Background

The BOD test was devised in the early 20th century and selected as an indicator of organic

enrichment in water bodies by the U.K Royal Commission on River Pollution in 1908. Subsequently, the

method was adopted by American Public Health Association Standard Methods Committee in 1936 as a

reference indicator to evaluate the biodegradation of chemicals and hazardous substances.

The BOD indicates the content of oxygen needed to decompose organic compounds in waste

water by bacteria. In most cases the special factor BOD 5 is perceived as the BOD, which requires a

detailed definition (5 represents the 5 days analysis time). For the determination of BOD 5 there are

nitrification inhibitors added to the samples, which suppress the degradation of nitrogen compounds.

Consequently, it results in the determination of the decomposition of carbon compounds only

(carbonaceous BOD, cBOD). Due to this limitation, an essential process of sewage treatment is not

considered: The nitrification. Obviously, a WWTP can only be controlled and monitored reliably by total

BOD measurements, instead of the determination of the insufficient BOD 5. In the real sense, BOD

measurements are respiration measurements. Due to their rapidity, respiration measurements are preferred

for online analysis. Provided that the conditions are known, respiration measurements [mg/(l*min)] can

be converted into BOD measurements [mg/l].

Due to the 5 day analysis time and the measurement of the carbonaceous BOD instead of total

BOD, the BOD5 is not suitable to assess the current capacity of the waste waters' degradation by bacteria.

The BOD5 is only a time-delayed information about the pollution of waste water and cannot be used for

optimization or control of a WWTP. Alternatively, BOD analysers or respiration analysers can be used,

which enable measurements within 5 to 60 minutes. Thus, estimations can be made promptly for the

biodegradability of the waste water and its behavior in the plants.

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 The market is dominated by short-time respiration measurements by O 2 electrodes. Due to the

low oxygen solubility of the waste water, the small respirations are extrapolated to the final result by

using factors.  Essentially, only the easy biodegradable substances are detected this way.

Alternatively, LAR AG provides an online respirometer that operates like a miniature waste water

treatment plant: The BioMonitor. This BOD analyser degrades nitrogen and carbon compounds in special

waste water cascades, so that the significant total BOD is determined. Due to the multi-stage cascade

structure also difficult to degrade components are reliably detected. The oxygen required for the

degradation is measured by an O2 sensor. Especially advantageous is the use of the plant's activated

sludge, whereby the conditions at the WWTP are simulated reliably.

The COD value has been developed analogically to the BOD measurement. Since there are many

organics which are rather hard or not possible to decompose biologically, a parameter has been defined

indicating the amount of oxygen which would be needed when all organic ingredients would be oxidised

completely. As, according to the name, the oxidation takes place chemically, the chemical oxygen

demand can only be defined indirectly. A chemical oxidant is added to the sample in question, the

consumption of which is then determined. The internationally dominant method today is the so-called

'Dichromate' method [5][6] which is characterized by the acidification of the sample with sulphuric acid

and the addition of silver sulphate. To avoid false measurements in chloride-containing samples, the

chloride must be masked by mercuric sulphate first. Due to the application of hazardous chemicals and

having an analysis time of 2 hours the method is not suitable for online use.

Definition and significance

BOD is defined as the amount of oxygen taken up through the respiratory activity of

microorganisms growing on organic material in the sample. The test is conducted in airtight bottles in the

absence of light and under a controlled temperature (20°C ± 1°C) for a set time period. The widely

employed 5 days interval was selected as this the time taken from source to sea for the longest U.K river.

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Hence, the parameter provides a measurement of the carbonaceous organic pollution of water that can be

degraded biologically and is expressed in milligrams of O2 per litre (see Table 1 for expected levels from

a range of aquatic habitats).

