BOD and COD

Biochemical oxygen demand (BOD) is the amount of dissolved oxygen needed by aerobic
biological organisms in a body of water to break down organic material present in a given water sample at
certain temperature over a specific time period. The term also refers to a chemical procedure for
determining this amount. This is not a precise quantitative test, although it is widely used as an indication
of the organic quality of water. The BOD value is most commonly expressed in milligrams of oxygen
consumed per litre of sample during 5 days of incubation at 20 C and is often used as a robust surrogate
of the degree of organic pollution of water.
BOD can be used as a gauge of the effectiveness of wastewater treatment plants. It is listed as a
conventional pollutant in the U.S. Clean Water Act.
BOD is similar in function to chemical oxygen demand (COD), in that both measure the amount
of organic compounds in water. However, COD is less specific, since it measures everything that can be
chemically oxidized, rather than just levels of biologically active organic matter.
Background
Most natural waters contain small quantities of organic compounds. Aquatic microorganisms
have evolved to use some of these compounds as food. Microorganisms living in oxygenated waters use
dissolved oxygen to oxidatively degrade the organic compounds, releasing energy which is used for
growth and reproduction. Populations of these microorganisms tend to increase in proportion to the
amount of food available. This microbial metabolism creates an oxygen demand proportional to the
amount of organic compounds useful as food. Under some circumstances, microbial metabolism can
consume dissolved oxygen faster than atmospheric oxygen can dissolve into the water or the autotrophic
community (algae, cyanobacteria and macrophytes) can produce. Fish and aquatic insects may die when
oxygen is depleted by microbial metabolism.
Biochemical oxygen demand is the amount of oxygen required for microbial metabolism of
organic compounds in water. This demand occurs over some variable period of time depending on
temperature, nutrient concentrations, and the enzymes available to indigenous microbial populations. The
amount of oxygen required to completely oxidize the organic compounds to carbon dioxide and water
through generations of microbial growth, death, decay, and cannibalism is total biochemical oxygen
demand (total BOD). Total BOD is of more significance to food webs than to water quality. Dissolved

oxygen depletion is most likely to become evident during the initial aquatic mic robial

population

explosion in response to a large amount of organic material. If the microbial population deoxygenates the
water, however, that lack of oxygen imposes a limit on population growth of aerobic aquatic microbial
organisms resulting in a longer term food surplus and oxygen deficit.
A standard temperature at which BOD testing should be carried out was first proposed by the
Royal Commission on Sewage Disposal in its eighth report in 1912:
" (c) An effluent in order to comply with the general standard must not contain as discharged more than 3
parts per 100,000 of suspended matter, and with its suspended matters included must not take up at 65F
(18-3C.) more than 2.0 parts per 100,000 of dissolved oxygen in 5 days. This general standard should be
prescribed either by Statute or by order of the Central Authority, and should be subject to modifications
by that Authority after an interval of not less than ten years.
This was later standardised at 68 F and then 20 C. This temperature may be significantly
different from the temperature of the natural environment of the water being tested. Investigators also
decided to eliminate anaerobic conditions.
Although the Royal Commission on Sewage Disposal proposed 5 days as an adequate test period
for rivers of the United Kingdom of Great Britain and Ireland, longer periods were investigated for North
American rivers. Incubation periods of 1, 2, 5, 10 and 20 days were being used into the mid-20th century.
Keeping dissolved oxygen available at their chosen temperature, investigators found up to 99 percent of
total BOD was exerted within 20 days, 90 percent within 10 days, and approximately 68 percent within 5
days. Variable microbial population shifts to nitrifying bacteria limit test reproducibility for periods
greater than 5 days. The 5-day test protocol with acceptably reproducible results emphasizing
carbonaceous BOD has been endorsed by the United States Environmental Protection Agency. This 5-day
BOD test result may be described as the amount of oxygen required for aquatic microorganisms to
stabilize decomposable organic matter under aerobic conditions. [6] Stabilization, in this context, may be
perceived in general terms as the conversion of food to living aquatic fauna. Although these fauna will
continue to exert biochemical oxygen demand as they die, that tends to occur within a more stable
evolved ecosystem including higher trophic levels.[3]
Carbonaceous biochemical oxygen demand or CBOD is a method defined test measured by the
depletion of dissolved oxygen by biological organisms in a body of water in which the contribution from
nitrogenous bacteria has been suppressed. CBOD is a method defined parameter is widely used as an

indication of the pollutant removal from wastewater. It is listed as a conventional pollutant in the U.S.
Clean Water Act.
Nitrogenous oxygen demand is the result of the breakdown of proteins. Proteins contain sugars
linked to
nitrogen. After the nitrogen is "broken off" a sugar molecule, it is usually in the form of ammonia,
which is readily converted to nitrate in the environment. The conversion of ammonia to nitrate
requires more than four times the amount of oxygen as the conversion of an equal amount of
sugar to carbon dioxide and water.

