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BIOLOGICAL TRANSFORMATIONS OF NITROGEN IN SOIL Animal residues Plant residues Animals Plants Plant roots Nitrate Ammonia Microorganisms Humus Nitrogen Nitrous oxide Nitrite N.E.R. Campbell and H. Lees

BIOLOGICAL TRANSFORMATIONS OF NITROGEN IN … · BIOLOGICAL TRANSFORMATIONS OF NITROGEN IN SOIL Animal residues ... NITRIFICATION Oxidation of ... such as thiourea

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BIOLOGICAL TRANSFORMATIONS OF NITROGEN IN SOIL

Animal residuesPlant residues

Animals

Plants

Plant roots

Nitrate

Ammonia

Microorganisms

Humus

NitrogenNitrous oxide

Nitrite

N.E.R. Campbell and H. Lees

<

NITROGEN CYCLENITROGEN CYCLE

Nitrogen Distribution in 10 Virgin Soilsand Their Cultivated Counterparts

Nitrogen Distribution in 10 Virgin Soilsand Their Cultivated Counterparts

Virgin Soil Cultivated SoilVirgin Soil Cultivated Soil

Nonhydrolyzable ( 6N HCl )

Hydrolyzable

Nonhydrolyzable ( 6N HCl )

Hydrolyzable

Total

Ammonium

Hexoseamine

Amino Acid

Unidentified

Total

Ammonium

Hexoseamine

Amino Acid

Unidentified

25.4 24.0

74.6

22.2

4.9

26.5

21.0

74.6

22.2

4.9

26.5

21.0

76.0

24.7

5.4

23.4

22.5

76.0

24.7

5.4

23.4

22.5

1 to 3 % of this N is mineralized each year.1 to 3 % of this N is mineralized each year.

Approximately 0.02 to 2.5 % of soil is as Nitrogen.

In a 2 % OC soil ( Ohio ) the value would be about 0.2% Nitrogen.

Approximately 0.02 to 2.5 % of soil is as Nitrogen.

In a 2 % OC soil ( Ohio ) the value would be about 0.2% Nitrogen.

<

NITROGEN MINERALIZATIONNITROGEN MINERALIZATION

Conversion of organic nitrogen to the moremobile, inorganic stateConversion of organic nitrogen to the moremobile, inorganic state

AMMONIFICATON

Formation of ammonia from organic matterFormation of ammonia from organic matter

NITRIFICATION

Oxidation of ammonium to produce nitrateOxidation of ammonium to produce nitrate

N = Inorganic Nitrogen

N = Nitrogen Assimilated by microorganisms

N = Nitrogen removed by Plants

N = Nitrogen lost via Leaching

N = Nitrogen lost via Denitrification

N = Inorganic Nitrogen

N = Nitrogen Assimilated by microorganisms

N = Nitrogen removed by Plants

N = Nitrogen lost via Leaching

N = Nitrogen lost via Denitrification

N = Organic matter mineralized - (N + N + N + N )N = Organic matter mineralized - (N + N + N + N )

i

i

A

A

P

P

L

L

D

D

The disappearance of N following the addition

of a nitrogen - poor crop residue is called immobilization .

Immobilization is the result of microbial assimilation

of inorganic nitrogen and is the converse of

mineralization .

The disappearance of N following the addition

of a nitrogen - poor crop residue is called immobilization .

Immobilization is the result of microbial assimilation

of inorganic nitrogen and is the converse of

mineralization .

I

Ammonium is the most readily assimilated N source

for soil microorganisms.

Ammonium is the most readily assimilated N source

for soil microorganisms.

NH > NO > Organic NNH > NO > Organic N4 3+ -

Whether immobilization or mineralization of Nitrogen occurs

depends on the C:N ratio. The C:N ratio where the two

processes are in equilibrium is approximately 30 ( 1.5 % N )

Whether immobilization or mineralization of Nitrogen occurs

depends on the C:N ratio. The C:N ratio where the two

processes are in equilibrium is approximately 30 ( 1.5 % N )

C:N > 30 N is taken from mineral

pool or degradation is slowed

C:N > 30 N is taken from mineral

pool or degradation is slowed

C:N < 30 Mineral N is releasedC:N < 30 Mineral N is released

I

I

I

Immobilization

Mineralization

Nitrogen Factor

The number of units of N immobilized for each 100

units of material being decomposed, i.e. the amount

of N that must be added to avoid immobilization.

