THE BIOREACTOR LANDFILL PARADIGM Frederick G. Pohland, Ph.D., P.E. Professor and Weidlein Chair of Environmental Engineering University of Pittsburgh Pittsburgh, PA 15261, USA 2003 EPA Bioreactor Landfills Workshop Arlington, VA OUTLINE OF PRESENTATION • Fundamental Definitions • From the Way We Were • Today and Beyond FUNDAMENTAL DEFINITIONS • Reactor – a containment structure in which reactions are initiated and controlled to optimize a desired outcome • Bioreactor – a biologically-mediated reactor • Bioreactor Landfill – a bioreactor where the containment structure is a landfill or a portion of a landfill FUNDAMENTAL DEFINITIONS (Cont’d.) • Paradigm – an example, model or archetype of which all things of the same type are representatives or copies • Bioreactor Landfill Paradigm – a landfill archetype with leachate recirculation to accelerate and/or enhance biodegradation and stabilization FROM THE WAY WE WERE • Past Landfill Practices – uncontrolled dumping/impacts • The Emergence of a Paradigm – leachate and gas management – engineered landfill systems • Scientific and Technical Renaissance – translation of fundamental scientific principles into rationale design, operation and control • Regulatory Impacts – away from command and control ORGANIC POLYMER-CONTAINING WASTE H2O MONOMERS ALCOHOLS ORGANIC ACIDS Legend : Electron donors Fe(III) - NO3 2- SO4 : Electron acceptors : Precursor byproducts : End products Fe(II) NH3 H2S N2 H2 HAc - HCO3 CH4 Waste Conversion Sequences in Landfill Bioreactor Systems Phase III Phase V Phase I Phase II Acid Phase IV Initial Transition Methane Fermentation Final Formation Maturation 8 150 3000 pH 100 7 50 2000 pH 0 Ammonia 6 -50 1000 ORP, mV Ec -100 Ammonia, mg/L 1.0 5 100 ORP 50 -150 0 3 N2 0.8 80 40 Incremental Gas Production 0.6 60 COD 30 CH4 0.4 40 TVA 20 COD, TVA, g/L TVA, COD, CO2 25 H2S O2 20 0.2 20 10 15 Gas Composition, % by Volume 10 Incremental Gas Production, m H O 2 2 5 Sulfide, mg/L Sulfide, 0.0 0 0 0 0 200 400 600 Stabilization Time, Days Stabilization characteristics within a bioreactor landfill unit Redox Half-reaction Responsible during Anaerobic Stabilization in Bioreactor Landfills Oxidations (Electron Donating Reactions)a ∆G, kJ ↔ - ↔ - + Caproate Propionate CH3(CH2)4COO +2H2O 2CH3CH2COO + H +2H2 +48.3 ↔ - ↔ - + Caproate Acetate CH3(CH2)4COO + 4H2O 3CH3COO + 2H + 4H2 +96.7 ↔ - ↔ - - + Caproate Butyrate + Acetate CH3(CH2)4COO + 2H2O CH3(CH2)2COO + CH3COO + H + 2H2 +48.4 ↔ - ↔ - - + Propionate Acetate CH3CH2COO + 3H2O CH3COO + HCO3 + H + 3H2 +76.1 ↔ - ↔ - + Butyrate Acetate CH3CH2CH2COO + 2H2O 2CH3COO + H + 2H2 +48.1 ↔ ↔ - + Ethanol Acetate CH3CH2OH + H2O CH3COO +H + 2H2 +9.6 ↔ - ↔ - - + Lactate Acetate CH3CHOHCOO + 2H2O CH3COO + HCO3 + H + 2H2 -4.2 ↔ - ↔ - Acetate Methane CH3COO + H2O HCO3 + CH4 -31.0 Reductions (Electron Accepting Reactions)a - ↔ - + ↔ - HCO3 Acetate 2HCO3 + 4H2 + H CH3COO + 4H2O -104.6 - ↔ - + ↔ HCO3 Methane HCO3 + 4H2 +H CH4 + 3H2O -135.6 2- + ↔ - SO4 + 4H2 + H HS + 4H2O -151.9 Sulfate ↔ Sulfide - 2- + ↔ - CH3COO + SO4 + H 2HCO3 + H2S -59.9 - + ↔ + NO3 + 4H2 + 2H NH4 + 3H2O -599.6 Nitrate ↔ Ammonia - - + ↔ - + CH3COO + NO3 + H + H2O 2HCO3 + NH4 -511.4 ↔ - + ↔ Nitrate Nitrogen Gas 2NO3 + 5H2 + 2H N2 + 6H2O -1,120.5 Note: a pH 7, 1 atm, 1 kg/mol activity, 25oC Bioreactor landfill attenuation of representative recalcitrant organic and inorganic constituents* Constituents Dominant Attenuation Mechanisms during Landfill Stabilization Phases Heavy Metals