Effluent Control 1

Y.P.
Ting
CN4240R Processes for Effluent Control
Department of Chemical & Biomolecular Engineering

Instructor: A/Prof Y.P. Ting
Office: E5-02-20
Telephone: 6516-2190
Email: [email protected]

Module description:
Provides students with a working knowledge of unit operations and
processes for the control of effluent from chemical process industries.
Overview of the characteristics of effluent from chemical plant operations, and its
impact on the environment. Applications of processes (physical, chemical and
biological) for the treatment of effluent from plant facilities.

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Learning Outcomes:
1. Describe the important physical, chemical and biological characteristics of
trade, domestic and industrial effluent.
2. Identify the sources of pollutants and their environmental impact.
3. Explain the working principles of the various effluent treatment technologies
(physical, chemical and biological).
4. Evaluate the various treatment options.
5. Apply design equations for the design of various primary, secondary and
tertiary treatment processes and operations

Recommended/Reference books:
1. Reynolds, T.D, and Richards, P.A., Unit Operations and Processes in
Environmental Engineering, PWS Publishing Company, 2nd Ed, 1996.
2. Eckenfelder, W. W. Jr., Industrial Water Pollution Control, 3rd Ed, McGraw-Hill,
2000.
3. Peavy, H.S., Rowe, D.R. and Tchobanoglous, G. Environmental Engineering,
McGraw-Hill, 1986.
4. Davis, M.L. and Cornwell, D.A., Introduction to Environmental Engineering, 4th
Ed, McGraw-Hill, 2008.
5. Metcalf & Eddy Inc., Wastewater Engineering: Treatment Disposal Reuse, 4th Ed,
2003, McGraw-Hill.

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Requirements and Grading:
Examination: 22 Nov 2014 (Sat) 9:00 am. Closed book, 2.5hr,
Tutorial: Tutorial assignments will be given throughout the semester
Grading: Final grades will be calculated according to the following scale:
Term Paper 10%
Mid-term / End-of-term Quizzes 30%
Final Exam 60%
http://www.lyricsmode.com/lyrics/a/albert_hammond/down_by_the_river.html
McQ and short questions
Cheat sheet

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1 Trade, Industrial and Domestic Effluent - GENERAL CONSIDERATIONS
Characteristics of wastewater
Sources of Water Pollutants and Its Environmental Impacts
Biochemical & Chemical Oxidation Demand - calculations

2. PRETREATMENT AND PRIMARY TREATMENT
Screening and Degritting
Equalisation
Sedimentation

3. PHYSICO-CHEMICAL TREATMENT SYSTEMS
Flotation
Coagulation and Flocculation

4 BIOLOGICAL TREATMENT SYSTEMS
Microbial Growth and Metabolism
Application of Growth Kinetics to Treatment Processes
Aerobic Treatment Systems
Anaerobic Sludge Digestion

5. DISINFECTION

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Effluent: An outflow or discharge of liquid waste. (cf emission)
Industries: e.g. chemical, petrochemical, refinery, pulp & paper, textiles and dyes, soaps &
detergent, food & beverage, pharmaceutical, metal finishing & electroplating, semiconductors
& microelectronics. Difference in effluent characteristics.

Wastewater (or used water (PUB))
Greywater = w/w from sinks, showers, laundry (excluding toilet wastes).
Black water = w/w in contact with fecal matter. Fecal coliform 10
4
-10
7
/100 mL.

Pollutants - substances that have the potential to have negative effects on the natural
environment, to cause damage to infrastructure or harm to human health.

Agricultural wastewater pesticides, fertilizers and salts;
Municipal wastewater human sewage;
Power plants water discharged at high temperature;
Industrial wastewater wide range of chemical pollutants and organic wastes.

Water Pollution:
.. Presence of any material in water that is harmful to plants or animals, or affects its
taste and odor, or detracts from any use that can be made of it.
Alteration in the composition or condition of water directly or indirectly as a result of the
activities of men, so that it is less suitable for any or all the purposes for which it is suitable in
its natural state.
Metals are toxic
Color
Sewage treatment plant/waste
treatment plant name changed to
water reclamation plant
Indicator of bacteria
Waste consumes oxygen giving anaerobic conditions in
pipes. Hydrogen sulfide will be produced from bacteria.
H2S can be oxidized into sulphuric acid which corrodes
the pipes, "crown sewer."
Dissolved oxygen concentration
of high temp water is lower

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Uses of water in industry: Raw material, Cleaning or reagent solvent, Heat transfer
medium, Conveyance medium, Reaction product, and Fire extinguishing
medium.

Wastewater combination of the liquid or water-carried wastes removed from
residences, institutions, and commercial and industrial establishments, together
with such groundwater, surface water, and stormwater as may be present.

Unit Operations contaminant removal by physical forces.
Unit Processes biological/chemical reactions.

An effluent treatment system is composed of a combination of unit operations
and unit processes designed to reduce certain constituents of w/w to an
acceptable level. For public health and the environment. Many different
combinations are possible. (See diagram).

To protect public health and the environment need knowledge of
constituents of concern,
impacts of constituents,
transformation and long term fates of constituents,
treatment methods, and
beneficial use, and appropriate disposal of solids/effluent after treatment.

Treatment to desired level
without over treatment
Singapore, need not remove nitrogen and
phosphorus. No specific treatment to reduce it.
Of concern if disposed into a closed water body
with no dilution

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Code of Practice on Pollution Control (3
rd
ed; amendments Feb 2004)
http://www.nea.gov.sg/cms/pcd/coppc_2002.pdf
(See Appendix 9)

Public Utilities Board, Singapores national water agency.
http://www.pub.gov.sg/Pages/default.aspx

Glossary of Terms compiled by PUB
http://www.pub.gov.sg/atoz/Pages/default.aspx

Water Reclamation Plants (WRP)
http://www.pub.gov.sg/products/usedwater/Pages/WaterReclamationPlants.aspx

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Inputs: (i) Point Source, (ii) Diffuse source

Point Source
Well-defined point of discharge. (Usually continuous).
Can be located and identified with a particular discharger.
Principal source: (i) municipal point source, and (ii) industrial
discharges

Non-point Source
Origin of discharge is diffused, i.e. not possible to relate the
discharge to a specific and well-defined location. (Usually
transient in time).
Principal source: Agriculture, silviculture, atmospheric, urban
and suburban runoff, and groundwater.
Others: groundwater infiltration, drainage from abandoned
mines and construction activities, leaching from land disposal of
solid wastes.

