Project: Using Nitrate Produced From Leachate To Control Landfill Odors Funded by: Presented by: Youneng Tang (PI, FAMU-FSU COE) Tarek Abichou (co-PI, FAMU-FSU COE)

News on landfill odors after hurricanes Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach News on landfill odors after hurricanes “The sulfur-smell moving throughout the county is coming from a landfill off Collier Boulevard, according to the Collier County Solid Waste Department. There was an increase in the amount of garbage collected after Hurricane Irma hit Southwest Florida, according to solid waste officials. The excess trash and recent rains created a strong odor.” http://www.winknews.com/2017/10/08/county-wide-stench-coming-from-collier-landfill/ “After Hurricane Andrew struck in August 1992, Broward residents deposited debris and waste from the massive reconstruction projects, changing the nature of the landfill gas. The level of hydrogen sulfide increased to as much as 5,000 ppm, creating severe odors.” http://americancityandcounty.com/mag/government_oxidation_system_stops

Hurricanes exacerbate the odor problems Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Hurricanes exacerbate the odor problems Key West after Hurricane Irma Drywall: Gypsum: 90% (CaSO4)

Existing landfill odor control methods Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Existing landfill odor control methods Collect & Treat Mask Do not eliminate the odor Expensive

Using NO3- to suppress H2S production: being practiced in oil industry Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Using NO3- to suppress H2S production: being practiced in oil industry Sea water (SO42-) Oil Bacteria NO3- Sea water (SO42-) Reference: Voordouw et al. Sulfide remediation by pulsed injection of nitrate into a low temperature Canadian heavy oil reservoir. Environmental Science & Technology, 2009, 43(24), 9512-8.

Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Where is nitrate from? Commercially available nitrate salts (e.g., fertilizers) Waste Landfill leachate contains NH4+ (1000 mg N/L), which can be converted to NO3- (focus of this project)

Thermodynamic preference Nitrite is toxic to sulfate-reducing bacteria Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Microbial principles Thermodynamic preference Nitrate oxidize H2S Nitrite is toxic to sulfate-reducing bacteria Reference: Sungthong & Reinhart. Control of hydrogen sulfide emissions using autotrophic denitrification landfill biocovers: engineering applications. Frontiers of Environmental Science & Engineering in China, 2011, 5(2), 149-158.

Case 1: Landfills with leachate recirculation (19% in FL) Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Case 1: Landfills with leachate recirculation (19% in FL) Leachate containing NO3- Oxidation Pond Infiltration gallery Landfill Odor source Leachate Storage Pond Leachate containing NH4+ (1000 mg N/L) Reactions in landfill: BOD + NO3-  N2 + CO2 + H2O BOD + H2O  CO2 + CH4 BOD + SO42-  H2S + CO2 + H2O 5H2S + NO3- 5SO42- + 4N2+ 4H2O + 2H+ Reactions in oxidation pond: NH4+ + 2O2  NO3- + H2O + 2H+ Reference: Townsend et al. Assessing options for on-site leachate and groundwater management strategies at Florida landfills. 2014, https://www.essie.ufl.edu/media/essieufledu/home/townsend/HC13TAGMAY27.pdf

Case 2: Landfills with leachate discharge to WWTP Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Case 2: Landfills with leachate discharge to WWTP Reactions in portable oxidation tank : NH4+ + 2O2  NO3- + H2O + 2H+ Portable oxidation tank Leachate containing NH4+ (1000 mg N/L) Infiltration gallery Landfill Odor source Discharge to wastewater treatment plant Reactions in landfill: BOD + NO3-  N2 + CO2 + H2O BOD + H2O  CO2 + CH4 BOD + SO42-  H2S + CO2 + H2O 5H2S + NO3- 5SO42- + 4N2+ 4H2O + 2H+

Advantages of the proposed approach Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Advantages of the proposed approach Likely to be effective (used in oil industry) Inexpensive (nitrate from on-site leachate) Sustainable (beneficial reuse of leachate) Environmentally friendly (end product N2)

