CVL100 Environmental Science

Lecture 4: Oxygen demanding substances

(Aug 9th, 2016)

by Dr. Arun Kumar (arunku@civil.iitd.ac.in)

Objective: To learn about oxygen demanding

substances

August 11, 2016 Arun Kumar 1

(arunku@civil.iitd.ac.in)
 This week
• Tuesday
• Wed
• Friday
• All three days

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 Parameters
• Oxygen demanding wastes

• Pathogens (parameters: indicators: fecal

coliforms, total coliforms, coliphage; direct
measurement of pathogens)

• Inorganic ions (arsenic ions; chromium ions,

nitrates; phosphates)

• Excess nutrients (ammonium ions; phosphates)

Drain discharging wastewater to stream
Qmix=Qstream+Qdrain
Cmix=(CstreamQstream+CdrainQdrain)/Qmix where C : parameter

stream (Qstream;Cstream)
Drain(Qdrain;Cdrain)
upstream

After mixing (Qmix;Cmix)

downstream

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(Source: Environmental Science: A Global Concern, 3rd ed. by W.P Cunningham and B.W. Saigo, WC Brown Publishers, © 1995)

Dissolved Oxygen Depletion

 Dissolved oxygen (DO)
• Important for aquatic species-need some minimum level of
DO
• Important for aquatic plants
• Lack of DO can result in development of anaerobic
conditions which can be result in anaerobic breakdown;
generation of methane and carbon dioxide
 Dissolved oxygen (DO)
• What are factors that affect the amount of dissolved oxygen
concentration in a river?
• What is the approximate dissolved oxygen concentration in
a healthy natural water body?
• Which are the steps in developing a DO sag curve?
• How is the lowest DO concentration point in the sag curve
called?
• If there was no change in the waste addition in a stream
throughout the year, will the DO be higher in winter or
summer?
 Oxygen Demanding Wastes-
measurement/estimation
• Estimated stoichiometrically by theoretical oxygen
demand (ThOD)

• Measured by oxygen demand potential

– biochemical oxygen demand (BOD)
– Nitrogenous oxygen demand (NBOD)
– chemical oxygen demand (COD)
 Oxygen Demanding Wastes

Oxygen-Demanding Wastes
• When organic substances are broken
down in water, oxygen is consumed
organic C + O2 → CO2

• For example:
CH3COOH + 2O2 => 2CO2 + 2H2O
C6H15O6N + 6O2 => 6 CO2 + 6 H2O + NH3
 Oxygen Demanding Wastes

Oxygen-Demanding Wastes
• High oxygen levels necessary for healthy
stream ecology.
• For example:
– trout require 5-8 mg/L dissolved oxygen (DO)
– carp require 3 mg/L DO
 Effect of Oxygen Demanding
Wastes on Rivers
• Amount of dissolved oxygen (DO) in water is the most
commonly used indicator of a river’s health.
• The solubility of oxygen depends on temperature,
pressure, and salinity and the dissolved oxygen
concentration in a healthy stream ranges from 7-9 mg/L.
• As DO drops below 4 or 5 mg/L the forms of life that can
survive begin to be reduced.
• In an extreme case, when anaerobic conditions exist,
most higher forms of life are killed.
 Factors Affecting Amount of DO
Available in Rivers
• Oxygen demanding wastes affect available DO
• Tributaries bring their own oxygen supply
• Photosynthesis adds DO during the day but the
same plants remove oxygen at night
• Respiration of organisms living in water as well as in
sediments remove oxygen
• In the summer rising temperatures reduce solubility
of oxygen
• In the winter oxygen solubility increases, but ice may
form blocking access to new atmospheric oxygen
 BOD
The amount of oxygen required by
microorganisms to oxidize organic
wastes aerobically is called biochemical
oxygen demand (BOD)
microorganisms
Organic matter + O2 CO2+ H2O + New Cells + Stable
Products
 BOD
• It is expressed in mg of oxygen required
per liter of wastewater (mg/L)
• The five-day BOD (BOD5) is the total
amount of oxygen consumed by
microorganisms during the first five days
of biodegradation
 Unseeded BOD test
• Put a sample of wastewater into a 300 mL bottle
• Incubate for 5 days at 20oC, in the dark, and with stopper on.
• Measure concentration of dissolved oxygen (DO) in the beginning,
and 5 days later
• Need at least 2 mg DO change in 5 days
• Usually need to dilute with water (oxygen saturated)
DOi − DO f
BOD5 =
P
P = dilution factor = volume of wastewater/total volume
DOi = initial dissolved oxygen
DOf = final dissolved oxygen
 Seeded BOD Test
• Take sample of waste, dilute with oxygen saturated water,
add nutrients and microorganisms (seed)
• Measure dissolved oxygen (DO) levels over 5 days
• Temperature 20°C, In dark (prevents algae from growing)
• Final DO concentration must be > 2 mg/L
• Need at least 2 mg/L change in DO over 5 days

