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IMPORTANCE OF NITROGEN IN THE

ENVIRONMENT
N2 comprises 80% of the atmosphere
N2 can not be used by most organisms
N2 is not a problem until its in a reactive form like NH3 or
NO3 and is out of balance in nature

N is the major component of proteins and nucleic


acids
Often the most limiting nutrient for plant growth

When out of balance, N can have both direct and


indirect negative impacts on the environment

THE NITROGEN CYCLE

N CYCLE

N enters the cycle through:


N fixation
Fertilization

N fixation
Non-biological
Lightning

Burning fossil fuels

N2 + O 2

2 NO

2NO + O2

2 N O2

2 N O2 + H2O

HNO 3 + HNO2

HNO3

H + + NO3- (Nitrate; Readily


used by plants)

Biological N fixation
Microorganisms
Nitrogenase

N2 + 6 e- + 8H+

2NH 3 (Ammonia)+ H2
Fe, Mo

Biological N fixation
Symbiotic N fixers
Responsible 70% of all N fixation
Microorganisms
Rhizobium bacteria
Infect roots of legume plants
Frankia bacteria
Infect the roots of certain trees

Process
Bacteria reduce N2 to NH3
Plants take up NH3 and combine it with Carbon skeletons to produce amino
acids
Other plants only have access to this fixed N by the plant dying and
becoming part of the soil organic matter-N pool
High levels of N will reduce biological N fixation

Free living N fixers


Responsible for 30% of world N fixation
Microrganisms
Cyanobacteria
Found in rice paddies
Azospirrilium, Azobacter, and Clostridium bacteria
Found in soil

Generate NH3 for their own use.

N fertilizer

Produced by the HaberBosch process


Developed in 1913
Process
High pressure High temperature
N2 + 3H2

NH 3
Fe catalyst

Primarily responsible for the


green revolution, but also
responsible to large
increase of reactive N in our
environment

Ammonification (Mineralization)
N in plant protein may become part of the soils OM
nitrogen pool by microbial degradation of:
Dead plant litter
Undigested protein in animal feces

OM-nitrogen converted to ammonia by soil bacteria


Process
R-NH2

NH3 + R

Done by both aerobic and anerobic bacteria


Increased by:

Increased soil OM-N pool


Increased soil temperatures
Soil pH > 7
High soil moisture

NH3 rapidly converted to NH4+ at pH < 7.5


NH4+ is relatively stable

N is digested by animals is excreted as urea


(mammals) or uric acid (poultry)

O
H2N C NH2

Urease
2NH3 + CO2

Urea

O
H
N

C
H

C
C

C
N
H
Uric acid

N
H

5 steps w/
Urease
O
4NH3 + 5CO2

FATE OF AMMONIA RELEASED BY


MINERALIZATION
Use by plants
Immobilization
Bacteria incorporate N into their own cells and contribute to
soil OM-N pool
Occurs in soils containing high C:N ratios

Leaching
Occurs in sandy soils
Have a low capacity for binding NH4+
Ammonium cations may leach into ground water as
precipitation infiltrates soils

Soils that are high in clay or organic matter can bind NH4+
which can only be lost with erosion

Nitrification
Highest proportion of NH4+ is converted to NO3 by aerobic
bacteria
Nitrosomas
Nitrobacter
O2
4H
O2
NH4
NO2
NO3
Rapid under conditions of:

Warm temperatures
Well aerated soils
Neutral pH
Moist soils
High fertility

Slow under conditions of:


Cold temperatures
Saturated soils
Low pH
During nitrification, soil pH may decrease as NH4 is converted to
NO3

Volatilization
NH4+ is not volatile
In soils with high pH (> 7.0), NH4+ is converted to NH3 which
can volatize into the atmosphere as a gas
NH3 is also released when the urea (in mammals) or uric
acid (in poultry) excreted in urine mixes with the urease or
uricase enzymes produced by the bacteria in the feces in in
manure in barns, outdoor lots, manure storage structures,
and in fields after application
Amounts of NH3 volatilized
20 to 70% of the N in manure
Ammonia losses from animal agriculture represents 75% of all
NH3 emitted in the U.S.

Rate of NH3 volatilization is increased by:


Soil pH > 7.0
Soil temperatures > 50 F
Greater air movement

FATE OF NO3 PRODUCED DURING


NITRIFICATION
Use by plants
Leaching into groundwater
NO3 is highly soluble in water and does not bind to soil
particles
During periods of excessive precipitation, NO3 transported
to ground water as water infiltrates the soil
Carries Ca, Mg, and K cations out of the soil reducing fertility
while leaving Al which is toxic to plants

NO3 may be transported to surface waters via tile


drainage
Factors that lead to increased leaching in spring
Build up on NH4+ in soil during winter
Increased NO3 in soil as nitrification increases with increased
soil temperatures
Low utilization of NO3 by immature plants
High soil moisture

Denitrification
Conversion of NO3 to N2 in anerobic conditions in soil or
manure storage areas
Process
C6H12O6 + 4 NO3

6CO2 + 6H2O + 2N2 + NOx

NOx = NO, NO2 or N2O

N2 and NOx are gases released into the environment


N2 is inert in the environment
NOx has numerous adverse effects on the environment

Denitrification is increased by:


