Waste Water

Characterization of Industrial Wastewaters
PIERO M. ARMENANTE NJIT
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 POTW s NPDES permit limit. In addition the industrial discharger must have a permit (different from the NPDES permit).
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)
Conventional Pollutants
BOD5 or carbonaceous BOD (CBOD) total suspended solids (TSS) fecal coliform oil and grease pH
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
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)
+ -
Undesired Characteristics of Industrial Wastewater (continued)

Oil and floating materials Color and turbidity Odor Recalcitrant (refractory) compounds Temperature pH Coliforms and other microorganisms
Problems Associated with Wastewater Pollutants

Pollutant Biodegradable organic compounds Suspended solids Environmental Problem Microbial growth in receiving bodies; possible toxicity; oxygen depletion Microbial growth in receiving bodies; deposition of sludge blanket; possible toxicity; turbidity Health problems
Coliform and other microorganisms

Problems Associated with Wastewater Pollutants (continued)

Pollutant pH Oil and grease Nutrients (nitrogen, phosphorous) Color Temperature
Environmental Problem Toxicity to flora, fauna, humans Fouling; damages to flora and fauna Toxicity to aquatic life; eutrophication Aesthetics; Inhibition of algal growth Toxicity to aquatic life

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

Pollutant Phenolic compounds Cyanides Environmental Problem Toxicity to flora, fauna, humans; odor Toxicity to flora, fauna, humans
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
Problems Associated with Nutrients (cont. d)

Ammonia can be converted by the nitrifying bacteria to nitrite and nitrate in a two-step sequence:
. NH3 + 15 O2 Nitrosomonas HNO2 + H 2O HNO2 + 0.5 O2 Nitrobacter HNO3 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)

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

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

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

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
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.
Typical Industrial Wastewater Contaminants (continued)

Industry Breweries and distilleries Characteristics of Wastewaters 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
After Goronsky et al., Chemical Engineering, June 1992, p. 80. PIERO M. ARMENANTE NJIT

Industry Characteristics of Wastewaters Petroleum refining Phenolics, free and emulsified oils, and other dissolved organics Pulp and paper Plastics and resins Dissolved and suspended organics and inorganics Dissolved organics, including acids, aldehydes, phenolics, cellulose, alcohols, surfactants and oils

Industry Explosives Rubber Textiles Characteristics of Wastewaters Organic acids and alcohols, soaps and oils Dissolved and suspended organics and oils Dissolved and suspended organics, fats and oil

Industry Leather tanning and finishing Coke and gas Characteristics of Wastewaters Dissolved and suspended organics, fats and oils, organic nitrogen, hair and fleshings High in phenolics, ammonia and dissolved organics
Major Wastewater Contaminants from Industrial Sources

Industry (Food) Canning Origin of Contaminants Fruit and vegetable preparation Whole milk dilutions, buttermilk Grain, distillation Characteristics of Contaminants Colloidal, dissolved organic matter, suspended solids Dissolved organic matter (protein, fat, lactose) Dissolved organics, nitrogen fermented starches
Dairy Brewing, distilling
After Corbitt, The Standard Handbook of Environmental Engineering, 1990, p. 6.31
Major Wastewater Contaminants from Industrial Sources (continued)

Industry (Food) Meat, poultry Origin of Contaminants Slaughtering, rendering of bones and fats, plucking Handling juices, condensates Yeast filtration Lime water, seeds, syrup Characteristics of Contaminants Dissolved organics, blood, proteins, fats, feathers Dissolved sugar and protein Solid organics Suspended solids, dissolved organics, variable pH
Sugar beet Yeast Pickles

Industry (Food) Coffee Fish Rice Soft drinks Origin of Contaminants Pulping and fermenting beans Pressed fish, wash water Soaking, cooking, washing Cleaning, spillage, washing Characteristics of Contaminants Suspended solids Organic solids, odor Suspended and dissolved carbohydrates Suspended and dissolved carbohydrates

Industry (Pharm., Textile) Antibiotics Textiles Leather Origin of Contaminants Mycelium, filtrate, washing Desizing of fabric Cleaning, soaking, bathing Washing fabrics Characteristics of Contaminants Suspended and dissolved organics Suspended solids, dyes, alkaline Solids, sulfite, chromium, lime, sodium chloride Turbid, alkaline, organic solids
Laundry

