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NITROGEN CYCLE

NITROGEN CYCLE. SOIL 5813 Soil-Plant Nutrient Cycling and Environmental Quality Department of Plant and Soil Sciences Oklahoma State University Stillwater, OK 74078. GLOBAL WARMING. ATMOSPHERE. 3H 2 + N 2 2NH 3. N 2 O NO N 2. INDUSTRIAL FIXATION. LIGHTNING, RAINFALL.

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NITROGEN CYCLE

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  1. NITROGEN CYCLE SOIL 5813 Soil-Plant Nutrient Cycling and Environmental Quality Department of Plant and Soil Sciences Oklahoma State University Stillwater, OK 74078

  2. GLOBAL WARMING ATMOSPHERE 3H2 + N2 2NH3 N2O NO N2 INDUSTRIAL FIXATION LIGHTNING, RAINFALL N2 FIXATION PLANT AND ANIMAL RESIDUES HABER BOSCH SYMBIOTIC NON-SYMBIOTIC (1200°C, 500 atm) MESQUITE RHIZOBIUM ALFALFA SOYBEAN BLUE-GREEN ALGAE AZOTOBACTER CLOSTRIDIUM MATERIALS WITH N CONTENT > 1.5% (COW MANURE) MATERIALS WITH N CONTENT < 1.5% (WHEAT STRAW) FERTILIZATION PLANT LOSS AMINO ACIDS MICROBIAL DECOMPOSITION NH3 AMMONIA VOLATILIZATION IMMOBILIZATION AMINIZATION HETEROTROPHIC ORGANIC MATTER R-NH2 + ENERGY + CO2 BACTERIA (pH>6.0) FUNGI (pH<6.0) pH>7.0 R-NH2 + H2O AMMONIFICATION NH2OH IMMOBILIZATION R-OH + ENERGY + 2NH3 N2O2- Pseudomonas, Bacillus, Thiobacillus Denitrificans, and T. thioparus MICROBIAL/PLANT SINK 2NH4+ + 2OH- MINERALIZATION + NITRIFICATION FIXED ON EXCHANGE SITES +O2 NO2- Nitrosomonas DENITRIFICATION NO3- POOL NITRIFICATION 2NO2- + H2O + 4H+ OXIDATION STATES Nitrobacter + O2 DENITRIFICATION LEACHING LEACHING VOLATILIZATION NITRIFICATION ADDITIONS NH3 AMMONIA -3 NH4+ AMMONIUM -3 N2 DIATOMIC N 0 N2O NITROUS OXIDE 1 NO NITRIC OXIDE 2 NO2- NITRITE 3 NO3- NITRATE 5 Joanne LaRuffa Wade Thomason Shannon Taylor Heather Lees Department of Plant and Soil Sciences Oklahoma State University TEMP 50°F LEACHING LEACHING LOSSES OXIDATION REACTIONS LEACHING REDUCTION REACTIONS pH 7.0

  3. Applications of the Nitrogen and Carbon Cycles: • Ammonium Nitrate Fertilizer Spill • Urea • Temperature and pH • Tillage (zero vs. conventional) • C:N ratios (high, low lignin) • Mechanistic models would ultimately lead to many 'if-then' statements/decisions that could be used within a management strategy. >50°F <50°F Denitrification Volatilization Leaching Leaching Winter/Summer ? 7.0soil pH

  4. Bidwell (1979), Plant Physiology, 2nd Ed. Metabolism associated with nitrate reduction photosynthesis carbohydrates respiration reducing power carbon skeletons NADH or NADPH amino NH NO NO 3 3 2 acids nitrate nitrite reductase reductase ferredoxin siroheme Francis, D.D., J.S. Schepers, and M.F. Vigil. 1993. Post-anthesis nitrogen loss from corn. Agron. J. 85:659-663.

  5. Fertilizer SpillCan I speed up the N Cycle? 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) Plants remove O2 to incorporate N into amino forms amino NH NO NO 3 3 2 acids nitrate reductase nitrite reductase

  6. 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.

  7. Soil-Plant Inorganic N Buffering Point where increasing applied N no longer increases grain yield 500 400 300 200 100 0 4000 3000 2000 1000 0 Soil Profile Inorganic N Accumulation, kg/ha Range (buffer) where increasing applied N does not increase grain yield, but also where no increase in soil profile inorganic N is observed Grain yield, kg/ha Point where increasing applied N increases soil profile inorganic N accumulation 0 40 80 120 160 200 240 Annual Nitrogen Fertilizer Rate, kg/ha

  8. NH4, NO3 Fertilizer Organic Matter Pool Inorganic Nitrogen

  9. 30 100 200 300 400 0 30 60 60 90 90 120 150 120 180 150 N Rate kg ha-1 210 180 0 240 210 34 270 240 67 300 270 134 300 269 Udic Argiustoll, 0-240 cm, #502 Udic Argiustoll, 0-300 cm, #505 NO3--N, kg ha-1 NO3--N, kg ha-1 0 100 200 300 400 N Rate kg ha-1 0 Depth, cm Depth, cm 22 45 67 90 112

  10. 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 excess N applied to be lost via other pathways prior to leaching? Nitrogen Buffering Mechanisms 1. Increased Applied N results in increased plant N loss (NH3) 

  11. Lees, H.L., W.R. Raun and G.V. Johnson. 2000. Increased plant N loss with increasing nitrogen applied in winter wheat observed with 15N. J. Plant Nutr. 23:219-230.