BOD is a key water quality parameter used in a wide range of applications in the water industry

and for environmental monitoring:

 it is used under the WFD to assess the quality of water bodies (see Table 1);

 it is used to confirm wastewater discharge and the waste treatment procedure meets criteria set by

regulators (see Table 2);

 the ratio between BOD and COD (chemical oxygen demand) is indicative of the biodegradable

fraction of wastewater effluent;

 COD/BOD is also used as an indicator of the size of a wastewater treatment plant required for a

specific location.

 BOD is used to identify sources of organic pollution in river networks

Chemical oxygen demand (COD) is often used to measure organic matter in wastewater, treated

effluent, and receiving waters. Although COD measures more than organic constituents, the organic

fraction usually predominates and is the constituent of interest. Chemical oxygen demand was developed

as an alternative to the more lengthy BOD analysis.

Sources of COD in stormwater are varied. However, soluble organic compounds are most likely

to contribute to escalated COD concentrations. Residual food waste from bottles and cans, antifreeze,

emulsified oils are all high in COD and are common sources of COD for industrial stormwater. A typical

COD concentration for soda and beer is about 100,000 mg/L.

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 Material and methods

The Chemical Oxygen Demand (COD) method determines the quantity of oxygen required to

oxidize the organic matter in a waste sample, under specific conditions of oxidizing agent, temperature,

and time.

Since the test utilizes a specific chemical oxidation the result has no definite relationship to the

Biochemical Oxygen Demand (BOD) of the waste or to the Total Organic Carbon (TOC) level. The test

result should be considered as an independent measurement of organic matter in the sample, rather than as

a substitute for the BOD or TOC test.

The method can be applied to domestic and industrial waste samples having an organic carbon

concentration greater than 50 mg/L. For lower concentrations of carbon such as in surface water samples,

the Low Level Modification should be used. When the chloride concentration of the sample exceeds 2000

mg/L, the modification for saline waters is required.

Chemical Oxygen Demand (COD) analysis is a measurement of the oxygen-depletion capacity of

a water sample contaminated with organic waste matter. Specifically, it measures the equivalent amount

of oxygen required to chemically oxidize organic compounds in water.

What are the Current COD Methods Used?

The traditional chemical oxygen demand (COD) analysis method is the wet chemistry method.

This involves a two hour digestion at high heat under acidic conditions in which potassium dichromate

acts as the oxidant for any organic material present in a water sample. Silver sulfate is present as the

catalyst and mercuric sulfate acts to complex out any interfering chloride. Following the digestion, the

extent of oxidation is measured through indirect measurement of oxygen demand via electrons consumed

in the reduction of Cr6+ to Cr3+. This can be done by titration or spectrophotometry.

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 What are the Alternatives?

MANTECH has developed an automated COD method utilizing a new, rapid and green

technology called peCOD. This method directly measures the amount of oxidizable material in a sample

via photoelectrochemical oxidation in a microcell, eliminating the need for time consuming digestion and

hazardous chemicals, as only an electrolyte solution is required for analysis. Automated sample

homogenization always ensures a representative sample is analyzed, and multi-point calibration

guarantees the best accuracy and precision. Highly adaptable for wastewater and drinking water

applications, the PeCOD® COD Analyzer’s patented nanotechnology-based approach to COD analysis

will save you time and money while protecting the environment and the health and safety of your

workers.

MANTECH’s L100 PeCOD® Analyzer

BOD is affected by the same factors that affect dissolved oxygen (see above). Aeration of stream

water by rapids and waterfalls, for example will accelerate the decomposition of organic and inorganic

material. Therefore, BOD levels at a sampling site with slower, deeper waters might be higher for a given

volume of organic and inorganic material than the levels for a similar site in highly aerated waters.

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 Chlorine can also affect BOD measurement by inhibiting or killing the microorganisms that

decompose the organic and inorganic matter in a sample. If you are sampling in chlorinated waters, such

as those below the effluent from a sewage treatment plant, it is necessary to neutralize the chlorine with

sodium thiosulfate. (See APHA, 1992.)

