Nutrient Dynamics at the Estuarine Sediment-Water Interface during Large Pulses of High Nitrate Mississippi River Water

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Nutrient Dynamics at the Estuarine Sediment-Water Interface during Large Pulses of High Nitrate Mississippi River Water ERIC ROY, JOHN WHITE, SIBEL BARGU, EMILY SMITH, & NATHAN NGUYEN LOUISIANA STATE UNIVERSITY Wetland & Aquatic Biogeochemistry Lab Department of Oceanography & Coastal Sciences School of the Coast & Environment

Ancient Courses of the Mississippi River Images by Fisk (US Army Corps)

USGS-NWRC 2005-04-0068 Proposed & Built Diversions

The Mississippi River has Changed More nutrients, Less sediment For flood diversions, this results in a potential trade-off of ecosystem services: flood protection vs. water quality

Lake Pontchartrain: An Experiment in Nutrient Pulsing Image from The Times Picayune Lake Pontchartrain Image from NASA Spillway New Orleans Spillway Control Structure Bonnet Carré Spillway: Peak Flow = 250,000 cfs (~20.8% of river design flood ) Recent openings: 1997, 2008, 2011

2011 Bonnet Carré Spillway Opening: May 9 th to June 17 th Image: May 17, 2011 Concern: Harmful Algal Blooms of Cyanobacteria 2011 Event Total Nutrient Loads ~25,000 tons NO x -N ~700 tons NH 4 -N ~1000 tons SRP-P ~69,000 tons DSi Image from Naval Research Lab Stennis Space Center Inflow Molar Ratios DSi:DIN:SRP = 65:50:1

N-Limited Conditions (DIN:DIP < 16) Can favor N-fixing cyanobacteria Large External Pulse of N-Rich Freshwater Key Question: Where does all the nitrate go? P-Limited Conditions (DIN:DIP >> 16) Can favor diatoms, other unharmful species, or non-n fixing cyanobacteria Sediment-Water Interface: At what rate does nitrate diffuse into Lake Pontchartrain sediments? What process drives diffusion? 2011 Field Observations: Nitrate dynamics over time & space? Relationship between nitrate loss and primary productivity?

Methods Applied to Investigate Nitrate Flux into Sediments 1. Lab Experiment: Nitrate Flux in Intact Sediment Cores during Aerobic & Anaerobic Incubations (n = 3-4 at 2 sites) 2. 2011 Field Measurement: Porewater Profiles at Sediment-Water Interface using Peepers (n = 2 at one site)

LC SWI PS SWI = Spillway Inflow (Core Study) LC = Lake Center (Core Study) PS = Peeper Station (Peeper Study)

Flood 1 Flood 2 Nitrate Flux Into Sediments: Intact Core Experiment Results Flux Rate based on Mass Transfer (for 1.4 mg NO 3 -N L -1 ) = -21.0 mg NO 3 -N m -2 day -1 Aerobic Flux = Anaerobic Flux Indicates: Nitrification of sediment NH 4 not a significant source of NO x Flood 1 Flood 2 The most likely pathway in sediment is denitrification O 2 in Lake P bottom waters does not limit denitrification Roy et al. In Press. JEQ

Nitrate Flux into Sediments : Peeper Results #1: C/ z = 4.69 (r 2 = 0.95) #2: C/ z = 4.59 (r 2 = 0.86) Mean Fickean Diffusive Flux Rate = -29.7 mg NO 3 -N m -2 day -1 Flux Rate based on Mass Transfer = -21.0 mg NO 3 -N m -2 day -1 Modeled 2008 Spillway NO 3 - Loss by Denitrification 300-420 tons or 3.0-4.2% of total load

Image: May 17, 2011 Naval Research Lab Stennis Space Center 2011 Field Sampling: 13 Transect Runs 3 Outlets Samplings Chef Menteur Pass

June 15th & 16 th, 2011

2011 Nitrate and Phytoplankton Dynamics: -Rapid Collapse (~21 days) following Spillway Closure -Collapse corresponds to Chl a spike -Phytoplankton community never dominated by a single species -No harmful algal bloom of cyanobacteria observed

NO x -N Concentration Balance Uptake by Phytoplankton 0.36 1.06 mg L -1 (32 76 %) Spillway Inflow 1.14 1.40 mg L -1 Lake P Water Column Chef Pass (corrected for salinity) 0.28 0.74 mg L -1 (20 65 %) Flux into Sediment 0.04 0.06 mg L -1 (3 4 %) Based on Measured Nitrate Flux into Sediments Transect Observations on June 16 th Outlets Measurements for June 8 th, 15 th, and 25 th

N-Limited Conditions (DIN:DIP < 16) Can favor N-fixing cyanobacteria Key Question: Are sediments a significant source of P under P-depleted conditions? Large External Pulse of N-Rich Freshwater N- and P- Depleted Conditions P-Limited Conditions (DIN:DIP >> 16) Can favor diatoms, other unharmful species, or non-n fixing cyanobacteria Rapid Nutrient Uptake by Phytoplankton given Favorable Environmental Conditions (NO x depleted in 3 weeks)

Methods Applied to Investigate Phosphorus Flux out of Sediments 1. Lab Experiment: Phosphorus Flux in Intact Sediment Cores during Aerobic & Anaerobic Incubations (n = 3 at 3 sites)

Water Column SRP-P (mg L -1 ) P Flux from Sediments: Intact Core Experiment Results Field Observations Measured maximum rates of water column SRP increase in anaerobic intact cores: Predicted Diffusion Lake Center = 4.2 mg SRP-P m -2 d -1 Northwest Quadrant = 2.9 mg SRP-P m -2 d -1 Spillway Inflow = 3.9 mg SRP-P m -2 d -1 Roy et al. 2012. Hydrobiologia 684: 69-82.