(DOi − DO f ) - (Bi − B f )(1− P)

BOD5 =
P
P = dilution factor = volume of wastewater/total volume
DOi and DOf = initial and final (5 d) DO conc. of diluted sample
Bi and Bf = initial and final (5 d) DO conc. of seeded diluted water (blank)
 Example 1
• A BOD test was conducted in the
laboratory using wastewater being
dumped into Lake Spartan. The
samples are prepared by adding 3 mL
of wastewater to the 300 mL BOD
bottles. The bottles are filled to
capacity with seeded dilution water.
 Example 1

Time Diluted Blank Seeded

(days) sample Sample DO
DO (mg/L) (mg/L)
0 7.95 8.15
1 3.75 8.10
2 3.45 8.05
3 2.75 8.00
4 2.15 7.95
5 1.80 7.90
 Example 1

700

600

500
BOD (mg/L)

400

300

200

100

0
0 1 2 3 4 5 6
time (days)
 Modeling BOD, Lt and L0

6
5
Conc. (mg/L)

BOD exerted (BODt)

4 (organic matter oxidized)
3
BOD remaining (Lt)
2 (organic matter remaining)
1
0
0 10 20 30
Time (days)
 Modeling BOD, Lt and L0

(ultimate carbonaceous
L
0 oxygen demand)
8
Conc (mg/L)

6 L0- Lt = BODt
4

2 Lt (BOD remaining)

00 5 10 15 20 25 30
Time (days)
 Modeling BOD, Lt and L0

At any time, Lo = BODt + Lt (ultimate BOD equals the amount of DO

demand used up and the amount of DO that could be used up eventually)

BOD t = L 0 − L t
− kt
• Replace Lt using: L t = L oe
− kt
• To give: BOD t = L o − L o e

− kt
• Simplified to: BOD t = L o (1− e )
 Chemical Oxygen Demand
• Chemical oxygen demand - similar to
BOD but is determined by using a strong
oxidizing agent to break down chemical
(rather than bacteria)
• Still determines the equivalent amount of
oxygen that would be consumed
• Value usually about 1.25 times BOD
 COD measurement

• Potassium dichromate is a strong oxidizing

agent and it can be used to prepare
solution of exact normality.
• CnHaObNc+d Cr2O72- + (8d+c) H+ => nCO2
+[(a+8d-3c)/2]H2O+c NH4+ +2dCr3+ (1)
• Here d=(2n/3)+(a/6)-(b/3)-(c/2)

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 Nitrogenous Oxygen Demand
• So far we have dealt only with carbonaceous demand
(demand to oxidize carbon compounds)
• Many other compounds, such as proteins, consume
oxygen
• Additional oxygen demand required when nitrogen
compounds are oxidized
Nitrification (microorganisms convert ammonia to nitrite)
2 NH3 + 3O2 → 2 NO2- + 2H+ + 2H2O
2 NO2- + O2 → 2 NO3-

