Cls02-1 Characterization of Industrial Wastewater PDF

Characterization
of Industrial
Wastewaters
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Industrial Wastewaters Discharges

As previously examined an industrial discharger
can:
discharge to a body of water (through an
NPDES permit); or
discharge to a POTW (having its own NPDES
permit). In this case the industrial discharger
must pre-treat the wastewater to insure that
the POTW can discharge to the receiving body
of water treated wastewater within the POTWs
NPDES permit limit. In addition the industrial
discharger must have a permit (different from
the NPDES permit).
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Industrial Wastewaters Discharges

(continued)
In any case the wastewater must be treated, one
way or another, to the point where it can be
safely discharged to the receiving body of
water. EPA has defined effluent standards for the
following classes of water contaminants:
conventional pollutants
toxic pollutants (priority pollutants)
non-conventional pollutants
VOCs (Volatile Organic Compounds)
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Conventional Pollutants
BOD5 or carbonaceous BOD

(CBOD)
total suspended solids (TSS)
fecal coliform
oil and grease
pH
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Special Pollutants
Toxic pollutants (Priority pollutants). EPA has
promulgated a list and discharge standards for
organic and inorganic pollutants of special
concern
Non-conventional pollutants.
These are
pollutants that have been identified for control
in specific industries effluent guidelines
VOCs. The Clean Air Act will pose limits on
the concentration of VOCs in industrial
wastewaters directly discharged or discharged
to a POTW
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Undesired Characteristics of
Industrial Wastewater
Soluble organic materials
Suspended solids
Priority organic pollutants
Priority heavy metals
Volatile organic compounds (VOCs)

+
Nitrogen (typically as NH4 or NO3 )
Phosphorus (typically as phosphate)
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Undesired Characteristics of
Industrial Wastewater (continued)
Oil and floating materials
Color and turbidity
Odor
Recalcitrant (refractory) compounds
Temperature
pH
Coliforms and other microorganisms
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Problems Associated with

Wastewater Pollutants
Pollutant
Environmental Problem
Biodegradable
organic compounds
Microbial growth in receiving

bodies; possible toxicity; oxygen
depletion
Suspended solids
Microbial growth in receiving

bodies; deposition of sludge
blanket; possible toxicity; turbidity
Coliform and other

microorganisms
Health problems
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Wastewater Pollutants (continued)
Pollutant
pH
Toxicity to flora, fauna, humans
Oil and grease
Fouling; damages to flora and

fauna
Nutrients (nitrogen,
phosphorous)
Toxicity to aquatic life;

eutrophication
Color
Aesthetics; Inhibition of algal

growth
Temperature
Toxicity to aquatic life
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Pollutant
Surfactants
Toxicity to aquatic life; aesthetics
Mercaptans,
chlorine, smelly
compounds
Odors
Sulfides; sulfates
Toxicity; odor (H2S); pH
Heavy metals
Toxic compounds
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Pollutant
Phenolic
compounds
Toxicity to flora, fauna, humans;

odor
Cyanides
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Problems Associated with Nutrients

(Nitrogen, Phosphorous)
Nitrogen (as ammonia, nitrite and nitrate) and
phosphorous as orthophosphate (PO43-,
HPO42-, H2PO4-) or polyphosphates are present
in many wastewaters because of artificial
fertilizers, human excreta, farm animal waste,
and many industrial processes
These two nutrients can cause significant
problems in the environment if discharged in
appreciable amounts and concentrations
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Problems Associated with Nutrients (cont.d)

Ammonia can be converted by the nitrifying
bacteria to nitrite and nitrate in a two-step
sequence:
. O2 Nitrosomonas
HNO2 + H 2O
NH3 + 15
HNO3
HNO2 + 0.5 O2 Nitrobacter
NH3 + 2O2 HNO3 + H 2O
The rapid oxygen depletion that can result
(especially in warm weather) can result in the
deoxygenation of the water resulting in fish
killing and problems associated with anoxic
condition (e.g., odors)
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Ammonia is a weak base and dissociates in
water according to the reaction:
+
NH3 + H 2O NH 3 H 2O NH4 + OH
Ammonia (especially in its undissociated form)
can be toxic to aquatic life even in small
concentrations
Ammonia concentration below 0.02 mg/L is
considered to be acceptable for fish and other
aquatic life forms
The toxicity of ammonia depends on the pH, as
one can see from the above equation
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Nitrate in drinking water is relatively safe for
adults but quite hazardous for infants below 6
months
Infants do not have a fully developed digestive
tract. Hence, the pH in their stomach is about
4.0 (as opposed to 2.0 in adults). This higher
pH promotes the growth of a bacterium
capable of converting nitrate to nitrite
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Nitrite in the body can interfere with the
oxygen transport mechanism by binding with
hemoglobin
NO2 + Haemoglobin NO3 + Methaemoglobin
thus producing oxygen starvation (blue-baby

syndrome) and even death
Nitrate concentration in drinking water should
be below 50 mg/L
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Nitrogen and phosphorous are typically the limiting
nutrient for algae (since these organisms can fix
carbon from CO2 and inorganic carbonates via
photosynthesis, if light is present)
If nitrogen and phosphorous are abundant algae can
grow beyond control
This can produce significant increases in pH (due to
the high rate of utilization of inorganic carbonates
acting as buffer in the water), and fluctuation in pH,
as well as anaerobic conditions at night when the
algae respire
A water course in which such abnormal algal growth
condition takes place is said to be eutrophic
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Typical Industrial Wastewater

Contaminants
Industry
Characteristics of Wastewaters
Food Processing High in dissolved organics--mainly

(dairies)
protein, fat and lactose
Meat and poultry High in dissolved and suspended
processing
organics, including protein, blood,
greases, fats and manure
Fruit and
vegetable
canneries
High in dissolved and suspended

organics from natural products
After Goronsky et al., Chemical Engineering, June 1992, p. 80.

