6Reservoirs of Nitrogen Rocks - weatheringAtmosphere – 78% of atmosphereOceans – Soluble in waterFreshwater – Headwater Streams = sinksPrimary Producers – Use ammonium & nitrates to make proteinsConsumers – digest proteins into AA
7Nitrogen History• More money and effort are spent on the management of N and S than any other mineral nutrient: – Deficiencies are world wide, in cultivated and natural environments – Excesses cause a degradation of the quality of life, N pollution
8Nitrogen History• Adding N to soils is one of the most costly parts of agriculture
9Significance of N• Nitrogen (N) is an essential component of DNA, RNA and proteins, the building blocks of life • All organisms require nitrogen to live and grow • Although the majority of the air we breathe is N2, most of the nitrogen in the atmosphere is unavailable for use by organisms • This is because the strong triple bond between the N atoms in N2 molecules makes it relatively inert
10Significance of N Nitrogen is an incredibly versatile element, existing in both inorganic andorganic forms as well as many differentoxidation states• The movement of nitrogen between theatmosphere, biosphere and geospherein different forms is described by thenitrogen cycle
11Significance of N N2 gas must first be converted to more a chemically available form such as ammonium(NH4+), nitrate (NO3-), or organic nitrogen(e.g. urea - (NH3)2CO)• The inert nature of N2 means that biologicallyavailable nitrogen is often in short supply innatural ecosystems, limiting plant growth andbiomass accumulation
14Chemistry of N• The valence range which N undergoes in its biogeochemical cycling is full – Going from loss of all five of its outer shell electrons (+5) to other elements – To the gain of three electrons from other elements (-3) to complete all of the orbitals of its outer electron shell
15Chemistry of N On the right-hand side of the depicted N cycle, the N atom can eventually lose allfive of its outer shell electrons to O• With this, N can eventually become fullyoxidized as nitrate (NO3-)
16Chemistry of N• On the left-hand of the depicted N cycle, N can eventually add three electrons to fill all of its outer shell electron orbitals from elements such as hydrogen (H) and carbon (C) • With such gain of electrons, N can be fully reduced to ammonia (NH3) − which most commonly exists in its ionic form, ammonium (NH4+) • Or N can be fully-to-partially reduced in organic compounds
20Nitrogen fixation N2 → NH4+ • N2 is converted to ammonium • Essential because it is the only way that organisms can attain nitrogen directly from the atmosphereEnergy intensive process:N2 + 8H+ + 8e ATP = 2NH3 + H2 + 16ADP + 16 Pi
21Nitrogen fixation Certain bacteria, Rhizobium, are the only organisms that fix nitrogen through metabolicprocesses• N fixing bacteria often form symbioticrelationships with host plants (e.g. beans,peas, and clover)• N fixing bacteria inhabit legume root nodulesand receive carbohydrates and a favorableenvironment from their host plant in exchangefor some of the nitrogen they fix
22N fixation w/ Blue-Green Algae In aquatic environments, blue-green algae (really a bacteria called cyanobacteria) is an important free-living nitrogen fixerPlates 19 & 20Anacystis bloom; Ford Lake August 2002.
23Measuring water transparency with a Secchi disk on Ford Lake during a bloom of Aphanizomenon. August 2004.
24N Fixation Cont’d ½ can be contributed by N-fixing org. The rest comes from atmospheric deposition (lightning) or runoff.SalmonAlders
26Nitrification• NH4+ → NO3- or NO2 • Some of the ammonium produced by decomposition is converted to nitrate via a process called nitrification– Nitrosomonas and Nitrobacter • The bacteria that carry out this reaction gain energy • Requires the presence of oxygen – circulating or flowing waters and the very surface layers of soils and sediments
27Drinking WaterThe U.S. Environmental Protection Agency has established a standard for nitrogen in drinking water of 10 mg per liter nitrate-NUnfortunately, many systems (particularly in agricultural areas) already exceed this levelBy comparison, nitrate levels in waters that have not been altered by human activity are rarely greater than 1 mg/LWhere would there be higher levels of N in drinking water?
