Coupling of carbon and nitrogen cycles through humic redox reactions in an alpine stream

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Coupling of carbon and nitrogen cycles through humic redox reactions in an alpine stream. Diane McKnight, Matt Miller, Rose Cory and Mark Williams Depart. Civil, Environmental & Architectural Engineering, University of Colorado. NWTLTER: C & N transport and reactivity in Green Lakes Valley. - PowerPoint PPT Presentation

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  • Coupling of carbon and nitrogen cycles through humic redox reactions in an alpine streamDiane McKnight, Matt Miller, Rose Cory and Mark WilliamsDepart. Civil, Environmental & Architectural Engineering, University of Colorado

  • NWTLTER: C & N transport and reactivity in Green Lakes Valley Response of pristine, cold regions to climate change and N enrichment

  • Hyporheic Zone: hotspot of biogeochemical reactions driven by mixing across redox gradient

  • Redox CouplesOxidizing ConditionsReducing ConditionsO2 H2ONO3- N2, NH4+Mn(IV) Mn(II)Fe(III) Fe(II)Oxidized Humics Reduced HumicsSO42- H2S

  • Fe3+Fe2+NO3-NO2- + DOM DOM-NHumics act as electron shuttlePhotoreduction of Ferric to Ferrous IronFerrous Wheel Hypothesis

  • *elevation~3,750m*formed by snowmelt and glacial runoff*surrounded by alpine wetland*~150m in lengthTracer experiment:Navajo Meadow Stream

  • Approach: Tracer injection experiment and modeling with OTISMain Channel:Storage Zone:Advection

    DispersionLateral inflow Transient storagesTransient storage

  • Approach: Fluorescence index (Em450/Em500 @ 370 nm Ex, and EEMs (Excitation and emission over a range of wavelengths)Humic Peaks: (quinone moieties)Protein PeakExcitation (nm)Emission (nm)

  • Excitation-emission matrix(EEM)Comp. 1 Comp. 2 Comp. 3PARAFAC

  • Forms of this complex are found throughout cellsImportant in electron transfer reactions, such as the oxidation of NADHAlso known as coenzyme QQuinones found in enzymes, e.g ubiquinone, and formed by lignin oxidation. QHQUbiquinone

  • Quinone fluorescenceAQDS/AHDS useful as models for humic fluorescence

  • Stream Br- Addition, July 10Reach 1Reach 2Reach 3Background [Br-] = 0 mg/L

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    1

    Time of day (hr.)

    Br- (mg/L)

    br

    1.10E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0011.0336666667011.12011.23666666670

    1.10E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0012.0336666667012.07012.05333333330

    1.10E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0012.13366666671.2312.170.97812.18666666671.512

    1.11E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0012.18366666672.72112.20333333331.79912.23666666671.702

    1.11E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0012.23366666672.76212.271.85712.28666666671.718

    1.11E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0012.3172.83112.33666666671.88612.371.755

    1.11E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0012.38366666672.87812.38666666671.95412.421.732

    1.11E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0012.45033333332.79912.45333333331.95712.50333333331.744

    1.11E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0012.63366666672.78512.622.06212.63666666671.932

    1.12E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0012.78366666672.74912.75333333331.92412.78666666671.902

    1.12E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0012.9172.83412.921.83812.921.79

    1.12E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0012.98366666670.07813.03666666670.0513.00333333330.109

    1.12E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0013.05033333330.03313.070.02413.070.034

    1.12E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0013.1170.01913.13666666670.01513.15333333330.02

    1.12E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0013.18366666670.01613.20333333330.01113.20333333330.016

    1.13E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0013.2170.01313.25333333330.00913.28666666670.012

    1.13E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0013.2670.0113.320.00813.33666666670.011

    1.13E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0013.3170.00913.38666666670.00713.50333333330.009

    1.13E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0013.40033333330.00913.50333333330.00613.670.006

    1.13E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0013.50033333330.00713.68666666670.00613.870.006

    1.13E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0013.6670.00713.83666666670.00614.00333333330.005

    1.14E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0013.83366666670.00714.00333333330.00414.25333333330.005

    1.14E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0014.00033333330.00514.25333333330.00414.45333333330.004

    1.14E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0014.23366666670.00414.5033333333014.620.004

    1.14E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0014.50033333330.00414.63666666670

    1.14E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+0014.58366666670.003

    1.14E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.15E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.15E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.15E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.15E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.15E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.15E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.16E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.16E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.16E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.16E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.16E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.16E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.17E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

    1.17E+010.00E+000.00E+000.00E+000.00E+000.00E+000.00E+00

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