Nitrogen Factor

The number of units of N immobilized for each 100

units of material being decomposed, i.e. the amount

of N that must be added to avoid immobilization.

N? =100

Changes in inorganic N in soil receiving

various quantities of glucose

Changes in inorganic N in soil receiving

various quantities of glucose

Weeks

mg

Ino

rgan

icN

per

gS

oil

mg

Ino

rgan

icN

per

gS

oil

75 mg75 mg

0 mg0 mg

0

8

16

24

32

5 10 15 20

300 mg

300 mg

Changes in C:N ratio during the decomposition

of plant residues

Changes in C:N ratio during the decomposition

of plant residues

Weeks

C:N

Rati

oC

:NR

ati

o

Wheat

Polygonium

0

10

20

30

40

4 8 12 16

Alfalfa

C:N

SUMMARY

The lowering of the C:N ratio from an initailly high

value to a lower value occurs during decompostion.

The lowering of the C:N ratio from an initailly high

value to a lower value occurs during decompostion.

1

2

3

4

The rate and extent of immobilization through microbial

assimilation depends on the carbonaceous substances

undergoing decay.

The rate and extent of immobilization through microbial

assimilation depends on the carbonaceous substances

undergoing decay.

Whether N is immobilized or mineralized depends on

the nature of the microbial population.

Whether N is immobilized or mineralized depends on

the nature of the microbial population.

( BACTERIA < FUNGI < ACTINOMYCETES )( BACTERIA < FUNGI < ACTINOMYCETES )

NN

Mineraliztion

Organic Mineral formMineral form

Immobilization may be both harmful and beneficial.Immobilization may be both harmful and beneficial.

Harmful if crop plants also are competing for NHarmful if crop plants also are competing for N I

I

I

Beneficial in serving as a store for N during times

of low N requirements by plants

Beneficial in serving as a store for N during times

of low N requirements by plants

-+

FACTORS INFLUENCING MINERALIZATIONFACTORS INFLUENCING MINERALIZATION

Oxygen status

- Ammonifying population includes both

aerobes and anaerobes

Oxygen status

- Ammonifying population includes both

aerobes and anaerobes

1

2

3

4

5

Moisture Status

- Wet / dry cycles

Moisture Status

- Wet / dry cycles

pH

- greatest when the soil pH is near neutral

pH

- greatest when the soil pH is near neutral

C:N ratioC:N ratio

Temperature

- Optimum is at 40 - 60 C , which is higher

than most biological processes

Temperature

- Optimum is at 40 - 60 C , which is higher

than most biological processes

o

FATES OF NH PRODUCEDFATES OF NH PRODUCED4+

1. Taken up by plants

2. Taken up by microorganisms

3. Held onto the soil cation exchange sites

1. Taken up by plants

2. Taken up by microorganisms

3. Held onto the soil cation exchange sites

4. Is fixed within the clay lattice

5. Reacts with organic matter to formquinone - NH complexes

6. Lost to the atmosphere through volatilization

7. Used as an energy source by chemoautotrophs

4. Is fixed within the clay lattice

5. Reacts with organic matter to formquinone - NH complexes

6. Lost to the atmosphere through volatilization

7. Used as an energy source by chemoautotrophs

NH

NH

NH

NH

NH

NH

4

4

4

4

4

4

+

+

+

+

+

+

2

+ =

MIneralization of organic nitrogen and organic carbon are

closely related to one another. The ratio of CO - C to N

produced in an unamended soil is relatively constant,

ranging from 7 to 15 : 1 .

MIneralization of organic nitrogen and organic carbon are

closely related to one another. The ratio of CO - C to N

produced in an unamended soil is relatively constant,

ranging from 7 to 15 : 1 .

Techniques Used to Predict N ProductionDuring a Growing Season

Techniques Used to Predict N ProductionDuring a Growing Season

Determine the quantity of N producedduring a short laboratory incubationperiod.

Establishing what fraction of totalorganic nitrogen is correlated withnitrogen mineralization rate.

Determine the quantity of N producedduring a short laboratory incubationperiod.

Establishing what fraction of totalorganic nitrogen is correlated withnitrogen mineralization rate.