Industry (chemical) Acids Detergents Starch Explosives Insecticides Origin of Contaminants Wash waters, spillage Purifying surfactants Evaporation, washing Characteristics of Contaminants Low pH Surfactants Starch
Purifying and washing TNT, organic acids, acid, TNT, cartridges oil soaps Washing, purification Organics, benzene, acid highly toxic

Industry (chemical) Phosphate Origin of Contaminants Washing, condenser wastes Characteristics of Contaminants Suspended solids, phosphorous, silica, oils, fluoride, clays, low pH
Formaldehyde
Formaldehyde Residues from synthetic resin production and dyeing synthetic fibers

Industry (others) Pulp and paper Photographic products Steel Metal plating Origin of Contaminants Refining, washing, screening of pulp Spent developer and fixer Characteristics of Contaminants High solids, extremes of pH Organic and inorganic reducing agents alkaline
Coking, washing blast Acid, cyanogen, phenol, furnace, flue gases coke, oil Cleaning and plating Metals, acid

Industry (others) Iron foundry Oil Rubber Origin of Contaminants Various discharges Drilling, refining Washing, extracting impurities Polishing, cleaning Characteristics of Contaminants Sand, clay, coal Sodium chloride, sulfur, phenol, oil Suspended solids, chloride, odor, variable pH Suspended solids
Glass
Wastewater Characterization and Analysis

The characteristics of wastewater classified into three major categories: 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. can be
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
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
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)
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)
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
Solids Found in Wastewater
Suspended and Filterable Solids

Settleable Solids Suspended Solids Organic Non-Settleable Solids Sample Colloidal Solids Filterable Solids Organic Dissolved Solids Inorganic Organic Inorganic Inorganic Organic 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)
Total Solids
Evaporation
Sample
Total Solids
Temperature = 103-105 C Any low boiling point compounds in the water will vaporize and will be lost during this analysis.
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
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.
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.
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)
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.
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
2 HCO3 + HS
HS + H + H2S
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
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
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
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
Odorous Compounds Associated with Untreated Wastewater

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

Chemical Compound Carbon disulfide Acetaldehyde Hydrogen sulfide Nitrogen compounds Skatole Ethyl Mercaptan Methyl Mercaptan Chlorine Ammonia Perchloroethylene Phenol
Formula CS2 C2H4O H2S C9H9N C2H6S CH4S Cl2 NH3 C2CI6 C6H5OH
Odor Threshold (ppm by volume) 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
After Cheremisinoff, Nation. Environ. J., Feb. 1995, p. 29
Odor Threshold Concentrations

Chemical Compound Ammonia Chlorine Dimethyl sulfide Diphenyl sulfide Ethyl Mercaptan Hydrogen sulfide Indole Methyl Amine Methyl Mercaptan Skatole
Formula 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
Chemical Characteristics of Wastewater

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

H+ (pH) Alkalinity Heavy metals Nitrate and nitrite Ammonia Phosphorous Sulfate and sulfite Sulfide Chloride Oxygen
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
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
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
Determination of the Organic Content of Wastewaters (continued)

These methods are:
Total Volatile Solids (TVS) 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)
Total Volatile Solids (TVS)

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
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
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
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
100%
Cumulative Oxygen Uptake (%)
80%
Bottle #1 Bottle #2 Bottle #3
60%
40%
20%
0% 0 1 2 3 4 5 6 7
Time (days)
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.
BOD5 Apparatus
After Horan, Biological Wastewater Treatment Systems, 1990, p. 3 PIERO M. ARMENANTE NJIT
BOD Curve
400 350 300
BOD (mg/L)
BODNu
250 200 150 100 50 0 0 10 20 30 40 50
NBOD BODu
CBOD BOD5
Time (days)
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)

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
. NH3 + 15 O2 Nitrosomonas HNO2 + H 2O HNO2 + 0.5 O2 Nitrobacter HNO3 NH3 + 2O2 HNO3 + H 2O
The presence of nitrifying bacteria can be observed in the BOD curve

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
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
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)
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
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
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
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
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
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
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
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
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
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
Advantages and Disadvantages of BOD, COD, TOD and TOC Tests

