Transcript Document

3. NITROGEN CYCLE
SOIL 5813
Soil-Plant Nutrient Cycling and Environmental
Quality
Department of Plant and Soil Sciences
Oklahoma State University
Stillwater, OK 74078
email: [email protected]
Tel: (405) 744-6414
GLOBAL WARMING
ATMOSPHERE
N2O
NO
N2
PLANT
LOSS
INDUSTRIAL
FIXATION
N2 FIXATION
SYMBIOTIC
NON-SYMBIOTIC
MESQUITE
RHIZOBIUM
ALFALFA
SOYBEAN
BLUE-GREEN ALGAE
AZOTOBACTER
CLOSTRIDIUM
LIGHTNING,
RAINFALL
PLANT AND ANIMAL
RESIDUES
HABER BOSCH
(1200°C, 500 atm)
3H2 + N2
2NH3
MATERIALS WITH N
CONTENT > 1.5%
(COW MANURE)
FERTILIZATION
MATERIALS WITH N
CONTENT < 1.5%
(WHEAT STRAW)
AMINO
ACIDS
NH3
AMMONIA
VOLATILIZATION
AMINIZATION
ORGANIC
MATTER
HETEROTROPHIC
R-NH2 + ENERGY + CO2
BACTERIA (pH>6.0)
FUNGI (pH<6.0)
IMMOBILIZATION
Pseudomonas, Bacillus,
Thiobacillus Denitrificans,
and T. thioparus
R-OH + ENERGY + 2NH3
N2O2MINERALIZATION
+ NITRIFICATION
MICROBIAL/PLANT
SINK
2NH4+ + 2OHFIXED ON
EXCHANGE
SITES
NO2-
OXIDATION STATES
NH3 AMMONIA
-3
NH4+ AMMONIUM
-3
N2 DIATOMIC N
0
N2O NITROUS OXIDE 1
NO NITRIC OXIDE
2
NO2- NITRITE
3
NO3 NITRATE
5
pH>7.0
R-NH2 + H2O
AMMONIFICATION
NH2OH
NO3POOL
DENITRIFICATION
LEACHING
TEMP 50°F
LEACHING
NITRIFICATION
2NO2- + H2O + 4H+
Nitrobacter
LEACHING
VOLATILIZATION
NITRIFICATION
LEACHING
+ O2
Joanne LaRuffa
Wade Thomason
Shannon Taylor
Heather Lees
LEACHING
pH 7.0
+O2
Department of Plant and Soil Sciences
Oklahoma State University
ADDITIONS
LOSSES
OXIDATION REACTIONS
REDUCTION REACTIONS
Nitrogen cycle not well understood
Temperature and pH included
reduction/oxidation
tillage (zero vs. conventional)
C:N ratios (high, low lignin)
Fertilizer source and a number of other variables.
Mechanistic models would ultimately lead to many 'if-then' statements/decisions
that could be used within a management strategy.
>50°F
Denitrification
Volatilization
<50°F
Leaching
Leaching
7.0
soil pH
Assuming that we could speed up the nitrogen cycle what would you
change?
1. Aerated environment (need for O2)
2. Supply of ammonium
3. Moisture
4. Temperature (30-35C or 86-95F) <10C or 50F
5. Soil pH
6. Addition of low C:N ratio materials (low lignin)
Is oxygen required for nitrification?
Does nitrification proceed during the growing cycle? (low C:N ratio)
N recommendations
1. Yield goal (2lb N/bu)
a. Applies fertilization risk on the farmer
b. Removes our inability to predict 'environment' (rainfall)
2. Soil test
a. For every 1 ppm NO3, N recommendation reduced by 2lbN/ac
3. Potential yield (discussed later in the semester)
Nitrite accumulation?
1. high pH
2. high NH4 levels (NH4 inhibits nitrobacter)
Inorganic Nitrogen Buffering
Ability of the soil plant system to control the
amount of inorganic N accumulation in the rooting
profile when N fertilization rates exceed that required
for maximum yield.