  12. Nitrogen Buffering Mechanisms 1. Increased Applied N results in increased plant N loss (NH3) 2. Higher rates of applied N - increased volatilization losses

  13. 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 (0-15 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

  14. Burford and Bremner, 1975

  15. Aulakh, Rennie and Paul, 1984

  16. 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

  17. Experiment 406, Altus, OK 0.1 0.9 0.09 0.8 0.08 0.7 Total Soil N, % 0.07 Organic Carbon, % 0.6 0.06 TSN SED TSN = 0.002 0.5 0.05 SED OC = 0.03 OC 0.04 0.4 0 40 80 120 160 200 N Rate, kg/ha Raun, W.R., G.V. Johnson, S.B. Phillips and R.L. Westerman. 1998. Effect of long-term nitrogen fertilization on soil organic C and total N in continuous wheat under conventional tillage in Oklahoma. Soil & Tillage Res. 47:323-330.

  18. 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

  19. 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 40 20 0 Continued increase in grain N uptake, beyond the point where increasing applied N increases soil profile inorganic N accumulation Grain N uptake, kg/ha 0 40 80 120 160 200 240 Annual Nitrogen Fertilizer Rate, kg/ha

  20. Experiment 222, Stillwater, OK 80 Y = 29.7 + 0.28x - 0.00055x2 70 r2=0.90 9.4 =19% 60 50 Grain N Uptake, kg/ha 40 30 20 0 20 40 60 80 100 120 140 N rate, kg/ha SBNRC

  21. 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

  22. 1 Mills et al., 1974 Matocha, 1976 DuPlessis and Kroontje, 1964 Terman, 1979 Sharpe et al., 1988 N Buffering Mechanisms 1 4 0-50 kg N/ha/yr 15-40 kg N/ha/yr NH3 NH4+OH- NH3 + H2O Fertilizer N NO Volatilization N2O Urea Applied N2 3 NH4 fixation (physical) Denitrification 7-80 kg N/ha/yr NH3, N2 10-50 kg N/ha/yr 2 Microbial Pool Organic Immobilization NH4 NO3 NO2 5 Chaney, 1989 Sommerfeldt and Smith, 1973 Macdonald et al., 1989 Kladivko, 1991 NO3 5 Leaching 2 3 4 0-20 kg N/ha/yr Olson and Swallow, 1984 Sharpe et al., 1988 Timmons and Cruse, 1990 Francis et al., 1993 Hooker et al., 1980 O’Deen, 1986, 1989 Daigger et al., 1976 Parton et al., 1988 Aulackh et al., 1984 Colbourn et al., 1984 Bakken et al., 1987 Prade and Trolldenier, 1990

  23. Urea • Urea is the most important solid fertilizer in the world today. • In the early 1960's, ammonium sulfate was the primary N product in world trade (Bock and Kissel, 1988). • The majority of all urea production in the U.S. takes place in Louisiana, Alaska and Oklahoma. • Since 1968, direct application of anhydrous ammonia has ranged from 37 to 40% of total N use (Bock and Kissel, 1988) • Urea: high analysis, safety, economy of production, transport and distribution make it a leader in world N trade. • In 1978, developed countries accounted for 44% of the world N market (Bock and Kissel, 1988). • By 1987, developed countries accounted for less than 33%

  24. Koch Industries 7.5 million metric tons of N fertilizer/year World Total Production N, P, and K 216 million metric tons Qatar (go to map) 3.8 million metric tons ammonia, 5.6 million metric tons urea)

  25. Share of world N consumption by product group • 1970 1986 2004 • Ammonium sulfate 8 5 2 • Ammonium nitrate 27 15 14 Urea 9 37 50 • Ammonium phosphates 1 5Other N products (NH3) 36 29 30Other complex N products 16 8

  26. During hydrolysis, soil pH can increase to >7 because the reaction requires H+ from the soil system. • 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

  27. H20  H+ + OH- Equilibrium relationship for ammoniacal N and resultant amount of NH3 and NH4 as affected by pH for a dilute solution.

  28. N Rate = 112 kg/ha Soil surface pH and cumulative NH3 loss as influenced by pH buffering capacity (from Ferguson et al., 1984).

