 Biochemical Oxygen Demand

(BOD)

 Chemical Oxygen Demand

(COD)
Part 1. Biochemical Oxygen
Demand
 Bacteria and other microorganisms
use organic substances for food
 as they metabolize organic material,
they consume oxygen
 organics are broken down into simpler
compounds such as CO2 and H2O
 energy released is used for growth
and reproduction
 Biochemical Oxygen
Demand
 When this process occurs in water, the
oxygen consumed is dissolved oxygen
 if oxygen is not continuously replaced, the
D.O. level will decrease as the organics are
decomposed by microbes
 rate of decline approximates 0.20 mg
O2/L/hr (Boyd, 1990)
 the need for oxygen is referred to as
“biochemical oxygen demand”
 not: “biological oxygen demand”
 Biochemical Oxygen
Demand
 Organic waste in sewage is is one of
the major types of water pollutants
 impractical to isolate and identify
each specific organic chemical and
determine its concentration
 BOD is an indirect measure of the
total amount of biodegradable
organics in the water
 more organics = more BOD exerted
 Biochemical Oxygen
Demand
 Complete decomposition of organic
material by microorganisms takes time:
(approx. 20 days under normal conditions)
 the total amount of oxygen required to
“stabilize” all biodegradable organic
compounds is the UBOD or BODL
 amount expressed in mg/L of oxygen
 levels sometimes in excess of 1,500 mg/L
 normal sewage levels = 200 mg/L
 Biochemical Oxygen
Demand: how measured
 Empirical test using standardized lab
methods to determine the relative oxygen
requirements of waters
 test measures molecular oxygen utilized
during a specified incubation period
 thus, BOD is a function of time
 At time = 0, BOD is 0
 as each test day goes by, oxygen is used by
the microbes and the BOD increases
 generates a BOD curve
UBOD
 Biochemical Oxygen
Demand: measurment
 rate at which oxygen is
consumed is expressed by
a rate constant, k
 value of k depends upon
temperature, type of
organic material present,
species of microbes
exerting the BOD
 summary: BOD rate
increases with temp, but
UBOD doesn’t (implies
standardization)
 Biochemical Oxygen
Demand: measurement
 BOD = biochemical degradation of organic material
(carbonaceous demand) + oxidation of inorganic materials
(e.g., sulfides)
 can also measure the amount of oxygen used to oxidize
reduced forms of nitrogen (nitrogenous demand) unless
demand inhibited
 nitrogenous demand inhibited by 2-chloro-6
(trichloromethyl) pyridine (Hach,
 20 days is too long to wait for lab results (hard to
manage discharge from sewage treatment plants with
such a wait)
 more than 2/3 BOD exerted in first 5 days
 Biochemical Oxygen
Demand: measurement
 Oxygen demand and supply must be appropriate prior
to determining BOD by Standard Methods
 this is accomplished by dilution (3:1)
 also dilution water must contain N, P, trace metals
allowing for growth of heterotrophic bacteria
 dilution water must also be buffered so that respired
CO2 does not lower pH
 must be careful to check quality (BOD) of BOD
dilution water against a known organic mixture (e.g.,
glucose or glutamic acid)
 Biochemical Oxygen
Demand: measurement
 5 days a 20oC
 300 mL glass BOD bottles
 two D.O. readings: initial and after 5
days’ incubation in dark at 20oC
 BOD = D.O.Day 0 - D.O.5days
 very clean waters = BOD5 of 1.0 mg/L
 sewage level = BOD5 greater than 10
mg/L
Classification of surface water
quality based on BOD values
Degree of pollution BOD5 (mg/L O2)
Very clean < 1.0
Clean 1.1 – 1.9
Moderately polluted 2.0 – 2.9
Polluted 3.0 – 3.9
Very polluted 4.0 – 10.0
Extremely polluted > 10
BOD5 values for wastewaters

Type of wastewater BOD5 (mg/L

O2)
Very well treated effluent 3 - 5
Standard effluent 10 - 30
Badly treated sewage 40 - 80
Strong sewage 400 - 600
Trade effluent ( animal > 1000
and vegetable waste)
 Biochemical Oxygen
Demand: interpretations
 Accuracy of test is affected by a number of factors:
– soluble vs. particulate organics
– settleable vs. floatable solids
– oxidation of reduced sulfur/iron compounds
– lack of mixing
 Nitrogenous demand can be mediated by microbes and is
not a real indication of oxygen demand associated with
organic material
 can be estimated by ammonia nitrogen determinations
 nitrifiers are not usually found in sufficient numbers in
raw or primary settled sewage
Part 2: Chemical Oxygen
Demand
 This refers to chemicals present in the water
that are not biodegradable by microbes or are
at least slowly degraded
 measures all organics, including the
biodegradable (BOD) fraction)
 it is the amount of a specific oxidant
(potassium dichromate) that reacts with the
sample under controlled conditions
 So? Chemical not biological reaction
 Chemical Oxygen Demand
 COD values should always be higher than BOD values
(about 33% higher; Boyd, 1990)
 but no consistent correlation and cannot be used to
predict BOD due to site variance
 reaction takes place in less than 2 hrs, so more user
friendly
 the quantity of oxidant consumed is reported in terms
of its oxygen equivalence
 most aquaculture facilities are biological in their mode
of operation: BOD more commonly used (COD probably
best for sewage treatment, site selection)
 COD indicative of pollution
 METHODOLOGY-COD
o The sample is refluxed with excess
potassium dichromate in concentrated
sulfuric acid for 2 h.
o This oxidizes most of the organic
matter in the sample
o Silver sulfate is included as a catalyst
to speed up the oxidation process
 METHODOLOGY-COD
o After digestion, the unreacted
dichromate remaining in solution is
titrated with ferrous ammonium sulfate:
Cr2O72- + 6Fe2+ + 14H+  2Cr3+ + 6Fe3+ +
7H2O
The amount of dichromate consumed is
calculated and the oxidisable organic
matter is reported in term of oxygen
equivalent
 COD analysis
 COD (mg/L O2) = 8000 x M x (V1 –
V2)/Vs
 V1 is the volume of ferrous ammonium
sulfate titrant used to titrate the blank
(mL)
 V2 is the volume of ferrous ammonium
sulfate titrant used to titrate the
sample (mL)
 Vs is the volume of sample (mL)
 M is the exact concentration of ferrous
ammonium sulfate titrant (M)
 Example
 Calculate the COD of a solution
containing 425 mg/L potassium
hydrogen phtalate?
Mr KC8H5O4=204, Mr O2= 32.
 Answer :
KC8H5O4 + 7.5O2  2H2O + 8CO2 + K+ +OH-
425 mg/L KC8H5O4= 0.425/204 mol/L
= 7.5 x 0.425/204 mol/L O2 =
7.5 x 0.425/204 x 32 x 1000 mg/L O2
= 500 mg/L = 500 ppm O2
Part 3: Ozone and Related
Species

