Reminder about EEOB 698.02 • Still spaces available on the Lake Guardian for EEOB 698.02 – Great Lakes Limnology • Week-long cruise on Lake Erie; June 23-30 • See course website for more information Finishing up Inorganic Carbon • Hall Lake Free CO2, pH, HCO3 • Distribution in time and space • Effect of turnover and stratification • Changes in pH associated with photosynthesis and reduction Nitrogen in Lakes and Streams Wetzel Chapter 12 pp. 205-237 Introduction • Where does the Nitrogen come from? – Biological Fixation • By bacteria and Cyanobacteria • Lightning Fixation – Reduction of N2 in the atmosphere • Human Fixation – Crop production – Energy Production Sources and Forms of N in Water • Forms: – Dissolved N2 • Oxidation State = 0 – Ammonia NH4+ • Oxdn State = -3 – Nitrate NO3- • Oxdn State = +6 – Nitrite NO2- • Oxdn State = +3 – Organic Nitrogen • Various States • Sources – Precipitation – Fixation – Surface/Groundwater Drainage • Losses – Effluent Outflow – Reduction with loss of gaseous N2 – Adsorption with Sedimentation Nitrogen Fixation • Bacterial • Cyanobacterial – Only forms with heterocysts are capable of Nfixation • N-fixation mainly light-dependent • Requires reducing power and ATP – Both of these come from photosynthesis • Expensive energetically – 12-15mol ATP: 1mol N2 reduced • Dark rate <10% of light rates Nitrogen Fixation continued • N-fixation curve follows the same path as the photosynthesis curve • Photosynthetic and Heterotrophic bacteria may also contribute to the fixed N pool • Fixation by shrubs on wetland, river, and lake shores can also contribute to N in water Inorganic and Organic Nitrogen • Influents bring significant sources of N into lakes and streams • Common Amounts in Lakes – NH4 – 0-5mgL-1; higher in anaerobic hypolimnions of eutrophic waters – NO2-N – 0-0.01mgL-1; possibly higher in interstitial waters of deep sediments – NO3-N – 0-10mgL-1; highly variable seasonally and spatially – Organic N – up to 50% of Total Dissolved N Inorganic and Organic N continued • N concentrations can have an effect on algal productivity but it is more likely the phosphorus is the limiting factor • Growth rates for algae are higher with more reduced forms: NH4-N>NO3-N>N2-N Generation and Distribution of Various Forms of Nitrogen • Ammonia – – – – – End product of deamination of organic material Present in non-oxygenated areas – highly reduced Used rapidly in trophogenic zone Sorbs quickly to particles and can sediment out Can be higher at sediment interface due to reduced adsorptive properties of sediments under anoxic conditions or due to excretion products of benthic heterotrophs Variation by lake status Generation and Distribution continued • Nitrification – biological conversion of nitrogen from a reduced state to a more oxidized state NH4++3/2O22H++NO2-+H20 G0=-66kcalmol-1 - Nitrosomonas also methane-oxidizing bacteria capable of producing this reaction Generation and Distribution continued • Nitrification cont. • NO2-+1/2O2NO3G0=-18kcalmol-1 • Nitrobacter responsible – NOTE: less energy is given off by this oxidation • Overall: NH4++2O2NO3-+H20+2H+ Need oxygen for this reaction • Denitrification – biochemical reduction of oxidized nitrogen anions with concomitant oxidation of organic matter • Occurs in both aerobic and anaerobic areas but is highly important under anerobic conditions • Examples: C6H12O6+12NO3-12NO2-+6CO2+6H20 G0=-46kcalmol-1 Seasonal Distribution • Interaction of Stratification, Anoxia, and Circulation with Biology control distributions Seasonal Distribution continued Seasonal Distribution continued Seasonal Distribution continued Carbon:Nitrogen Ratios • Indicative of nutrient availability but also of relative amount of proteins in organic matter • Approximate indication of phytoplankton status – C:N >14.6 – nitrogen limitation • Nitrogen-Fixing phytoplankton become more abundant – C:N <8.3 – no N-deficiency Nitrogen Cycle Nitrogen Cycle Nitrogen Cycle in Streams and Rivers • Nutrient Spiraling – net flux downstream of dissolved nutrients that can be recycled over and over while moving downstream • Spiraling Length (S) – average distance a nutrient atom travels downstream during one cycle through the water and biotic compartments • S = distance traveled until uptake (Sw uptake length) + distance traveled within biota until regenerated (SB turnover length) Conclusions • Nitrogen is very important to aquatic ecosystem function • Different forms occur at different times and depths • Occurrence controlled by the interaction between Biology, Chemistry, and Physics