ENVE 3002

Environmental Engineering Unit Processes

Introduction to Wastewater Treatment

Assoc. Prof. A. Evren Tugtas

 Unit Operations and Processes
• Unit Operations: Physical treatment
• Sedimentation
• Filtration typically
• Mixing
• Unit Processes: Chemical or biological
treatment
• Coagulation
• Adsorption
• Ion Exchange
• Activated Sludge
• Aerobic or Anaerobic Digestion
2
 Biological Treament

• Activated Sludge
• Trickling Filters and Biological Conductors
• Stabilization ponds and Lagoons
• Anaerobic or Aerobic Digestion
• Nitrification/Denitrification
• Phosphorus removal

3
 Wastewater

• Domestic – Sewage / Treatment Plant

• Industrial – Regulations

• Municipal – Combining pretreated industrial ww

4
 Industrial Wastewater
• Effluents resulting from human activities associated
w/ raw material processing and manufacturing
Industrial Agro – Industrial
•Chemical •Slaughter Houses
•Pharmaceutical •Fisheries
•Petrochemical •Seed Oil Processing
•Food Processing •Animal Husbandry
•Electronics
•Electrochemical
•Washing •Extraction
•Cooking •Reaction by-products
•Cooling •Separation etc.
•Heating 5
 Domestic Wastewater
• Primarily water
• Contains large numbers of microorganisms (some pathogenic)
• Contains inorganic constituents
• chlorides,
• phosphates,
• sulfates,
• various forms of nitrogen and phosphorus,
• Carbonates and bicarbonates
• 90% of organic matter is carbohydrates and proteins
• Shows diurnal/seasonal variations – relatively constant composition
• Biodegradability can be estimated considering
• COD:BOD5  1.5:1
• BOD5:N:P  25:4:1
• Activated sludge 100:5:1
• Anaerobic treatment 250: 5:1 – 500:5:1
• pH 6-9
• Plant design BOD5: TSS:TKN  250:300:40 mg/L
6
 Domestic vs. Industrial Wastewater
Industrial Wastewater
• Shows high variability in terms of composition (Food, pharmaceutical etc.)
• Can be ,
• Organically strong
• Inhibitory
• Easily biodegredable
• Largely inorganic
• TSS, TKN, BOD5 values can be in thousands
• Organic matter may contain proteins, carbohydrates, and/or fats
• pH values can be well beyond the range of 6-9.
• Flow pattern depends on the factory manufacturing schedule
• Biodegradability estimation is complicated.
• Microorganisms may be an issue in effluents of agro-industries.

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Typical Composition of
Domestic Wastewater •Ref: Metcalf & Eddy, 2004

•Metcalf &
Eddy, Inc.
(2004).
Wastewater
Engineering-
Treatment and
Reuse, 4th ed.,
McGraw-Hill,
New York, NY.

•Wastewater flow Lcd 750 460 240

8
 Constituents of Wastewater

Physical Chemical Biological

Organic •Microorganisms
•Solids Inorganic
•Aggregate
•Turbidity •Nutrients(N,P) organic •Pathogenic
constituents organisms
•Color •Metals
Typical domestic ww 40-60% protein
•Temperature •Gases 25-50% carbonhydrate
•Individual 8-12% oil-fat.
•Density •pH
compounds
•Conductivity •Chloride •VOCs,
phenols,
•Sulfur pesticides.

•Alkalinity 9
 Classification of Solids

•Metcalf & Eddy,

Inc. (2004). Wastewater
Engineering-Treatment
and Reuse, 4th ed.,
McGraw-Hill, New
York, NY.

10
 Measurement of Solids

•Metcalf & Eddy, Inc.

(2004). Wastewater
Engineering-Treatment
and Reuse, 4th ed.,
McGraw-Hill, New
York, NY.

