Nutrient Loading Module

Introduction to Nutrient LoadingThomas Meixner, Devin Castendyk: State University of New York, OneontaCathy Gibson:, Skidmore College NSF TUES Project:The use of high-frequency data to engage students in quantitative reasoning and scientific discourse

NutrientsNutrients are chemicals that plants and animals need to grow and survive. Because water is a universal solvent, all life on Earth utilizes liquid water to obtain and circulate nutrientsYoung men are 64% water by weightYoung women are 53% water by weightThe search for extra terrestrial life is focused on finding planets that have liquid waterFor plants:Primary macronutrients include carbon (C), nitrogen (N), phosphorous (P), and potassium (K). Secondary macronutrients include calcium (Ca), magnesium (Mg) and sulfur (S)Micronutrients include copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), zinc (Zn) and nickel (Ni), and sometimes boron (B), silicon (Si), cobalt (Co).

Nutrients vs. ToxinsMicronutrient: a small amount is needed for biological functionPlants: CopperHumans: Cadmium, selenium Toxin: a chemical, physical, or biological agent that causes disease or some alteration of the normal structure and function of an organism.Acute toxicity: Immediate impactChronic toxicity: Impact after a long period of exposureWhen does a nutrient become a toxin???Very few elements are toxic at all concentrationsMercury, arsenicFor most, concentration in dictates toxicity

Nitrogen: Nutrient or ToxinNitrogen is used by organisms to produce amino acids, proteins, and nucleic acids.80% of the atmosphere is nitrogen gas (N2)Most plants can only take up nitrogen in two forms from soil water, making nitrogen a limiting nutrient in plant growth: Ammonium (NH4+ ) Extremely toxic to plants at high concentrationsComponent of animal wasteNitrate (NO3- )Toxic to humans in drinking water above 10 mg/L NO3-NBlue baby syndrome (NO3 binds to hemoglobin = asphyxiation)

The Nitrogen CycleFixation: Soil bacteria, lighting, and solar flares (aurora) convert N gas to usable NO3-Most N stored as living and dead organic matterMineralization: Decomposition of organic matter in soils produces ammonium (NH4+)Nitrification: Oxidation of ammonium to Nitrite (NO2-):NH4+ + O2 = 4H+ + NO2- (N loses 6 electrons)Oxidation of Nitrite to Nitrate (NO3-):2NO2- + O2 = 2NO3- (N loses 2 electrons)Denitrification: Conversion to N gas by bacteria2 NO3 + 10 e + 12H+ = N2 + 6 H2O

Sources of Excess NutrientsFertilizerAny material of natural or synthetic origin applied to soils or to plant tissues (leafs) to supply one or more plant nutrients essential to the growth of plants.More fertilizer addition = Higher crop yield = More $$$ No incentive to conserveRunoff (Non-point Source) from agricultural fields, lawns, golf coursesWaste Water Effluent Contains excess C, N and P not used by animalsDirect input (Point Source) from waste water treatment plants and/or septic systemsRunoff (Non-point Source) from high-density animal feedlots and mega farms (cows, chickens, other)

Synthetic Nitrogen FertilizersAll nitrogen fertilizers are made from ammonia (NH3), which is produced by the Haber-Bosch process pioneered during the rise of the petrochemical industry, 1910 to 1920. Energy-intensive process, natural gas (CH4) supplies the hydrogen and the nitrogen (N2) is derived from the air. This ammonia is used as a feedstock for all other nitrogen fertilizers, such as anhydrous ammonium nitrate (NH4NO3) and urea (CO(NH2)2). The development of synthetic fertilizer has significantly supported global population growth half the people on the Earth are currently fed as a result of synthetic nitrogen fertilizer use.Link: Synthetic fertilizer production-population growth-nutrient impacts

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pE Gradients and Transformations

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Redox Reactions

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Experimental Design

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Transect

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Transect

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Nitrate vs. NH4 and SO4

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NO3, DOC and N2O

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Transect Depth

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Tracer Experiment

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DOC Addition

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A 24 hour sampling indicates that possible periphyton communities are assimilating NO3.

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The hyporheic zone borders and underlies the stream.

Water flows between the hyporheic zone and the stream channel over short distances (qhin and qhout), ranging from centimeters to tens of meters.