Grain yield, kg/ha
4000
Point where increasing
applied N no longer
increases grain yield
500
400
3000
Range (buffer) where increasing
applied N does not increase
grain yield, but also where no
increase in soil profile
inorganic N is observed
2000
300
Point where200
increasing
applied N increases soil
profile inorganic
100 N
accumulation
1000
0
0
0
40
80
120
160
Soil Profile Inorganic N
Accumulation, kg/ha
Soil-Plant Inorganic N Buffering
200
Annual Nitrogen Fertilizer Rate, kg/ha
240
NH4, NO3
Fertilizer
Organic Matter Pool
Inorganic
Nitrogen
Udic Argiustoll, 0-240 cm, Udic Argiustoll, 0-300 cm,
#502
#505
NO3--N, kg ha-1
100 200 300 400
30
60
60
90
90
120
150
180
210
240
270
300
N Rate kg ha-1
0
22
45
67
90
112
Depth, cm
Depth, cm
30
0
NO3--N, kg ha-1
0
120
100
200
300
400
N Rate kg ha-1
150
0
180
34
210
67
240
134
270
269
300
If the N rate required to detect soil profile NO3 accumulation always exceeded
that required for maximum yields, what biological mechanisms are present
that cause
leaching?
excess N
applied to be lost via other pathways prior to
Nitrogen Buffering Mechanisms
1. Increased Applied N results in increased plant N loss (NH3)
Bidwell (1979), Plant Physiology, 2nd Ed.
Metabolism associated with nitrate reduction
photosynthesis
carbohydrates
respiration
reducing power
carbon skeletons
NADH or NADPH
NO 3
NH3
NO 2
nitrate
reductase
ferredoxin
siroheme
nitrite
reductase
amino
acids
Nitrogen Buffering Mechanisms
1. Increased Applied N results in increased plant N loss (NH3)
2. Higher rates of applied N - increased volatilization losses
Nitrogen Buffering Mechanisms
1. Increased Applied N results in increased plant N loss (NH3)
2. Higher rates of applied N - increased volatilization losses
3. Higher rates of applied N - increased denitrification
Burford and Bremner (1975) found that denitrification losses increased
under anaerobic conditions with increasing organic C in surface soils (015 cm) (wide range in pH & texture).
Denitrifying bacteria responsible for reduction of nitrate to gaseous
forms of nitrogen are facultative anaerobes that have the ability to use
both oxygen and nitrate (or nitrite) as hydrogen acceptors. If an
oxidizable substrate is present, they can grow under anaerobic conditions
in the presence of nitrate or under aerobic conditions in the presence of
any suitable source of nitrogen
Burford and
Bremner, 1975
Aulakh, Rennie and Paul, 1984
Nitrogen Buffering Mechanisms
1. Increased Applied N results in increased plant N loss (NH3)
2. Higher rates of applied N - increased volatilization losses
3. Higher rates of applied N - increased denitrification
4. Higher rates of applied N - increased organic C, - increased
organic N
0.1
0.9
0.09
0.8
0.08
0.7
0.07
0.06
0.05
0.04
0
0.6
TSN
OC
40
SED TSN = 0.002
SED OC = 0.03
80 120 160
N Rate, kg/ha
0.5
0.4
200
Organic Carbon, %
Total Soil N, %
#406
Nitrogen Buffering Mechanisms
1. Increased Applied N results in increased plant N loss (NH3)
2. Higher rates of applied N - increased volatilization losses
3. Higher rates of applied N - increased denitrification
4. Higher rates of applied N - increased organic C, - increased
organic N
5. Increased applied N - increased grain protein
Grain N uptake, kg/ha
Increased grain N uptake
(protein) at N rates in
excess of that required
for maximum yield
Point where increasing
applied N no longer
increases grain yield
80
60
Continued increase in
grain N uptake, beyond the
point where increasing
applied N increases soil
profile inorganic N
accumulation
40
20
0
0
40
80
120
160
200
