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2 20-10-2006
Objectives and aims
• ‘A conference at the forefront of scientific developments in an area where scientific interdisciplinary progress is needed’
• Aim for a set of papers for a peer reviewed journal to provide the state of knowledge, gaps and ways to make progress.
• Plenary presentations, discussions, posters and informal exchange of ideas both inside and outside the lecture room will be encourage to reach the targets.
3 20-10-2006
Conference issues
• Program:• Posters• Papers: Environmental
Pollution (150)• Deadline: December 15
(electronic system)• Guest editors: Mark
Sutton, Peringe Grennfeltand me
• Availability of presentations
www.ecn.nl
Reduced forms of Nitrogen in Ecology and the Environment
Jan Willem Erisman
5 20-10-2006
Outline of presentation
• The earth system• Reduced nitrogen in ecology• Industrial production• Environment• N management• Discussion items
6 20-10-2006
Our milky way with a developing solar system ( )
First atmosphere: H2, He
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The earth began as a gas bulb, which slowly cooled down, which is still going on. Through this process the earth is shrinking.
The chemical climate of the earth startedwith gases from volcanic eruptions
Second atmosphere: H2O, CO2, SO2, CO, N2, CH4 and NH3
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Ammonia cloud on Jupiter
NASA, GalileoJune 26, 1996
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When O2 increased the reducing conditions disappeared: photosynthesis
Gas VolumeNitrogen (N2) 780,840 ppmv (78.084%)Oxygen (O2) 209,460 ppmv (20.946%)Argon (Ar) 9,340 ppmv (0.9340%)Carbon dioxide (CO2) 381 ppmvNeon (Ne) 18.18 ppmvHelium (He) 5.24 ppmvMethane (CH4) 1.745 ppmvKrypton (Kr) 1.14 ppmvHydrogen (H2) 0.55 ppmv
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Reduced nitrogen in nature• Ammonia and ammonium salts• The major amines in both air and rain are trimethylamine and
methylamine, but dimethylamine, diethylamine and triethylamine.• Life sustained by amino acids
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Key issues: life and production
World production (2004): 142 Millions MT/year
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All organisms depend on NH3
• Insufficient protein in the diet may prevent the body from producing adequate levels of peptide hormones and structural proteins to sustain normal bodily functions
……... too little …….. too much
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Nitrogen cycles between oxidized & reduced forms in the biosphere
degradation(animals & microorganisms)
synthesis(microorganisms, plants & animals)
amino acids & other organic compounds
(Rhizobium & some other bacteria)
(anaerobic bacteria)
nitrification(Nitrobacter & other soil bacteria)
nitrification
(Nitrosomonas & other soil bacteria)
NO2-
nitrite
nitrogen fixation
denitrification
nitrate NH4+ ammonium N2
reduction(plants & some anaerobic bacteria)
NO3-
more oxidized more reduced
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Nodules on the roots of leguminous plants fix N2via bacteria containing nitrogenase
bacteroids(rod-like bacteria)
plant cell nucleus
Lehninger
Nitrogenase from Azobacter vinelandii
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glycine
alanine
tryptophan
histidine
glucosamine-6-P
carbamoyl-phosphate
CTP AMP
Glutamine serves as a donor of amine groups for synthesis of many other molecules
In most terrestrial animals, Gln also carries ammonia in the blood to the liver & kidneys for excretion as urea.
Glu
NH4+ + ATP ADP + Pi
H2OGln
OC-NH2
CO2-
+H3N-C-H
CH2
CH2
α-keto-glutarate(1) glutamate dehydrogenase
(2) glutamine synthetaseoccurs in all organisms.
(3) occurs in plants & bacteria, but not animals
2
CO2-
CO2-
O=C
CH2
CH2
CO2-
CO2-
+H3N-C-H
CH2
CH2Glu
3
CO2-
CO2-
O=C
CH2
CH2
CO2-
CO2-
+H3N-C-H
CH2
CH2
α-keto-glutarate
NADH NAD+
NH4+
1
Ammonia is incorporated into many biological molecules through glutamine and glutamate
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NH3 Creation by Nature and Humans
• Since 1960:- Flows of biologically
available nitrogen in terrestrial ecosystems doubled
- > 50% of all the synthetic nitrogen fertilizer ever used has been used since 1985
• Humans produce as much biologically available N as all natural pathways and this may grow a further 65% by 2050
Human-produced Reactive Nitrogen
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Historical development Closed nutrient cycles
Increased production
Fertilizer
Intensive livestockbreeding
Manure = food
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Intensification of agriculture
Nitrogen Cycle
Manure
Animals
Crops
Soil
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N Fertilizer Produced
100
The fate of fertilizer Nitrogen
Galloway JN and Cowling EB. 2002
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N Fertilizer Produced
100
NConsumed
14
The fate of fertilizer Nitrogen
14% of the N produced in the Haber-Bosch process enters thehuman mouth……….