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Classification of Water Pollutants:

Pathogenic organisms
Oxygen-demanding substances
Plant nutrients
Toxic organics
Inorganic chemicals
Sediments
Radioactive substances
Heat
Oil
Point source
Diffuse source
Will get oxidized as substance is
unstable. Reduces other substances,
eats oxygen
Might kill the bacteria, which
reduces the BOD. However not all
bacteria might be killed. Shows
overlapping factors

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Preliminary treatment removal of w/w constituents (e.g. rags, sticks, floatables,
grit and grease) that may cause maintenance or operational problems.

Primary treatment removal of suspended solids or organic matter from w/w.
Sedimentation, used to remove the floating & settleable solid in w/w.

Secondary treatment removal of biodegradable organic matter (in solution or
suspension). Biological & chemical processes. Usually biological conversion of
dissolved & colloidal organics into biomass, which can subsequently be removed by
sedimentation.

Tertiary treatment additional combination of unit operations & processes that are
used to further remove constituents (e.g. N, P) which are not removed by
secondary treatment.

Advanced Wastewater Treatment operations and processes that are used to
remove more contaminants than are taken out by conventional treatment. NOT
synonymous with tertiary treatment. Tertiary treatment is a 3rd step; advanced
wastewater treatment may replace unit operations and processes in
secondary or even primary treatment.

Easy removal
Solubles
Biomass - solids

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Raw sewage
from sewers
Bar screen
Grit
chamber
Settling tank Aeration tank Settling tank
Chlorine
disinfection tank
Sludge
Sludge digester
Activated sludge
Air
pump
(kills bacteria)
To river, lake,
or ocean
Sludge drying bed
Disposed of in landfill or
ocean or applied to cropland,
pasture, or rangeland
Primary Secondary

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COD BOD SS NH3 (N) PO
4
(P)

600 300 500 40 -

300 150 150 50 -

100 20 20 50 3-14

15 <5 <5 10-15 1-2

Screening
Grit removal
Primary settlement/sedimentation
Secondary biological treatment
Secondary settlement
Tertiary treatment

Surface water discharge
Typical sewage effluent characteristics at various treatment stages
Levels in mg/l

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Processes for
specific pollutant

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Fixed-Inorganic
Volatile-Organic

Volatile has higher oxygen demand.
Bacteria eats the carbon to grow
1 question of BOD5 in finals
Nitrates are the most oxidized nitrogen.
Ammonia is the least oxidized.
Different oxygen demand.
Haemoglobin has higher affinity for nitrites
(NO2-). Competes with oxygen to transport
around the body

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Nitrogen is a component of amino acids and urea. Amino acids are the building blocks of all proteins. Proteins comprise not only
structural components such as muscle, tissue and organs, but also enzymes and hormones essential for the functioning of all living
things. Urea is a byproduct of protein digestion. We use the term "organic nitrogen" to describe a nitrogen compound that had its
origin in living material. The nitrogen in protein and urea is organic nitrogen. Organic nitrogen can enter septic systems as bodily
wastes, discarded food material, or as components of cleaning agents.. Amines and amides

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CHARACTERISTICS SOURCES
PHYSICAL PROPERTIES
Colour Domestics and industrial wastes, natural decay of
organic materials
Odour Decomposing wastewater, industrial wastes
Solids Domestic waster supply, domestic and industrial
wastes, soil erosion, inflow/infiltration.
Temperature Domestic and industrial wastes
CHEMICAL CONSTITUENTS
Gases
Hydrogen sulphide Decomposition of domestic wastes
Methane Decomposition of domestic wastes
Oxygen Domestic water supply; surface water infiltration
BIOLOGICAL CONSTITUENTS
Animals Open watercourses and treatment plants
Plants Open watercourses and treatment plants
Protists
Bacteria Domestic water supply; surface-water infiltration,
treatment plants
Viruses Domestic wastes

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CHARACTERISTICS SOURCES
CHEMICAL CONSTITUENTS
Organic
Carbohydrates Domestic, commercial and industrial wastes
Fats, oils and grease Domestic, commercial and industrial wastes
Pesticides Agricultural wastes
Phenols Industrial wastes
Proteins Domestic, commercial and industrial wastes
Priority pollutants Domestic, commercial and industrial wastes
Surfactants Domestic, commercial and industrial wastes
Volatile organic cpds Domestic, commercial and industrial wastes
Others Natural decay of organic materials
Inorganics
Alkalinity Domestic wastes, domestic water supply, groundwater infiltration
Chlorides Domestic wastes, domestic water supply, groundwater infiltration
Heavy metals Industrial wastes
Nitrogen Domestic and agricultural wastes
pH Domestic, commercial and industrial wastes
Phosphorus Domestic, commercial and industrial wastes; agricultural runoff
Priority pollutants Domestic, commercial and industrial wastes
Sulphur Domestic water supply; Domestic, commercial and industrial wastes
Priority cause it
is dangerous or
carcinogenic...

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Important contaminants of concern in effluent treatment

Contaminants Reason for importance
Suspended solids Can lead to the development of sludge deposits and
anaerobic conditions when untreated wastewater is
discharged in the aquatic environment.
Biodegradable
organics
Composed principally of proteins, carbohydrates and fats.
Measured in terms of BOD (Biochemical Oxygen
Demand) and COD (Chemical Oxygen Demand). If
discharged untreated to the environment, their biological
stabilization can lead to the depletion of natural oxygen
resources and to the development of septic
conditions.
Pathogens Communicable diseases can be transmitted by the
pathogenic organisms in wastewater.
Nutrients Nitrogen and phosphorus, along with carbon, are
essential nutrients for growth. When discharged to the
environment, these nutrients can lead to growth of
undesirable aquatic life. When discharged in excessive
amounts on land, they can lead to the pollution of
groundwater.
Blocks oxygen flow, anaerobic
conditions lead to methane and
other gas formation
Lead to bacteria growth

Blue baby syndrome, nitrites
block haemoglobins ability to
bind to oxygen

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Important contaminants of concern in effluent treatment (contd)

Contaminants Reason for importance
Priority pollutants Organic and inorganic compounds selected on the basis
of their known or suspected carcinogenicity,
mutagenicity, teratogenicity, or high acute toxicity.
Refractory organics
(resistant to treatment)
Compounds that resist conventional methods of
wastewater treatment. Typical examples include
surfactants, phenols and agricultural pesticides .
Heavy metals Usually added to wastewater from commercial and
industrial activities and may have to be removed if the
wastewater is to be reused.
Dissolved inorganics Inorganic constituents such as Ca
2+
, Na
+
and SO
4
2-

added to the original domestic water supply as a result of
water use, and may have to be removed if the w/w is
to be reused .
PP includes heavy metals, pesticides, PAHs, PCBs.
Coliform bacteria: a group of bacteria commonly found in intestines of animals and
humans beings. Coliform count - hygiene indicator. Membrane filtration, and filters
placed onto selective agar. After incubation, plates are counted and suspect colonies
confirmed with confirmation tests (lactose fermentation)
Contaminated by feces

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Total solids (TS) test quantifies all solids in the water suspended solids,
dissolved solids organic, inorganic.