NO - N (at time of planting ) prior toside - dressingNO - N (at time of planting ) prior toside - dressing

1

2

2

3 3

i

i

i

-

DECOMPOSTION OF AMINO ACIDSDECOMPOSTION OF AMINO ACIDS

( removal of amino group )( removal of amino group )

Transamination (some directly enter TCA cycle )Transamination (some directly enter TCA cycle )1

2 Oxydative deaminationOxydative deamination

+ +3

2

R C COOH + NAD NADH ( H ) + R C COOH + NHR C COOH + NAD NADH ( H ) + R C COOH + NH

H

NH

H

NH

H OH O2

R C COOH + NADH (H ) RCH COOH + NHR C COOH + NADH (H ) RCH COOH + NH

H

NH

H

NH

H

NH

H

NH

H OH O2

O

R C COOH + O H O + R C COOH + NHR C COOH + O H O + R C COOH + NH

O

amino acid dehydrogenaseamino acid dehydrogenase

3

2 2 3

2

H

NH

H

NH2

H

NH

H

NH2

Reductive deaminationReductive deamination

2

2

32+

4 Hydrolysis

2

H

OH

R C COOH + H O R C COOH + NHR C COOH + H O R C COOH + NH3

R C CH COOH R CH CHCOOH + NHR C CH COOH R CH CHCOOH + NH3

5 Desaturation

2

DECOMPOSITION OF NUCLEIC ACIDS

N

NH

CN

N

HC

C

CHC

N

N

HC

CH

CHHC

Purine Base Pyrimidine Base

(Base - Sugar - P) Base - Sugar - P Base - Sugar Sugar + Purine

or Pyrimidine BaseN

Nucleic Acid Mononucleotide

Pathway of Metabolism of Purines and Pyrimidines

Purine bases Pyrimidine bases

Adenine

Hypoxanthine

Cytosine

Guanine Uracil

XanthineBarbituric

acid

Uric acid

Urea

Allantoin

Allantoic acid

Glyoxylicacid

Malonicacid Alanine

Urea

Ureidopropionicacid

NH3

B-

B-

NITRIFICATION

The biological formation (oxidation) ofammonium to produce nitrite and nitrate

NITRIFICATION

The biological formation (oxidation) ofammonium to produce nitrite and nitrate

NH NO NONH NO NO4 2 3- -

MICROORGANISMS INVOLVEDMICROORGANISMS INVOLVED

1 Obligate aerobes

2 Derive their carbon solely from CO or carbonates

3 Derive their energy from oxidation of NH or NO

1 Obligate aerobes

2 Derive their carbon solely from CO or carbonates

3 Derive their energy from oxidation of NH or NO

2

24

4

-

3-

2-

2-

+

+NITROSOMONAS NH NO

NITROBACTER

NITROSOMONAS NH NO

NITROBACTER NO NONO NO

Nit

roso

mo

nas

Nit

rob

acte

r

GValance

StateValance

State

-3

+3.9

-68.9

-1

+1

+3

+5

-18.2

Postulated Steps in NitrificationPostulated Steps in Nitrification

NH OHhydroxylamine

NH OHhydroxylamine

2

NHammonium

NHammonium

4+

(NOH)nitroxyl radical

(NOH)nitroxyl radical

2 2N O + H ON O + H O

2NOnitriteNO

nitrite

-

3NOnitrateNO

nitrate

-

+

21/2 O

H

1/2 O

H

2H OH O

+

21/2 O

H

1/2 O

H

2 2NO H Ohydrated nitrite

NO H Ohydrated nitrite

-.

2

2

1/2 O

H O

1/2 O

H O

2

2

1/2 O

H O

1/2 O

H O

1 Hydrazine ( HN = NH ) strongly inhibits NH OH NO

but weakly inhibits NH NH OH.

1 Hydrazine ( HN = NH ) strongly inhibits NH OH NO

but weakly inhibits NH NH OH.

BIOCHEMICAL MECHANISMS

OF NITRIFICATION

BIOCHEMICAL MECHANISMS

OF NITRIFICATION

NH + 1/2 O NH OH + H NONH + 1/2 O NH OH + H NO4 2 2

2

4

2

2

2+ + -

EVIDENCE FOR HYDROXYLAMINE INTERMEDIATEEVIDENCE FOR HYDROXYLAMINE INTERMEDIATE

-

+

2

2 2

2 Results have shown that NH OH can accumulate in small

amounts in Nitrosomonas treated with hydrazine.