The shorter hyporheic flowpath the greater the biogeochemical interaction is between stream water nutrients and sediment surfaces. Both nitrification and denitrification can occur depending on O2 and DOC levels

Most models are simplified one dimensional models; though considered valid if solute is assumed to be uniformly distributed over the cross-sectional area

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Plant Growth Example: CyanobacteriaSingle-celled plants that float within a water column (phytoplankton) ; previously called blue-green algaeResponsible for development of oxygen on Earth beginning 3.5 billion years ago

Cyanobacteria BloomsNutrient pollution is one of America's most widespread, costly and challenging environmental problems, and is caused by excess nitrogen and phosphorus in the air and water (US EPA) Blooms are events where excessive cyanobacteria production occurs over a very short period of time. In extreme cases, this can result in a thick, green scum over a lake surface. which is unpleasant to look at, smells, and greatly depreciates the aesthetic and recreational value of the lake.

Impact on Aesthetic ValueVisualOlfactory (smell)Loss of recreational value Loss of tourist revenue Example: Lake Atitlan, Guatemala

Impact on Eutrophication in LakesEutrophication is the normally slow aging process by which a lake evolves into a bog or marsh and ultimately assumes a completely terrestrial state and disappears. During eutrophication the lake becomes so rich in nutritive compounds, especially nitrogen and phosphorus, that cyanobacteria and other microscopic plant life become superabundant, thereby "choking" the lake with organic matter.Eutrophication may be accelerated by human activities, speeding up the filling of a lake.

Impact on Ecosystem and FisheriesHypoxia: Low oxygen. Hypoxic waters have dissolved oxygen concentrations of less than 2-3 ppm. Dead cyanobacteria settle to the bottom of the water column and decompose. Oxygen is consumed; process called decompositionDOC + O2 CO2 This forces fish to either swim away or die and can suffocate plants living in the water. Low oxygen water called Dead Zone.Examples: Gulf of Mexico and Chesapeake Bay

Slides on Fish kills in lakes

2013 Gulf of Mexico Hypoxic Zone

Chesapeake Bay Largest estuary in the U.S.

Impact on Drinking Water SupplyMany municipalities obtain drinking water from lakes and reservoirsToledo, Ohio: Lake ErieChicago: Lake MichiganNew York City: Catskill ReservoirsLos Vegas: Lake MeadThe health of citizens depends upon lake and reservoir water quality

Which ecosystem has lower water quality? A small stream with a high concentration (>14 mg/L) of NO3?A large river with a low (< 0.5 mg/L) concentration of NO3?

Which system causes greater downstream impact on lakes or estuaries?A small stream (low Q) with a high concentration (high C) of N?A large river (high Q) with a low concentration (low Q) of N?How can be best compare systems?

Stream LoadMass of substance (Nitrogen, Phosphorous, Sediment, etc.) transported by a stream per unit of timeLoad (M, mass/time) = Discharge (Q, vol/time) * Concentration (C, mass/vol)

Management: The Clean Water ActThe U.S. Clean Water Act (CWA) is a series of federal legislative acts that form the foundation for protection of U.S. water resources:Water Quality Act of 1965,Federal Water Pollution Control Act of 1972, Clean Water Act of 1977, and Water Quality Act of 1987. The goal of the Clean Water Act (CWA) is "to restore and maintain the chemical, physical, and biological integrity of the Nation's waters"

State 303(d) ListsUnder section 303(d) of the CWA, states, territories, and authorized tribes, collectively referred to in the act as "states," are required to develop lists of impaired and threatened waters (stream/river segments, lakes) These are waters for which technology-based regulations and other required controls are not stringent enough to meet the water quality standards set by states.The law requires that states establish priority rankings for waters on 303(d) lists All states to submit 303(d) lists for EPA approval every two years on even-numbered years.

Total Maximum Daily Load (TMDL)A calculation of the maximum daily load of a pollutant that a waterbody can receive and still meet water quality standardsThe load is allocated among the various sources of that pollutantTMDLs must also include a margin of safety (MOS) to account for the uncertainty Predicting how well pollutant reduction will meet water quality standardsAccount for seasonal variations Under the CWA, states establish priorities for development of TMDLs from waters on 303(d) lists based on the severity of the pollution and the sensitivity of the uses States then provide a long-term plan for completing TMDLs within 8 to 13 years from first listing.

AssignmentWhy is nutrient load important? Qualitative understanding discharge-nitrate concentrations correlation Quantitative correlation analysis Calculate nutrient loads for a single location Understand the impact of sampling frequency on load estimates

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NO3Diel Variations of NO3

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NO3

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NO3Diel Variations of NO3

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