NO x 0 NO x 0 SRP-P for Transect Stations 0.9-11.1 km from Spillway Inflow

Conclusions : Nutrient Dynamics @ the Sediment-Water Interface Significant denitrification during diversion events (300-420 tons NO x -N in 2008) Relatively minor role (~3-4%) in the transformation of the very large amount of nitrate received at these times. [Algal uptake & transport to coastal ocean dominate NOx loss] Lake Pontchartrain sediments are a significant source of P under P-depleted water column & can restore N-limited conditions rapidly following Spillway events

N-Limited Conditions (DIN:DIP < 16) Can favor N-fixing cyanobacteria Large Internal Pulse of P from Sediments due to Increased Concentration Gradient Large External Pulse of N-Rich Freshwater < 1 month N- and P- Depleted Conditions P-Limited Conditions (DIN:DIP >> 16) Can favor diatoms, other unharmful species, or non-n fixing cyanobacteria Rapid Nutrient Uptake by Phytoplankton given Favorable Environmental Conditions (NO x depleted in 3 weeks) Roy et al. 2012. Hydrobiologia 684: 69-82. Bargu et al. 2011. Hydrobiologia 661: 377-389

Supported by: Louisiana Sea Grant, National Science Foundation, Louisiana State University Board of Regents Fellowship Program Advisors/Co-authors: Dr. John White, Dr. Sibel Bargu, Emily Smith, Nathan Nguyen Thanks to Greg LeBlanc, Carey Gelpi, Jared Theriot, Ben Branoff, Anthony Nguyen, & Christine VanZomeren for field assistance! Thanks to Dr. Nan Walker from the LSU Earth Scan Lab for images. QUESTIONS?

EXTRA SLIDES

June 16th Transect Plume Region I Higher nitrate & SRP, ph < 6, lower water clarity Plume Region II Secchi > 0.5 m Rapid uptake of nutrients by algae, DO spike, ph > 6 Plume Region III P-limited Plume Region IV Dilution zone impacted by saltier, nutrient-poor estuarine water

NO x -N for Transect Stations 0.9-11.1 km from Spillway Inflow

2011 Bonnet Carré Spillway Event Field Sampling 19 Total Sampling Trips from May 8 th to Sept 13 th 13 Transect Runs 3 Lake-wide Cruises 3 Outlets Samplings Spillway 30 km 10-station transect

Flood 1 Flood 2 Exponential trendlines were determined for each core. C(t) = C(0) * e^[(p / h)*t] p = mass transfer coefficient = -0.015 m day -1 Flood 1 Flood 2 F = rate of nitrate flux into sediment F = p * C F = -0.015(1.4 mg L -1 *1000) F = -21.0 mg NO 3 -N m -2 day -1

Nitrogen Biogeochemistry & Eutrophication N 2 gas Freshwater Input Phytoplankton DIN DON Particulate N DIN DON, PON, PIN Exchange w/ Outer Estuary Water Column Diffusion Settling/Resuspension Sediment Porewater DIN Particulate (org + inorg) N Denitrification

TOTAL SPILLWAY LOADS 1997 2008 2011 2011/1997 2011/2008 Mississippi River Water Influx (km 3 ) 11.7 a 7.5 b 21.9 1.9 2.9 % of Lake Volume 176 a 113 b 330 1.9 2.9 Nitrate+Nitrite (tons NO x -N) 13110 c 9714 b 25395 1.9 2.6 Ammonia (tons NH 4 -N) 330 d 224 b 690 2.1 3.1 DIN (tons N) 13440 9939 b 26085 1.9 2.6 DIP (tons P) 526 e 400 e 1122 2.1 2.8 DSi (tons Si) 35258 f 19347 69017 2.0 3.6 DSi:DIN:DIP Inflow Molar Ratio g 74:57:1 57:59:1 65:50:1 - - a Perret et al. 2007, b White et al. 2010, c Turner et al. 2004, d Based on mean NOx-N to NH4-N ratio in 2008 and 2011 of ~40, e Roy et al. 2012, f 1997 DSi concentration is estimated based on mean concentrations measured at the Spillway inflow in Lake Pontchartrain in 2008 and 2011, as well as measurements made by Lane et al. (2004) in 2001. g Based on mean concentrations measured in Spillway inflow water for 2008 and 2011. 1997 values are based on USGS measurements in the Mississippi River at Baton Rouge.

2008 Bonnet Carré Spillway Opening Total nitrate load = ~10,000 metric tons NO 3 -N over 49 days Mass NO 3 -N denitrified = sum[ A(t) * F * 10-9 ] for 0 t 49 A(t) = freshwater plume area F = flux rate of nitrate into the sediment = -29.7 mg NO 3 -N m -2 d -1 Mass NO 3 -N denitrified = 420 metric tons NO 3 -N = ~4% of total load