2 Results have shown that NH OH can accumulate in small

amounts in Nitrosomonas treated with hydrazine.

3 Oxidation of ammonium is blocked by copper enzyme poisons

such as thiourea. However, NH OH NO is not

affected by thiourea.

3 Oxidation of ammonium is blocked by copper enzyme poisons

such as thiourea. However, NH OH NO is not

affected by thiourea.

-

R

R

R

R

NH + NO N - N = O + OHNH + NO N - N = O + OH

R

R

R

R

-

and dehydrogenation ( hydrogen removal ) reactionand dehydrogenation ( hydrogen removal ) reaction

NITROSAMINE FORMATIONNITROSAMINE FORMATION

Secondary Amine NitrosamineSecondary Amine Nitrosamine

2

21 The oxygen in the nitrate product is from H O,

not molecular oxygen

2 This is an example of a hydration ( water addition )

1 The oxygen in the nitrate product is from H O,not molecular oxygen

2 This is an example of a hydration ( water addition )

-

-3

-2

2

2H O NO 2NO + 4H

4H + O 2H O

2NO + O 2NO

2H O NO 2NO + 4H

4H + O 2H O

2NO + O 2NO

--2 32

2

2

.

NH OH + O HNO + H ONH OH + O HNO + H O2

2

2 2

( NOH ) NO NO( NOH ) NO NO -

2 21/2 N O + 1/2 H O1/2 N O + 1/2 H O

1 Incubation of hydroxylamine and Nitrosomonas

causes production of NO and N O

1 Incubation of hydroxylamine and Nitrosomonas

causes production of NO and N O2

2

2

2

2

2

2 N O is not an intermediate in nitrification

because it is not converted to NO

2 N O is not an intermediate in nitrification

because it is not converted to NO

3 Mechanisms are speculative. N O may be

produced from NO still present in the

Nitrosomonas

3 Mechanisms are speculative. N O may be

produced from NO still present in the

Nitrosomonas

-

-

Chlorate ( Dinitrophenol ) inhibits the formation of nitrate

from nitrite by Nitrobacter. This can be used to study the

Chlorate ( Dinitrophenol ) inhibits the formation of nitrate

from nitrite by Nitrobacter. This can be used to study the

reaction facilitated by Nitrosomonas.reaction facilitated by Nitrosomonas.

NH NO NONH NO NO4 2 3+ - -chlorate

blocks reaction

chlorate

blocks reaction

The formation of nitrite from ammonium can thus be measured.

This reaction is important because it is the rate limiting step.

The formation of nitrite from ammonium can thus be measured.

This reaction is important because it is the rate limiting step.

FACTORS AFFECTING NITRIFICATIONFACTORS AFFECTING NITRIFICATION

NITRIFICATION

1 Acidity

2 Aeration

3 Moisture

4 Temperature

5 Organic Matter

1 Acidity

2 Aeration

3 Moisture

4 Temperature

5 Organic Matter

Beneficial or Harmful?Beneficial or Harmful?

Increases loss of N due to leaching

Increases loss of N due to denitrification

Increases risk of NO toxicity

Increases loss of N due to leaching

Increases loss of N due to denitrification

Increases risk of NO toxicity

Increases soil acidity

May allow easier uptake of N by plants

It is a necessary intermediate in returningN to the atmosphere

Increases soil acidity

May allow easier uptake of N by plants

It is a necessary intermediate in returningN to the atmosphere

3-

1

2

3

4

5

6

1

2

3

4

5

6

The end product of fertilizer N is nitrate whether the fertilizeris added as urea, anhydrous ammonia, or ammonium nitrate.The end product of fertilizer N is nitrate whether the fertilizeris added as urea, anhydrous ammonia, or ammonium nitrate.