11
 Characterization of Organic Content

• BOD (Biochemical Oxygen Demand)

• COD (Chemical Oxygen Demand)
• TOC (Total Organic Carbon)
• ThOD (Theoretical Oxygen Demand)
• UV absorbing organic constituents

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 BOD (Biochemical Oxygen Demand)
•Measurement of the dissolved oxygen used by microorganisms
in the biochemical oxidation of organic matter

→ CBOD (carbonecous BOD): oxygen demand exerted by the

oxidizable carbon in the sample

→ NBOD (nitrogenous BOD): oxygen demand associated with

the oxidation of ammonia to nitrate (nitrification)

13
cBOD & nBOD

•Metcalf & Eddy, Inc.

(2003). Wastewater
Engineering-Treatment and
Reuse, 4th ed., McGraw-
Hill, New York, NY.

14
 Reproductive rate of nitrifiers is slow 
it normally takes from 6-10 days for
them to reach significant numbers to
exert a measurable oxygen demand

However; if a sufficient number of nitrifying bacteria is present initially

interference of cBOD measurement caused by nitrifiers can be significant

•To supress nitrification;

•Methylene blue
• ATU (Allythiourea)

15
 COD (Chemical Oxygen Demand)
Measure the oxygen equivalent of the organic material in
wastewater that can be oxidized chemically using dichromate in
an acid solution

a  8d  3c
CnHaObNc  dCr2O7  (8d  c)H  nCO2 
2 
H2O  cNH4  2dCr 3
2

2n a b c
where d   
3 6 3 2

16
 cBOD vs COD

1. Many organic substances which are difficult to oxidize

biologically (e.g lignin) can be oxidized chemically.

2. Inorganic substances that are oxidized by dichromate (e.g

sulfide,sulfite, ferrous ion)

3. Certain organic substances may be toxic to microorganisms

used in the BOD test.

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 BOD/COD

Typical BOD/COD of untreated domestic wastewater: 0.5-0.8

If BOD/COD ratio is 0.5:

→Waste is considered to be easily treatable by biological means

If BOD/COD ratio is 0.3:

→Organics in wastewater may be refractory
→Organics in wastewater are degradable. However, another
substance in wastewater leads to inhibition of bacteria that uses
organic matter
→Bacteria is not acclimated to wastewater

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 TOC (Total Organic Carbon)
→ Done instrumentally (5-10 min) to determine total organic carbon in
aqueous sample (mg C/L)

→ This test measures all C as CO2

→ Inorganic C (CO2, HCO3) present in wastewater must be removed

prior to analysis

by acidification and aeration of sample prior to analysis

Typical BOD5/TOC of untreated domestic wastewater 1-1.6 mg O2/mg C

19
 ThOD (Theoretical Oxygen Demand)
→ ThOD of a wastewater is calculated as the oxygen required to
oxidize the organics to end products

Example : glycine CH2(NH2)COOH

→ CH2(NH2)COOH + 3/2 O2 NH3 + 2 CO2 + H2O

For nitrogenous oxygen demand :

→ NH3 + 3/2 O2 HNO2 + H2O
→ HNO2 + 1/2 O2 HNO3 + H2O
→ ThOD = (3/2 + 3/2 + 1/2) mol O2 / mol glycine

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 UV Absorbing Constituents

→ Humic substances
→ Lignin Strongly absorb UV
→ Tannin
→ Various aromatic compounds

UV absorption has been used as a surrogate measure for the

organic compounds cited above

UV wavelength = 200 – 400 nm (254 nm most common)

21
Ref: Metcalf &
Eddy, 2004

22
COD Fractionation

•Metcalf & Eddy, Inc.