Filtration does not divide solids into suspended & dissolved fraction. Some
colloids may pass through the filter, & be measured with the dissolved solids,
while some dissolved solids may absorb onto filter material. Depends on
size & nature of solids
pore size & surface characteristics of filter material.

Therefore, use of the terms
FILTERABLE RESIDUES (relates more to dissolved solids)
- NON-FILTERABLE RESIDUES (relates more to suspended solids)

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Ionic
Use imhoff cone, to measure
settlement in 30mins

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Evaporation and
drying at 105 C
Evaporation
and drying at
105 C

Ignition at 500 C
TS = TVS + TFS
TS = organic + inorganic

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Laboratory procedure to determine total solids and
total volatile solids concentrations of a water or wastewater sample.
Laboratory procedure to determine the total suspended-solids and
volatile suspended-solids concentrations of a water or wastewater sample.

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.
Suspended solids (SS)
Sources:
Natural inorganic particles (clay, silt, and soil constituents)
- organic solids (plant fibers and biological solids, dead
vegetation and animals);
Domestic inorganic and organics (large amounts);
Industrial various inorganic and organic, immiscible liquids such as
oil, grease, etc.

Impact:
Aesthetically displeasing;
Increase turbidity; aquatic plants unable to photosynthesize, thus
lowering dissolved oxygen (DO) level. Microbes use SS as food, thus
lowering DO level;
Adsorption sites for chemical and biological agents;
Some organic solids may be degraded to form by-products; Biologically
active solids may include disease-causing organisms.

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Turbidity
Measure of extent to which light is either absorbed or scattered by
suspended material in water. Determination of solids in potable water
supplies, natural waters, and secondary effluents.

Sources:
Natural surface water erosion of colloidal materials, e.g.
clay, silt, rock fragments, etc. Also, m/o contribute to turbidity;
Household & industrial wastewaters - (e.g. soaps, detergents,
emulsifying agents, etc).

Impact Colloidal matter associated with turbidity provides adsorption sites
for chemicals that may be harmful, or cause undesirable tastes & odours.
Also, disinfection of turbid water difficult because of adsorptive
characteristics of some colloids, & also because the solids may partially
shield the m/o from the disinfectant. In natural water, turbidity may affect
light penetration, & hence photosynthesis in streams & lakes.

Measurement (i) Formazin turbidity unit FTU; (ii) nephelometry turbidity
unit NTU

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Colour
Pure water is colourless. Colour is caused by foreign organic and inorganic
materials.

Sources:
Natural organic debris in water such as leaves, weeds or wood
resulting in tannins, humic acids, and humates: yellowish-brown
hues. Iron oxides (reddish), and manganese oxides (brown or
blackish)
Industrial wastewaters operations may add substantial
colour, e.g. textiles and dyes

Impact:
Aesthetically displeasing;
Organic compounds causing colour may exert a chlorine demand,
and cause taste and odour problems.
May contribute to disinfection by-product which are carcinogenic
(e.g. THMs).

Tri halo methanes

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Odours
Caused by gases produced from decomposition of organic matter. Most
characteristic odour of stale w/w is H
2
S, produced by anaerobic m/o that
reduces sulphates to sulphides.

Major categories of offensive odors
Compound Typical formula Odor quality
Amines CH
3
NH
2
, (CH
3
)
3
N Fishy
Ammonia NH
3
Ammoniacal
Diamines
NH
2
(CH
2
)
4
NH
2
,
NH
2
(CH
2
)
5
NH
2
Decayed flesh
Hydrogen sulfide H
2
S Rotten eggs
Mercaptans CH
3
SH, CH
3
(CH
2
)
3
SH Skunk
Organic sulfides (CH
3
)
2
S, CH
3
SSCH
3
Rotten cabbage
Skatole C
8
H
5
NHCH
3
Fecal

Threshold Odour Number: ratio by which sample has to be diluted for the
odour to become virtually unnoticeable. E.g. dilute a 50 ml sample to 200 ml
=> TON = 4.
Source of smell from n and S,
remove them to remove smell

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Temperature

Sources: Temperature of w/w is normally higher than natural and
subsurface water due to industrial operations (e.g. for cooling).

Impact: Effect on (i) aquatic life; (ii) chemical reactions & reaction
rates; (iii) suitability of the water for beneficial uses; (iv)
thermal stratification in lakes

Solubility of O
2
in water decreases with | temperature. Increase in rates
of biochemical reaction that accompanies an increase in temperature,
combined with the decrease in dissolved oxygen (D.O.) can cause
serious depletion of D.O. concentration.

Warm water also leads to | growth of algae, with natural secretion of oils
by algae in the mats, & decay products of algae lead to taste & odour
problems.

Sudden changes in temperature can affect mortality of aquatic life.
(Also, species distribution, e.g. 20 25
o
C diatoms, 30 35
o
C green
algae, > 35
o
C blue green algae)
TER: T<45
o
C
Warm water tends to rise to the
surface, leads to poor mixing of
the water. Affects solubility
Growth in algae and decrease in DO compounds the effect of oxygen level in water

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Water Quality parameters
Gross measures no distinction made between individual physical,
chemical and biological species. E.g. suspended solids, odour, colour,
BOD. Most easily measured and interpreted.

Specific measures necessary when single characteristic (e.g. toxic
compound, heavy metal ion, or species of fish) is of concern. Applies to
particular uses.

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Chemical Characteristics

Total Dissolved Solids (TDS)
Source: Solvent action of water on solids, liquids and gases results in the
formation of TDS.

Impact:
Displeasing colour, odour and taste problems.
Toxicity and carcinogenicity.
Suitability of use of water for industrial operations.

pH
Range conducive to biological life is narrow & critical.
Metal specification = f (pH) e.g. carcinogenic of Cr
6+
vs Cr
3+

Impact:
Affects aquatic animals and plants sensitive to pH.
Metal speciation (and toxicity).
Chemical reactions as well as treatment processes.