Overall reaction:
NH3 + 2O2 → NO3- + H+ + H2O
 NH3 + 2O2 → NO3- + H+ + H2O

• NBOD = oxygen needed to convert NH3 to NO3-

• Theoretical NBOD can be determined using the

ratio:
 32 g 
(2 moles ) 
g oxygen used  mole  4.57 g O2
= =
g of nitrogen used  14 g  g N
(1 mole ) 
 mole 
 6
5
Conc. (mg/L)

BOD exerted (BODt)

4 (organic matter oxidized)
3
BOD remaining (Lt)
2 (organic matter remaining)
1
0
0 10 20 30
Time (days)
 Questions to think

• Why do the COD analysis and BOD

analysis give different results for the same
waste?
• What could be inferred from the following
samples concerning the relative ease of
biodegradability: Sample A (5-d
BOD/COD=24/30) and Sample B (5-d
BOD/COD=10/50)?

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 River Water Quality

Objective: To introduce river water quality

concepts and fundamentals

August 11, 2016 Arun Kumar 29

(arunku@civil.iitd.ac.in)
Implications of wastewater discharge
on river water quality
• What happens when wastewater is discharged in river?
• Which parameter to study first?
• How to track trend of important parameter with time and
distance along the movement of river?
• What other parameters to measure?
(Source: Environmental Science: A Global Concern, 3rd ed. by W.P Cunningham and B.W. Saigo, WC Brown Publishers, © 1995)

Dissolved Oxygen Depletion

 Modeling DO in a River
• To model all the effects and their
interaction is a difficult task
• The simplest model focuses on two
processes:
– The removal of oxygen by microorganisms
during biodegradation (de-oxygenation)
– The replenishment of oxygen at the
interface between the river and the
atmosphere (re-aeration)
Dissolved Oxygen Sag Curve
 Mass Balance Approach
• River described as “plug-flow reactor”

• Mass balance
• Oxygen is depleted by BOD exertion (de-
oxygenation)
• Oxygen is gained through re-aeration
 Steps in Developing the DO Sag Curve
1. Determine the initial conditions
2. Determine the de-oxygenation rate from
BOD test and stream geometry
3. Determine the re-aeration rate from
stream geometry
4. Calculate the DO deficit as a function of
time
5. Calculate the time and deficit at the
critical point (worst conditions)
 1. Determine Initial Conditions

Mass Balance for Initial Mixing

Qw = waste flow (m3/s)

DOw = DO in waste (mg/L)
Lw = BOD in waste (mg/L)

Qr = river flow (m3/s) Qmix = combined flow (m3/s)

DOr = DO in river (mg/L) DO = mixed DO (mg/L)
Lr = BOD in river (mg/L) La = mixed BOD (mg/L)
 1. Determine Initial Conditions

a. Initial dissolved oxygen concentration:

QwDOw + Qr DOr
DO =
Qw + Qr
b. Initial DO deficit:
Da = DOs − DO

where:
Da=initial DO deficit (mg/L)
DOs=saturation DO conc.(mg/L)
 1. Determine Initial Conditions

Therefore, the initial deficit after mixing is

Qw DOw + Qr DOr
Da = DOs −
Qmix
where Da is the initial deficit (mg/L)

Note: DOs is a function of temperature,

atmospheric pressure, and salinity. Values
of DOs are found in tables.
 1. Determine Initial Conditions

Solubility of Oxygen in Water

(DOs = DOsaturation)
DOs is a function of temperature, atmospheric pressure
and salinity
 1. Determine Initial Conditions

c. Initial ultimate BOD concentration:

If, the BOD data for the waste or river are in
terms of BOD5, calculate L for each

BODt
L=
1 − e −kt
Therefore, initial ultimate BOD concentration

Qw Lw + Qr Lr
La =
Qw + Qr
 2. Determine de-oxygenation rate

2. Determine De-oxygenation Rate

rate of de-oxygenation = kdLt

where: kd = de-oxygenation rate coefficient (day-1)

