Wastewater Composition

and
Characterization

Nirmal Ghimire
theneermal@gmail.com
Why do we use water?

• For transporting waste

• Washing car
• Cleaning dishes or clothes
• Flusing toilets

• Majority of water consumed is

used in transportation of waste!!!

• During the waste transportation,

several contaminants need to be
handled or removed before
discharge.
Wastewater contaminants
• Physical characteristics
• TS, TSS, VS, VSS, TDS, Turbidity, Odor, Color etc.
• Inorganic chemical characteristics
• NH4+, NO3-, PO43-, alkalinity, chloride, metals, various gases etc.
• Organic chemical characteristics
• BOD, COD, TOC etc.
• Biological characteristics
• Coliform organisms, specific microorganisms, toxicity etc.
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Principal Wastewater contaminants
• Suspended solids
• Biodegradable organics
• Pathogens
• Nutrients
• Priority pollutants
• Refractory organics
• Heavy metals
• Dissolved inorganics
Important constituents in
water and wastewater
Important constituents in
water and wastewater
Characterization by size

• Elemental composition is often

characterized into size fractions:

Soluble: Si [g/m3]
Colloidal: Ci [g/m3]
Particulate: Xi [g/m3]
Total: it = (Si+Ci+Xi) [g/m3]

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Suspended versus dissolved
• The most basic characteristic used for water and wastewater analysis
introduced by Goldberg (1952)
• Analysis by filtration, e.g.: GF/C filter (Depth filter based on random
glass fibers, nominal pore size: 1.2µm) Suspended: Any spherical
particle, or aggregate, larger than a cut off size: e.g. > 1 µm
• Dissolved: Any spherical particle, aggregate, or molecule smaller than
the cut off size: < 1 µm A: GF/C depth filter
B: 0.45 µm cellulose-
acetate
C: 1 µm Polycarbonate
Nucleopore

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Organic versus Inorganic
• The second most basic characteristic is the distinction made between
organics and inorganics.
• Organics: Any material that will be oxidized to CO2, H2O by oxygen
(air); Combusted ® Volatilize

• Inorganics: Any material not combusted (volatilized) ® Non-

volatilized.
• Normally determined by heating (550°C) in air (oxygen).
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Solids

• Total solids- the matter that remains as residue upon evaporation and drying at 103 to 105 °C
• Dissolved solids: solids present in a sample which are not retained on a filter
• Suspended solids: solids present in a sample which are retained on a filter.
• Volatile solds: solids which volatilize or ignite when heated to 550 °C. These solids are
interpreted as the organic fraction of the solids
• Fixed solids: those solids which remain after ignition at 550 °C. They are classified as the
mineral or non-organic fraction.
• Settleable solids: solids in suspension that will settle under quiescent conditions in a
reasonable amount of time
Note: The most important factors concerning the strength of sewage are BOD5 and volatile
suspended solids. Most design is based upon these two parameters.

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Particle classification
• By composition:
• Organic/Volatile
• Inorganic/Fixed
• (Easily/Slowly) Biodegradable
• Non-biodegradable
• By size:
• Settleable
• Suspended
• Colloids
• Macromolecule/Polymers
• Dissolved/mono- and oligomeric
Sources of Inorganic Nonmetallic Constituents
• pH
• Chlorides
• Alkalinity
• Nitrogen
• Sources and Forms of Nitrogen
• Nitrogen Fractions in Wastewater
• Nitrogen Pathways in Nature
• Phosphorus
• Phosphorus in wastewater
• Sulfur
• Gases
• Oxygen (O2), Hydrogen sulfide (H2S) and Methane (CH4)
• Odor

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Alkalinity
• Alkalinity is defined as ability to buffer proton fluctuations (acids and bases).
• May be calculated by combining the buffering effect of all bases (minus the free
proton).
• Important for pH dependant biological and chemical reactions (treatment).
• In practise determined as the amount of strong acid (eg. HCl) needed to titrate a
solution to pH 4.5, known as the bicarbonate alkalinity.
• It is normally represented as the amount of CaCO3 equivalent amount of bases in
solution.
• Other base species also contribute: Silicates, Phosphates, Borate, Nitrogen species
and conjugated bases of organic acids.
• Hence; Alkalinity is an aggregate parameter (lumped parameter) determined
experimentally.
Nitrogen in wastewater
Human Secretion as urea
Part of particulate organics as amine groups on
proteins and DNA, nitrogroups on sugars
All species converted to Ammonia during hydrolysis
of urea and proteins = Ammonification
Oxidized by aerobic autotrophic chemolitotrophs,
Nitrifying bacteria, in the process of Nitrification.
Dominant N-species in raw wastewater:
CON2H4, C4H9N3O2, C5H4N4O3, R1R2NH2,
NH4+, NO2-, NO3-, NO2, NO, N2O, N2
Org-N + H2O à NH3/NH4+
NH4+ + O2 + CO2 à C5H7NO2 + NO2-
NO2- + O2 + CO2 à C5H7NO2 + NO3-

Nitrification proceede via the intermediate nitrite and

involves two groups of bacteria.
NO3- + org-C à C5H7NO2 + N2 + CO2
Reduced by facultative anaerobic heterotrophs to
nitrogen gas via a series of nitrogen oxide species =
Denitrification NO3- à NO2- à NO à N2O à N2
Nitrogen forms and lumped parameters
Nitrogen in aquatic systems
Phosphorous

• Two forms
Inorganic P: Salts from Phosphoric
acid, Polyposphate
Organically bound P
• No gasous species.
• While N is limiting nutrient for
eutrophication in the sea, P is in
freshwater systems (normally).
• Low metals solubility products à
Precipitates with Fe3+ and other
metals.
Phosphorous in wastewater
TOTAL PHOSPHOROUS
Phosphate Polyphosphate
• Dissolved P: Organic P (dissolved) Particulate org. P
Particulate adsorbed P Amorphic P
• Phosphate, H0-3PO43-0

