Chemistry for Env.Eng.

& Science, Sawyer ,McCarty,Parkin

Environmental Chemistry, Manahan
www.lenntech.com/periodic/elements/n.htm
https://www.hccfl.edu/media/520095/nitrogenppt
a colorless, odorless, gaseous element/ chemical element that constitutes about
four-fifths of the volume of the atmosphere and is present in combined form in
animal and vegetable tissues, especially in proteins: used chiefly in the
manufacture of ammonia, nitric acid, cyanide, explosives, fertilizer, dyes, as a
cooling agent, etc. Symbol: N; atomic weight: 14.0067; atomic number: 7; density:
1.2506 g/l at 0°C and 760 mm pressure.
 The atmosphere is
primarily composed
of nitrogen (N2, 78%),
oxygen (O2, 21%), and
argon (Ar, 1%).
 A number of other
very influential
components are also
present: the water
(H2O, 0 to 7%),
"greenhouse" gases
or ozone (O, 0 to
0.01%), carbon
dioxide (CO2, 0.01to
0.1%).
 Senyawa Nitrogen
•Air
•Atmosfir
•Proses kehidupan tanaman dan binatang

Nitrogen can be found in all living organisms on Earth

while also being present in soil, water and air.

It is an important component in biological compounds

found all throughout nature

There is also nitrogen present in water, which benefits

both aquatic and land plants and animals.

While nitrogen is essential to all living organisms on

Earth, it can be dangerous in large amounts for humans,
animals and plant life, too.
Kimia dari nitrogen kompleks :
•Bilangan oksidasi yang banyak.
•Perubahan bilangan oksidasi dapat berlangsung oleh
organisma hidup
 amino acids
 nucleic acids (purine, pyrimidine)
 cell wall components of bacteria (NAM).
 Lightning
 Inorganic fertilizers
 Nitrogen Fixation
 Animal Residues
 Crop residues
 Organic fertilizers
 Proses biologis
 Proses kimia
 Proses Photokimia
 Urea  CO(NH2)2
 Ammonia  NH3 (gaseous)
 Ammonium  NH4
 Nitrate  NO3
 Nitrite  NO2
 Atmospheric Dinitrogen N2
 Organic N
 Unlike carbon or oxygen, nitrogen is not
very available to life.
 It’s conversion requires biological activity
 nitrogen cycle is required by life, but also
driven by it.
 Cycle is rather complex and has evolved as
the atmosphere became oxygenated.
 As we know, Earth’s original atm was
oxygen-poor.
Four processes
participate in the
cycling of nitrogen
through the biosphere:

1) Nitrogen fixation
2) Decay
3) Nitrification
4) Denitrification

Microorganisms play
major roles in these
processes
 Biogeochemical cycle

NH4+, NO2-,NO3- terlarut dalam air

N2, N2O,NO, NO2 dalam bentuk gas sedikit dapat larut dalam air.
 The Nitrogen cycle
Involves the following microbial biogeochemical actions:
(1) nitrogen fixation
(2) ammonification
(3) nitrification
(4) denitrification
Kecuali N2, di atm
senyawa nitrogen
Semua dl status
teroksidasi

Perubahan melalui
natural biological
Chemical dan proses
photochemical
  Atmospheric fixation
by lightning.
 Three “Fixation”  Biological fixation by
processes are certain microbes -
responsible for most alone or in a symbiotic
of the nitrogen relationship with
fixation in the plants.
biosphere are …  Industrial fixation.
 The proteins made by plants enter and pass through
food webs just as carbohydrates do. At each trophic
level, their metabolism produces organic nitrogen
compounds that return to the environment, chiefly in
excretions.

 The final beneficiaries of these materials are

microorganisms of decay.