Waste Must be within pH 6-9

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Nitrogen Inorganic NH
3
, NO
3
-
, NO
2
-
Organic -- Urea, proteins, amino acids
Phosphates orthophosphate
PO
4
3-
, H
3
PO
4
, H
2
PO
4
-
, HPO
4
2-
Sulphur SO
4
2-
, H
2
S, SH
-
, S

TN = ON + NH
4
+
N + NO
2
N + NO
3
N
TKN = ON + NH
4
+
N Kjeldahl

TKN = 40% Organic + 60% Free Ammonia
Typical concentrations:
Ammonia-N = 10-50 mg/L
Organic N = 1035 mg/L

Impacts of Nitrogen
Impairs quality of receiving stream (Eutrophication: N & P)
Taste & odour (for drinking water); DO depletion (hypoxia), algal mats; toxins & fish
kills
Decreases chlorination efficiency (NH
4
+
)
Impairs suitability for water reuse
NH
4
+
toxicity
Contaminates groundwater (nitrate);
Drinking water; Methemoglobinemia (Blue Baby Syndrome)
WHO's Guideline Value for Drinking water: nitrate= 50 mg /l ; nitrite = 3mg/l
Total kjeldahl nitrogen
Eu good
Trophos food
When algae dies

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Algae-filled Chaohu Lake,
Hefei, Anhui (2009)
Generally accepted BOD/N/P mass
ratio required for biological treatment is
100/5/1 (i.e. 100 mg/l BOD to 5 mg/l
Nitrogen to 1 mg/l phosphorus).

Raw sanitary w/w has a ratio 100/17/3;
after primary settling ratio is 100/23/5,
thus there is abundant N and P for
microbial growth.

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Metals
Toxic metals: aluminium,arsenic, cadmium, chromium, cobalt, copper, lead,
mercury, nickel, zinc, etc,
Essential metals: serves biological functions, e.g. copper, zinc, etc
Metal toxicity; concentration and speciation.
Metals - non-biodegradable.

Zooplankton
0.123 ppm
Rainbow smelt
1.04 ppm
Water
0.000002 ppm
Phytoplankton
0.0025 ppm
Lake trout
4.83 ppm
Herring gull
124 ppm
Herring gull eggs
124 ppm
Bioaccumulation

Biomagnification
DDT (dichlorodiphenyltrichloroethane)

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Gases
Gases commonly found in untreated water
N
2
, O
2
, CO
2
common in the atmosphere, & found in all waters exposed to
air
H
2
S, NH
3
, CH
4
derived from decomposition of organic matter in w/w

D.O. required for respiration of aerobic m/o. & all other aerobic life forms.

O
2
slightly soluble in water; actual quantity in w/w depends on:
solubility of the gas
partial pressure of the gas in the atmosphere
temperature
purity of the water (e.g. a fixed temperature, solubility of O
2
+ with |
chloride conc.)

H
2
S formed from the decomposition of organic matter containing sulphur,
or from the reduction of mineral sulphites & sulphates.
Colourless, inflammable, rotten egg smell.
Blackening of w/w & sludge usually the result of H
2
S + Fe FeS

CH
4
principal by-product. Colourless, odourless, combustible & high fuel
value

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Standard Method of Analysis of Water and Wastewater

Standard methods for the analysis of most components in w/w.
Developed over many years & include:
Sampling procedure
Sample storage
Test methods
Interference and methods of overcoming these

Analytical procedures - see STANDARD METHODS FOR THE
EXAMINATION OF WATER & WASTEWATER (American Public Health
Association, Washington, D.C.)

Sampling programme requirements:
Sample must be truly representative of the existing conditions
Time between collection and analysis should be as short as possible.
Appropriate preservation technique should be applied to slow down biological
and chemical changes.
Accurate and through sampling records

Solids or liquid

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Grab sample. A single sample

Composite sample. A mixture of grab sample at the same location but at
timed intervals. Where quality and quantity change with time.
(Volume taken in proportion to flow rate, e.g. grab sample of 100 ml for flow
of 5 L/s; and grab sample of 200 ml for flow of 10 L/s.)

Integrated sample. A mixture of grab sample at the same time but from
different locations. Gives information on average concentration of
parameters of the whole system to account for variation in depth and width
of the system.
(spatial vs temporal)

Preservation of samples. Analyse ASAP. Retard biological changes,
chemical changes, reduce loss of components by evaporation or
adsorption. Except for refrigeration, preservation is not recommended
unless absolutely necessary. Choice of containers (glass, plastic).
Location vs time
Avoid, as concentration might be very low.
Storage could cause major changes.
Especially priority pollutant

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Under heavy loads of pollution, the
D.O. level may drop to zero. This
results in noxious odors and very
unsightly conditions in the water. With
additional time and distance
downstream, the water will eventually
be reaerated and water quality will be
restored.

Oxygen sag curve shows the effect of
organic pollution on the D.O. levels in a
stream or river. After the organics
decompose, surface reaeration will
restore the original water quality.
Stream self-purification.
FACTORS FOR DO LEVEL SLOPE
Photosynthetic
Time of the day
Flow rate
Surface area/depth area

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Clean Zone
Decomposition
Zone
Septic Zone
Recovery
Zone
Clean Zone
Normal clean water organisms
(trout, perch, bass,
mayfly, stonefly)
Trash fish
(carp, gar,
leeches)
Fish absent,
fungi,
sludge
worms,
bacteria
(anaerobic)
Trash fish
(carp, gar,
leeches)
Normal clean water organisms
(trout, perch, bass,
mayfly, stonefly)
8 ppm
Dissolved
oxygen
(ppm)
Biological
oxygen
demand
8 ppm
Types of
organisms
Pollution in Streams
DO replenishes

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Oxygen requirement of a waste

Biochemical oxygen demand (BOD)
Chemical oxygen demand (COD)
Total organic carbon (TOC)
Total oxygen demand (TOD)

BOD test measures the biodegradable organic carbon, & under
certain conditions, the oxidisable nitrogen present in the waste

COD test measures the total organic carbon, with the exception of
certain aromatics, such as benzene, which are not completely
oxidized in the reaction. The COD test is an oxidation-reduction
reaction, so other reduced substances (e.g. sulphides, sulphites &
Fe
2+
) will also be oxidized & reported as COD.
Ammonia also oxidized
Refractory

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Oxygen requirement of a waste

BOD
Amount of oxygen required by living organisms engaged in the utilization
& stabilization of the organic matter present in the w/w at a constant
temperature (20
o
C)
Measures the biodegradable organic carbon, & under certain conditions,
the oxidisable nitrogen present in the w/w.

Theory 2 Stage process
1) Stage 1 Organics used by microorganisms for energy & growth. This
utilizes O
2
, & new m/o are produced. (UTILIZATION). Process usually
takes 18-36 hours.
2) Stage 2 After the organics are removed, the cells then undergo
endogenous metabolism which eventually degrades the m/o present,
again using O
2
, after which only the non-biodegradable cellular residue
remains (STABILIZATION). This process usually takes about 20 days.
Milligram Oxygen per liter

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Reactions occurring in the BOD bottle. Rate of reaction of first
stage ~ 10-20 times faster than 2 stage
Cell growth

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Oxygen consumption in both processes = ULTIMATE BOD
Organics + O
2
+ N + P new cells + CO
2
+ H
2
O + non-biodegradable
soluble residue
Cells + O
2
CO
2
+ H
2
O + N + P + non-biodegradable soluble residue

TOC test measures all carbon as CO
2
, & hence inorganic carbon (CO
2
,
HCO
3
-
, etc) present in the w/w must be removed prior to the analysis, or
corrected for in the calculation.