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Contaminants (continued)
Industry
Breweries and
distilleries
High in dissolved and suspended

organics
Pharmaceuticals High in dissolved and suspended

organics,
including
some
surfactants and biological agent
Organic chemicals Dissolved organics, including acids,
aldehydes, phenolics, and free and
emulsified oils
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Industry
Petroleum refining Phenolics, free and emulsified oils,

and other dissolved organics
Pulp and paper
Dissolved and suspended organics

and inorganics
Plastics and
resins
Dissolved organics, including acids,

aldehydes, phenolics, cellulose,
alcohols, surfactants and oils

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Industry
Explosives
Organic acids and alcohols, soaps

and oils
Rubber
Dissolved and suspended organics

and oils
Textiles
Dissolved and suspended organics,

fats and oil

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Industry
Leather tanning
and finishing
Dissolved and suspended organics,

fats and oils, organic nitrogen, hair
and fleshings
Coke and gas
High in phenolics, ammonia and

dissolved organics

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Major Wastewater Contaminants from

Industrial Sources
Industry
(Food)
Origin of
Contaminants
Characteristics of
Contaminants
Canning
Fruit and vegetable

preparation
Colloidal, dissolved
organic matter,
suspended solids
Dairy
Whole milk dilutions,

buttermilk
Dissolved organic matter

(protein, fat, lactose)
Brewing,
distilling
Grain, distillation
Dissolved organics,
nitrogen fermented
starches
After Corbitt, The Standard Handbook of Environmental Engineering, 1990, p. 6.31
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Industrial Sources (continued)
Industry
(Food)
Origin of
Contaminants
Characteristics of
Contaminants
Meat, poultry
Slaughtering,
rendering of bones
and fats, plucking
Dissolved organics,
blood, proteins, fats,
feathers
Sugar beet
Handling juices,
condensates
Dissolved sugar and

protein
Yeast
Yeast filtration
Solid organics
Pickles
Lime water, seeds,

syrup
Suspended solids,
dissolved organics,
variable pH
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Industry
(Food)
Origin of
Contaminants
Characteristics of
Contaminants
Coffee
Pulping and
fermenting beans
Suspended solids
Fish
Pressed fish, wash

water
Organic solids, odor
Rice
Soaking, cooking,
washing
Suspended and
dissolved carbohydrates
Soft drinks
Cleaning, spillage,
washing
Suspended and
dissolved carbohydrates
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Industry
(Pharm., Textile)
Origin of
Contaminants
Characteristics of
Contaminants
Antibiotics
Mycelium, filtrate,
washing
Suspended and
dissolved organics
Textiles
Desizing of fabric
Suspended solids, dyes,

alkaline
Leather
Cleaning, soaking,
bathing
Solids, sulfite,
chromium, lime, sodium
chloride
Laundry
Washing fabrics
Turbid, alkaline, organic

solids
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Industry
(chemical)
Origin of
Contaminants
Characteristics of
Contaminants
Acids
Wash waters, spillage
Low pH
Detergents
Purifying surfactants
Surfactants
Starch
Evaporation, washing
Starch
Explosives
Purifying and washing TNT, organic acids, acid,

TNT, cartridges
oil soaps
Insecticides
Washing, purification
Organics, benzene, acid

highly toxic
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Industry
(chemical)
Origin of
Contaminants
Characteristics of
Contaminants
Phosphate
Washing, condenser
wastes
Suspended solids,
phosphorous, silica, oils,
fluoride, clays, low pH
Formaldehyde
Formaldehyde
Residues from
synthetic resin
production and dyeing
synthetic fibers
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Industry
(others)
Origin of
Contaminants
Characteristics of
Contaminants
Pulp and paper
Refining, washing,
screening of pulp
High solids, extremes of

pH
Photographic
products
Spent developer and

fixer
Organic and inorganic

reducing agents alkaline
Steel
Coking, washing blast Acid, cyanogen, phenol,

furnace, flue gases
coke, oil
Metal plating
Cleaning and plating
Metals, acid
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Industry
(others)
Origin of
Contaminants
Characteristics of
Contaminants
Iron foundry
Various discharges
Sand, clay, coal
Oil
Drilling, refining
Sodium chloride, sulfur,

phenol, oil
Rubber
Washing, extracting
impurities
Suspended solids,
chloride, odor, variable
pH
Glass
Polishing, cleaning
Suspended solids
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Wastewater Characterization and