(2004). Wastewater
Engineering-Treatment
and Reuse, 4th ed.,
McGraw-Hill, New
York, NY.
rbsCOD (soluble) : quickly assimilated by biomass
sbCOD (particulate) : must be firts dissolved by extracellular enzymes
assimilated much slower rate
nbVSS – nonbiodegredable particulate (nbpCOD): since it is organic material, it
will also contribute VSS.
Influent wastewater will also contain non-voltile suspended solids that add to the
MLSS concentration

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 COD Fractionation

• Carbonecous contents measured by COD or

BOD tests are critical to determine
• Aeration basin volume
• Oxygen transfer needs
• Sludge production amount
• BOD is common parameter to characterize
carbonecous matter, COD is becomming more
popular

24
 COD Fractionation

• Unlike BOD, some portion of COD is

biodegradable and some portion is non-
biodegredable
• Soluble, non-soluble (particulate) fractions of
COD is also needs to be considered

25
 Non-biodegradable COD Fractions
• Non-biodegradable soluble COD (nbsCOD)
• Will be found in the effluents
• Non-biodegradable particulate COD (nbpCOD)
• Will contribute to total sludge production
• Organic material – will contribute to VSS concentration
of wastewater – non-biodegredable volatile suspended
solids (nbVSS)
• Influent wastewater will contain non-volatile influent
suspended solids – will add to MLSS concentration -
influent inert TSS (iTSS)
iTSS = TSSinf - VSSinf
26
 Biodegredable COD
Readily biodegradable
Biodegredable COD (rbCOD)
COD
Slowly biodegradable
COD (sbCOD)
- Particulate or colloidal

• rbCOD is quickly assimilated into biomass

• sbCOD must first be dissolved by extracellular enzymes and are
assimilated in a slower rate

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 Biodegradable COD

• sCOD is determined by filtration through 0.45µm

filter
• sCOD contains readily biodegradable COD
(rbCOD) and non-biodegradable soluble COD
(nbsCOD)
• In domestic wastewater (SRT>4 days)
nbsCOD = sCODeffluent

28
• bCOD/BOD > UBOD/BOD
• Not all the bCOD is oxidized in the BOD test
• Some bCOD is converted to biomass
• For domestic wastewater
• UBOD/BOD = 1.5
• bCOD/BOD = 1.6 – 1.7

29
 bCOD/BOD

• bCOD/BOD can be estimated by;

𝑏𝐶𝑂𝐷 𝑈𝐵𝑂𝐷/𝐵𝑂𝐷
• =
𝐵𝑂𝐷 1.0−1.42𝑓𝑑 (𝑌𝐻)
• fd = fraction of cell mass remaining as cell debris
(g/g)
• YH= synthesis yield coefficients for heterotrophic
bacteria (g VSS/g COD)

30
bCOD/BOD= (uBOD/BOD) / (1-1.42 fd Yh)

For typical domestic ww:

fd=0.15, Yh=0.4, uBOD/BOD=1.5  bCOD/BOD=1.64

Not all of the bCOD is oxidized in the BOD test

Some of the bCOD is converted into biomass
 uBOD < bCOD

31
 rbCOD Determination

• Either determined from a

• biological response (Oxygen uptake rate)
• physical separation technique

32
 rbCOD Determination
Biological response test

 Watewater should be preaerated – high DO concentration

for the immediate measurement of OUR
 Wastewater sample and activated sludge is mixed in a batch
reactor with mixing
 During mixing DO concentration declines and it is measured
via a Do probe
 OUR in mg/L.h is calculated

33
 rbCOD Determination
Biological response test

 When DO concentration decreases to about 3.0 mg/L,

vigorous aeration is applied to elevate the DO concentration
to 5-6 mg/L so another OUR measurement can begin

 Slope of DO vs time graph

(mg/L DO) / time = OUR (Oxygen Uptake Rate)

34
Biological Response Test for rbCOD

VAS=volume of activated sludge used in the

test (mL)
OA  VAS  VWW  Vww=volume of ww (mL)
rbCOD   
1  YH,COD  VWW  OA=oxygen consumed in area A (mg/L)
YH,COD=synthesis yield coeff for
heterotrophic becteria (g cell COD/g COD
used)
35
 Physical seperation technique for rbCOD
(Mammais et al, 1993)

• Floc/filtration methode presented by Mammais et al.(1993)