Annual Nitrogen Fertilizer Rate, kg/ha
240
# 222
Grain N Uptake, kg/ha
80
Y = 29.7 + 0.28x - 0.00055x2
70
r2=0.90
9.4 =19%
60
50
40
30
20
0
20
40
60
80
N rate, kg/ha
100
120
140
Nitrogen Buffering Mechanisms
1. Increased Applied N results in increased plant N loss (NH3)
2. Higher rates of applied N - increased volatilization losses
3. Higher rates of applied N - increased denitrification
4. Higher rates of applied N - increased organic C, - increased
organic N
5. Increased applied N - increased grain protein
6. Increased applied N - increased forage N
7. Increased applied N - increased straw N
N Buffering Mechanisms
1
4
0-50 kg N/ha/yr
NH3
15-40 kg N/ha/yr
NO
N2O
N2
Denitrification
Fertilizer N
Applied
NH4+OH- NH3 + H2O
Urea
Volatilization
3
NH4 fixation (physical)
7-80 kg N/ha/yr
NH3, N2
Microbial Pool
2
10-50 kg N/ha/yr
Organic Immobilization
NH4
NO3
NO2
1
Mills et al., 1974
Matocha, 1976
DuPlessis and Kroontje, 1964
Terman, 1979
Sharpe et al., 1988
2
5
NO3
5
Leaching
Chaney, 1989
Sommerfeldt and Smith, 19
Macdonald et al., 1989
Kladivko, 1991
3
4
0-20 kg N/ha/yr
Olson and Swallow, 1984
Francis et al., 1993
Sharpe et al., 1988
Aulackh et al., 1984
Hooker et al., 1980
Timmons and Cruse, 1990
Colbourn et al., 1984
O’Deen, 1986, 1989
Bakken et al., 1987
Daigger et al., 1976
Prade and Trolldenier, 1990
Parton et al., 1988
NITROGEN Cyle Links
Legumes and the Nitrogen Cycle
Industrial view of the Nitrogen Cycle
Nutrient Overload: Unbalancing the Global Nitrogen Cycle
Enviro-Gardening (N cycle)
http://library.thinkquest.org/11226/protmap.htm
Urea
1. Urea is the most important solid fertilizer in the world today.
2. In the early 1960's, ammonium sulfate was the primary N product in
world trade (Bock and Kissel, 1988).
3. The majority of all urea production in the U.S. takes place in
Louisiana, Alaska and Oklahoma.
4. Since 1968, direct application of anhydrous ammonia has ranged
from 37 to 40% of total N use (Bock and Kissel, 1988)
5. Urea: high analysis, safety, economy of production, transport and
distribution make it a leader in world N trade.
6. In 1978, developed countries accounted for 44% of the world N
market (Bock and Kissel, 1988).
7. By 1987, developed countries accounted for less than 33%
Share of world N consumption by product group
Ammonium sulfate
Ammonium nitrate
Urea
Ammonium phosphates
Other N products (NH3)
Other complex N products
1970
1986
8
27
9
1
36
16
5
15
37
5
29
8
Urea Hydrolysis
increase pH (less H+ ions in soil solution)
CO(NH2)2 + H+ + 2H2O --------> 2NH4+ + HCO3pH 6.5 to 8
HCO3- + H+ ---> CO2 + H2O (added H lost from soil solution)
CO(NH2)2 + 2H+ + 2H2O --------> 2NH4+ + H2CO3 (carbonic acid)
pH <6.3
H2CO3  CO2 + H2O
During hydrolysis, soil pH can increase to >7 because the reaction requires
H+ from the soil system.
(How many moles of H+ are consumed for each mole of urea hydrolyzed?) 2
In alkaline soils less H+ is initially needed to drive urea hydrolysis on a soil
already having low H+.
In an alkaline soil, removing more H+(from a soil solution already low in H+),
can increase pH even higher
NH4+ + OH- ---> NH4OH ---->NH3 + H2O
pH = pKa + log [(base)/(acid)]
At a pH of 9.3 (pKa 9.3) 50% NH4 and 50% NH3
pH
Base (NH3)
Acid (NH4)
7.3
1
99
8.3
10
90
9.3
50
50
10.3
90
10
11.3
99
1
As the pH increases from urea hydrolysis, negative charges become
available for NH4+ adsorption because of the release of H+ (Koelliker
and Kissel)
Decrease NH3 loss with increasing CEC (Fenn and Kissel, 1976)
Assuming that pH and CEC are positively correlated, what is
happening?