Analysis
The characteristics of wastewater
classified into three major categories:
can
be
Physical characteristics
Chemical characteristics
Biological characteristics
Each one of these categories can be further
broken down and associated to different types of
tests and measurements.
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Units Commonly Used in

Wastewater Analysis
Physical Characteristics of Wastewater

The most important parameters used
characterize
the
physical
properties
wastewater are:
Solids content
Odors
Temperature
Density
Color
Turbidity
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to
of
Importance of Suspended Solids in

Wastewater Treatment
The solids content in industrial wastewater vary
greatly, depending on the process generating
the wastewater
Typically, suspended solids carry a significant
portion of organic material, thus significantly
contributing to the organic load of the
wastewater (solids can contribute up to 60% of
the BOD of a wastewater)
Hence, effective solids removal can significantly
contribute to wastewater treatment
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Size Range of Organic

Contaminants
Classification of Solids in Wastewaters

Total Solids (TS)
(Total) Suspended Solids ((T)SS)
Volatile Suspended Solids (VSS)
Fixed Suspended Solids (FSS)
Total Volatile Solids (TVS)
(Total) Dissolved Solids ((T)DS)
Volatile Dissolved Solids (VDS)
Fixed Dissolved Solids (FDS)
Total Fixed Solids (TFS)
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Additional Terms Used to

Characterize Solids in Wastewaters
Settleable solids
Filterable solids
Colloidal solids
Soluble solids
Volatile solids organic (do not confuse
with VOCs)
Nonvolatile solids inorganic
(Volatile organic compounds)
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Explanation of Terms in Wastewater

Solids Analysis
The term dissolved means in solution
(sometime also including colloidal particles)
The term suspended means in suspension
The term volatile means vaporized when
sample is heated to 550 50 C, and is
representative of the organic content of the
solids
The term fixed means residual when sample
is heated to 550 50 C, and is representative
of the inorganic content of the solids
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Solids Found in
Wastewater
Suspended and Filterable Solids

Settleable
Solids
Organic
Inorganic
Suspended
Solids
Organic
Non-Settleable Solids
Inorganic
Sample
Colloidal
Solids
Organic
Inorganic
Filterable
Solids
Organic
Dissolved
Solids
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Inorganic
Example of Classification of Solids in

Wastewater
Volatile
(80mg/L)
Non-Settleable
Solids (100 mg/L)
Fixed
(20 mg/L)
Total Suspended
Solids (250 mg/L)
Volatile
(110mg/L)
Settleable
Solids (150 mg/L)
Total Solids
(600 mg/L)
Fixed
(45 mg/L)
Volatile
(160mg/L)
Total Dissolved
Solids (350 mg/L)
Fixed
(190 mg/L)
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Total Solids
Sample
Evaporation
Total
Solids
Temperature = 103-105 C
Any low boiling point compounds in the water will
vaporize and will be lost during this analysis.
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Settleable Solids
Typically, most solids above 10 m can be
separated by sedimentation or filtration
A rough indication of the solids that can be
separated by sedimentation or filtration can be
obtained by determining the fraction of
settleable solids, defined as those solids that
will sediment in a 1-hour period in a standard
Imhoff cone
Solids below 1 m typically require other types
of separation methods to be removed
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Settleable Solids (continued)

Sample
Imhoff Cone
Settleable
Solids
60 minutes
Imhoff Cone
The results of this test are typically reported as volume of

solids (mL) per volume (L) of wastewater.
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Determination of Total Suspended

Solids by Filtration
This test is carried out by filtering the wastewater
through a 0.45 m membrane filter (or a fiber pad
filter) and then measuring the dry weight
(obtained by drying the filter and its content at
103-105 C) of the material so collected.
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Determination of Volatile and Fixed

Solids Fraction by Ignition
When a material is heated at 550 50 C (a
process called ignition) its organic content
is decomposed to water, carbon dioxide and
carbon monoxide, and ammonia, which are all
volatilized and removed from the sample
(volatile component)
The inorganic content of the material,
represented by oxides, carbonates and other
salts, is not volatilized and remains as residue
(fixed component)
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Suspended Solids in Activated Sludge

Reactors (MLSS and MLVSS)
In activated sludge reactors the biomass, in the form of
microbial flocs and suspended microorganisms, is
responsible for most of the degradation activity.
A measure of the biomass and the inerts in activated
sludge reactor is given by the mixed liquor suspended
solids (MLSS), i.e., the total suspended solids
concentration (in mg/L).
A more precise measure of the biomass concentration
alone is given by the mixed liquor volatile suspended
solids (MLVSS), since most of the organic material in
activated sludge reactor is present as biomass. The
MLVSS is typically 80% of the MLSS value.
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Generation of Odors in Wastewaters

Odors in wastes and wastewaters are typically the
result of the emission of gases resulting from the
anaerobic decomposition of organic matter
contained in the waste
Example: generation of hydrogen sulfide under
sulfidogenic
conditions
by
Desulfobacter
hydrogenophilus (using acetate as electron
donor):
CH3COO + SO4
HS + H + H2S
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2 HCO3 + HS
Importance of Odors
Odors have been rated as the number one
concern by local communities during siting
of new wastewater treatment facilities
Although most odorous substances are not
toxic at the concentrations at which they
can be detected by humans odors can
produce significant psychological stress
In a community the presence of odor can
result in public reaction, as well as a
decline of market and rental property
values
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Human Sensitivity to Odors