28MethemoglobinemiaNitrate is one of the most common groundwater contaminants in rural areas.It is regulated in drinking water primarily because excess levels can cause methemoglobinemia, or "blue baby" disease.Affects nursing infants b/c gut is too acidic (pH 2) for denitrifying bacteria to reduce nitrate to nitrite.Nitrite combines w/ hemoglobin to produce methemoglobin, does not break down easily or carry Oxygen.What is Methemoblobenemia
29MethemoglobinemiaNitrate in groundwater originates primarily from fertilizers, septic systems, & manure storage or spreading operations.Fertilizer nitrogen that is not taken up by plants, volatilized, or carried away by surface runoff leaches to the groundwater in the form of nitrate (nitrification NH4 → NO3).This not only makes the nitrogen unavailable to crops, but also can elevate the concentration in groundwater above the levels acceptable for drinking water quality.Nitrogen from manure similarly can be lost from fields, barnyards, or storage locations.Septic systems also can elevate groundwater nitrate concentrations because they remove only half of the nitrogen in wastewater, leaving the remaining half to percolate to groundwater.
31Denitrification NO3- → N2+ → N2O • Oxidized forms of nitrogen such as nitrate and nitrite (NO2-) are converted to dinitrogen (N2) and, to a lesser extent, nitrous oxide gas• An anaerobic process that is carried out by denitrifying bacteria, which convert nitrate to dinitrogen in the following sequence:• NO3- → NO2- → NO → N2O → N2.
32Denitrification Effluent of sewage treatment plants. Denitrification by bacteria converts nitrogen-oxygen compounds into nitrogen gas.N leaves treatment plant as a gas to reduce the amount of DIN in effluent.
33N Uptake/Assimilation NH4 + → Organic N• The ammonia produced by nitrogen fixingbacteria is usually quickly incorporated intoprotein and other organic nitrogencompounds, either by a host plant, thebacteria itself, or another soil organism• When organisms nearer the top of the foodchain eat, they are using nitrogen that hasbeen fixed initially by nitrogen fixing bacteria
34Ammonification or Mineralization NH4NO2R-NH2NONO2NO3
35Ammonification/Mineralization Organic N → NH4+• After nitrogen is incorporated into organicmatter, it is often converted back intoinorganic nitrogen• During this process, usually called decay, asignificant amount of the nitrogen containedwithin the dead organisms is converted toammonium• Once in the form of ammonium, nitrogen isavailable for use by plants
36Ammonia Volatilization • The process of nitrogen loss as ammonia gas from urea forms under alkaline conditions• During this process, ammonium is converted into NH3 gas which is then lost to the air• In cooler conditions the enzyme breaks down urea much slower• Thus, little ammonia gas is lost when urea is applied to cool soilsUrea may originate from animal manure, urea fertilizers and, to a lesser degree, the decay of plant materials.
37ExcretionN compounds are metabolized by animals for energy & NH3 is a waster product.If O2 is present = oxidized to NO3 or NO4If O2 is absent = NH3 will accumulate.Aquatic Snails – N is excreted by diffusion of (highly toxic) ammonia NH3 into the water.Terrestrial Snails – excrete N as cyclic C-N compounds (uric acid) b/c NH3 cannot be easily washed away. NH3 would poison their lungs.
39Human InfluenceEarly in the 20th century, a German scientist named Fritz Haber figured out how to fix nitrogen chemically at high temperatures and pressures, creating fertilizers that could be added directly to soilThis technology has spread rapidly over the past century, and, along with the advent of new crop varieties, the use of synthetic nitrogen fertilizers has led to an enormous boom in agricultural productivity
40Surface Contamination Added nitrogen can lead to nutrient overenrichment, particularly in coastal waters receiving the inflow from polluted riversThis nutrient over-enrichment, also calledeutrophication, has been blamed for Increased frequencies of coastal fish-kill events, increased frequencies of harmful algal blooms, and species shifts within coastal ecosystems
41Acid RainReactive nitrogen (like NO3- and NH4+) present in surface waters and soils, can also enter the atmosphere as the smog component nitric oxide (NO) an nitrous oxide (N2O)Eventually, this atmospheric nitrogen can be blown into nitrogen-sensitive terrestrial environments, causing long-term changesAcid rain from nitrogen oxides has been blamed for forest death and decline in parts of Europe and the Northeast United States
42Acid Rain and Species Shifts Increases in atmospheric nitrogen deposition have also been blamed for more subtle shifts in dominant species and ecosystemsOn nitrogen-poor serpentine soils of northern Californian grasslands, plant assemblages have historically been limited to native species that can survive without a lot of nitrogenThere is now some evidence that elevated levels of atmospheric N input from nearby industrial and agricultural development have paved the way for invasion by non-native plants