Conversion to a reduced oxidation state with complex formation and volatilization (Fe, Cr, (Cd, Cu, Cr, Fe, Hg, Ni, Pb, Hg). Zn) Mobilization and salt formation in leachate in the presence of organic (e.g., aromatic hydroxide, carboxylic acid, aromatic amine, humic and fulvic acid) and inorganic (e.g., chloride, sulfate, carbonate) ligands. Formation of sparingly soluble hydroxides (Cr) and sulfates (Cd, Cu, Fe, Hg, Ni, Pb, Zn) after sulfate reduction, and precipitation. Physical sorption and ion exchange within the waste matrix. Filtration and retention within stagnant pools of interstitial water. Organic Compounds** Halogenated Aliphatics Volatilization and mobilization in gas and leachate prior to abiotic and biotic reductive (PCE, TCE, DBM) dehalogenation under methanogenic, methanotrophic, sulfate reducing and denitrifying conditions. Chlorinated Benzenes Volatilization and sorptive matrix capture prior to partial reductive dechlorination. (HCB, TCB, DCB) Phenolics and Mobilization in leachate prior to dechlorination or nitro-group reduction, biodegradation Nitroaromatics and complexation. (DCP, NP, NB) Phthalate Esters (BEHP), Low volatility and mobility in gas and leachate prior to complete or partial biodegradation. Polynuclear Aromatics (NAP), and Pesticides (LIN, DIEL) * References: Pohland et al. (2002). ** Perchloroethene (PCE), Trichloroethene (TCE), Dibromomethane (DBM), Hexachlorobenzene (HCB), Trichlorobenzene (TCB), Dichlorobenzene (DCB), Dichlorophenol (DCP), Nitrophenol (NP), Nitrobenzene (NB), Bis (2-ethylhexyl)phthalate (BEHP), Naphthalene (NAP), Lindane (LIN), Diedrin (DIEL); includes daughter products. TODAY AND BEYOND • Needs Assessment and Resolution – Scientific and technical inquiry/discovery/application • Rational Management and Oversight – Checks and balances • Stakeholder Harmonization – Perspective and participation • Sustainability – Goals achievement DIRECT USE PIPELINE GAS ON-LINE QUALITY TREATMENT FLARING LANDFILL Phase III Phase V Phase I Phase II Acid Phase IV Initial Transition Methane Fermentation Final Formation Maturation 8 150 3000 pH 100 7 50 2000 pH 0 Ammonia 6 -50 1000 ORP, mV Ec -100 mg/L Ammonia, 1.0 5 100 ORP 50 -150 0 3 N2 0.8 80 40 Incremental Gas Production 0.6 60 COD 30 CH4 0.4 40 TVA 20 COD, TVA, g/L TVA, COD, CO2 25 H2S O2 20 0.2 20 10 15 Gas Composition,Volume% by 10 Incremental Gas Production, m H O 2 2 5 Sulfide, mg/L Sulfide, 0.0 0 0 0 0 200 400 600 Stabilization Time, Days IN SITU VS. LEACHATE RECYCLE EXTERNAL TREATMENT EXTERNAL TREATMENT BIOLOGICAL TREATMENT PHYSICAL/CHEMICAL TREATMENT ACTIVATED SLUDGE ANAEROBIC FILTER PRECIPITATION/COAGULATION AERATED LAGOON ANAEROBIC CONTACT CHEMICAL OXIDATION/REDUCTION STABILIZATION POND NITRIFICATION ADSORPTION TRICKLING FILTER DENITRIFICATION ION EXCHANGE REVERSE OSMOSIS COMBINED TREATMENT DISINFECTION POTW DISCHARGE OPTION LAND APPLICATION Bioreactor Landfill with Leachate and Gas Treatment Options Leachate Recharge/Gas Extraction Wells Final Cover External Leachate Recirculation Pump Station Dedicated Tre atment Zone Leachate Gas Flare Recirculation Field Compartment Internal Primary Leachate Limit Pump Station Internal Leak Detection Monitoring Well Gas Gravel Packed Recovery Trench with Perforated Pipe Isolation Berm External Treatment External Pump Plant Station er at Leachate Storage Primary Leachate w m Collection System or St Leak Detection System Groundwater Monitoring Well Operational features of a bioreactor landfill.