• may not give the exact results as the rbCOD concentration determination by
respirometry, but it provides a reasonable estimate

• used widely because of its simplicity

• The procedure is based on the assumption that suspended solids and colloidal
material can be captured effectively and removed by flocculation with a zinc
hydroxide precipitate to leave only truly dissolved organic material after filtration

36
 Physical seperation technique for rbCOD
(Mammais et al, 1993)

Procedure:
• 1 ml of a 100 g/L ZnSO4 solution is added to 100 ml of sample with vigorous
mixing for 1 min
• The pH is raised to about 10.5 using 6 M NaOH with 5-10 min of gentle mixing for
floc formation
• The sample is settled for 10-20 min and the supernatant is withdrawn and filtered
using a 0.45 µm membrane filter
• The filtrate is analyzed for COD conc.  rbCOD
• rbCOD = CODww – COD act. sludge treated sample

37
sCOD= soluble COD Filtration through 0.45µm membrane filter
sBOD= soluble BOD
Non – biodegradable VSS
bpCOD bCOD BODBOD  sBOD

pCOD COD  sCOD

Summary
COD= bCOD+nbCOD
bCOD= 1.6 BOD (for domestic wastewater)
nbCOD= sCODe+nbpCOD
bCOD= sbCOD+rbCOD
38
 Nitrogen Forms in Wastewater
• Ammonia (NH3)
NH4 + NH3 + H+

• Ammonium (NH4+) pH>7 rxn. shifts right

pH<7 rxn. shifts left

• Nitrite (NO2-)

• Nitrate (NO3-)

• Organic nitrogen

Total Nitrogen = Organic N+NH3+NH4+NO2-+NO3-

Total Kjeldahl Nitrogen (TKN) = Organic N+NH3+NH4
39
Nitrogen Transformations in Biological
Treatment Processes

•Metcalf & Eddy, Inc. (2003). Wastewater

Engineering-Treatment and Reuse, 4th ed., McGraw-
Hill, New York, NY.

40
 •Metcalf & Eddy, Inc.
(2003). Wastewater
Engineering-Treatment and
Reuse, 4th ed., McGraw-
Hill, New York, NY.

•about 60-70% of the

influent TKN

•readily available for

bacterial synthesis and •will be removed more •will be captured
nitrification. slowly than soluble •will be found in in the activated
degradable organic the secondary sludge floc and
nitrogen because a clarifier effluent exit in waste
hydrolysis reaction is •(<3% of sludge
necessary first influent TKN) 41
 Phosphorus
→ Orthophosphate (PO4-3 , HPO4-2 , H2PO4- , H3PO4)

available for biological metabolism without further breakdown

→ Polyphosphate

Undergo hydrolysis (quite slow) and convert to orthophosphate form

→ Organic phosphate

minor importance in most domestic wastes

42
 Chloride

Human excreta contains ≈ 6g chloride /person /day

Conventional methods of waste treatment  do not remove Cl-

Higher tan usual Cl- conc.  •indication that a body water is

being used for waste disposal

•Infiltration of grounwater into

sewers adjacent to ea water

43
 Sulfate

Occurs naturally in most water supplies and is present in

wastewater as well

Crown corrosion problem in sewers:

Org. Matter + SO4-2 S-2 + H2O +CO2

S-2+2H+H2S (under anaerobic conditions)

H2S collected at the crown of sewer not flowing fullH2SO4

(seriously threaten structural
integrity of pipe

44
 Color

Give rough information about age of wastewater

Fresh wastewater  light brownish gray color

As the travel time in the collection system increases

more anaerobic conditions develop

color of wastewater sequentially changes

graydark gray black (SEPTIC)

45
 Odor
Gases found in untreated wastewater
N2, O2, CO2 (from in all waters exposed atmosphere)

H2S, NH3, CH4 (from the decomposition of organic matter )

H2S:
from the anaerobic decomposition of organic matter
Org. Matter + SO4-2 S-2 + H2O +CO2
S-2+2H+H2S