Test BOD Advantages Simple, familiar to most engineers, very common; no special apparatus required Disadvantages Long incubation periods; poor reproducibility (15%); results are affected by microorganisms in seed; results may not represent actual reactor conditions
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 Rapid; excellent reproducibility (3-6%); can be automated Same as TOD Requires expensive apparatus and skilled technician Same as TOD; interference from inorganic carbonates; less familiar units
TOD
TOC
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
Typical Relationships Among BOD, COD, and TOC

Ratio BOD5/ThOD COD/ThOD TOC/ThOD BOD5/COD BOD5/TOC COD/TOC Typical Value of Ratio 45-55% 80% 30% 50-60% 130-250% 175-665%
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
Typical Composition of Domestic Wastewater and Removal Efficiency of Conventional Treatment Plants
Parameter Concentr. Range (mg/L) 100-400 200-1,000 200-1100 100-400 Typical Concentr. (mg/L) 250 500 500 250 % Removal % Removal (Primary (Secondary Treatment) Treatment) 10-30% 10-30% 10-30% 10-30% >90% 70-80% 70-80% 60-80%
BOD5 COD TOD TOC
After Sundstrom and Klei, 1979, Wastewater Treatment, p. 11.
Parameter Concentr. Range (mg/L) 15-90 5-40 10-50 Typical Concentr. (mg/L) 40 25 25 40% % Removal % Removal (Primary (Secondary Treatment) Treatment) 35% 50-80% 0-20% Produced Produced
Total N Organic N Ammonia Nitrites Nitrates
Parameter Concentr. Range (mg/L) 5-20 1-5 5-15 7-7.5 units 30-50 30-85 20-60 Typical Concentr. (mg/L) 12 2 10 7.0 units 40 50 15 % Removal % Removal (Primary (Secondary Treatment) Treatment) 0-15% 20-40%
Total P Organic P Inorganic P pH Calcium Chloride Sulfate
Parameter Concentr. Range (mg/L) 300-1,200 50-200 100-400 70-300 250-850 100-300 Typical Concentr. (mg/L) 700 100 220 150 500 150 90% 50-90% 60-90% 5% 30% % Removal % Removal (Primary (Secondary Treatment) Treatment)
Total Solids Total Settleab. Solids TSS TVS TDS Total Dissolv. Volatile Solids
Composition of Effluents from Typical Industrial Facilities
Composition of Effluents from Different Industrial Plants

Parameter BOD5 (mg/L) COD (mg/L) SS (mg/L) Ammonia (as N; mg/L) Total N (mg/L) pH
Pharmac. Industry 15,250 28,540 5,400 5,166 9.3
Textile Industry 2,000 5,000 4,000 12.0
Beet-Sugar Coke-Oven Waste Liquor 930 1,601 1,015 6.3 16.4 7.1 1,200 3,900 950 450 490 5.5
After Horan, Biological Wastewater Treatment Systems, 1990, p. 28
Composition of Leachates from Typical Landfill Sites

Parameter BOD5 (mg/L) COD (mg/L) SS (mg/L) Ammonia (as N; mg/L) Total N (mg/L) pH
Leeds (UK) 6,000 12,000 600 6.2
Bucks County (USA) 12,500 18,500 686 70 748 6.7
New York (USA) 10,040 7,500 900 150 350 4.3
After Horan, Biological Wastewater Treatment Systems, 1990, p. 29
Typical Industrial Wastewater Effluent Limitations