Amorphic P
• Polyphosphate

5%
Particulate
adsorbed P
10%
• Organic Phosphorous
Phosphate
• Particulate P: 38%

• Organic P Particulate
org. P
29%
• Particle adsorbed P
• Amorphic mineral P
Organic P Polyphosphate
(dissolved) 9%
9%
BOD and COD
• Biochemical oxygen demand and chemical oxygen demand (mg/L)
• Add organic compound to a water source. What will happen?
• The microorganisms in the water body will eat the organic compound
• Their cellular respiration will increase
• They will consume dissolved oxygen
• They will reproduce
• The new microorganisms will consume organic compound and demand dissolved
oxygen

• BOD is the demand for oxygen- caused by an organic material being broken down by
microbes
• COD is the measure of the oxygen equivalent of the organic material in wastewater that can be
oxidized chemically (using dichromate in an acid solution).
• COD is always higher than BOD. Why?
Theoretical COD
Propionate:

• The oxygen consumed by any

C3H6O2 + a O2 à 3 CO2 + 3 H2O
compound may be theoretically
estimated assuming full oxidation of the
electron donor to CO2/HCO3-, H2O, H+ a = 3.5 mole O2/mole S
and NH3/NH4+. = 1.51 g O2/g S
• The theoretically estimated oxygen
demand is also called ThCOD
(theoretical chemical oxygen demand).
• The general formula for C,H,O,N CnHaObNc + d O2 à n CO2 + (a/2 – 3c/2) H2O + c NH3
containing compounds is:
• ThCOD is always given as mass units: a b 3× c
d = n+ - -
!"! 4 2 4
32 #$%&
ThCOD = d.!" " !

,"#$"%&'%(
Chemical principles for ThCOD

• All Carbon is converted to CO2 (full oxidation)

• All excess hydrogen forms H2O (full oxidation)
• All inorganic species (apart from reduced S) keep their degree of reduction (no e-
transferred)
• Use protons (H+) for balancing charge
• Example: C12H19O6N4P
C12H19O6N4P + 12 O2 à 12 CO2 + 4NH3 + H3PO4 + 2 H2O

ThCOD = 1.1 g/g

Usefulness of COD
• COD is an easy way of measuring organic
substrate concentration in undefined mixes.
• COD represents the theoretical oxygen
The primary
demand for full oxidation. chemical
• COD represents the primary saprobiation characteristic
potential posed by effluents. used in
• COD is a useful indication of the heterotrophic
growth potential of substrates. wastewater
• COD is a conserved parameter during calculations,
reactions, and through that simplifies especially by
stoichiometric calculations.
engineers for
• COD relates to the biological oxygen demand
through the yield. design!
BOD5

• Biochemical oxygen demand is a measure of the

biodegradable organics in the waste. The
subscript «5» indicates a typical length of the
test in days. 5, 7 and 28 days are common.
• About 70 % of ultimate oxygen uptake occurs
during a 5-day BOD test. The figure varies with
the composition of the waste. The test has about
a 10 % margin of error.
• Nitrogen oxidation also occurs (Nitrification).
• Oxygen concentration should not drop below 2-
3 mg/L.

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BOD curve

BODt= UBOD(1 – e -kt)

Or
BODt= UBOD(1 – e -Kt)

k=2.303.K
Ultimate BOD
• Ultimate Oxygen Demand (UBOD) is the maximum oxygen required
to completely consume all of the organic waste: it takes time to use
up the «food».

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Measuring BOD in lab
• Initial DO of water (I) is measured
• Water is put into an air-tight container
• Why should the container be air-tight
• Water incubates in the dark at a fixed temp
• Seeding (adding microbes) might be necessary, in such case DO lost due to
the seed water has to be considered.
• Final DO of water (F) is measured
• BOD = I – F
• Dilution is ofter used when BOD would otherwise remove all the available
DO
Dilution (D) =
)*%'+ ,*%%+( -*+#.(
/'.0+( -*+#.(
BOD = (I-F)*D

3/11/22 29
BOD analysis considerations
• A 3 or 5 day lab analysis may not reveal the true strength of waste
• If «ultimate» BOD is desired, much longer analysis may be needed
• Rate constants vary widely depending on source of waste
• Low rate constant may mask the true effects of a waste with high UBOD
• Same BOD5, different UBOD
• Same UBOD, different BOD5

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In class exercises
1. Modeling of BOD reaction: Show that the BOD exerted up to time t is
given by BODt = UBOD (1 – e–kt)
2. If the BOD of a municipal wastewater at the end of 8 days is 180.9 mg/L
and the ultimate BOD is 212.0 mg/L,what is the rate constant (k) ?
3. Determine the 1-d BOD and ultimate first-stage BOD for a wastewater
whose 5-d, 20 °C BOD is 200 mg/L. What would have been the 5-d BOD
if the test had been conducted at 25 °C? The reaction constant k (base e) =
0.23 day-1 and θ = 1.047.
4. Determine the theoretical BOD and COD for the compound C5H7NO2.
Assume the value of the BOD first-order reaction rate constant (k) is 0.23
day-1.
5. What is the COD of Toulene (C6H5CH3)?

3/11/22 31
Answers
• 2: 0.24 per day
• 3: UBOD = 293 mg/L, BOD1 = 60.1 mg/L and BOD5 at 25 °C = 224
mg/L.
• 4: COD = 1.42 mg O2/ mg C5H7NO2; BOD = 0.97 mg BOD/ mg
C5H7NO2
• 5: COD = 3.13 g O2/g Toulene

3/11/22 32
Questions?