From: Hochheimer, J.N. and Wheaton, F.W.,

1995. Ozone use in aquaculture. In:
Aquaculture Engineering and Waste
Management (Timmons, M.B., Ed.), NRAES
90; pg. 127-166.
 Preliminary Ozone Notes
 pungent and unstable gas
 tri-molecular oxygen
 most common use as disinfectant
 oxidizer: remove turbidity, algae, color, odor and
taste
 has industrial and aquaculture uses
 aquaculture: both recirc and flow-through
applications
 remove disease, dissolved/suspended organic
compounds
 treatment prior to discharge
Ozone Chemical Properties

Wow!
Ozone Chemical Properties
 As a dipole, it reacts with organic
molecules at double bonds
 result: carbonyl compound + H2O2
 can also undergo electrophilic
reactions (aromatic hydrocarbons)
 chlorinated organics are difficult to
break down with ozone
Ozone Chemical Properties
 As a strong oxidant, it is very unstable
in both gaseous and aqueous forms
 decomposition in water is a function of
pH, ultraviolet light, ozone
concentrations, presence of inhibiting
compounds
 very rapid decomposition to
superoxide anion (O2-) in presence of
hydroxide ions, peroxides, humics
Ozone Chemical Properties
 Can react directly with ammonia to
form nitrate, but at a very slow rate
 other break-down chemicals react
faster
 treatment design should therefore
favor formation of radicals
 Ozone Oxidizing Potential
 Bacterial disinfection
 viral inactivation
 precipitation of metals (Fe, Mn)
 decomplexing organically-bound heavy metals
 flocculent for precipitation of dissolved organics
 taste, odor, color, algae control
 destruction inorganics (sulfides, nitrites)
 degradation of pesticides, detergents
 nitrification enhancement
 Aquaculture Use
Characteristics
 Powerful oxidizing agent
 very rapid reaction times
 3-5 x more effective as a disinfectant
than chlorine
 short contact times
 complete reaction w/residual half-life of
20-30 min
 residual is oxygen (beneficial)
 other residuals easily removed
 Major Disadvantages
 High capital equipment costs
 high operating costs (corona discharge)
 some residuals can be toxic to
fish/shrimp
 dangerous to humans to breathe
 on-site generation required
 inefficient energy: only 10% of power
required generates ozone (rest is heat)
Ozone as a Disinfectant
 Usually applied at end of water
treatment process
 remove most demand first by
mechanical means and then apply O3
 0.4 mg/L residual kills 99.9% bacteria
in drinking water in less than 4 min
 wastewaters have higher ozone
demand = more difficulty establishing
a residual
 Ozone Generation
 Usually by either corona discharge
(electrical spark) or by low wavelength UV
 cannot be stored (pressure = heat =
dissociation
 corona: passing dry air or oxygen between
two surfaces having an electric potential
 as oxygen passes through field, it is
excited to energy level conducive to
formation of ozone
 O3 Corona Discharge
 feed gas must be dry, free of impurities
(e.g., N2 in feed = nitric acid)
 pure O2 = 2x more O3 than ambient air
 Factors affecting output: frequency
of electricity, concentration of O2 in
feed gas, gap between plates, plate
thickness
 air as feed: 60 g O3/kWh
 oxygen as feed: 120 g O3/kWh
 UV Ozone Generation
 Exposure of air or oxygen to UV light at 140
- 190 nm
 factors: voltage, lamp glass quality, gas
used in packing lamp
 problems: cost of lamps, cheap knock-offs,
health hazards
 cheap models: 1/3 O3/kWh of corona, poor
lamp life
 good models: equal, but less electrical cost,
3 yr lamp life
 Ozone Toxicity
 Mutagen, oxidizing compound
 humans should avoid exposure to
concentrations in air of more than 0.3 mg/L
 for most species: 0.5 mg/L achieves good
water quality, but high mortality of eggs and
larvae (fish, bivalves)
 0.1 mg/L residual had no effect on
cutthroat and steelhead trout fry (Colberg
et al., 1977)
 Ozone Toxicity
 Toxicity may be a function of organic
material on gills
 susceptibility largely result of
activated species present
 some decomposition products are
toxic
 check out situation first with
bioassay