BOD measurement requires taking two samples at each site. One is tested immediately for

dissolved oxygen, and the second is incubated in the dark at 20 C for 5 days and then tested for the

amount of dissolved oxygen remaining. The difference in oxygen levels between the first test and the

second test, in milligrams per liter (mg/L), is the amount of BOD. This represents the amount of oxygen

consumed by microorganisms to break down the organic matter present in the sample bottle during the

incubation period. Because of the 5-day incubation, the tests should be conducted in a laboratory.

Sometimes by the end of the 5-day incubation period the dissolved oxygen level is zero. This is

especially true for rivers and streams with a lot of organic pollution. Since it is not known when the zero

point was reached, it is not possible to tell what the BOD level is. In this case it is necessary to dilute the

original sample by a factor that results in a final dissolved oxygen level of at least 2 mg/L. Special

dilution water should be used for the dilutions. (See APHA, 1992.)

It takes some experimentation to determine the appropriate dilution factor for a particular

sampling site. The final result is the difference in dissolved oxygen between the first measurement and the

second after multiplying the second result by the dilution factor. More details are provided in the

following section.

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 How to Collect and Analyze Samples

The procedures for collecting samples for BOD testing consist of the same steps described for

sampling for dissolved oxygen (see above), with one important difference. At each site a second sample is

collected in a BOD bottle and delivered to the lab for DO testing after the 5-day incubation period.

Follow the same steps used for measuring dissolved oxygen with these additional considerations:

 Make sure you have two BOD bottles for each site you will sample. The bottles should be

black to prevent photosynthesis. You can wrap a clear bottle with black electrician's tape if you

do not have a bottle with black or brown glass.

 Label the second bottle (the one to be incubated) clearly so that it will not be mistaken for

the first bottle.

 Be sure to record the information for the second bottle on the field data sheet.

The first bottle should be analyzed just prior to storing the second sample bottle in the dark for 5

days at 20 C. After this time, the second bottle is tested for dissolved oxygen using the same method that

was used for the first bottle

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 Conclusions

 The ultimate BOD is always higher than the seven day BOD.

 BOD of primary effluent is greater than the secondary effluent since primary contains more

organic matter.

 There are no nitrifiers for this experiment.

 COD is not higher than BOD which are a result of some errors that may have been performed in

the experiment.

 Potential errors could have occurred do to malfunctioning dissolved oxygen meters and

temperature differences.

 Another error could also have been a result of over dilution of the samples and not mixing the

sources of effluent prior to sampling.

Bibliography

 Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 550, Method 508 (1975).

 Annual Book of ASTM Standards, Part 31, "Water", Standard D 1252-67, p 473 (1976).
 APHA. 1992. Standard methods for the examination of water and wastewater. 18th ed. American

Public Health Association, Washington, DC.

Appendix – Sample Calculations

BOD5=biochemical oxygendemand after five days (mg/ L )

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Lo=ultimate carbonaceous BOD(mg/L)

DOs ,i=initial dissolved oxygenconcentration of sample (mg/L )

DOs ,5=five−day dissolved oxygen concentration of sample(mg/L )

DOb ,i=initial dissolved oxygenconcentration of blank(mg/L )

DOb ,5=five−day dissolved oxygenconcentration of blank(mg/L )

P=dilution factor

volume of sample (mL)

total volume of BOD bottle(mL)k=BOD reactionrate constant (days−1)

BOD5= [(DOs ,i−DOs , 7 )−(DOb , i−DOb , 7)] / [P]

= [(8.57−2.66 )−(8.735−8.32)] / [0.02]

=274.75 mg /L

Lo= BOD5 / 1−e−k∗t= 274.75 / 1-e-(7*0.24) = 337.69 mg/l

y=0.0008x

y=absorbance (nm)x=COD(mg /L)

COD= (0.1185) / (0.0008)= 148.125 mg/l