CEC
pH
** on soils where organic matter
dominates the contribution to
CEC then there should be a
positive relationship of pH and
CEC.
Relationship of pH and BI (?) none
In acid soils, the exchange of NH4+ is for H+ on the exchange
complex (release of H here, resists change in pH, e.g. going up)
In alkaline soils with high CEC, NH4 exchanges for Ca, precipitation
of CaCO3 (CO3= from HCO3- above) and one H+ released which helps
resist the increase in pH
However, pH was already high,
SOIL SURFACE pH
8
7
6
12
5
kg NH3 -N/ha VOLATILIZED
N Rate =
112 kg/ha
9
0
2
4
6
8 10 12 14 16 18 20
10
8
SOIL MIX 3-High Buffering Capacity
6
SOIL MIX 2-Moderate Buffering Capacity
SOIL MIX 1-Low Buffering Capacity
4
2
0
0
2
4
6
8 10 12 14 16 18 20
DAYS AFTER APPLICATION
Soil surface pH and cumulative NH3 loss as influenced by pH
buffering capacity (from Ferguson et al., 1984).
Ernst and Massey (1960) found increased NH3 volatilization when
liming a silt loam soil. The effective CEC would have been
increased by liming but the rise in soil pH decreased the soils
ability to supply H+
Rapid urea hydrolysis: greater potential for NH3 loss. Why?
Management:
•dry soil surface
•Incorporate
•localized placement- slows urea hydrolysis
H ion buffering capacity of the soil:
Ferguson et al., 1984
(soils total acidity, comprised
nonexchangeable titratable acidity)
of
exchangeable
acidity
+
A large component of a soils total acidity is that associated with the
layer silicate sesquioxide complex (Al and Fe hydrous oxides). These
sesquioxides carry a net positive charge and can hydrolyze to form H+
which resist an increase in pH upon an addition of a base.
H+ ion supply comes from:
1. OM
2. hydrolysis of water
3. Al and Fe hydrous oxides
4. high clay content (especially 2:1, reason CEC’s are higher in
non-weathered clays is due to isomorphic substitution – pH
independent charge)
Soil with an increased H+ buffering capacity will also show less NH3 loss
when urea is applied without incorporation.
1. hydroxy Al-polymers added (carrying a net positive charge) to increase
H+ buffering capacity.
2. strong acid cation exchange resins added (buffering capacity changed
without affecting CEC, e.g. resin was saturated with H+).
resin: amorphous organic substances (plant secretions), soluble in
organic solvents but not in water (used in plastics, inks)
Consider the following
1. H+ is required for urea hydrolysis
2. Ability of a soil to supply H+ is related to amount of NH3 loss
3. H+ is produced via nitrification (after urea is applied): acidity
generated is not beneficial
4. What could we apply with the urea to reduce NH3 loss?
an acid; strong electrolyte; dissociates to produce H+;increased H+
buffering; decrease pH
reduce NH3 loss by maintaining a low pH in the vicinity of the fertilizer
granule (e.g. H3PO4)
Comment: Ferguson et al. (1984).