Odor :rotten egg

Colorless
Inflammable 46
 Odor
H2S poisoning is one of the leading cause of accidents in WWTP

5ppm moderate odor

10ppm eye irritation begins

30ppmstrong,unpleasent odor of rotten egg

100 ppm loss of smell

>300ppm unconsciousness, death

47
 Odor
Mercaptan
formed during anaerobic decomposition of organic matter

may cause odor more offensive than that of H2S

Methane(CH4)
principal by-product from the anaerobic decombosition of organic
matter

Colorless, odorless, combustible hydrocarbon with high flue value

Explosion risk

48
 PLANT EMPLOYEES SHOULD BE INSTRUCTED IN SAFETY

MEASURES WHILE WORKING IN AND ABOUT STRUCTURES

WHERE H2S AND CH4 MAY BE PRESENT

VENTILATION, GAS SENSORS, ALARM SYSTEMS

49
 Temperature
Temperature of domestic wastewater is commonly higher than
that of local water supply, because of the addition of warm water
from households

Alkalinity
Domestic wastewater is normally alkaline receiving its alkalinity
from the water supply, the groundwater, the materials added during
domestic use

Metals
Discharged from residental dwellings, groundwater infiltration,
commercial and industrial discharge

50
 Oil and Grease
term used for fats, oils, waxes
Surfactants
•Surface active agents
•Large organic molecules that are slightly soluble in water
•Cause foaming in ww treatment plants
•During aeration of ww  these compounds collect on the
surface of the air bubble and thus
create a very stable foam
•Cause foaming in the surface water into which ww is discharged

51
 Surfactants (cnt’d)
Before 1965  ABS (Alkly-benzene-sulfonate)
resistant to breakdown by biological means

After 1965  LAS (linear –alkly-sulfonate

biodegradable

Come primarily from synthetic detergents

52
PRINCIPAL CONSTITUENTS OF CONCERN IN MUNICIPAL
WASTEWATER TREATMENT
Constituent Reason of Importance Unit operation and process
used to remove
Suspended Solids Can lead to development of sludge Screening
deposits and anaerobic conditions Grit Removal
when untreated wastewater is Sedimentation
discharged Flotation
Chemical precipitation
Filtration
Biodegradable If discharged untreated to the Aerobic suspended growth
organics environment their biological variations
stabilization can lead to the depletion Aerobic attached growth
of natural oxygen resources and to variations
the development of septic conditions Anaerobic suspended growth
variations
Lagoon variations
Chemical oxidation
Advanced oxidation
Membrane filtration
53
 PRINCIPAL CONSTITUENTS OF CONCERN IN MUNICIPAL
WASTEWATER TREATMENT
Constituent Reason of Importance Unit operation and
process used to remove
Nutrients (Nitrogen Both nitrogen and phosphorus, For Nitrogen;
and phosphorus) along with carbon are essential suspended growth
nutriens for growth. When nitrification-denitrification
discharged to aquatic environment variations
these nutrients can lead to the attached growth
growth of undesirable aquatic life. nitrification-denitrification
may cause eutrophication variations
NO2:extremely toxic to fish air stripping
NO3:fatal effects on infants (blue ion exchange
baby sendrome) breakpoint chlorination
For phosphorus;
biological phosphorus
removal
chemical precipitation
Pathogens Communicable diseases can be Chlorine compounds
transmitted by the pathogenic Chlorine dioxide
organisms that may be present in ozonation
wastewater Ultraviolet (UV) radiation
54
Classification of Biological Treatment Processes

• Suspended Growth
• Attached Growth
• Lagoon

55
 Classification of Biological Treatment Systems

Suspended Growth Systems

• Biological treatment processes in which the
microorganisms responsible for the conversion
of the organic matter or other constituents in the
wastewater to gases and cell tissue are maintained
in suspension within the liquid.