The human nose is a very sensitive
detection instrument for a number of
organic
and
inorganic
compounds
(typically
containing
sulfur
and/or
nitrogen), such as hydrogen sulfide,
ammonia, chlorine, mercaptans, etc.
On the other hand many inorganic gases
such as methane, carbon dioxide, carbon
monoxide, nitrogen, and oxygen (even
dissolved oxygen in water) are odorless
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Odor Measurement
Compounds that can be easily detected by
instruments (e.g., hydrogen sulfide) are
typically analyzed with portable detector
The measurement of other odorous
compounds and complex odors is typically
carried out using a sensory method in
which a panel of human subjects are
exposed to odor samples diluted with odorfree air
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Minimum Detectable Threshold Odor

Concentration and D/T Value
The smallest concentration at which an odor
can be detected by the average person (50%
percentile) is called the minimum detectable
threshold odor concentration (MDTOC)
The number of dilutions required to bring the
odor concentration below the minimum
detectable threshold odor concentration
(MDTOC) is called the dilution to threshold
(D/T), and is an indication of the concentration
of the odor
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Odorous Compounds Associated

with Untreated Wastewater
Compound
Formula
Odor Quality
Amines
CH3NH2, (CH3)3H
Fishy
Ammonia
NH3
Ammoniacal
Diamines
NH2(CH2)4NH2, NH2(CH2)5NH2
Decayed flesh
Hydrogen sulfide
H2 S
Rotten eggs
Mercaptans (e.g.,
methyl and ethyl)
CH3SH, CH3(CH2)SH
Decayed
cabbage
Mercaptans (e.g.,
butyl and crotyl)
(CH3)3CSH, CH3(CH2)3SH
Skunk
Organic sulfides
(CH3)2S, (C6H2)2S
Rotten cabbage
Skatole
C9 H9 N
Fecal matter
After Metcalf and Eddy, Wastewater Engineering, 1989, p. 57

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Selected Odor Threshold Concentrations

Chemical Compound
Formula
Odor Threshold (ppm by volume)
Carbon disulfide
Acetaldehyde
Hydrogen sulfide
Nitrogen compounds
Skatole
Ethyl Mercaptan
Methyl Mercaptan
Chlorine
Ammonia
Perchloroethylene
Phenol
CS2
C2H4O
H2S
0.21
0.21
0.00047
0.00021-100.0
0.019
0.001-0.00026
0.041-0.0021
0.314
37
4.68
0.6
C9H9N
C2H6S
CH4S
Cl2
NH3
C2CI6
C6H5OH
After Cheremisinoff, Nation. Environ. J., Feb. 1995, p. 29

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Odor Threshold Concentrations

Chemical Compound
Formula
Ammonia
Chlorine
Dimethyl sulfide
Diphenyl sulfide
Ethyl Mercaptan
Hydrogen sulfide
Indole
Methyl Amine
Methyl Mercaptan
Skatole
NH3
Cl2
(CH3)2S
(C6H5)2S
CH3CH2SH
H2S
C8H7N
CH3NH2
CH3SH
C9H9N
Odor Threshold (ppm by volume)

Detection
Recognition
17
0.080
0.001
0.0001
0.0003
< 0.00021
0.0001
4.7
0.0005
0.001
37
0.314
0.001
0.0021
0.001
0.00047
0.001
0.019
After Metcalf and Eddy, Wastewater Engineering, 1989, p. 58

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Chemical Characteristics of Wastewater

The most important parameters used
characterize
the
chemical
properties
wastewater are:
Organic material
Inorganic material
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to
of
Organic Material in Wastewater
Total organic material

Proteins
Carbohydrates
Fats, oils, and grease
Pesticides
Phenols
Priority pollutants
Refractory pollutants
Surfactants
Volatile organic compounds
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Inorganic Material in Wastewater
H+ (pH)
Alkalinity
Heavy metals
Nitrate and nitrite
Ammonia
Phosphorous
Sulfate and sulfite
Sulfide
Chloride
Oxygen
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Analysis of Organic Compounds in

Wastewaters
Specific organic compounds can be detected in
wastewater
samples
using
standard
analytical
techniques such as:
Gas chromatography (GC)
High performance liquid chromatography (HPLC)
Spectrophotometry (ultraviolet (UV), visible, infrared
(IR))
Mass Spectroscopy
Gravimetric methods
Colorimetric methods
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Analysis of Inorganic Compounds in