CONTROL OF NITRIFICATIONCONTROL OF NITRIFICATION

DESIRABLE CHARACTERISTICSOF NITRIFICATION INHIBITORSDESIRABLE CHARACTERISTICSOF NITRIFICATION INHIBITORS

1 Control of nitrification inhibitors

2 Use of nitrogen compounds that release N slowly

1 Control of nitrification inhibitors

2 Use of nitrogen compounds that release N slowly

because of limited solubility in water or slow rate

of microbial decomposition

because of limited solubility in water or slow rate

of microbial decomposition

3 Use of nitrogen compounds coated with material

that will delay the release of N

3 Use of nitrogen compounds coated with material

that will delay the release of N

1 Specific in blocking NH NO

2 Able to move with fertilizer through soil

3 Non-toxic to plants

1 Specific in blocking NH NO

2 Able to move with fertilizer through soil

3 Non-toxic to plants

4 Non-toxic to plant root micro-environment

5 Not easily bio- or chemical degradable

4 Non-toxic to plant root micro-environment

5 Not easily bio- or chemical degradable

4 3+ -

NITRIFICATION INHIBITORSNITRIFICATION INHIBITORS

POTENTIAL ADVANTAGES

DISADVANTAGES

1 Reduced gaseous loss of N

2 Reduced loss of NO by leaching and runoff

3 Reduced risk of NO toxicity

1 Reduced gaseous loss of N

2 Reduced loss of NO by leaching and runoff

3 Reduced risk of NO toxicity

1 Increased gaseous loss of N ( NH Volatilization )

2 Increased fixation or immobilization of NH

3 Some plants do not use NH , but primarily NO

1 Increased gaseous loss of N ( NH Volatilization )

2 Increased fixation or immobilization of NH

3 Some plants do not use NH , but primarily NO

3

3

34

-

-

-

-

4+

4+

+

NCl CCl

3

MOST EFFECTIVE INHIBITORS OF NITRIFICATIONMOST EFFECTIVE INHIBITORS OF NITRIFICATION

1 N - SERVE1 N - SERVE

2 - Cloro - 6 - ( Trichloromethyl ) - Pyridine2 - Cloro - 6 - ( Trichloromethyl ) - Pyridine

2 - Amino - 4 - Cloro - 6 - Methyl - Pyrimidine2 - Amino - 4 - Cloro - 6 - Methyl - Pyrimidine

2 3( or Na CS )( or Na CS ) Sodium TrithiocarbamateSodium Trithiocarbamate

4 - Amino - 1, 2, 4 - Triazole4 - Amino - 1, 2, 4 - Triazole

3 ATC

2 AM

N

2NHH CH C

Cl

3N

N N

HC CH

N

N N

HC CH

N

NH2

24 CS4 CS

2Na CS + 2H O + 5CO 4NaHCO + 3CS2Na CS + 2H O + 5CO 4NaHCO + 3CS2 2 2 23 3

5 DWELL5 DWELL

S

H C OC N

N C CCl

S

H C OC N

N C CCl

5 2

3

N

DENITRIFICATION

The reduction of nitrate to nitrite and then to gaseous nitrogen

products which are lost from the aquatic or soil system. It is

The reduction of nitrate to nitrite and then to gaseous nitrogen

products which are lost from the aquatic or soil system. It is

a dissimilatory reduction reaction.a dissimilatory reduction reaction.

ASSIMILATORY NITRATE REDUCTIONASSIMILATORY NITRATE REDUCTION

NO NHNO NH3 4

+

The ammonium is used for cell growth. This reaction is oxygen

insensitive and is inhibited by reduced N compounds

The ammonium is used for cell growth. This reaction is oxygen

insensitive and is inhibited by reduced N compounds

DISSIMILATORY NITRATE REDUCTIONDISSIMILATORY NITRATE REDUCTION

NO N , N ONO N , N O3 2 2

This reaction provides energy for growth, but the nitrogen

is not used directly for synthesis of microbial products.

This reaction provides energy for growth, but the nitrogen

is not used directly for synthesis of microbial products.

This reaction is very oxygen sensitive and ammonium insensitive.This reaction is very oxygen sensitive and ammonium insensitive.