56
 Classification of Biological Treatment Systems

Attached Growth (Fixed-film) Systems

• Microorganisms are attached to some inert
medium, such as rocks, slag or especially
designed ceramic or plastic materials.

http://hosted-
p0.vresp.com/567666/4b7fb499d1/
ARCHIVE

57
 Classification of Biological Treatment Systems

Lagoon Systems
• A generic term applied to treatment processes
that take place in ponds or lagoons with various
aspect ratios and depths.

http://www.blackwarriorriver.org/images/Lower
%20Black%20Warrior/lower%20black%20warri
or%20moundville%20lagoon.htm 58
 Objectives of Biological Treatment

1. Transform (i.e. oxidize) dissolved and particulate biodegradable

constituents into acceptable end products.

2. Capture and incorporate suspended and non-settleable colloidal

solids into a biological floc or biofilm

3. Transform or remove nutrients (nitrogen and phosphorus)

4. In some cases, remove specific trace organic constituents and

compounds

59
 Industrial Wastewater Treatment
Important parameters to consider:
• Variable Influent Characteristics
• Suspended Solids
• Organic Loads
• Temperature
• Oil and Grease
• Organic content in terms of BOD and COD
• Refractory substances
• Volatile materials (H2S etc. )
• pH
• Salinity
• Toxic compounds
• Specific metals and/or specific organic compounds (trace/toxic organics)
• Nitrogen and/or phosphorus
• Indicator micro-organisms (e.g. E. Coli) or specific microorganisms.

60
Difficulties Encountered in Biological Treatment of Industrial
Wastewater
High Organic Strength
• Industrial operations generate effluents with high COD conc.
(>1000 mg/L)
• COD values may even exceed 200 g/L in industries such as
polyester manufacturing, olive mills, textile, beverage
production etc.
• High COD values do not have to be a problem as long as
sufficient HRTs are applied.
• Problem is expected when COD concentrations vary too
much.
• In aerobic systems, OUR responds quickly to increased influent
COD and therefore, loading can be controlled.
• In anaerobic systems, overloading can cause system failure due to
increase in VFAs. Overloading may result in decreased removal
efficiency, decreased CH4 production etc.

61
Difficulties Encountered in Biological Treatment of Industrial
Wastewater
pH
• Most treatment plants operate at neutral pH
• Neutralization is the easiest method to deal with
fluctuating influent pH values
• Excessive use of chemicals may be required  spent
caustic from petrochemical industry (pH 12), textile
industry (pH 10).
• Incidental pH shock may also affect the trace metal
availability.
• Bioaugmentation of microorganisms to low or high pH
values may be beneficial. However, it has not been
achieved yet.

62
Difficulties Encountered in Biological Treatment of Industrial
Wastewater

Salinity
• Textile (≈ reactive dyes 60 -100 g/L), petroleum,
leather processing, and food industries may have
saline effluents.
• High salt concentration coincides with high pH –
usually due to use of NaOH to remove H2S.
• Halophilic bacteria can be used in the treatment
of saline wastewater.
• Fluctuation in salinity is not generally observed.
63
Difficulties Encountered in Biological Treatment of Industrial
Wastewater
Temperature
• Most aerobic plants are operated at ambient temperatures
around 20oC
• Most anaerobic systems are operated at 30-35oC (mesophilic).
• Some industries generate high temperature effluents, which
increased use of thermophilic anaerobic systems  Heating
and cooling cost can be avoided
• Use of high temperature aerobic plants are limited due to
problems associated with oxygen solubility at high
temperatures.  Few plant operations have been reported.
• Temperature fluctuations are more of a problem due to direct
effect on microbial efficiency. Fluctuations mostly occur due to
process shifts and shut downs.

64
Difficulties Encountered in Biological Treatment of Industrial
Wastewater

Toxic Compounds
• Industrial wastewaters may contain large variety of
potentially toxic compounds (constant/incidental
appearance)
• Phenols
• Aromatics
• VOCs
• Heavy metals
• Surfactants
• Biocides

65