOD on the River Water (contd.)
Mass-balance for BOD and DO Mixing.
• Mass of DO in wastewater = QWDOW
• Mass of DO in river = QrDOr
• Where QW = volumetric flow rate of wastewater (m3/s)
• Qr = volumetric flow rate of the river (m3/s)
• DOW=dissolved oxygen concentration in the wastewater (mg/L)
• DOr = dissolved oxygen concentration in the river (mg/L)

• The mass of DO in the river after mixing equals the sum of the mass fluxes.
Mass of DO after mixing =QWDOW + QrDOr
For ultimate BOD (BODu),
Mass of BOD after mixing = QWLW+QrLr
LW = ultimate BOD of the wastewater (mg/L)
Lr = ultimate BOD of the river (mg/L)
 Effects of BOD on the River Water (contd.)

• The concentration of DO and BOD

after mixing are the respective
masses per unit time divided by
the total flow rate( i.e. sum of river
flow and wastewater flows)

QW DOW  Qr DO r
DO 
QW  Qr
QW LW  Qr Lr
La 
QW  Qr

• La is the initial ultimate BOD after

mixing.
DO Sag Curve
Cumulative Oxygen Supply + Demand
Plotting the two kinetic equations
separately on a cumulative basis
and adding these graphically
produce the DO sag curve
 Streeter-Phelps’ Model*

Mass Balance for the Model

Not a Steady-state situation
rate O2 accum. = rate O2 in – rate O2 out + produced – consumed

Kinetics
Both reoxygenation and deoxygenation are 1st order

* Streeter, H.W. and Phelps, E.B. Bulletin #146, USPHS (1925)

 Kinetics* for Streeter-Phelps’ Model

• Deoxygenation
L = BOD remaining at any time
dL/dt = Rate of deoxygenation equivalent to rate of BOD removal
dL/dt = -k1L for a first order reaction
k1 = deoxygenation constant, function of waste type and temp.

d [ L] C dL t

dt
 kL C0 L
  k  dt
0

L L kt
ln   kt or  e   L  L0 e kt
L0 L0
*See Kinetics presentation if unfamiliar with the mathematical processing
Developing the Streeter-Phelps Equation

Rate of reoxygenation = k2D

D = deficit in D.O.
k2 = reoxygenation constant*
Where

k2 
3.9v
1
2
1.025 (T  20)

1
2
– T = temperature of water, ºC
– H = average depth of flow, m
3 – ν = mean stream velocity, m/s
2
H
D.O. deficit
= saturation D.O. – D.O. in the water
There are many correlations for this. Typical values for k2 at 20 °C, 1/d (base e) are as follows:
small ponds and back water 0.10 - 0.23
The simplest one, used here, is from sluggish streams and large lakes 0.23 - 0.35
O’Connor and Dobbins, 1958 large streams with low velocity 0.35 - 0.46
large streams at normal velocity 0.46 - 0.69
swift streams 0.69 - 1.15
rapids and waterfalls > 1.15
Combining the kinetics

Net rate of change of

oxygen deficiency, dD/dt
dD/dt = k1L - k2D
where L = L0e-k1t

So,
dD/dt = k1L0e-k1t - k2D
 Integration and substitution
The last differential equation can be integrated to:
k1 Lo  k1t  k 2t  k 2t
D (e  e )  Do e
k 2  k1
It can be observed that the minimum value, Dc is achieved when dD/dt = 0:
dD
 k1 Lo e  k1t  k 2 D  0
dt
k1
Dc  Lo e k1t
k2 , since D is then Dc

Substituting this last equation in the first, when D = Dc and solving for t = tc:

1  k2  Do (k 2  k1 )  

tc  ln  1  
k 2  k1  k1  k1 Lo 
 Example: Streeter-Phelp

Wastewater mixes with a river resulting in a

BOD = 10.9 mg/L, DO = 7.6 mg/L
The mixture has a temp. = 20 C
Deoxygenation const.= 0.2 day-1
Average flow = 0.3 m/s, Average depth = 3.0 m
DO saturated = 9.1 mg/L
• Find the time and distance downstream at which the
oxygen deficit is a maximum
• Find the minimum value of DO
 Solution for Some Values Needed
• Initial Deficit
Do = 9.1 – 7.6 = 1.5 mg/L
(Now given, but could be calculated from proportional mix of river DO,
presumably saturated, and DO of wastewater, presumably zero)

• Estimate the reaeration constant:

k2 = 3.9 v½ (1.025T-20)½
H3/2

k2 = 3.9 x (0.3m/s)½ (1.02520-20)½ = 0.41 d-1

(3.0m)3/2
 Solution for Time and Distance

1  k 2  DOo (k 2  k1 )  
tc  ln  1  
k 2  k1  k1  k1 Lo  
1  0.41  1.5(0.41  0.2)  
 ln  1  
(0.41  0.2)  0.2  0.2 10.9  
 2.67days

xc  vtc  0.3m / s  86,400s / day  2.67days  69,300m

Note that the effects will be maximized almost 70 km downstream
 Solution for Maximum DO Deficiency

k1  k1t
Dc  Lo e
Note that this BOD could have been
calculated from mixing high-BOD
k2 wastewater with zero or near-zero BOD

0.2  (0.2day1 )(2.67days)

 (10.9 mg/L) e
0.41
 3.1 mg/L

The minimum DO value is 9.1-3.1 = 6 mg/L

Implication: DO probably not low enough for a fishkill, but if continued could
lead to species differentiation and discourage sensitives species like trout.