Parameter COD BOD Oil & Grease/TPH TSS pH Temperature Color NH3/NO3 Concentration (mg/L) 300-2,000 100-300 15-55 15-45 6.0-9.0 < 40 C 2 color units 1.0-10 0.2 0.1-5.0 0.5-1.0 (total) 0.01-0.1
Phosphates Heavy Metals Surfactants Sulfides
Pollutants Used in the Definition of Effluent Standards for Different Industries (EPA, 1973)
Parameter Automobile Beverage Canning Fertilizer Inorgan. Organ. Chemicals Chemicals Meat Products BOD5 COD TOC TOD pH Total Solids Susp. Solids Settleable Solids Tot. Diss. Solids Vol. Susp. Solids Oil & Grease
Pollutants Used in the Definition of Effluent Standards for Different Industries (continued)
Parameter Automobile Beverage Canning Fertilizer Inorgan. Organ. Chemicals Chemicals Meat Products Heavy Metals Chromium Copper Nickel Iron Zinc Arsenic Mercury Lead Tin Cadmium
Parameter Automobile Beverage Canning Fertilizer Inorgan. Organ. Chemicals Chemicals Meat Products Calcium Fluoride Cyanide Chloride Sulfate Ammonia Sodium Silicates Sulfite Nitrate Phosphorous Urea & Org. N
Parameter Automobile Beverage Canning Fertilizer Inorgan. Organ. Chemicals Chemicals Meat Products Color Total Coliform Fecal Coliform Toxic Materials Temperature Turbidity Foam Odor Phenols Chl. Benz. & PAH Mercapt/sulfide
Pollutants Used in the Definition of Effluent Standards for Different Industries (EPA, 1973)
Parameter Metal Finishing Plastics & Synthetics Pulp & Paper Petroleum Refining Steel Textiles Dairy BOD5 COD TOC TOD pH Total Solids Susp. Solids Settleable Solids Tot. Diss. Solids Vol. Susp. Solids Oil & Grease
Parameter Metal Finishing Plastics & Synthetics Pulp & Paper Petroleum Refining Steel Textiles Dairy Heavy Metals Chromium Copper Nickel Iron Zinc Arsenic Mercury Lead Tin Cadmium
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
Parameter Metal Finishing Plastics & Synthetics Pulp & Paper Petroleum Refining Steel Textiles Dairy Color Total Coliform Fecal Coliform Toxic Materials Temperature Turbidity Foam Odor Phenols Chl. Benz. & PAH Mercapt/sulfide
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.
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.

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Characterization of Industrial Wastewaters

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Industrial Wastewaters Discharges

Industrial Wastewaters Discharges (continued)

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Undesired Characteristics of Industrial Wastewater

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Undesired Characteristics of Industrial Wastewater (continued)

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Problems Associated with Wastewater Pollutants

Coliform and other microorganisms

Problems Associated with Wastewater Pollutants (continued)

Problems Associated with Wastewater Pollutants (continued)

Environmental Problem Toxicity to aquatic life; aesthetics Odors

Problems Associated with Wastewater Pollutants (continued)

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Problems Associated with Nutrients (Nitrogen, Phosphorous)

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Problems Associated with Nutrients (cont. d)

Problems Associated with Nutrients (cont. d)

Problems Associated with Nutrients (cont. d)

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Problems Associated with Nutrients (cont. d)

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Problems Associated with Nutrients (cont. d)

Typical Industrial Wastewater Contaminants

High in dissolved and suspended organics from natural products

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

Typical Industrial Wastewater Contaminants (continued)

Typical Industrial Wastewater Contaminants (continued)

Typical Industrial Wastewater Contaminants (continued)

Typical Industrial Wastewater Contaminants (continued)

Major Wastewater Contaminants from Industrial Sources

Dairy Brewing, distilling

After Corbitt, The Standard Handbook of Environmental Engineering, 1990, p. 6.31

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Major Wastewater Contaminants from Industrial Sources (continued)

Sugar beet Yeast Pickles

After Corbitt, The Standard Handbook of Environmental Engineering, 1990, p. 6.31

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Major Wastewater Contaminants from Industrial Sources (continued)

After Corbitt, The Standard Handbook of Environmental Engineering, 1990, p. 6.31

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Major Wastewater Contaminants from Industrial Sources (continued)

After Corbitt, The Standard Handbook of Environmental Engineering, 1990, p. 6.31

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Major Wastewater Contaminants from Industrial Sources (continued)

After Corbitt, The Standard Handbook of Environmental Engineering, 1990, p. 6.31

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Major Wastewater Contaminants from Industrial Sources (continued)

After Corbitt, The Standard Handbook of Environmental Engineering, 1990, p. 6.31

PIERO M. ARMENANTE NJIT

Major Wastewater Contaminants from Industrial Sources (continued)

After Corbitt, The Standard Handbook of Environmental Engineering, 1990, p. 6.31

PIERO M. ARMENANTE NJIT

Major Wastewater Contaminants from Industrial Sources (continued)

After Corbitt, The Standard Handbook of Environmental Engineering, 1990, p. 6.31

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Wastewater Characterization and Analysis

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Units Commonly Used in Wastewater Analysis

Physical Characteristics of Wastewater