Everything about Nitrogen Fixation totally explained
Nitrogen fixation is the process by which
nitrogen is taken from its natural, relatively inert molecular form (N
2) in the
atmosphere and converted into nitrogen compounds (such as
ammonia,
nitrate and
nitrogen dioxide).
Nitrogen fixation is performed naturally by a number of different
prokaryotes, including
bacteria,
actinobacteria, and certain types of
anaerobic bacteria. Microorganisms that fix nitrogen are called
diazotrophs. Some higher plants, and some animals (
termites), have formed associations with diazotrophs.
Nitrogen fixation also occurs as a result of non-biological processes. These include
lightning, industrially through the
Haber-Bosch Process, and combustion.
Biological nitrogen fixation was discovered by the Dutch microbiologist
Martinus Beijerinck.
Biological nitrogen fixation
Biological Nitrogen Fixation (
BNF) occurs when atmospheric nitrogen is converted to ammonia by a pair of bacterial enzymes called
nitrogenase. The great majority of legumes have this association, but a few genera (for example,
Styphnolobium) do not. In many traditional and organic farming practices, fields are rotated through various types of crops, which usually includes one consisting mainly or entirely of clover or buckwheat (family
Polygonaceae), which were often referred to as "green manure", since the other natural way of adding nitrogen to the soil is via animal waste products. The entire plant is often ploughed back into the field, thus not only adding more nitrogen, but also improving the soil's organic content and volume.
Non-leguminous nitrogen-fixing plants
Although by far the majority of nitrogen-fixing plants are in the legume family
Fabaceae, there are a few non-leguminous plants that can also fix nitrogen. These plants, referred to as
actinorhizal plants, consist of 22 genera of woody shrubs or trees scattered in 8 plant families. The ability to fix nitrogen isn't universally present in these families. For instance, of 122 genera in the
Rosaceae, only 4 genera are capable of fixing nitrogen.
Family: Genera
Betulaceae (Birch):
Alnus (Alder)
Casuarinaceae (she-oaks):
» Allocasuarina
Casuarina » Gymnostoma
Coriariaceae:
Coriaria
Datiscaceae:
Datisca
Elaeagnaceae (oleaster):
» Elaeagnus (silverberry)
Hippophae (sea-buckthorn) » Shepherdia (buffaloberries)
Myricaceae:
» Morella arborea
Myrica » Comptonia
Rhamnaceae (buckthorn):
» Ceanothus
Colletia » Discaria
Kentrothamnus » Retanilla
Trevoa
Rosaceae (rose):
» Cercocarpus (mountain mahogany)
Chamaebatia (mountain misery) » Purshia (bitterbrush or cliff-rose)
Dryas
There are also several nitrogen-fixing symbiotic associations that involve
cyanobacteria (such as
Nostoc). These include some lichens such as
Lobaria and
Peltigera:
Microorganisms that fix nitrogen
Diazotrophs
Cyanobacteria
Azotobacteraceae
Rhizobia
Frankia
Nitrogen Fixation by Cyanobacteria
Cyanobacteria inhabit nearly all illuminated environments on Earth and play key roles in the carbon and nitrogen cycle of the biosphere. Generally, cyanobacteria are able to utilize a variety of inorganic and organic sources of combined nitrogen, like nitrate, nitrite, ammonium, urea or some amino acids. Several cyanobacterial strains are also capable of diazotrophic growth. Genome sequencing has provided a large amount of information on the genetic basis of nitrogen metabolism and its control in different cyanobacteria. Comparative genomics, together with functional studies, has led to a significant advance in this field over the past years. 2-oxoglutarate has turned out to be the central signalling molecule reflecting the carbon/nitrogen balance of cyanobacteria. Central players of nitrogen control are the global transcriptional factor NtcA, which controls the expression of many genes involved in nitrogen metabolism, as well as the PII signalling protein, which fine-tunes cellular activities in response to changing C/N conditions. These two proteins are sensors of the cellular 2-oxoglutarate level and have been conserved in all cyanobacteria. In contrast, the adaptation to nitrogen starvation involves heterogeneous responses in different strains.
Chemical nitrogen fixation
Nitrogen can also be artificially fixed for use in fertilizer, explosives, or in other products. The most popular method is by the Haber process. This artificial fertilizer production has achieved such scale that it's now the largest source of fixed nitrogen in the Earth's ecosystem.
The Haber process requires high pressures and very high temperatures and active research is committed to the development of catalyst systems that convert nitrogen to ammonia at ambient temperatures. Many compounds can react with atmospheric nitrogen under ambient conditions (eg lithium makes lithium nitride if left exposed), but the products of such reactions are not easily converted into biologically accessible nitrogen sources. After the first dinitrogen complex was discovered in 1965 based on ammonia coordinated to ruthenium ([Ru(NH3)5(N2)]2+), research in chemical fixation focused on transition metal complexes. Since that time a large number of transition metal compounds that contain dinitrogen as ligand have been discovered. The dinitrogen ligand can be bound either to a single metal or bridge two (or more) metals. The coordination chemistry of dinitrogen is rich and under intense study. This research may lead to new ways of using dinitrogen in synthesis and on an industrial scale.
The first example of homolytic cleavage of dinitrogen under mild conditions was published in 1995. Two equivalents of a molybdenum complex reacted with one equivalent of dinitrogen, creating a triple bonded MoN complex. Since this triple bounded complex has been used to make nitriles .
The first catalytic system converting nitrogen to ammonia at room temperature and 1 atmosphere was discovered in 2003 and is based on another molybdenum compound, a proton source and a strong reducing agent.
Unfortunately, the catalytic reduction only undergoes a few turnovers before the catalyst dies.
In contrast to the graphic shown above, the major product of this reaction is ammonia (NH3) and not an ammonium salt ([NH4][X]). In fact, approximately 75% of the ammonia produced can be distilled away from the reaction vessel (suggesting the ammonia isn't protonated) into a vessel containing HCl as a trap. This method of trapping the NH3 was doubtlessly chosen because it makes the product easier to handle. Also, note that because only 1 equiv of Cl anion is available under catalytic conditions (via reduction of the precatalyst molbdenum chloride, shown) therefore it's unlikely that the product ammonium salt would always have this counterion.
Note also that although the dinitrogen complex is shown in brackets this species can be isolated and characterized. Here the brackets don't indicate that the intermediate isn't observed.
Further Information
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