Research objectives and tasks Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Research objectives and tasks Demonstrate proof-of-concept Determine the required leachate volume (NO3-: SO42- and NO3-: H2S) Task 1 (landfill tests): Test five lab-scale landfills until H2S is generated Task 2 (leachate treatment tests): Test one lab-scale leachate treatment reactor until ammonium is converted to nitrate Task 3 (landfill + leachate treatment tests): Apply the nitrate-containing leachate at different volumes to the H2S-generating landfills

Task 1: Test five lab-scale landfills Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Task 1: Test five lab-scale landfills until H2S is generated

Task 1: Test five lab-scale landfills Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Task 1: Test five lab-scale landfills until H2S is generated Gas collection Leachate collection Landfill Rainwater infiltration

Task 1 Composition of solid waste mixture in the lab-scale landfills Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Task 1 Composition of solid waste mixture in the lab-scale landfills Categories Component Composition (wet weigh) Drywall, major source of sulfate (10%) Drywall 10% Municipal solid waste, major source of organic matters (90%) Grass 6% Leaves 5% Branches 4% Wood 7% Food 19% Plastic Metal Glass Coated paper 2% Old newsprint 8% Corrugated containers 18% Office paper Note: Modified based on Barlaz (1998)

Summary of the sample measurement Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Task 1 Summary of the sample measurement Samples Parameters to measure Methods Leachate   NH4+, NO2-, NO3-, SO42-, SO32- Ion chromatographic method S2- Standard method 4500 Chemical oxygen demand (COD) Colorimetric method Acetate pH Electrometric method Gas CO2, H2S, CH4, N2, O2 Gas chromatographic method volume Water displacement method Solid CaSO4 and S0 Scanning electron microscope and RAMAN spectrometry

Task 1 Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Task 1 Samples Parameters Results Leachate NH4+ 180±1 mg N/L NO2- NO3- 0.68 mg N/L Dissolved organic nitrogen (DON) 30.3 mg N/L SO42- 212 mg S/L SO32- S2- 0.04 mg S/L Chemical oxygen demand (COD) 11,600±232 Dissolved organic carbon (DOC) 7470±110 mg C/L Acetate 1610 mg C/L pH 5.88 Gas   H2S To be measured CH4 0.04% CO2 0% N2 To be calculated O2 volume

All five lab-scale landfills Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Task 2: Test one lab-scale leachate treatment reactor until ammonium is converted to nitrate Activated sludge Treated leachate All five lab-scale landfills Biological reactor Magnetic stirring bar Magnetic stirrer Leachate Reactions: NH4+ + 2O2  NO3- + H2O + 2H+ BOD + O2  CO2 + H2O

Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Task 3: Apply the nitrate-containing leachate at different volumes to the H2S-generating landfills Biological reactor

1 Graduate student (Zhiming zhang) Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach PI (Dr. Youneng Tang, FAMU-FSU COE) Landfill managers 1 Graduate student (Zhiming zhang) New method FDEP Co-PI (Dr. Tarek Abichou, FAMU-FSU COE) Scientists

Project timeline, milestones, and deliverables Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Project timeline, milestones, and deliverables Project Duration 09/01/2018 – 08/31/2019 Tasks Month 1 2 3 4 5 6 7 8 9 10 11 12 Task 1: Landfill tests X   Task 2: Leachate treatment tests X  Task 3: Landfill + leachate tests  X Deliverables Abstract submission Project website development TAG-1: Technical Awareness Group Meeting 1 TAG-2: Technical Awareness Group Meeting 2 Quarterly reports (#) # Draft final report (†), final report (*), journal papers and conference presentations (+) † *+ Metrics & in-state travel When requested by the Center

Developed a project website Class project Presentations Problem statement Proposed solution Three tasks Team & benefits Timeline Education & outreach Developed a project website Class project Presentations

Acknowledgement