High soil N levels
Anerobic soils
Flooded soil
Compacted soil

Warm temperatures
High OM in soil

POSITIVE EFFECTS OF INCREASING THE AMOUNTS


OF REACTIVE N IN THE ENVIRONMENT
Increased yields and nutritional value of feeds
Increased wealth of the human population
Increased productivity of N-limited crops and
ecosystems
Increased yields per acre
Could reduce cultivation of marginal and forested lands

Increased carbon sequestration

ADVERSE EFFECTS OF NITROGEN IN THE


ENVIRONMENT

ADVERSE EFFECTS OF NITRATE (NO3) IN THE


ENVIRONMENT
Enters drinking water supplies
Hazard (Blue Baby Syndrome)
Formation of methemoglobin that prevents hemoglobin in
red blood cells from carrying oxygen to peripheral tissues
Normal:
O2
Hemoglobin in
red blood cells

Oxygenated hemoglobin

Peripheral tissue
(Uses O2)
Nitrate toxicity: Gut bacteria
NO3
NO2
O2
Hemoglobin in
red blood cells
Peripheral tissue

Hazardous level: 10 ppm in water

Methemoglobin

ADVERSE EFFECTS ON AMMONIA IN THE


ENVIRONMENT
Hazards
Odor
Direct toxin
Physiological effects and amounts
Livestock (<100 ppm, usually found in livestock facilities)
Eye irritation
Respiratory tract irritation
Reduced disease resistance
Humans (OSHA limit is 50 ppm)
9 ppm
Eye, nose and throat irritation
50 150 ppm
Severe cough and mucous production
Nasal irritation
> 150 ppm
Scarring of the upper and lower respiratory tract
Pulmonary edema
Chemical burns of eyes
500 ppm
Acute death

Problem for workers and animals in confinement


Limited threat to the community
Recommended limits (One-hour average exposure)
Measurement
Neighboring residence
Property line

Concentration Dilution
< 150 ppb
1:7
< 70 ppb
1:15

Toxicity in aquatic environments (Manure spills)


Most natural water sources
NH4-N at 2 ppm is toxic to fish

In alkaline waters at high temperatures


NH4-N at 0.1 ppm is toxic to fish

Particulate matter less than 2.5 um (PM 2.5)


Formed when atmospheric NH3 reacts with SO2, NOx, and
volatile organic compounds (VOCs)
Produce (NH4)2SO4, NH4NO3, and NH4HSO4
Forms in rain clouds and fog
Dispersed to ground as rainfall and snow (Wet deposition)
Released in air as aerosols (Dry deposition)

Sources of components of PM2.5


Agriculture
Burning fossil fuels

Hazards of PM2.5
Human health
Penetrate into lungs
Increased hospital emissions
Increased respiratory diseases
Decreased lung function
Alteration in lung tissue and respiratory defense
mechanisms
Chronic bronchitis
Increased risk of myocardiac infarctions
N deposition in the environment
Acidifying lakes and streams
Algae bloom in water sources
Depletion of minerals in soils
Decreased biodiversity of ecosystem

Health-based standard for PM2.5


Annual average 15 ug/m3
24 hr standard 65 ug/m3
Monitored at 1100 sites across the US

Acidify soil
Process
During nitrification, H+ are released that lower pH of soil
NH4
NO 3
4H+
Reduces ability of plants to uptake nutrients

Total Ammonia Emissions by County


for 1995

ADVERSE EFFECTS ON NOx IN THE


ENVIRONMENT
Major sources
Combustion of fossil fuels
Agriculture

Hazards
Component of PM2.5; NO2
Acid rain; NO2
NOx + H
HNOx
Effects
Damages lung tissue
Increases acid in waters
Harms fish population
Increases acid in soil
Harms trees
Damages buildings and statues

Formation of ground level ozone; NO2


Formed when volatile organic compounds (VOCs) react with
NOx in the presence of heat and sunlight
Effects
Health
Respiratory infections and diseases
Premature aging of lungs
Ecosystems
Reduced agricultural and forest yields
Reduced survivability of tree seedlings
Increased susceptibility of plants to stress and
disease
Damage to foliage of plants
Forms smog with PM reducing visibility

Destruction of stratospheric ozone; N2O


In upper atmosphere, N2O triggers reactions that deplete the
stratospheric ozone layer which protects the earth from
ultraviolet radiation
Human skin cancer
Damages plant foliage

Greenhouse gas; N2O


N2O has 310 x the greenhouse gas effect of CO2
Contributes to global warming

ADVERSE EFFECTS OF NH3, NO3, AND NOx IN


AQUATIC AND TERRESTRIAL ENVIRONMENTS
In aquatic environments
Mobile aquatic
communities move
Increased N

Algae bloom
in marine
environment

Pfisteria
(Red tides)

Decay of dying
algae reduce
dissolved O2 in
water
Produce toxins

Hypoxic
zone
(Gulf of
Mexico)
Fish kills

Fish lesions
Fish and
shellfish kills
Memory loss,
confusion,
gastrointestinal
problems
(Humans)

In terrestrial environment
Increased soil N favors
growth of plants with high
N needs
Alterations of soil chemistry
Loss of Ca, Mg and K
Build up of Al

National Atmospheric Deposition Program 1999 Annual Summary

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