IMPORTANCE OF DENITRIFICATIONIMPORTANCE OF DENITRIFICATION

1

4

Represents a major loss pathway of nitrogen from soils ( 30% )Represents a major loss pathway of nitrogen from soils ( 30% )

2 Nitrous oxide, a product of denitrification, may lead to

destruction of the ozone layer

Nitrous oxide, a product of denitrification, may lead to

destruction of the ozone layer

3 Importance in commercial wastewater treatment plants

to reduce nitrate levels

Importance in commercial wastewater treatment plants

to reduce nitrate levels

A key intermediate, nitrite, readily reacts with secondary

amines to produce carcinogenic nitrosamines

A key intermediate, nitrite, readily reacts with secondary

amines to produce carcinogenic nitrosamines

5 N cycling on global basisN cycling on global basis

R

RR

R

NH + NO N NO + OHNH + NO N NO + OH2

A key feature distinguishing denitrification from asssimilatory nitrate reduction

is the formation of a nitrogen - nitrogen bond in denitrification.

A key feature distinguishing denitrification from asssimilatory nitrate reduction

is the formation of a nitrogen - nitrogen bond in denitrification.

Note!

ASSIMILATORY REACTION

DENITRIFICATION

4+

3

3

2

2

2NO 2NO 2NH OH 2NH2NO 2NO 2NH OH 2NH

2NO 2NO ? N O N2NO 2NO ? N O N

2

+5 +3 -1 -3

2 2

Time

Normal Sequence of EventsNormal Sequence of Events

mg

of

Nit

rog

en

mg

of

Nit

rog

en

3NO 2N

N ON O2

2NO

+5 +3 +1 0

1

2

3

4

5

Nonrecovery of total N or N nitrogenNonrecovery of total N or N nitrogen

Disappearance of denitrification intermediatesDisappearance of denitrification intermediates

METHODS OF DETERMINING DENITRIFICATION RATESMETHODS OF DETERMINING DENITRIFICATION RATES

A. Sensitivity of detection losses are low

B. Short term studies not possible

C. Analytical errors are important

A. Sensitivity of detection losses are low

B. Short term studies not possible

C. Analytical errors are important

A. NO or NO disappearance

( works only if nongaseous N losses are minimal )

A. NO or NO disappearance

( works only if nongaseous N losses are minimal )

3 2

B. N O disappearance

- nondisturbing to soil system and specific to

one step of denitrification pathway

B. N O disappearance

- nondisturbing to soil system and specific to

one step of denitrification pathway

2

- difficult to calculate data ( on a soil basis )- difficult to calculate data ( on a soil basis )

Production of N O and NProduction of N O and N2

A. Sensitive and very precise

B. Background of N is high, making a natural system

difficult to use

A. Sensitive and very precise

B. Background of N is high, making a natural system

difficult to use2

Inhibition of N O reduction by acetyleneInhibition of N O reduction by acetylene2

N O N is inhibited by C HN O N is inhibited by C H2 2 2 2

Denitrification is measured by the accumulation

of N O in the presence of C H

Denitrification is measured by the accumulation

of N O in the presence of C H2 22

Isolation and enumeration of denitrifiersIsolation and enumeration of denitrifiers

15

FACTORS WHICH CONTROL DENITRIFICATION IN SOILFACTORS WHICH CONTROL DENITRIFICATION IN SOIL

1 Oxygen and redox potential

2 Water content

3 Concentration of NO or NO

4 Organic C

5 pH ( optimum is 7.0 - 8.0 )

6 Temperature

1 Oxygen and redox potential

2 Water content

3 Concentration of NO or NO

4 Organic C

5 pH ( optimum is 7.0 - 8.0 )

6 Temperature

3 2- -

3-

2-

First order to zero order reaction ratesoccur at low concentrations of NO or NOKm = 4 - 7 uM

First order to zero order reaction ratesoccur at low concentrations of NO or NOKm = 4 - 7 uM

3-NO inhibits NO N so that early

intermediates accumulateNO inhibits NO N so that earlyintermediates accumulate

22-

2

23-NO inhibitions cause greater N O production

relative to NNO inhibitions cause greater N O productionrelative to N

Optimum occurs between 60 - 75 C. Whether chemicalprocesses are of great importance in this temperaturerange is still not known.