“When urea is applied to the soil surface, NH3 volatilization probably
will not be economically serious unless the soil surface pH rises
above 7.5”
UREASE inhibitors
“Agrotain” n-butyl thiophosphoric triamide
http://www.gov.mb.ca/agriculture/news/topics/daa11d05.html
http://www.ag.auburn.edu/aaes/information/highlights/spring9
8/urea.html
http://www.agrotain.com
Nitrosomonas inhibitors
“NSERVE” 2-CHLORO-6-(TRICHLOROMETHYL) PYRIDINE
NEED for INCREASED NUE
Computation/commodity
World consumption of fertilizer-N
Fert-N used in cereals (60% of total applied)
0.60 * 82,906,340 =
Production, mT
82,906,340
49,743,804
World Cereal Production, mT
Sorghum
3%
Millet
1%
Rye
1%
Oats
2%
Wheat
28%
Barley
8%
Rice
28%
Corn
29%
World grain N removal, 1996
Wheat
Corn
Rice
Barley
Sorghum
Millet
Oats
Rye
Total N removed in cereals
%N
2.13
1.26
1.23
2.02
1.92
2.01
1.93
2.21
mT
12,502,267
7,439,266
7,007,101
3,154,192
1,356,807
580,032
596,012
508,788
33,144,465
N removed in cereals
(from soil & rain, 50% of total)
NUE = ((N removed - N soil&rain)/total N applied)
16,572,232
33%
Savings/yr for each 1% increase in NUE
Value of fertilizer savings $479/mT N
489,892 mT
$234,658,462
____________________________________
 World cereal grain NUE
33%
 Developed nation cereal NUE
42%
 Developing nation cereal NUE
29%
____________________________________
 1% increase in worldwide cereal NUE
= $234,658,462 fertilizer savings
 20% increase in worldwide cereal NUE
= $4.7 billion
Flowchart for NUE
http://www.dasnr.okstate.edu/nitrogen_use/NUE_etc.htm
Role of NH4 nutrition in Higher Yields (S.R. Olsen)
•Glutamine-major product formed in roots absorbing NH4
•NO3 has to be transported to the leaves to be reduced
•Wheat N uptake was increased 35% when supplying 25% of the N
as NH4 compared to all N as NO3 (Wang and Below, 1992).
•High-yielding corn genotypes were unable to absorb NO3 during
ear development, thus limiting yields otherwise increased by
supplies of NH4 (Pan et al., 1984).
•Assimilation of NO3 requires the energy equivalent of 20
ATP/moleNO3, whereas NH4 assimilation requires only 5 ATP/mole
NH4 (Salsac et al., 1987).
•This energy savings may lead to greater dry weight production for
plants supplied solely with NH4 (Huffman, 1989).
Bidwell (1979), Plant Physiology, 2nd Ed.
Metabolism associated with nitrate reduction
photosynthesis
carbohydrates
respiration
reducing power
carbon skeletons
NADH or NADPH
NO 3
NH3
NO 2
nitrate
reductase
ferredoxin
siroheme
nitrite
reductase
amino
acids
FYI
Discussion:
Global Population and the Nitrogen Cycle
p.80 nitrous oxide
Increasing use of fertilizer N results in increased N2O. Reaction of nitrous
oxide (N2O) with Oxygen contribute to the destruction of ozone.
Atmospheric lifetime of nitrous oxide is longer than a century, and every
one of its molecules absorbs roughly 200 times more outgoing radiation
than does a single carbon dioxide molecule.
“In just one lifetime, humanity has indeed developed a profound chemical
dependence.”
Factors Affecting Soil Acidity
Acid: substance that tends to give up protons (H+) to some other
substance
Base:
Anion:
Cation:
accepts protons
negatively charged ion
positively charged ion
Base cation: ? (this has been taught in the past but is not correct)
Electrolyte: nonmetallic electric conductor in which current is
carried by the movement of ions
H2SO4 (strong electrolyte)
CH3COOH (weak electrolyte)
H 2O
HA --------------> H+ + Apotential
active
acidity
acidity
1. Nitrogen Fertilization
A. ammoniacal sources of N
2. Decomposition of organic matter
OM ------> R-NH2 + CO2
CO2 + H2O --------> H2CO3 (carbonic acid)
H2CO3 ------> H+ + HCO3- (bicarbonate)
humus contains reactive carboxylic, phenolic groups that behave as
weak acids which dissociate and release H+
3. Leaching of exchangeable bases/Removal
Ca, Mg, K and Na (out of the effective root zone)
-problem in sandy soils with low CEC
a. Replaced first by H and subsequently by Al (Al is one of the
most abundant elements in soils. 7.1% by weight of earth's crust)
b. Al displaced from clay minerals, hydrolyzed to hydroxy
aluminum complexes
c.
Hydrolysis of monomeric forms liberate H+
d.