Wastewaters
Specific inorganic compounds can be detected in
wastewater samples using standard analytical
techniques such as:
Atomic absorption
Ion sensitive electrodes
Ion chromatography
Gravimetric methods
Colorimetric methods
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Determination of the Organic Content

of Wastewaters
A number of methods have been devised over
the years to measure the gross concentration
of organic matter present in wastewater
All these methods are non-specific
These methods assume that the organic matter
can (1) either be attacked by aerobic
microorganisms, or (2) be chemically oxidized.
In both cases, the degradation reactions
consume measurable amounts of oxygen or
produce measurable amounts of products
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Determination of the Organic Content

of Wastewaters (continued)
These methods are:
Biological Oxygen Demand (BOD) including
5-day BOD (BOD5), ultimate BOD (BODu),
carbonaceous BOD (CBOD)
Chemical Oxygen Demand (COD)
Total Oxygen Demand (TOD)
Theoretical Oxygen Demand (ThOD)
Total Organic Carbon (TOC)
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Total volatile solids and volatile solids in
general (as determined by the ignition
test) are only a crude measure of organic
matter
TVS determinations are not typically used
to assess and report the concentration of
organics in wastewater
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Biological Oxygen Demand (BOD)

Under aerobic conditions the microorganisms
contained in the wastewater typically have the
ability to attack and degrade the organic
matter in the wastewater according to the
following reaction:
Organic Matter + O2 Bacteria
New Microorganisms + CO2
+ Waste Products + NH 3
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BOD (Continued)
The BOD of a wastewater is defined as the amount
of oxygen required by aerobic microorganisms to
(partially) oxidize the organic matter in a known
volume of wastewater according to a standardized
test
BOD is typically expressed in mg of oxygen/L of
wastewater
The test consists of incubating for a fixed period of
time a sample of the wastewater (appropriately
diluted) at constant temperature, and measuring
the amount of residual oxygen at the end of the
test to determine the amount of oxygen consumed
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BOD (Continued)
When different BOD bottles are identically set up different
BOD curves may result depending on the concentration of
microorganisms and the initial rate s of oxidation
Cumulative Oxygen Uptake (%)
100%
Bottle #1
Bottle #2
Bottle #3
80%
60%
40%
20%
0%
0
Time (days)
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BOD5
In order to reduce the scatter in BOD results due
to different initial oxidation rates the BOD at 5
days is determined. Such a BOD test is typically
referred to as BOD5 test.
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BOD5 Apparatus
After Horan, Biological Wastewater Treatment Systems, 1990, p. 3

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BOD Curve
400
350
BOD (mg/L)
300
BODNu
250
NBOD
200
BODu
150
100
CBOD
50
BOD5
0
0
10
20
30
Time (days)
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40
50
BOD Curve (Continued)

Typically, during the first 5 days some 60-70%
of the biodegradable organic material has
been oxidized
If the process is allowed to continue typically
95-99% of the biodegradable organic material
is oxidized by day 20
Eventually, for t all the biodegradable
organic material is oxidized and yielding the
ultimate BOD (BODu)
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After some 12 days the slower-growing
nitrifying bacteria present in the wastewater
may have grown to the point where their
presence begins to be felt. These organisms
oxidize ammonia, consuming extra oxygen
. O2 Nitrosomonas
HNO2 + H 2O
NH3 + 15
HNO3
HNO2 + 0.5 O2 Nitrobacter
NH3 + 2O2 HNO3 + H 2O
The presence of nitrifying bacteria can be
observed in the BOD curve
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One of the reasons to limit the BOD test at t = 5
days is to minimize the effect of the presence
of nitrifying organism on BOD determination
To eliminate the interference due to
bacteria inhibitors (methylene blue,
allyl thiourea) can be added. The
obtained is called Carbonaceous
CBOD
nitrifying
thiourea,
BOD so
BOD or
The extra BOD resulting from the presence of

nitrifying bacteria is called Nitrogenous BOD
or NBOD
PIERO M. ARMENANTE
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Popularity of BOD Test

Despite its limitation BOD tests are routinely
performed for a number of reasons:
the test has been in use a long time and is
familiar to most scientist and engineers
is used to determine compliance
it is an approximate measure of the
degradation capacity of organic matter by
microorganisms
can be used to preliminary design some
treatment facilities
is a measure of process efficiency
PIERO M. ARMENANTE
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Limits of BOD Test

The BOD test has significant limitations:
does not have stoichiometric validity at all
times since the microorganisms go through
different phases of utilization of organic matter
is a lengthy test
only biodegradable organics are measured
the results may change depending on how well
the microbial population is acclimated to the
pollutants in the wastewater (this is especially
true for industrial wastewaters)
PIERO M. ARMENANTE
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Chemical Oxygen Demand (COD)

The COD is the equivalent amount of oxygen
required to chemically oxidize the organic matter
contained in a known volume of wastewater using
a standard test in which a strong oxidant
(potassium dichromate) is used
COD is typically expressed in mg of oxygen/L of
wastewater
The test consists of adding to a wastewater
sample a solution of a strong oxidizing agent
(potassium dichromate) in a strongly acidic
medium (H2SO4) containing a silver sulfate
catalyst. The sample is refluxed at 150 C for 2-3
hours
PIERO M. ARMENANTE
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COD (continued)
Nearly all organic material is typically oxidized
in this test. Example: reaction of a known
organic material (potassium phtalate) during
the COD test:
2 KC8 H 5O4 + 10 K2Cr2O7 + 41H 2SO4