 They breakdown the molecules in excretions and dead

organisms into ammonia (NH3).
 The term nitrification refers to the conversion of ammonium to
nitrate (pathway 3-4 opposite).
 Responsible: nitrifying bacteria known as chemoautotrophs.
 These bacteria gain their energy by oxidizing NH3, while using
CO2 as a source of carbon to synthesize organic compounds.
 By this process, NO3 in soil or water is converted into atm
N2, nitric oxide or nitrous oxide.
 This must occur under anaerobic conditions (anaerobic
respiration).
 Presence of O2 can reverse the reaction.
 Again, mediated by bacteria (Pseudomonas sp., Alkaligenes
sp. and Bacillus sp.).
 Nitrogen Metric tons Actively cycled
Reservoir nitrogen
Atmosphere 3.9*1015 No
Ocean 
soluble salts 6.9*1011 Yes
Biomass 5.2*108 Yes

Land  organic
matter 1.1*1011 Slow
 Biota 2.5*1010 Yes
Nitrifikasi Manahan
Reservoar nitrogen adalah atmosfir
Pembebasan secara electrical
Fiksasi nitrogen oleh bakteri dan algae
URINE

ANIMAL FECES
Nitrogen Fixation
Nitrifikasi

Perubahan dari N(-III) menjadi N(V)

 Optimal pH is between 6.6-8.0
 If pH < 6.0  rate is slowed

 If pH < 4.5  reaction is inhibited

Reduksi Nitrate

Denitrifikasi

1/5 NO3- + ¼ {CH2O} + 1/5 H+ ---- 1/10 N2 +1/4 CO2 +1/20 H2O
 For aquaculturists, cycling transforms usually begin with the
decomposition of organic matter from either plant or animal
sources.
 major source in aquaculture: feeds
 Ultimately excreted as amine groups on amino acids or
excreted in soluble form primarily as NH3/NH4+, other
compounds.
 NH3 separated from organic protein via microbial activity.
 Process referred to as deaminification or ammonification.
 NH3 is released to water column (mineralization) and
assimilated into primary productivity (NH3 + H+ --> NH4+).
 ammonification is heterotrophic, under aerobic or anaerobic
conditions.
 NH3 and NH4+ are both either assimilated by
aquatic plants for growth or nitrified (oxidized)
to NO3- (nitrate).
 Nitrate can also be used as a growth substrate
(Guillard’s F medium).
 Two step process:
NH4+ + 1.5O2  NO2- + 2H+ + H2O
NO2- + 0.5O2  NO3-
 Note: these are oxygen-driven reactions.
 Conversion of ammonia (NH3) to nitrate (NO3-)
is via chemoautotrophic bacteria.
 First step by Nitrosomonas sp.
 second step by Nitrobacter sp.
 Both steps/reactions use NH4+ and NO2- as an
energy source, CO2 as a carbon source.
 This is a non-photosynthetic type of growth.
 Reaction runs best at pH 7-8 and 25-30oC.
 however; under low DO, it runs in reverse.
 NO3- is converted to NO2= and other forms.
 Can go all the way backwards to NH3.
 Occurs in the hypolimnion under eutrophic
(stagnant) conditions.
 REM: nitrogen also fixed by leguminous plants,
free living bacteria, blue-green algae.
 Magnitude of this transform not well studied.
 Gaseous form of nitrogen (N2) is most prevalent.
 Followed by: nitrite, nitrate, ammonia or
ammonium.
 Nitrite is seldom a problem unless DO levels are
low (to be discussed later).
 Ratio of NH3:NH4+ rises with pH.
 Unfertilized ponds: NH3 +NH4+ = 0.05-0.075
mg/L.
 Fertilized ponds: NH3 +NH4+ = 0.5 mg/L, 0.075
mg NO3-
Aquatic Concerns with Nitrogen

An Indicator of Sanitary Quality.

methemoglobinemia
 Nutritional and related problems

Oxidation in Rivers and Estuaries

Control of Biological Treatment Processes

Methods of analysis

Ammonia Nitrogen

•Direct Nesslerization
•Direct Phenate Addition
•Distillation
•Volumetric Analysis
Organic Nitrogen

Nitrite Nitrogen

Nitrate Nitrogen
Screening by Ultraviolet Spectrophotometry
Ion Chromatographic and Capillary Ion Electrophoresis
Nitrate Electrode
Cadmium Reduction

Total Nitrogen
Application of Nitrogen Data

Wastewater Treatment
Application of Nitrogen Data

Wastewater Treatment
PR

Bab 25 Halaman 647 : 25.1, 25.2, 25.6, 25.10