03 N-CYCLE (1)

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    THE NITROGEN CYCLE

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    Nitrates are essential for plant growth

    Root

    uptake

    Nitrate

    NO3-

    Plant

    protein

    2008 Paul Billiet ODWS

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    Nitrates are recycled via microbes

    Nitrification

    Nitrification

    Ammonium NH4+

    Ammonification

    Nitrite NO2-

    Soil organic nitrogen

    Animal

    protein

    Root

    uptake

    Nitrate

    NO3-

    Plant

    protein

    2008 Paul Billiet ODWS

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    Ammonification Nitrogen enters the soil through the

    decomposition of protein in dead organic

    matter

    Amino acids + 11/2O2 CO2+ H2O + NH3 + 736kJ

    This process liberates a lot of energy which

    can be used by the saprotrophic microbes

    2008 Paul Billiet ODWS

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    Nitrification

    This involves two oxidation processes

    The ammonia produced by ammonification is anenergy rich substrate for Nitrosomasbacteria

    They oxidise it to nitrite:

    NH3+ 11/2O2 NO2-+ H2O + 276kJ

    This in turn provides a substrate for Nitrobacterbacteria oxidise the nitrite to nitrate:

    NO3-+ 1/2O2 NO3

    - + 73 kJ

    This energy is the only source of energy forthese prokaryotes

    They are chemoautotrophs

    2008 Paul Billiet ODWS

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    Root uptake

    Nitrate NO3-

    Plant

    proteinSoil organic

    nitrogen

    Nitrogen from the atmosphere

    Biological

    fixation

    Atmospheric

    fixationOut

    gassin

    g

    Atmospheric Nitrogen

    4 000 000 000 Gt

    2008 Paul Billiet ODWS

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    Atmospheric nitrogen fixation Electrical storms

    Lightning provides sufficient energy to split

    the nitrogen atoms of nitrogen gas,

    Forming oxides of nitrogen NOxand NO2

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    Atmospheric Pollution

    This also happens inside the internal combustionengines of cars

    The exhaust emissions of cars contribute a lot toatmospheric pollution in the form of NOx

    These compounds form photochemical smogs They are green house gases

    They dissolve in rain to contribute to acid rainin theform of nitric acid

    The rain falling on soil and running into rivers They contribute to the eutrophicationof water

    bodies

    2008 Paul Billiet ODWS

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    Biological nitrogen fixation

    Treatments Yield / g

    Oats Peas

    No nitrate & sterile soil 0.6 0.8

    Nitrate added & sterile soil 12.0 12.9

    No nitrate & non-sterile soil 0.7 16.4

    Nitrate added & non-sterile soil 11.6 15.3

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    Conclusion

    Adding nitrate fertiliser clearly helps the growth ofboth plants

    The presence of microbes permits the peas to growmuch better than the oats

    The peas grow better in the presence of themicrobes than they do with nitrate fertiliser added

    The difference is due to the present of mutualisticnitrogen fixing bacteria which live in the pea roots.

    2008 Paul Billiet ODWS

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    University of Sydney

    Alafalfa (Medicago sativa)

    USDA - ARS

    Root nodules

    http://www.bio.usyd.edu.au/DavidDay/root_nodules.jpghttp://www.ars.usda.gov/main/site_main.htm?modecode=36401000http://www.ars.usda.gov/main/site_main.htm?modecode=36401000http://www.ars.usda.gov/main/site_main.htm?modecode=36401000http://www.ars.usda.gov/main/site_main.htm?modecode=36401000http://www.ars.usda.gov/main/site_main.htm?modecode=36401000http://www.bio.usyd.edu.au/DavidDay/root_nodules.jpg
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    Only prokaryotes show nitrogen

    fixation These organisms possess the nifgene complex which make the

    proteins, such as nitrogenase enzyme, used in nitrogen fixation

    Nitrogenaseis a metalloprotein, protein subunits beingcombined with an iron, sulphur and molybdenum complex

    The reaction involves splitting nitrogen gas molecules and adding

    hydrogen to make ammonia

    N2 2N - 669 kJ

    2N + 8H+ NH3+ H2 + 54 kJ

    This is extremely energy expensive requiring 16 ATP moleculesfor each nitrogen molecule fixed