TOD test measures organic carbon & unoxidised nitrogen & sulphur

(BOD)
5
Historically, furthest point in England from the sea by river was 5
days. Consequently, the amount of O
2
utilised by a waste stream (over 5
days) seems a sensible criteria.
Bacteria C5H7NO2
Deoxygenation
mg carbon per liter
Acidification

Y.P. Ting
Uses of BOD Test
1) Assessment of quality of river waters
2) Determination of oxygen demand of w/w, effluents & other polluted
water
3) Assessment of effect of discharge to water courses
4) Design & assessment of performance of sewage works & other w/w
Treatment plant
5) Guide to the biodegradability or treatablility of a particular effluent

BOD typical range:
6 mg/l clean river water
10-15 mg/l good sewage effluent
30-60 mg/l poor sewage effluent
60-120 mg/l settled sewage
120-240 mg/l raw sewage, industrial effluent

Royal Commission Effluent Standard - 20 mg/l BOD, 30 mg/l SS

Which is easier or difficult to breakdown
What can be biologically oxidized
can be chemically oxidized.not the
other way round

Use of BOD/COD ratio = <1

High ratio indicates very
biodegradable. Biologically
treatable

Y.P. Ting
P
DO DO
BOD
F I
=
Procedure for BOD test
BOD measured by determining the O
2
consumed from a sample placed in an
air-tight container, & kept in a controlled environment for a preselected time.
Standard test 300ml bottle, sample incubated at 20
o
C for 5 days. Light must
be excluded from the incubator to prevent algae growth that may produce O
2
in
the bottle. Because the saturation conc. of O
2
in water at 20
o
C is ~9 mg/l,
dilution of sample with BOD-free, O
2
-saturated water is necessary to measure
BOD values greater than just a few mg/l.
Range of BOD covered by various dilutions see table.
These values assume an initial DO conc. = 9 mg/l & minimum of 2 & maximum
of 7 or 8 mg/l O
2
being consumed.
BOD of a diluted sample is calculated from:

where DO
I
= initial dissolved O
2
conc. (mg/L)
DO
F
= final dissolved O
2
conc. (mg/L)
P = decimal fraction of sample in the 300mL bottle
As BOD > DO
level. Dilution
is necessary
As it is a biological test, it is
not very accurate.
Dilution would affect results

Y.P. Ting

Procedure for setting
up BOD test bottles.
(a) with unseeded
dilution water and (b)
seeded dilution water.
Control

Y.P. Ting
300
mL of waste
Make up total vol to
300

Y.P. Ting
Schematic representation of the oxygen consumed (uptake) in the BOD
determination.

D1 = DO of diluted sample 15 minutes after preparation, g/m
3
D2 = DO of diluted sample after incubation, g/m
3
B1 = DO of seeded dilution water before incubation, g/m
3
B2 = DO of seeded dilution water after incubation, g/m
3
D1-D2 = Oxygen consumer (uptake) in sample, g/m
3
B1-B2 = Oxygen consumed (uptake) in blank, g/m
3

P
f B B D D ) ( ) ( 2 1 2 1

For Seeded dilution
Fraction

Y.P. Ting
P
f B B D D ) ( ) ( 2 1 2 1
BOD is computed using the following equation:

BOD =

where
BOD = biochemical oxygen demand,
D1 = DO of diluted sample 15 minutes after preparation, g/m
3
D2 = DO of diluted sample after incubation at 20
o
C, g/m
3
B1 = DO of seeded dilution water before incubation, g/m
3
B2 = DO of seeded dilution water after incubation at 20
o
C, g/m
3
f = ratio of seed in sample to seed in control
= (% seed in D1) / (% seed in B1)
P = decimal fraction of sample used
= (mL of sample, Vs) / 300 mL

For an unseeded sample the terms for the blank (B1 and B2) are omitted in the
computation of the BOD.

Y.P. Ting
Wastewater
used (mg/L)
DO
I
(mg/L)
DO
F
(mg/L)
O
2
(mg/L)
P BOD
5
(mg/L)
5
10
20
9.2
9.1
8.9
6.9
4.4
1.5
2.3
4.7
7.4
0.0167
0.033
0.067
138
142
110
Example: Determine BOD5 of a w/w, where BOD is suspected to range from
50 to 200 mg/l. Prepare 3 dilutions to cover this range.

note + DO
I
expected

If the third sample is disregarded (DO
F
is less than 2 mg/L or if change in DO
< 2.0), then average, BOD
5
of w/w is ~140mg/L
Dilution factor =
ww used /300

Y.P. Ting
Toxicity in a waste is evidenced by so-called sliding BOD values, i.e. an
increasing calculated BOD with increasing dilution. If this situation exists, it is
necessary to determine the dilution value below which the computed BOD
5
are
consistent. (Highest value obtained in valid tests, i.e. the average of the highest dilution providing a
minimum uptake of 2.0 mg/l DO).

Advantages
Test is biological
Simple equipment
Cheap
Labour -- non intensive

Disadvantages
Long time (5-20 days)
Toxins, heavy metals affect test
Choice & acclimatisation of culture necessary
Variables: T, pH, seed level must be controlled
Extent of nitrification not quantified
Estimates of K, (BOD)u depends on method of analysis
Cannot be used reliably for comparative purposes.
Toxicity kills bacteria. Dilution
would allow bacteria to live due to
lower conc of toxic. Necessary to
conduct this test

Y.P. Ting
Problem: A series of BOD tests were run at four different dilutions. The results
were as
follows:

# Dilution Do initial DO final BOD (mg/l)
1. 100 10.0 2.5 750
2. 200 10.0 6.0 800
3. 400 10.0 7.5 1000
4. 600 10.0 8.0 1200

What is the BOD?

750 or less. Because with
increase in dilution BOD
increases

Y.P. Ting
Influence of toxic substances on BOD:
1 without toxic substance,
2,3,4 presence of toxic substances.

2decrease of BOD process rate,
3delay of the start,
4total stoppage of BOD process
BOD curve, depending on temperature
Grows the fastest but can't sustain

Y.P. Ting
Biochemical oxidation is a slow process, & theoretically takes an infinite
time to go to completion.
20 days, [O] about 95-99% complete.
5 days, [O] about 60-70% complete.