  29. R. B. Ferguson, D. E. Kissel, J. K. Koelliker and  Wes Basel2 Abstract The influence of soil pH and soil cation exchange capacity on ammonia volatilization from surface applied ammoniacal nitrogen has been reported in previous studies. Since the hydrolysis of urea containing N fertilizers causes an increase in alkalinity, a soil's inherent H+buffering capacity (defined as the soil's total acidity, comprised of exchangeable acidity plus non-exchangeable, titratable acidity), should exert a dominant influence on the maximum soil pH at the site of urea fertilizer application. The objective of this study was to demonstrate the importance of a soil's H+ buffering capacity in affecting NH3 volatilization from surface-applied urea. The H+ buffering capacity of two soils was increased by adding hydroxy-Al polymers to one soil, and weak and strong acid cation exchange resins to the other soil. Care was taken to keep cation exchange capacity and initial pH close to the same on amended and unamended (control) soils. Urea was surface-applied to amended and unamended soils and ammonia volatilization and soil surface pH were measured. The increase of H+ buffering capacity of soils was found to reduce soil surface pH and NH3 volatilization after application of urea. It is concluded from this work that H+ buffering capacity of a soil is a better indicator of NH3 loss potential than a soil's initial pH. doi:10.2136/sssaj1984.03615995004800030022x

  30. H ion buffering capacity of the soil: • Ferguson et al., 1984 • (soils total acidity, comprised of exchangeable acidity + nonexchangeable titratable 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)

  31. 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

  32. 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).

  33. UREASE inhibitors “Agrotain” n-butyl thiophosphoric triamide http://www.agrotain.com Nitrosomonas inhibitors “NSERVE” 2-CHLORO-6-(TRICHLOROMETHYL) PYRIDINE http://jeq.scijournals.org/cgi/content/abstract/32/5/1764 Concept promoted fall application of NH3 in the corn belt, and that would keep N in the ammonium form

  34. 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-)

  35. 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. CO(NH2)2 + 2H2O ----> (NH4)2CO3 • b. (NH4)2CO3 + CaX ----> (NH4)2X + CaCO3 • c. (NH4)2X + 4O2 nitrification >2HNO3 + H2X +2H2O • d. 2HNO3 +CaX ----> Ca(NO3)2 + H2X • e. H2X + CaCO3 neutralization >CaX + H2O + CO2 • Resultant acidity = 2H+ /mole of CO(NH2)2

  36. 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 • ______________________________________________________________________

  37. 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.

  38. Discussion: Global Population and the Nitrogen Cycle 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.” Smil, 1997

  39. pH = pKa + log [(base)/(acid)] • pKw = pH + pOH • 14.00 = pH + pOH • 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 Chemicals A and B react to form C and D A + B = C + D Equilibrium Constant (K) K = [C][D] / [A][B]

  40. 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? • 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, ** on soils where organic matter dominates the contribution to CEC then there should be a positive relationship of pH and CEC. CEC pH

  41. Urea Hydrolysis • increase pH (less H+ ions in soil solution) urease enzyme required • CO(NH2)2 + H+ + 2H2O --------> 2NH4+ + HCO3- • pH 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

  42. 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 hydrolysis2. Ability of a soil to supply H+ is related to amount of NH3 loss3. H+ is produced via nitrification (after urea is applied): acidity generated is not beneficial4. What could we apply with the urea to reduce NH3 loss?

  43. 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”

  44. 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 NH4+ + OH- Nitrification: biological oxidation of ammonia to nitrate 2NH4+ + 3O2 2NO2- + 2H2O + 4H+ 2NO2- + O2 2NO3- +H2O

  45. NEED for INCREASED NUE Computation/commodity Production, mT World consumption of fertilizer-N 90,000,000 Fert-N used in cereals (60% of total applied) 0.60 * 82,906,340 = 54,000,000 World Cereal Production, mT Rye 1% Oats Sorghum Millet 2% 3% 1% Wheat Barley 28% 8% Rice 28% Corn 29%

  46. World grain N removal, 1996 %N mTWheat 2.13 12,502,267 Corn 1.26 7,439,266 Rice 1.23 7,007,101 Barley 2.02 3,154,192 Sorghum 1.92 1,356,807 Millet 2.01 580,032 Oats 1.93 596,012 Rye 2.21 508,788 Total N removed in cereals 33,144,465 N removed in cereals (from soil & rain, 50% of total) 16,572,232 NUE = ((N removed - N soil&rain)/total N applied) 33% Savings/yr for each 1% increase in NUE 489,892 mT Value of fertilizer savings $479/mT N $234,658,462 2005 >$400,000,000

  47. ____________________________________ • 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 1999 = $4.7 billion 2005, > 10 billion

  48. Flowchart for NUE http://www.nue.okstate.edu/NUE_etc.htm

  49. Factors Affecting Soil Acidity • Acid: substance that tends to give up protons (H+) to some other substance • Base: accepts protonsAnion: negatively charged ionCation: 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) • H2O • HA --------------> H+ + A- • potential active • acidity acidity

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