    The microbes that can fix nitrogen need a good supply of energy

    2008 Paul Billiet ODWS

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    The nitrogen fixers

    Cyanobacteriaare nitrogen fixers that also

    fix carbon (these are photosynthetic)

    Rhizob iumbacteria are mutualisticwithcertain plant species e.g. Legumes

    They grow in root nodules

    Azotobacterare bacteria associated with the

    rooting zone (the rhizosphere) of plants ingrasslands

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    Nitrate NO3-

    Atmospheric

    fixation

    Out

    gassin

    g

    Plant

    protein

    Atmospheric Nitrogen

    Ammonium

    NH4+

    Soil organic

    nitrogen

    The human impact

    Biological

    fixation

    Industrial

    fixation

    2008 Paul Billiet ODWS

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    Industrial N-Fixation

    The Haber-Bosch ProcessN2+ 3H2 2NH3 - 92kJ

    The Haber process uses an iron catalyst

    High temperatures (500C) High pressures (250 atmospheres)

    The energy require comes from burning fossil

    fuels (coal, gas or oil) Hydrogen is produced from natural gas

    (methane) or other hydrocarbon

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    The different sources of fixed nitrogenSources of fixed nitrogen Production / M tonnes a-1

    Biological 175

    Industrial 50

    Internal Combustion 20

    Atmospheric 10

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    Eutrophication Nutrient enrichment of water bodies Nitrates and ammonia are very soluble in

    water

    They are easily washed (leached) from freedraining soils

    These soils tend to be deficient in nitrogen

    When fertiliser is added to these soils it too

    will be washed out into water bodies There algae benefit from the extra nitrogen

    This leads to a serious form of water pollution

    2008 Paul Billiet ODWS

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    Fertilisers washed into river or lake

    New limiting factor imposes itselfSewage or

    other organic

    waste

    Eutrophication

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    Increased Biochemical

    Oxygen Demand (BOD)

    Hot water

    from industry

    (Thermal

    pollution)

    Pollution

    from oil ordetergents

    Reduction in dissolved O2

    Making things worse!

    2008 Paul Billiet ODWS

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    The death of a lake

    Death/emigration

    of freshwater

    fauna

    Methaemoglobinaemia in infants

    Stomach cancer link

    (WHO limit for nitrates 10mg dm-3)

    Increased nitrite

    levels

    NO3- NO2

    -

    Reduction in dissolved O2

    2008 Paul Billiet ODWS

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    The future of industrial nitrogen fixation Food production relies heavily upon synthetic

    fertilisers made by consuming a lot of fossilenergy

    Food will become more expensive to produce

    Nitrogen fixing microbes, using an enzymesystem, do the same process at standardtemperatures and pressures essentially usingsolar energy

    Answer: Genetically engineered biologicalnitrogen fixation?

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    Making things better

    The need for synthetic fertilisers can be reduced bycultural practices

    Avoiding the use of soluble fertilisers in sandy (free

    draining soil) prevents leaching

    Rotating crops permits the soil to recover fromnitrogen hungry crops (e.g. wheat)

    Adding a nitrogen fixing crop into the rotation cycle

    Ploughing aerates the soil and reduces

    denitrification

    Draining water logged soil also helps reduce

    denitrification

    2008 Paul Billiet ODWS

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    Return to the atmosphere:Denitrification Nitrates and nitrites can be used a source of

    oxygen for Pseudomonasbacteria

    Favourable conditions: Cold waterlogged(anaerobic) soils

    2NO3- 3O2+ N2providing up to 2385kJ

    2NO2- 2O2+ N2

    The liberated oxygen is used as an electron

    acceptor in the processes that oxidiseorganic molecules, such as glucose

    These microbes are, therefore, heterotrophs

    2008 Paul Billiet ODWS

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    Sediments 10 Gt

    Nitrification

    Root

    uptake

    Biological

    fixation

    Nitrification

    Ammonium NH4+

    Ammonification

    Nitrite NO2-

    Dissolved in water

    6000 Gt

    Denitrification

    LeachingNitrate

    NO3-

    Soil organic nitrogen9500 Gt

    Atmospheric

    fixation

    Outgassin

    g Industrialfixation

    Plant protein

    3500 Gt

    Animal

    protein

    Atmospheric Nitrogen

    4 000 000 000 Gt

    O S

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