Lt = ultimate BOD remaining at time (of
travel down-stream) t

− kd t
If kd (stream) = k (BOD test) and Lt = L0 e

rate of de - oxygentation = k d L0e − kd t

 3. Determine re-aeration rate

3. Determine Re-aeration Rate

rate of re-aeration = kr D

kr = re-aeration constant (time -1)

D = dissolved oxygen deficit (DOs-DO)
DOs = saturated value of oxygen
DO = actual dissolved oxygen at a given
location downstream
 3. Determine re-aeration rate

• O’Connor-Dobbins correlation:
1/ 2
3.9u
kr = 3/ 2
h
where kr = re-aeration coefficient @ 20ºC (day-1)
u = average stream velocity (m/s)
h = average stream depth (m)
• Correct rate coefficient for stream temperature
k r = k r , 20 ΘT − 20
where Θ = 1.024
 4. Calculate DO deficit as a function of time

4. DO as function of time (Streeter-Phelps

equation or oxygen sag curve)
• Rate of increase of DO deficit = rate of
deoxygenation – rate of reaeration
dD
= k d Lt − k r D
dt
• Solution is:
k d Lo − kd t
Dt =
kr − kd
( ) ( )
e − e − k r t + Da e − kr t
 4. Calculate critical time and DO

5. Calculate Critical time and DO

Critical Point = point where steam conditions are at their worst

1  kr  k r − k d 
tc = ln  1 − Da 
kr − kd  kd  k d La 

k d La − kd tc
Dc =
kr − ka
e ( )
− e − kr tc + Da e − k r tc

D = dissolved oxygen deficit

 Example 1

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 Parameter Measurements

Objective: To introduce parameters to indicate

pollution and methods to measure them

August 11, 2016 Arun Kumar 52

(arunku@civil.iitd.ac.in)
 Salts

Salts
• Dissolved solids, or salts, may be present as any
number of ions
– cations: Na+, K+, Mg2+, Ca2+
– anions: Cl-, SO42-, HCO3-
• Typically measures as total dissolved solids (TDS)
• Water classification
– freshwater <1500 mg/L TDS
– brackish water 1500 – 5000 mg/L
– saline water >5000 mg/L
– sea water 30-34 g/L
 Salts

Salts
• Sources
– industrial discharges
– deicing
– evaporative losses
– minerals
– sea water intrusion
• Effects
– natural fresh water population threatened
– limits use for drinking
– crop damage/soil poisoning (cannot use for
irrigation)
 Suspended Solids

Suspended Solids
• Organic and inorganic particles in water are
termed suspended solids
• May be distinguished from colloids, particles that
do not settle readily
• Problems
– sedimentation
• Sources – may exert oxygen demand
– storm water – primary transport
mechanism for many metals,
– wastes organics and pathogens
– erosion – aesthetic
– complicates drinking water
treatment
 Solids
• Used in controlling biological process; drinking water
quality, etc.
• Gravimetric analysis is based on the determination of
constituents or categories of materials by measurement
of their weight.
• Three analytic operations:filtration, evaporation, and
combustion.
– Filtration is used to separate suspended or particulate (non-filterable)
fraction from dissolved or soluble (filterable) fractions.
– Evaporation separates water from material dissolved or suspended in it.
– Combustion differentiates between organic and inorganic matter.
Organic matter will be destroyed completely by burning at 550oC for 30
min.
• AWWA, WEF, APHA, 1998, Standard Methods for the Examination of Water
Ref:
and Wastewater (2540 D. Total Suspended Solids Dried at 103-105oC; 2540 E.
Augustand
Fixed 11, 2016
Volatile Solids Ignited at 550oC) 56
 Total Suspended Solids
Procedure:
• Filter samples (50 ml); Oven dry at 103oC for 30 min ; At this stage
all water will be evaporated and only suspended solids will be
retained on filter.

• Total suspended solids

mg total suspended solids =1000*(A-B)/(sample volume in mL) (1)

Weight crucibles (mass=C) and then weight crucible and filter (total
mass=E); Initial filter weight=B; Weigh filters now (mass =A g).