Optimum occurs between 60 - 75 C. Whether chemicalprocesses are of great importance in this temperaturerange is still not known.

o

2-

At low pH, more N O is produced relative to N

NO can accumulate at low pH

At low pH, more N O is produced relative to N

NO can accumulate at low pH2 2

DECOMPOSITION OF UREA

AllophanicAcid

Urea

Urease

AmmoniumCarbamate

2 2 2 232H OH O

H N - C - NH H NCONH 2NH + CO2

O

2 2 2 23H N - C - NH + CO H NCNHCOOH 2NH + CO2

O O

Advantages

Disadvantages

USE OF UREA AS A N SOURCE IN SOILS

Rapid hydrolysis to ammonium carbamate

1 Raises pH and causes voloatilization losses of N

2 Nitrite toxicity

3 Seedling germination can be inhibited

1 High N content (45-46% N)

2 Low cost of manufacture, transport, storage, and distribution

3 High solubility in water

4 Ease in handling (nonexplosive, noncaking)

5 Suitable for dry blends or in solution blends

6 Can be applied as a foliar spray

7 Used in production of compound fertilizers (Urea phosphates)

FACTORS PROMOTING NH VOLATILIZATION LOSSESFACTORS PROMOTING NH VOLATILIZATION LOSSES3

1 pH values > 6

2 Low moisture content

3 High temperatures

1 pH values > 6

2 Low moisture content

3 High temperatures

4 Low CEC of soils

5 Addition of highly nitrogenous fertilizerN sources without incorporation

4 Low CEC of soils

5 Addition of highly nitrogenous fertilizerN sources without incorporation

APPROACHES USED TO DECREASE VOLATILIZATION

LOSSES FROM UREA

APPROACHES USED TO DECREASE VOLATILIZATION

LOSSES FROM UREA

1 Urease inhibitors

2 Slow release urea fertilizers

3 Addition of divalent cations with application of urea

1 Urease inhibitors

2 Slow release urea fertilizers

3 Addition of divalent cations with application of urea

Hg, Ag are the most effective inorganic inhibitors

Catechol, hydroquinone - most effective organic inhibitors

Hg, Ag are the most effective inorganic inhibitors

Catechol, hydroquinone - most effective organic inhibitors

Conversion to acidic derivative (urea phosphate )Conversion to acidic derivative (urea phosphate )

Formation of water insoluble urea compounds ( urea-forms )

Coat urea granule with an inert or water resistant

material (sulfur-coated

Formation of water insoluble urea compounds ( urea-forms )

Coat urea granule with an inert or water resistant

material (sulfur-coated urea )urea )

+ =

Phosphorodiamides,

NBPT N ( n - butyl ) thiophosphoric triamide

(oxon form is active form )

Phosphorodiamides,

NBPT N ( n - butyl ) thiophosphoric triamide

(oxon form is active form )

(NH ) X + CaCO (NH ) CO H O + CaX

where X = SO or HPO

(NH ) X + CaCO (NH ) CO H O + CaX

where X = SO or HPO

4

4

4

4

4

4

4

4

4

4

4

2

2

2

2 2

2

2 2

2 24 2

4 2

22

2

2

2 2

2

2

2

4 23

3

3

3

3

3

3

3

3

3

23

42 -

- -

-

43 -

(NH ) CO H O 2NH OH + CO and

NH + OH NH OH NH + H O

(NH ) CO H O 2NH OH + CO and

NH + OH NH OH NH + H O

.

.

.

.

.

+

at alkaline pH the reactiongoes to the right

at alkaline pH the reactiongoes to the right

2NH X + CaCO ( NH ) CO H O + CaX

X = Cl , NO , H PO

2NH X + CaCO ( NH ) CO H O + CaX

X = Cl , NO , H PO- -

CO ( NH ) + 3H O ( NH ) CO H OCO ( NH ) + 3H O ( NH ) CO H Ourease

soluble salt ofdivalent cationssoluble salt of

divalent cations

urea

(NH ) CO H O + 2H 2NH + CO + 2H O(NH ) CO H O + 2H 2NH + CO + 2H O+ + 6

7

5

4

3

2

1

(NH ) CO H O + CaX CaCO + 2NH X(NH ) CO H O + CaX CaCO + 2NH X

From Fenn, Taylor, and Matocha, SSSAJ, 1981, 45:777From Fenn, Taylor, and Matocha, SSSAJ, 1981, 45:777

CaCO precipitation and pH depression ( exchange of Ca for H on exchange

sites ) as mechanisms of ammonia volatilization reduction!

CaCO precipitation and pH depression ( exchange of Ca for H on exchange

sites ) as mechanisms of ammonia volatilization reduction!

+3

[ see equations 6 and 7 ][ see equations 6 and 7 ]