16 CO2 + 46 H2O + 10 Cr2 (SO4 )3 + 11K2SO4
Each molecule of potassium dichromate has
the same oxidizing power as 1.5 molecules of
O2
PIERO M. ARMENANTE
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COD (continued)
The residual concentration of dichromate at
the end of the reaction is determined by back
titration with ferrous sulfate:
3 Fe 2+ + Cr 6 + 3 Fe 3 + + Cr 3 +
Ferroin (1,10-phenanthroline) is used as endpoint indicator since it forms a red compound
in the presence of Fe2+ ions but is colorless in
the presence of Fe3+
Some aromatic compounds (such as pyridine,
benzene, toluene) as well as ammonia will not
be oxidized during the test
PIERO M. ARMENANTE
NJIT
COD (continued)
Chloride ions can interfere with the test by
reacting with the dichromate. These ions can
be removed by first adding mercury sulfate to
the sample
Since nearly all the organic material is
oxidized in the COD test (whereas the same
may not be true for the BOD test) the COD
values are typically higher than the
corresponding BOD values
PIERO M. ARMENANTE
NJIT
Total Oxygen Demand (TOD)

The TOD of a wastewater is defined as the
amount of oxygen required to oxidize the
organic matter in a known volume of
wastewater using a high temperature oxidation
process
TOD is typically expressed in mg of oxygen/L
of wastewater
The test consists of introducing a small
volume sample (typically 40 L) in a stream of
a carrier gas containing oxygen, that is then
passed on a catalyst bed at 900 C
PIERO M. ARMENANTE
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TOD (continued)
All organic and inorganic materials in the
sample are oxidized to their respective oxides
A detector is used to determine
concentration of oxygen at the outlet.
knowing the concentration of oxygen in
carrier gas it is possible to determine
oxygen consumed in the process
the
By
the
the
The test is typically quite rapid (less than 5

minutes) and can be automated
PIERO M. ARMENANTE
NJIT
TOD (continued)
Non-biodegradable compounds (e.g., plastics)
are also oxidized in the test, and the oxygen so
consumed also enters the TOD value
Since all organic and inorganic materials are
oxidized in the TOD test (whereas the same
may not be true for the BOD test and even the
COD test) the TOD values are typically
significantly higher than the corresponding
BOD values and slightly higher than the COD
values
PIERO M. ARMENANTE
NJIT
Theoretical Oxygen Demand (ThOD)

The ThOD of a wastewater is the theoretical
amount of oxygen necessary to oxidize all
organic matter in a known volume of wastewater
ThOD is typically expressed in mg of oxygen/L of
wastewater
ThOD can only be calculated only if the species
being oxidized and their concentrations in the
wastewater are known.
Example: ThOD of
glucose:
C6 H12O6 + 6 O2 6 CO2 + 6 H2O

For each mmol/L of glucose in solution (180
mg/L) the ThOD is 192 mg/L
PIERO M. ARMENANTE
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Total Organic Carbon (TOC)

The TOC of a wastewater is the amount of
organic carbon present in a known volume of
wastewater as measured in a standard test
TOC is typically expressed in mg of carbon/L
of wastewater
The test is similar to the TOD test in that the
sample is injected in a stream of a carrier gas
containing oxygen, that is then passed on a
catalyst bed at 900 C.
However, the
concentration of carbon dioxide generated in
the process is measured and converted to the
corresponding carbon concentration
PIERO M. ARMENANTE
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TOC (continued)
Inorganic carbonates could contribute to the
generation of carbon dioxide. Therefore they
are typically removed prior to the TOC analysis
by acidification and/or air stripping
PIERO M. ARMENANTE
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Advantages and Disadvantages of

BOD, COD, TOD and TOC Tests
Test
Advantages
Disadvantages
BOD
Simple, familiar to most

engineers, very common;
no special apparatus
required
COD
Simple; good reproducibil- Some aromatics and ammonia are not

oxidized; not representative of
ity (5-10%); no special
biodegradation; interference from chlorides
apparatus required
TOD
Rapid; excellent
reproducibility (3-6%);
can be automated
Requires expensive apparatus and skilled

technician
TOC
Same as TOD
Same as TOD; interference from inorganic

carbonates; less familiar units
PIERO M. ARMENANTE
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Long incubation periods; poor

reproducibility (15%); results are affected
by microorganisms in seed; results may not
represent actual reactor conditions
Correlations Among BOD, COD, TOD

and TOC
In general, the results of each test are highly
dependent on the wastewater being tested
To date, no successful correlation has been
generated among BOD, COD, TOD and TOC
This is not surprising since the ratios among
these variables can be calculated to be
different for different pollutants
PIERO M. ARMENANTE
NJIT
Typical Relationships Among BOD,

COD, and TOC
Ratio
Typical Value of Ratio
BOD5/ThOD
45-55%
COD/ThOD
80%
TOC/ThOD
30%
BOD5/COD
50-60%
BOD5/TOC
130-250%
COD/TOC
175-665%
PIERO M. ARMENANTE
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Determination of Nitrogen
Concentration in Wastewaters
Organic nitrogen is determined via the Kjeldahl
method consisting of a digestion process
through which the nitrogen is converted to
ammonia followed by the titration of ammonia
Concentration of nitrites is not typically
measured since they are easily converted to
nitrates
Nitrate concentration is determined with
colorimetric methods or via specific electrodes
PIERO M. ARMENANTE
NJIT
Typical Composition of Domestic Wastewater and