August 11, 2016 57

 Volatile and Fixed Suspended Solids
• Put crucibles with filter paper in muffle furnace and Ignite at 550oC
for 15 min. At this stage all volatile components of solids will be
volatilized and only fixed inert solid materials will be left in crucible.
Weigh crucible after proper cooling (mass=D g).

• Volatile suspended solids (F) :

mg volatile suspended solids/L =1000*(E-D)/(sample volume in mL) (2)

• Fixed suspended solids (G) :

mg volatile suspended solids/L =1000*(D-C)/(sample volume in mL)
•
•

August 11, 2016 58

 3. Organics

Volatile Organic Compounds (VOCs)

• Chlorinated solvents
– C1 and C2 aliphatics

Cl Cl Cl H Cl H
Cl C Cl H C Cl Cl C C H C C
Cl Cl Cl H H H

carbon tetrachloride chloroform 1,1,1-trichloroethane vinyl chloride

– widely used in degreasing, dry cleaning, extraction

– somewhat soluble, volatile, difficult to degrade
 3. Organics

Pesticides (hydrophobic organic

compounds)
• Organochlorine Insecticides: were commonly used
in the past (e.g. DDT and chlordane).
• Organophosphate Pesticides: most are
insecticides, some are very poisonous (they were
used in World War II as nerve agents)
• Carbamate Pesticides: affect the nervous system
• Pyrethroid Pesticides: were developed as a
synthetic version of the naturally occurring pesticide
pyrethrin, which is found in chrysanthemums
 3. Organics

Polycyclic Aromatic Hydrocarbons (PAHs)

Polycyclic aromatic
hydrocarbons (PAHs) are a
group of over 100 different
naphthalene anthracene phenanathrene
chemicals that are formed
during the incomplete
burning of coal, oil and gas,
garbage, or other organic
substances.
pyrene benzo[a]pyrene

They are potent carcinogens, hydrophobic organic

compounds and they tend to associate with particles.
 3. Organics

Polychlorinated biphenyls (PCBs)

Cl

Cl

Cl
Biphenyl 2,3',4-trichlorobiphenyl

• Polychlorinated biphenyls are mixtures of individual chlorinated

compounds (known as congeners).
• PCBs are either oily liquids or solids that are colorless to light
yellow.
• PCBs have been used as coolants and lubricants in
transformers, capacitors, and other electrical equipment.
• The manufacture of PCBs was stopped in the U.S. in 1977.
• They are hydrophobic and they bio-accumulate in the food chain.
 3. Organics

Volatile Organic Compounds (VOCs)

• Petroleum constituents:
– benzene and substituted benzenes
CH3 CH2CH3 CH3

CH3
Benzene Toluene Ethylbenzene m-Xylene

– prevalent in gasoline, diesel fuel, heating oil

– most easily transported, slow degradation, toxic
 3. Organics

Volatile Organic Compounds (VOCs)

• Oxygentated gasoline additives
CH3
CH3 C O CH3
CH3
Methyl tertiary butyl ether (MTBE)

– added to gasoline to improve air quality

– very soluble, resistant to degradation, toxic
– attempt to solve one problem caused another
(spills)
 Why do we measure in EnvEngg.
• Quality of what we • Air
want to treat – Emissions
– Ambient
• Quality of finished
product • Water & Wastewater
– Supply/raw
• Performance of – During treatment
process – Discharge/Distribution
• Environmental/health • Land
impact – Solid & Haz Waste
– Leachate impacts
– Air impacts
August 11, 2016 Arun Kumar 65
Courtesy: Dr. Charles Haas (arunku@civil.iitd.ac.in)
 Water Test Kit

Thermometer
August 11, 2016 Arun Kumar
Test strip in Water 66
Courtesy: Shamia Hoque (arunku@civil.iitd.ac.in)
 August 11, 2016 Arun Kumar 67
Courtesy: Shamia Hoque (arunku@civil.iitd.ac.in)