Denitrification

Although it is important to transform the nitrogen in wastewater from ammonia to nitrate, excessive amounts of nitrate are also harmful.  At high concentrations they threaten the health of babies, as their digestive systems are not capable of transforming the nitrates into less harmful forms of nitrogen.  Once nitrates enter the infant's bloodstream they interfere with oxygen transfer; starving the body of the oxygen it needs.  In most places nitrate levels are not high enough to significantly threaten infant health, but lower concentrations still have effects on the ecosystem.  Nitrate can be used directly by plants and algae as their nitrogen source.  Releasing large amounts of nitrates into surface waters is like adding fertilizer to the system.  With the added nitrogen algal growth can increase to damaging levels.  The high algae concentration blocks sunlight needed by other plants uses the oxygen required for all marine life.

Reactions and Yield Constants

Denitrification is essentially the conversion of nitrate to nitrogen gas.  Denitrification is a natural process carried out by many microorganisms when sufficient oxygen is lacking.  Instead of using oxygen as the final electron acceptor in metabolism nitrate is used.  The process involves many steps, and many undesirable intermediates.  If the microbes are stressed, their metabolism is incomplete and these intermediates may be produced in relatively high amounts.

The denitrification reactions are closely tied to cellular metabolism, producing energy for growth or as heat.  Using the organic matter in typical wastewater, the reaction can be written as:

When this energy is used for growth, maximum yield constants are nearly as high as for aerobic metabolism.  When written for the production of biomass, the equation becomes:


This reaction has a maximum yield of 0.44 kg biomass/kg organic matter, compared to about 0.50 kg biomass/kg organic matter for aerobic metabolism.

In most wastewater ammonium ions (NH4+) will be present, and if present the microbes will nearly always use them as a nitrogen source.  This reaction can be written as:

This reaction has an even better yield, 0.47 kg biomass/kg organic matter.

 

Rates of Reaction

Rates of denitrification can be described by the Monod equation, but in most cases extra substrate is provided to prevent substrate limitations, and as a result the observed rate is nearly equal to the maximum possible rate.  The general substrate removal rate can be expressed as:


where:

When substrate limitations are limited the rate expression can be simplified to:

   
as

     SNO3 >> KS,NO3
      S >> Ks


Rates of reaction are strongly influenced by a number of factor that including the kind of substrate, the system pH, and amount of oxygen.
 
Substrate Dependence:  Denitrifying bacteria are highly sensitive to the substrate available for their use.  Easily degraded materials such as methanol and acetic acid give the highest rates of denitrification.  Raw wastewater does not yield such a high degradation rate, but it is significantly higher than what is observed with non organic carbon sources.

Temperature Dependence:  Rates of denitrification reactions increase with temperature in a manor similar to what rates in nitrification reactions.  They are not as limited in range though, as some bacteria can continue to carry out the processes at temperatures up to  60°C.  These bacteria are relatively rare, and as a result reactions are not usually carried out at such high temperatures despite the expected increases in reaction rate.  Click Here to see the effect temperate has on reaction rates for several different substrates.

Oxygen Inhibition:  Oxygen inhibits denitrification by providing a better electron acceptor for metabolism.  When oxygen is present, the microorganisms will use oxygen instead of nitrate.  The concentration of oxygen of importance is the concentration at the cell's surface, which may be significantly different than the bulk concentration.

pH Dependence:  The optimum pH for denitrification is in the 7-9 range, with rates falling off sharply outside this region (see figure).  At lower pH the generation of N2O and NO is increaced.
 

Additional Link(s)

Denitrification (in greater depth)

References

Created by: Renay Jacob and Emily Cordaro , RPI, Fall 2000


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