Removal Efficiency of Conventional Treatment Plants
Parameter
Concentr.
Range
(mg/L)
Typical
Concentr.
(mg/L)
% Removal % Removal
(Primary
(Secondary
Treatment) Treatment)
BOD5
100-400
250
10-30%
>90%
COD
200-1,000
500
10-30%
70-80%
TOD
200-1100
500
10-30%
70-80%
TOC
100-400
250
10-30%
60-80%
After Sundstrom and Klei, 1979, Wastewater Treatment, p. 11.
PIERO M. ARMENANTE
NJIT

Parameter
Concentr.
Range
(mg/L)
Typical
Concentr.
(mg/L)
Total N
15-90
40
Organic N
5-40
25
Ammonia
10-50
25
% Removal % Removal
(Primary
(Secondary
35%
40%
50-80%
0-20%
Nitrites
Produced
Nitrates
Produced
PIERO M. ARMENANTE
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Parameter
Concentr.
Range
(mg/L)
Typical
Concentr.
(mg/L)
Total P
5-20
12
Organic P
1-5
Inorganic P
5-15
10
pH
7-7.5 units
7.0 units
Calcium
30-50
40
Chloride
30-85
50
Sulfate
20-60
15
% Removal % Removal
(Primary
(Secondary
0-15%
20-40%
PIERO M. ARMENANTE
NJIT

Parameter
Concentr.
Range
(mg/L)
Typical
Concentr.
(mg/L)
% Removal % Removal
(Primary
(Secondary
Total Solids
300-1,200
700
Total Settleab.
Solids
TSS
50-200
100
100-400
220
50-90%
TVS
70-300
150
60-90%
TDS
250-850
500
5%
Total Dissolv.
Volatile Solids
100-300
150
30%
90%
PIERO M. ARMENANTE
NJIT
Composition of Effluents
from Typical Industrial
Facilities
Composition of Effluents from

Different Industrial Plants
Parameter
Pharmac.
Industry
Textile
Industry
Beet-Sugar Coke-Oven
Waste
Liquor
BOD5 (mg/L)
15,250
2,000
930
1,200
COD (mg/L)
28,540
5,000
1,601
3,900
SS (mg/L)
5,400
4,000
1,015
950
Ammonia
(as N; mg/L)
6.3
450
Total N (mg/L)
5,166
16.4
490
pH
9.3
12.0
7.1
5.5
PIERO M. ARMENANTE
NJIT
Composition of Leachates from

Typical Landfill Sites
Parameter
Leeds (UK)
Bucks County
(USA)
New York (USA)
BOD5 (mg/L)
6,000
12,500
10,040
COD (mg/L)
12,000
18,500
7,500
600
686
900
SS (mg/L)
Ammonia
(as N; mg/L)
70
150
Total N (mg/L)
748
350
pH
6.2
6.7
4.3

PIERO M. ARMENANTE
NJIT

Effluent Limitations
Parameter
Concentration (mg/L)
COD
300-2,000
BOD
100-300
Oil & Grease/TPH
15-55
TSS
15-45
pH
6.0-9.0
Temperature
< 40 C
Color
2 color units
NH3/NO3
1.0-10
Phosphates
0.2
Heavy Metals
0.1-5.0
Surfactants
0.5-1.0 (total)
Sulfides
0.01-0.1
Pollutants Used in the Definition of Effluent

Standards for Different Industries (EPA, 1973)
Parameter
BOD5
COD
Automobile
Beverage
Canning
Fertilizer
TOC
Total Solids
Susp. Solids
Settleable Solids
Tot. Diss. Solids
Meat
Products
TOD
pH
Inorgan.
Organ.
Chemicals Chemicals
Vol. Susp. Solids

Oil & Grease
PIERO M. ARMENANTE
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Standards for Different Industries (continued)
Parameter
Automobile
Beverage
Canning
Fertilizer
Inorgan.
Organ.
Chemicals Chemicals
Heavy Metals
Chromium
Copper
Nickel
Iron
Zinc
Arsenic
Mercury
Lead
Tin
Cadmium
PIERO M. ARMENANTE
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Meat
Products

Parameter
Automobile
Beverage
Canning
Fertilizer
Calcium
Fluoride
Cyanide
Chloride
Sulfate
Ammonia
Sodium
Silicates
Sulfite
Nitrate
Phosphorous
Urea & Org. N
PIERO M. ARMENANTE
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Inorgan.
Organ.
Chemicals Chemicals
Meat
Products

Parameter
Automobile
Beverage
Color
Total Coliform
Fecal Coliform
Toxic Materials
Temperature
Turbidity
Foam
Canning
Fertilizer
Inorgan.
Organ.
Chemicals Chemicals
Odor
Phenols
Chl. Benz. & PAH