Al(H2O)6+3 + H2O -----> Al(OH)(H2O)++ + H2O+
monomeric: a chemical compound that can undergo polymerization
polymerization: a chemical reaction in which two or more small
molecules combine to form larger molecules that contain repeating
structural units of the original molecules
4. Aluminosilicate clays
Presence of exchangeable Al
Al+3 + H2O -----> AlOH= + H+
5. Acid Rain
NITROGEN:
Key building block of protein molecule
Component of the protoplasm of plants animals and microorganisms
One of few soil nutrients lost by volatilization and leaching, thus requiring continued
conservation and maintenance
Most frequently deficient nutrient in crop production
Nitrogen Ion/Molecule Oxidation States
Range of N oxidation states from -3 to +5.
oxidized: loses electrons, takes on a positive charge
reduced: gains electrons, takes on a negative charge
Illustrate oxidation states using common combinations of N with H and O
H can be assumed in the +1 oxidation state (H+1)
O in the -2 oxidation state (O=)
Aminization: Decomposition of proteins and the release of
amines and amino acids
OM (proteins)  R-NH2 + Energy + CO2
Ammonification:
R-NH2 + HOH  NH3 + R-OH + energy
+H2O
NH4+ + OH-
Nitrification: biological oxidation of ammonia to nitrate
2NH4+ + 3O2  2NO2- + 2H2O + 4H+
2NO2- + O2  2NO3-
Ion/molecule
Name
Oxidation State
NH3
ammonia
-3
NH4+
ammonium
-3
N2
diatomic N
0
N2O
nitrous oxide
+1
NO
nitric oxide
+2
NO2-
nitrite
+3
NO3-
nitrate
+5
H2S
hydrogen sulfide
-2
SO4=
sulfate
+6
N: 5 electrons in the outer shell
loses 5 electrons (+5 oxidation state NO3)
gains 3 electrons (-3 oxidation state NH3)
O: 6 electrons in the outer shell
is always being reduced (gains 2 electrons to fill the outer shell)
H: 1 electron in the outer shell
N is losing electrons to O because O is more electronegative
N gains electrons from H because H wants to give up electrons
Hydrogen:
Electron configuration in the ground state is 1s1 (the first electron shell has only
one electron in it), as found in H2 gas.
s shell can hold only two electrons, atom is most stable by either gaining
another electron or losing the existing one. Gaining an electron by sharing
occurs in H2, where each H atom gains an electron from the other resulting in a
pair of electrons being shared. The electron configuration about the atom,
where: represents a pair of electrons, and may be shown as
H:H and the bond may be shown as H-H
Hydrogen most commonly exists in ionic form and in combination with other
elements where it has lost its single electron. Thus it is present as the H+ ion or
brings a + charge to the molecule formed by combining with other elements.
Oxygen:
Ground state of O, having a total of eight electrons is 1s2, 2s2, 2p4.
Both s orbitals are filled, each with two electrons.
The 2p outer or valence orbital capable of holding six electrons, has only four
electrons, leaving opportunity to gain two. The common gain of two electrons
from some other element results in a valence of -2 for O (O=). The gain of two
electrons also occurs in O2 gas, where two pairs of electrons are shared as
O::O and the double bond may be shown as O=O
Nitrogen:
Ground state of N is 1s2, 2s2, 2p3.
Similar to that for oxygen, except there is one less electron in the valence 2p
orbital. Hence, the 2p orbital contains three electrons but, has room to accept
three electrons to fill the shell. Under normal conditions, electron loss to for N+,
N2+ or N3+ or electron gain to form N-, N2-, or N3- should not be expected.
Instead, N will normally fill its 2p orbital by sharing electrons with other elements
to which it is chemically (covalent) bound. Nitrogen can fill the 2p orbital by
forming three covalent bonds with itself as in the very stable gas N2.
Nitrogen Cycle:
•Increased acidity?
Ammonia Volatilization
· Urease activity (organic C)
· Air Exchange
· Temperature
· N Source and Rate
· CEC (less when high)
· Application method
· H buffering capacity of the soil
· Crop Residues
· Soil Water Content
NH4+  NH3 + H+
If pH and temperature can be kept low, little potential exists for NH3
volatilization. At pH 7.5, less than 7% of the ammoniacal N is actually in
the form of NH3 over the range of temperatures likely for field conditions.