Theoretical oxygen demand (ThOD) is the calculated amount of oxygen required to oxidize a
compound to its final oxidation products.[1] However, there are some differences between standard
methods that can influence the results obtained: for example, some calculations assume that nitrogen
released from organic compounds is generated as ammonia, whereas others allow for ammonia oxidation
to nitrate. Therefore in expressing results, the calculation assumptions should always be stated.
In order to determine the ThOD for glycine (CH2(NH2)COOH) using the following assumptions:
1. In the first step, the organic carbon and nitrogen are converted to carbon dioxide (CO2) and
ammonia (NH3), respectively.
2. In the second and third steps, the ammonia is oxidized sequentially to nitrite and nitrate.
3. The ThOD is the sum of the oxygen required for all three steps.
We can calculate by following steps:
1. Write balanced reaction for the carbonaceous oxygen demand.
CH2(NH2)COOH + 1.5O2 NH3 + 2CO2 + H2O
2. Write balanced reactions for the nitrogenous oxygen demand.
NH3 + 1.5O2 HNO2 + H2O
HNO2 + 0.5O2 HNO3
NH3 + 2O2 HNO3 + H2O

3. Determine the ThOD.

ThOD = (1.5 + 2) mol O2/mol glycine
= 3.5 mol O2/mol glycine 32 g/mol O2 / 75 g/mol glycine
= 1.49 g O2/g glycine
The theoretical oxygen demand represents the worse case scenario. The actual oxygen demand of any
compound depends on the biodegradability of the compound and the specific organism metabolizing the
compound. The actual oxygen demand can be measured experimentally and is called the biochemical
oxygen demand (BOD).
The BOD5 test
Dilution method
This standard method is recognized by U.S. EPA, which is labeled Method 5210B in the Standard
Methods for the Examination of Water and Wastewater [7] In order to obtain BOD5, dissolved oxygen (DO)
concentrations in a sample must be measured before and after the incubation period, and appropriately
adjusted by the sample corresponding dilution factor. This analysis is performed using 300 ml incubation
bottles in which buffered dilution water is dosed with seed microorganisms and stored for 5 days in the
dark room at 20 C to prevent DO production via photosynthesis. In addition to the various dilutions of
BOD samples, this procedure requires dilution water blanks, glucose glutamic acid (GGA) controls, and
seed controls. The dilution water blank is used to confirm the quality of the dilution water that is used to
dilute the other samples. This is necessary because impurities in the dilution water may cause significant
alterations in the results. The GGA control is a standardized solution to determine the quality of the seed,
where its recommended BOD5 concentration is 198 mg/l 30.5 mg/l. For measurement of carbonaceous
BOD (cBOD), a nitrification inhibitor is added after the dilution water has been added to the sample. The
inhibitor hinders the oxidation of ammonia nitrogen, which supplies the nitrogenous BOD (nBOD). When
performing the BOD5 test, it is conventional practice to measure only cBOD because nitrogenous demand
does not reflect the oxygen demand from organic matter. This is because nBOD is generated by the
breakdown of proteins, whereas cBOD is produced by the breakdown of organic molecules.
BOD5 is calculated by:

BODu or Ultimate Biochemical Oxygen Demand- the amount of oxygen consumed when all of
the biodegradable organic matter has been oxidized. The Ultimate BOD utilizes the notation Lo, referring
to its potential for oxygen consumption when proceeding to complete oxidation.
Formula:
Lo = y5 / [1 e^(-kLt)]
Where:
kL = BOD reaction rate coefficient
t = time

Chemical oxygen demand

In environmental chemistry, the chemical oxygen demand (COD) test is commonly
used to indirectly measure the amount of organic compounds in water. Most applications of
COD determine the amount of organic pollutants found in surface water (e.g. lakes and rivers) or
wastewater, making COD a useful measure of water quality. It is expressed in milligrams per
liter (mg/L) also referred to as ppm (parts per million), which indicates the mass of oxygen
consumed per liter of solution.

Overview

The basis for the COD test is that nearly all organic compounds can be fully oxidized to
carbon dioxide with a strong oxidizing agent under acidic conditions. The amount of oxygen
required to oxidize an organic compound to carbon dioxide, ammonia, and water is given by:

This expression includes the oxygen demand caused by the oxidation of ammonia into
nitrate. The process of ammonia being converted into nitrate is referred to as nitrification. The
following is the correct equation for the oxidation of ammonia into nitrate.

It is applied after the oxidation due to nitrification if the oxygen demand from
nitrification must be known. Dichromate does not oxidize ammonia into nitrate, so this
nitrification can be safely ignored in the standard chemical oxygen demand test.
The International Organization for Standardization describes a standard method for measuring
chemical oxygen demand in ISO 6060.
History

For many years, the strong oxidizing agent potassium permanganate (KMnO4) was used
for measuring chemical oxygen demand. Measurements were called oxygen consumed from
permanganate, rather than the oxygen demand of organic substances. Potassium permanganate's
effectiveness at oxidizing organic compounds varied widely, and in many cases biochemical
oxygen demand (BOD) measurements were often much greater than results from COD
measurements. This indicated that potassium permanganate was not able to effectively oxidize

all organic compounds in water, rendering it a relatively poor oxidizing agent for determining
COD.
Since then, other oxidizing agents such as ceric sulphate, potassium iodate, and
potassium dichromate have been used to determine COD. Of these, potassium dichromate
(K2Cr2O7) has been shown to be the most effective: it is relatively cheap, easy to purify, and is
able to nearly completely oxidize almost all organic compounds.
In these methods, a fixed volume with a known excess amount of the oxidant is added to
a sample of the solution being analyzed. After a refluxing digestion step, the initial concentration
of organic substances in the sample is calculated from a titrimetric or spectrophotometric
determination of the oxidant still remaining in the sample. As with all colorimetric methods
blanks are used to control for contamination by outside material.