O
2
is consumed by the m/o for energy, & new cell mass synthesized.

Organics + O
2
+ N + P new cells + CO
2
+ H
2
O + non-biodegradable
soluble residue

Organisms also undergo autoxidation (endogenous respiration)

Cells + O
2
CO
2
+ H
2
O + N + P + non-biodegradable soluble residue

Y.P. Ting
Nitrogenous BOD (NBOD)
Non-carbonaceous matter, e.g. NH
3
produced hydrolysis of proteins. Some
autotrophic bacteria is capable of using O
2
to oxidise NH
3
NO
2
-
NO
3
-
Growth of nitrifying bacteria is very slow, normally 6-10 days to reach
significant numbers.

Nitrification: nitrosomonas
Step 1: NH
4
+
+ 3/2 O
2
----------------------> NO
2
-
+ 2 H
+
+ H
2
O
nitrobacter
Step2: NO
2
-
+ 1/2 O
2
-------------------------> NO
3
-
Overall: NH
4
+
+ 2 O
2
--------------------------> NO
3
-
+ 2 H
+
+ H
2
O
cf photoautotroph & chemoautotroph
Self feeding bacteria, don't need
free form nitrogen.
Energy from light Energy from chemicals

Y.P. Ting
Nitrification involves the energy-generating oxidation of ammonia (NH
3
).
Organisms that perform these reactions are strict aerobes because oxygen is
the electron acceptor during the oxidation of ammonia.

Nitrifiers such as Nitrosomonas spp. oxidize ammonia to nitrite (NO
2
-
) via:

(a) Generation of the intermediate hydroxylamine (NH
2
OH)
NH
3
+ O
2
+ 2H
+
+ 2e- ----> NH
2
OH + H
2
O + energy
The enzyme ammonia monooxygenase catalyzes this reaction

(b) Production of nitrite from hydroxylamine:
NH
2
OH + H
2
O-----------> NO
2
-
+ 2H
+
+ 2e
-
+ energy

Nitrifiers such as Nitrobacter spp. oxidize nitrite to nitrate (NO
3
-
)
NO
2
-
+ H
2
O -------------> NO
3
-
+ 2H
+
+ 2e
-
+ energy

Y.P. Ting

BOD = CBOD + NBOD

Exertion of the carbonaceous and
nitrogenous biochemical oxygen demand in
a waste sample.
Nitrate inhibitor:
2-chloro-6- (trichloro
methyl) pyridine (TCMP)

Where effluent from
biological treatment
units are to be
analysed, presence of
nitrifiers may be high,
and hence may need to
add inhibitor, in order to
determine the treatment
efficiency of the
treatment units.
Nitrifiers bacteria are slow
growing, more than 6 days for
NBOD to be shown

Y.P. Ting

BOD curves showing both carbonaceous and nitrogenous BOD
NBOD comes earlier, due to
nitrification during treatment

Y.P. Ting

L
t
= BOD remaining at time t, mg/l
L
o
= ultimate BOD
Y
t
= BOD exerted after time t, mg/l
k = reaction rate constant d
-1
(base e)
K = reaction rate constant d
-1
(base 10)

Means oxygen consumed

Y.P. Ting
Kinetics formulated according to 1
st
order Kinetics

t
t
L k
dt
dL
' =
where L
t
is the amount of first-stage BOD remaining in w/w at time t.

Integrating,

o
t
L
L

where L
0
or BOD
u
= BOD remaining at time t = 0
(i.e. the total or ultimate BOD initially present).
303 . 2
' k
K =
= e
-kt
= 10
-Kt

Y.P. Ting
At any time t,
L
t
= L
o
(10
-Kt
)
BOD
t
= y
t
= L
o
- L
t
= Lo (1-10
-Kt
)

where y
t
= amount of BOD that has been exerted at any time t
Therefore, 5-day BOD

y
5
= L
o
-L
5
= L
o
(1-10
-5K
)

Typically, for polluted water and w/w, K (base 10, 20
o
C) = 0.1 d
-1
.
K varies, depending on the waste, from 0.05 to 0.3d
-1
(base e) or more.

BOD test varies with temperature.
Vant Hoff-Arrhenius relationship

K
T
= K
20
u
(T- 20)

20-30
o
C, u = 1.056, Often used value, u = 1.047
4-20
o
C, u = 1.135
Range of number

Y.P. Ting

Typically, for polluted water and w/w, K (base 10, 20
o
C) = 0.1 d
-1
.
K varies, depending on the waste, from 0.05 to 0.3d
-1
(base e) or more.

BOD test varies with temperature.
Vant Hoff-Arrhenius relationship

K
T
= K
20
u
(T- 20)

20-30
o
C, u = 1.056, Often used value, u = 1.047
4-20
o
C, u = 1.135

Energy Activation =
a
E
)
1 1
( ) ln(
1 2 1
2
T T R
Ea
k
k
Ae k
RT
E
a
=
=

Y.P. Ting
BOD exerted = f(K),
and K = f (T)
= f (nature of organic matter)
= f (ability of m/o to utilize the waste)

For a constant ultimate BOD, the value of K determines the rate of
the BOD reaction. Value of K depends on the nature of the organic
molecules.
sugar, starches (easy to digest), high value of K;
complex molecules, e.g. phenol, difficult to digest, low value of
K.

k assumes microbes able to use
the waste to grow

Y.P. Ting

Y.P. Ting

Y.P. Ting
Q1. As the technical manager, your environmental control engineer
reported to you that the wastewater treatment plant is apparently not
performing as expected. He reported that the BOD removal efficiency
was lower that the expected 90%, since the average influent BOD
5
and
the average effluent BOD
5
were found to be 120 mg/l and 40 mg/l
respectively. List a few key questions you would ask him in order to
ascertain if the wastewater treatment plant is indeed not performing as
expected. What follow-up action (if any) should be taken by the
engineer in order to confirm this?

Q2. A sample of the influent to a wastewater treatment plant, and the
effluent after the treatment were obtained at the same time. BOD
5

analyses of the two samples yielded values of 188 mg/l and 33 mg/l
respectively. The plant was designed to produce an effluent of 30 mg/l
or less when the influent BOD
5
is 200 mg/l. What can you conclude (if
any) concerning the adequacy of the plant?
Check DO
Check nutrient level
Nitrifiers could have been encountered in the
plant, increasing BOD. Effluent might include
NBOD and CBOD while influent only has CBOD
The plant is not optimized
Possibly temp, nutrients
Can't be conclusive, need to take
several readings.
Sample at same time, plant might
not be steady state.

Y.P. Ting
Example
If the BOD
3
of a waste is 75 mg/l and the K is 0.150 day
1
, what is the
ultimate BOD?