10
NH 3
9
pH
8
NH
7
6
H20  H+ + OH-
0
20
+
4
40
60
80
100
%
Equilibrium relationship for ammoniacal N and
resultant amount of NH3 and NH4 as affected by pH
for a dilute solution.
Chemical Equilibria
A+B AB
Kf
= AB/A x B
AB  A+B
Kd = A x B/AB
Kf
= 1/Kd (relationship between formation and dissociation constants)
Formation constant (Log K°) relating two species is numerically equal to the
pH at which the reacting species have equal activities (dilute solutions)
pKa and Log K° are sometimes synonymous
Henderson-Hasselbalch
pH = pKa + log [(base)/(acid)]
when (base) = (acid), pH = pKa
Acidification from N Fertilizers (R.L. Westerman)
1. Assume that the absorbing complex of the soil can be
represented by CaX
2. Ca represents various exchangeable bases with which the
insoluble anions X are combined in an exchangeable form and
that X can only combine with one Ca
3. H2X refers to dibasic acid (e.g., H2SO4)
(NH4)2SO4 -----> NH4+ to the exchange complex, SO4= combines with
the base on the exchange complex replaced by NH4+
Volatilization losses of N as NH3 preclude the development of H+
ions produced via nitrification and would theoretically reduce the
total potential development of acidity.
Losses of N via denitrification leave an alkaline residue (OH-)
Reaction of N fertilizers when applied to soil (Westerman, 1985)
______________________________________________________________________
1.
Ammonium sulfate
a.
(NH4)2SO4 + CaX ----> CaSO4 + (NH4)2X
b.
(NH4)2X + 4O2 nitrification >2HNO3 + H2X + 2H2O
c.
2HNO3 + CaX ----> Ca(NO3)2 + H2X
Resultant acidity = 4H+ /mole of (NH4)2SO4
2.
Ammonium nitrate
a.
2NH4NO3 + CaX ----> Ca(NO3)2 + (NH4)2X
b.
(NH4)2X + 4O2 nitrification >2HNO3 + H2X + 2H2O
c.
2HNO3 + CaX ----> Ca(NO3)2 + H2X
Resultant acidity = 2H+ /mole of NH4NO3
3.
Urea
a.
b.
c.
d.
e.
CO(NH2)2 + 2H2O ----> (NH4)2CO3
(NH4)2CO3 + CaX ----> (NH4)2X + CaCO3
(NH4)2X + 4O2 nitrification >2HNO3 + H2X +2H2O
2HNO3 +CaX ----> Ca(NO3)2 + H2X
H2X + CaCO3 neutralization >CaX + H2O + CO2
Resultant acidity = 2H+ /mole of CO(NH2)2
4.
Anhydrous Ammonia
a.
2NH3 +2H2O ----> 2NH4OH
b.
2NH4OH + CaX ----> Ca(OH)2 + (NH4)2X
c.
(NH4)2X + 4O2 nitrification >2HNO3 + H2X +2H2O
d.
2HNO3 + CaX ----> Ca(NO3)2 + H2X
e.
H2X + Ca(OH)2 neutralization > CaX + 2H2O
Resultant acidity = 1H+/mole of NH3
5.
Aqua Ammonia
a.
2NH4ON + CaX ----> Ca(OH)2 + (NH4)2X
b.
(NH4)2X + 4O2 nitrification >2HNO3 + H2X +2H2O
c.
2HNO3 +CaX ----> Ca(NO3)2 + H2X
d.
H2X + Ca(OH)2 neutralization > CaX +2H2O
Resultant acidity = 1H+/mole of NH4OH
6.
Ammonium Phosphate
a.
2NH4H2PO4 + CaX ----> Ca(H2PO4)2 + (NH4)2X
b.
(NH4)2X + 4O2 nitrification >2HNO3 + H2X +2H2O
c.
2HNO3 +CaX ----> Ca(NO3)2 + H2X
Resultant acidity = 2H+/mole of NH4H2PO4
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