Mercapt/sulfide
PIERO M. ARMENANTE
NJIT
Meat
Products

Standards for Different Industries (EPA, 1973)
Parameter
Metal
Finishing
Pulp &
Paper
Petroleum
Refining
BOD5
COD
Plastics &
Synthetics
TOC
Steel
Textiles
Dairy
TOD
pH
Total Solids
Susp. Solids
Settleable Solids
Tot. Diss. Solids
Vol. Susp. Solids
Oil & Grease
PIERO M. ARMENANTE
NJIT

Parameter
Heavy Metals
Metal
Finishing
Plastics &
Synthetics
Pulp &
Paper
Chromium
Copper
Petroleum
Refining
Steel
Nickel
Iron
Zinc
Arsenic
Mercury
Lead
Tin
Cadmium
PIERO M. ARMENANTE
NJIT
Textiles
Dairy

Parameter
Metal
Finishing
Plastics &
Synthetics
Pulp &
Paper
Petroleum
Refining
Steel
Textiles
Dairy
Calcium
Fluoride
Cyanide
Chloride
Sulfate
Ammonia
Sodium
Silicates
Sulfite
Nitrate
Phosphorous
Urea & Org. N
PIERO M. ARMENANTE
NJIT

Parameter
Metal
Finishing
Plastics &
Synthetics
Color
Total Coliform
Fecal Coliform
Toxic Materials
Pulp &
Paper
Steel
Textiles
Foam
Odor
Phenols
Chl. Benz. & PAH
Mercapt/sulfide
PIERO M. ARMENANTE
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Dairy
Temperature
Turbidity
Petroleum
Refining
Additional Information and Examples

on Industrial Wastewaters
Additional information and examples can be found in the
following references:
Corbitt, R. A. 1990, The Standard Handbook of
Environmental Engineering, McGraw-Hill, New York, pp.
6.1-6.49.
Droste, R. L., 1997, Theory and Practice of Water and
Wastewater Treatment, John Wiley & Sons, New York,
pp. 94-132; 157-180; 181-193.
Eckenfelder, W. W., Jr., 1989, Industrial Water Pollution
Control, McGraw-Hill, New York, pp. 1-32.
PIERO M. ARMENANTE
NJIT
Additional Information and Examples

on Industrial Wastewaters (cont.d)
Horan, N. J., 1990, Biological Wastewater Treatment
Systems, Treatment and Operation, John Wiley &Sons,
New York, pp. 1-40.
James M. Montgomery Consulting Engineering, Inc.,
1985, Water Treatment Principles and Design, WileyInterscience, John Wiley & Sons, New York, pp. 3-64.
Metcalf & Eddy, 1991, Wastewater Engineering:
Treatment, Disposal, and Reuse, McGraw-Hill, New York,
pp. 47-119.
Sundstrom, D. W. and Klei, H. E., 1979, Wastewater
Treatment, Prentice Hall, Englewood Cliffs, NJ, pp. 3-27.
PIERO M. ARMENANTE
NJIT

Cls02-1 Characterization of Industrial Wastewater PDF

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Characterization

Industrial Wastewaters Discharges

Industrial Wastewaters Discharges

toxic pollutants (priority pollutants)

VOCs (Volatile Organic Compounds)

BOD5 or carbonaceous BOD

total suspended solids (TSS)

oil and grease

Soluble organic materials

Priority organic pollutants

Priority heavy metals

Volatile organic compounds (VOCs)

Nitrogen (typically as NH4 or NO3 )

Phosphorus (typically as phosphate)

Oil and floating materials

Color and turbidity

Recalcitrant (refractory) compounds

Coliforms and other microorganisms

Problems Associated with

Microbial growth in receiving

Microbial growth in receiving

Coliform and other

Problems Associated with

Toxicity to flora, fauna, humans

Oil and grease

Fouling; damages to flora and

Toxicity to aquatic life;

Aesthetics; Inhibition of algal

Toxicity to aquatic life

Problems Associated with

Toxicity to aquatic life; aesthetics

Toxicity; odor (H2S); pH

Toxicity to flora, fauna, humans

Toxicity to flora, fauna, humans

Problems Associated with

Toxicity to flora, fauna, humans;

Toxicity to flora, fauna, humans

Problems Associated with Nutrients

Problems Associated with Nutrients (cont.d)

Problems Associated with Nutrients (cont.d)

Problems Associated with Nutrients (cont.d)

Problems Associated with Nutrients (cont.d)

NO2 + Haemoglobin NO3 + Methaemoglobin

thus producing oxygen starvation (blue-baby

Problems Associated with Nutrients (cont.d)

Typical Industrial Wastewater

Food Processing High in dissolved organics--mainly

High in dissolved and suspended

After Goronsky et al., Chemical Engineering, June 1992, p. 80.

Typical Industrial Wastewater

High in dissolved and suspended

Pharmaceuticals High in dissolved and suspended

Typical Industrial Wastewater

Petroleum refining Phenolics, free and emulsified oils,

Dissolved and suspended organics

Dissolved organics, including acids,

After Goronsky et al., Chemical Engineering, June 1992, p. 80.

Typical Industrial Wastewater

Organic acids and alcohols, soaps

Dissolved and suspended organics

Dissolved and suspended organics,

After Goronsky et al., Chemical Engineering, June 1992, p. 80.

Typical Industrial Wastewater