Note that the rate constant is given in base 10 (i.e. K, not k).
Substitute the given value into previous equation, solve for L
o
.

Y
t
= L
0
-L
t
= L
0
(1-10
-Kt
)
75 = L
0
(1-10
-(0.150)(3)
) = 0.645 L
o

Or, using base e,
k' = 2.303(K) = 0.345 and
75 = L
0
(1- e
-(0.345)(3)
) = 0.645 L
0
so
L
0
= 116 mg/l

Y.P. Ting
Example
Determine the 1-day BOD (i.e. BOD exerted after 1-day) and the ultimate
first-stage BOD for a wastewater whose 5-day 20
o
C BOD = 200 mg/l
k = 0.23d
-1

L
t
= L
0
e
-kt
y
5
= L
0
L
5
= L
0
(1-e
-5k
)

200 = L
0
(1- e
5 * 0.23
)
L
0
= 293 mg/l
L
t
= L
0
e
-kt
= 293(e
-0.23
) = 233 mg/l

BOD exerted after 1 day = y
1
= L
0
L
1
= 293-233 = 60 mg/l
Or, y
1
= L
0
L
1
= L
0
(1-e
-k
) = 293 (1-e
-0.23
) = 60.2 mg/l

Y.P. Ting
Example:
BOD
5
of w/w = 150 mg/l at 20
o
C, k=0.23d
-1
(BOD exerted after 5 days = 150
mg/l). What is BOD
8
at 15
o
C?

First, calculate ultimate BOD, i.e. L
0
y
t
= BOD
t
of w/w
= approaches L
o
asymptotically as t increases
(i.e. total (ultimate) BOD)

y
5
= L
0
- L
5
= L
0
(1-e
-5k)
150 = L
o
(1 - e
-5*0.23
)
L
0
= 220 mg/l

Correct for K at 15
o
C using K
T
= K
20
u
(T- 20)
K
15
= (0.23)(1.047
-5
) = 0.18
y
8
= L
o
(1-e
-0.18*8
) = 168 mg/l

Y.P. Ting
BOD
Time (days)
Estimate L
o
, then solve for K or k

Estimating parameters for L
o
and K, based on experimental results

Y.P. Ting
A. Least Square Method

Fit curve through set of data points so that sum of squares of residuals
(difference between the observed & fitted values) = minimum

Tabulate: Time (day) Oxygen used (mg/l)
t
1
y
1

: :
: : = k(L
0
-y
n
)
: :
t
n
y
n

since rate of consumption of O
2
amount of BOD left (i.e. L
0
-y
n
) = L
n

Residual error R =

= k(L
0
-y
n
)-y
= kL
o
ky
n
y
= a + by y a = kL
0
, -b = k

)
dt
dy
( - ) y - (L k'
n o
dt
dy

Y.P. Ting

R
2
, take differentials
da
d and
db
d
Minimise sum of square of residuals, R

c
c
R
a
2
=
=
c
c
0 2
a
R
R

c
c
R
b
2
=
=
c
c
0 2
b
R
R
Since R = a + by y

na + by - y = 0

and a y + by
2
- yy = 0 n = no. of data points

Y.P. Ting
B. Log-Difference Method

y = L
0
(1-e
-kt
)

dt
dy
= L
0
ke
(-kt)
= R = Differential rate of oxygen consumption

ln R = ln (L
0
k) kt

y = b + mx

plot ln R vs. t,

slope = -k
intercept = ln (L
0
k)

Y.P. Ting

Thomas recognised that the (1-10
-Kt
) term is similar to the function
2.3Kt [ 1 + (2.3Kt)/6]
-3

Compare
(1-10
-Kt
) = 2.3Kt [ 1 (2.3Kt)/2 + (2.3Kt)
2
/6 (2.3Kt)
3
/24 + ]

2.3Kt [ 1 + (2.3Kt)/6]
-3

= 2.3Kt [ 1 (2.3Kt)/2 + (2.3Kt)
2
/6 (2.3Kt)
3
/21.6 + ]

So, y = L
0
(1-10
-kt
) can be linearised as:
y = 2.3 L
0
Kt [ 1 + (2.3Kt)/6]
-3

Linearizing
) (
y
t
1/3
= (2.3 L
0
K)
-1/3
+ {K
2/3
/(3.43 L
0
1/3
)}t

) (
y
t
1/3
vs t, slope = b intercept = a

K (reaction rate constant base 10) = 2.61
a
b
L
0
(ultimate BOD) = (2.3Ka
3
)
-1

Plot
C. Thomas Method

Amount of BOD exerted at any time t
y = L
0
L
t
= L
0
(1-10
-Kt
)

Y.P. Ting
Example

Compute L
o
& k using the Least Square Method
t (days) 2 4 6 8 10
Y (mg/l) 11 18 22 24 26
Set up computation table
T (days)

y y2

y yy
2
4
6
8
Sum
11
18
22
24
75
121
324
484
576
1505
4.50
2.75
1.50
1.00
9.75
49.5
49.5
33.0
24.0
156.0
Slope y computed from
t
y y
y
dt
dy n n
A
= =
+
2
'
1 1

Y.P. Ting
na + by - y = 0
a y + by
2
- yy = 0

4a + 75b 9.75 = 0
75a + 1505b 156 = 0

a = 7.5, b = -0.271
but -b = k , a = kL
0

k= 0.271 d
-1
(base e),

L
0
=
l mg
b
a
/ 7 . 27 =

Y.P. Ting
t
Example 2
Same set of data, using Thomas method
t (days) 2 4 6 8 10
y (mg/l)

11

0.57
18

0.61
22

0.65
24

069
26

0.727
) (
y
t
1/3
) (
y
t
K =
53 . 0
02 . 0
* 61 . 2 * 61 . 2 =
a
b
= 0.099 d
-1

k = 2.303K = 2.303 * 0.099 = 0.228 d
-1

L
0
= 1/(2.3 Ka
3
) = (2.3 * 0.099 * 0.53
3
)
-1

= 29.5 mg/l

k = 0.228 d
-1
L
0
= 29.5 mg/l
1/3
a = 0.53
Slope = 0.02 = b

Y.P. Ting
Biological Processes and Energy

Microorganisms would like to obtain as much energy from a reaction as
possible. Hence, they would prefer to use oxygen as an electron acceptor.
However, not all microorganisms can use oxygen as an electron acceptor.
(When oxygen is absent, anaerobes will dominate.)

Order of preference for electron acceptor, based on energy
considerations:
(i) oxygen, (ii) nitrate, (iii) sulphate, (iv) carbon dioxide, and finally
(v) fermentation.