Galloway JN and Cowling EB. 2002
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N Fertilizer Produced
N Fertilizer Consumed
-6 -47
100
N in Crop
N Harvested
Nin Food
NConsumed
-12
144794 31 26
-5
The fate of fertilizer Nitrogen
-16
14% of the N produced in the Haber-Bosch process enters thehuman mouth……….if you are a vegetarian.
Galloway JN and Cowling EB. 2002
23 20-10-2006
N Fertilizer Produced
N Fertilizer Applied
-6 -47
100
N in Crop
N In Feed
Nin Store
NConsumed
-3
44794 31 7
-24
The fate of fertilizer Nitrogen
-16
4% of the N produced in the Haber-Bosch process and usedfor animal production enters the human mouth.
Galloway JN and Cowling EB. 2002
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Industrial production of NH3
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Production volume and price
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Ammonia products
ExplosivesAquarium test kid
Fibers
Household application
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Industrial ammoniaAmmonia levels Health effects
– 5ppm Olfactory detection
– 20-25ppm Eye irritation
– ~ 1,500ppm Cough and froth at the mouth
– 5,000ppm Deadly
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Nitrogen excess
N2
Manure
Fertilizerindustry
Combustion
Sources
Nitrate
NitrateAmmonium-
NH4
Chemical/physical interactions
Materialsand culturalheritage
Human and animal health
Climate changeGHG interactions
Ecosystemsand
biodiversity
Effects
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Ammonia in the atmosphere
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Paleo records and wet deposition of ammonium
0
50
100
150
200
1840 1860 1880 1900 1920 1940 1960 1980 2000Dating
NH
4
East Rongbuk Glacier, Mt. Everest, Chemistry and Stable Isotope Data Hou Shugui, et al., 2003
00,20,40,60,8
11,21,41,61,8
2
1860 1880 1900 1920 1940 1960 1980 2000Year
NH
4co
ncen
tratio
n (m
g/l)
050100150200250300350400450500
Amm
onia
em
issi
on (k
ton/
y)
WitteveenGroningenAmmonia emission
Netherlands
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Deposition maps of Europe
Reduced nitrogen (NHx) Oxidised nitrogen (NOx)1 – 20 kg/ha 1 – 20 kg/ha
Source: EMEP
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Effects on the environment
• Human health: PM, NOx/O3, NO3 drinking water, plagues, pests and diseases
• Ecosystems: direct effects, plagues, pests and diseases, loss of biodiversity, plant/forest vitality, ecosystem functioning
• (Ground)water pollution• Eutrophication: Gulf of Mexico Hypoxia Zone.• Global warming (N2O) and cooling (aerosols)• GHG interactions affecting sinks • Reduces visibility (haze);
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Radiative forcing and Nitrogen
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0
0.2
0.4
0.6
0.8
1
1.2
Basis So2-25%
NOx-25%
NH3-25%
Comb,nh3 -0%
Comb,nh3 -25%
Comb,nh3 -50%
0
0.2
0.4
0.6
0.8
1
1.2
Basis So2-25%
NOx-25%
NH3-25%
Comb,nh3 -0%
Comb,nh3 -25%
Comb,nh3 -50%
NO3NH4SO4
Germany Southern Sweden
Effect of NH3 reductions on secondary PM
Agriculture and PM
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Regulator for other processes, e.g. co-deposition between SO2 and NH3
020406080
100120140160180
Speulder forest Melpitz Auchencorth
Rc
(s/m
)
00.10.20.30.40.50.60.70.80.9
NH
4/(S
O4+
NO
3)
Rc NH3 Rc SO2 NH4/(SO4+NO3)
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Park Grass experiment, Rothamsted since 1856
Effects: biodiversity
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Effects of reactive nitrogen in the environment
Overall effects
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Hours days Weeks months years decades centuries
materialsclimate change
Vegetation changessoil processes
forest ecosystem health
soil nutrient reserves
Carbon sequestration
air concentrationsvisibility
Depositionhealth (acute) health (chronic)
aquatic (episodic) aquatic (chronic)plant responses
Cascade effect of reactive nitrogen (excess)
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Effective measures
0
0,5
1
0 20 40 60 80 100 120
Time
Econ
omic
s/so
cial
acc
epta
nce
Increase Neffthroughmanagement andeducation
Close nutrient cycles atDifferent scales (ERTechnology)
Sensor basedPrecisionagriculture
Spatial optimizationIndustrializedMeat production
Gene modification
Transition tosustainableagriculture
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New items for reduced nitrogen
• Increasing demand of fertilizer: food, biofuels• NH3 as a transport fuel?
Ammonia fuelled car, Rjukan 1933