Note that some microorganisms (e.g. E. coli) have the ability to use several
different electron acceptors, including oxygen, nitrate and organic matter in
fermentation. Others, such as methanogens, can only carry out methane-
forming reactions.

Y.P. Ting
Energy Source:

Aerobes require free dissolved oxygen in decomposing organic matter to
gain energy for growth and multiplication.

Anaerobes oxidize organics in the complete absence of dissolved oxygen by
using oxygen bound in other compounds, such as nitrate and sulphate.

Facultative bacteria use free dissolve oxygen when available, but can also live
in its absence by gaining energy from anaerobic reactions.

Aerobic:
Organics + oxygen CO
2
+ H
2
O + Energy

Anaerobic:
Organics + NO
3
-
CO
2
+ N
2
+ Energy
Organics + SO
4
2-
CO
2
+ H
2
S + Energy
Organics Organic acids + CO
2
+ H
2
O + Energy
Organic acids CH
4
+ CO
2
+ Energy

Y.P. Ting
Biological Processes and Energy

Free Energy
kJ/mol glucose
Aerobic oxidation
C
6
H
12
O
6
+ 6O2 6CO
2
+ 6H
2
O -2,880

Denitrification
(5C
6
H
12
O
6
+ 24NO
3
-
30CO
2
+ 42H
2
O + 12N
2
-2,720

Sulphate reduction
2C
6
H
12
O
6
+ 6SO
4

2-
+ 9H
+
12CO
2
+ 12H
2
O + 3H
2
S + 3HS
-
-492

Methanogenesis
C
6
H
12
O
6
3CO
2
+ 3CH
4
-428

Ethanol fermentation
C
6
H
12
O
6
2CO
2
+ 2CH
3
CH
2
OH -244

Note: cf nitrification

Y.P. Ting

Chemical Oxidation Demand (COD)
COD test - widely used as a means of measuring the organic strength of
domestic and industrial wastes. Measures a waste in terms of the total
quantity of oxygen required for oxidation to carbon dioxide and water
in accordance with the equation:

All organic compounds, with a few exceptions, can be oxidized by the action
of strong oxidizing agents under acid conditions. The amino nitrogen (with
an oxidation number of 3) will be converted to ammonia nitrogen (see
equation). However, organic nitrogen in higher oxidation states will be
converted to nitrates. (Most organic compound containing nitrogen are derived
from ammonia.)

3 2 2 2
)
2
3
2
( )
4
3
2 4
( cNH O H
c a
nCO O
c b a
n N O H C
c b a n
+ + + +

Y.P. Ting

Y.P. Ting
Chemical Oxidation Demand
A measure of concentration of waste of unknown chemical composition.
(Also includes oxidation of H
2
S, SO
3
2-
, S
2
O
3
2-
, NO
2
-
, Fe
2+
. .
)

Method:
A wet sample refluxed (2 hr 100
o
C) with acidified dichromate. Loss of
dichromate through oxidation of organic matter determined by titration.
Silver sulphate as catalyst - certain organic compounds, especially low
molecular weight fatty acids are not oxidised by Cr
2
O
7
2-
, unless Ag+ ions
as catalyst is present. catalyst + heat
e.g. C
a
H
b
O
c
+ Cr
2
O
7
2-
+ H
+
--------> Cr
3+
+ CO
2
+ H
2
O
organic matter
Sugars, branched chain aliphatics & substituted benzene rings are
completely oxidized with little or no difficulty.
Benzene, pyridine, toulene NOT oxidised by this method.
Chloride ions interfere with the method* & interference can be eliminated
by using mercuric sulphate (complex chloride)
Hg
2+
+ 2Cl
-
HgCl
2
* 6Cl
-
+ Cr
2
O
7
2-
+ 14H
+
3Cl
2
+ 2Cr
3+
+ 7H
2
O

Y.P. Ting
COD test - organic matter converted to CO
2
and H
2
O regardless of the
biological assimilability of the substances. E.g., glucose and lignin
are both oxidised completely. COD > BOD values and may be much
greater when significant amounts of biologically resistant organic
matter are present. Example: Wood-pulping wastes.

Limitations:
inability to differentiate between biologically oxidizable and
biologically inert organic matter.
does not provide any evidence of the rate at which the biologically
active material would be stabilized under conditions that exist in
nature.

Major advantage - short time required for evaluation. (3h rather than the
5 days required for the measurement of BOD.) May be used as a
substitute for the BOD test. COD data can often be interpreted in
terms of BOD values after sufficient experience has been
accumulated to establish reliable correlation factors.

Y.P. Ting

Relationship between BOD, COD and TOC

Relationship between these measures depends on the organic content of
the w/w (Recall definition of BOD, COD)
e.g. TOC is related to COD through the carbon-oxygen balance

C
6
H
12
O
6
+ 6 O
2
6 CO
2
+ 6 H
2
O

CH
4
+ 2 O
2
CO
2
+ 2 H
2
O

Depending on the organic in question, the COD/TOC ratio may vary from
ZERO (when organic material is resistant to dichromate oxidation), to 5.33
(for methane)

Since the organic content undergoes changes during biological oxidation,
therefore, COD/TOC ratio will also change, likewise, BOD/TOC
67 . 2
12 * 6
32 * 6
6
6 2
= = =
C
O
M
M
TOC
COD
33 . 5
12
32 * 2
1
2 2
= = =
C
O
M
M
TOC
COD
Compare rate constant K in waste stream with a single waste, and one where there is
multiple waste. Does K change? If so, how?

Y.P. Ting
Theoretical Oxygen Demand

Theoretical Oxygen Demand (ThOD) - stoichiometrically determined
oxygen needed to convert all carbon molecules in pollutants to CO
2
, and
all NH
3
and NO
2
to NO
3
by balancing equations.

ThOD calculation is possible on certain rather pure industrial wastes, but
is impractical for most wastewaters, especially those containing domestic
sewage or containing vegetable or animal wastes.

Y.P. Ting
Theoretical Oxygen Demand (THOD)
THOD of w/w = amount of O
2
required to oxidize organics to end products
Example:

THOD of Benzene Sulfonamide (C
6
H
5
SO
2
NH
2
)
1. Carbonaceous demand
C
6
H
5
SO
2
NH
2
+ 11/2 O
2
6 CO
2
+ NH
3
+ H
2
S + H
2
O

2. Nitrogenous demand
NH
3
+ 3/2 O
2
HNO
2
+ H
2
O
HNO
2
+ 1/2 O
2
HNO
3

H
2
S + 1/2 O
2
S + H
2
O
S + 3/2 O
2
+ H2O H
2
SO
4

Therefore, THOD of Benzene Sulfonamide = 9.5 moles of O
2
per mole B-S

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