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Advanced Leachate Treatment

Non-thermal Plasma Reduction
Arie Kremen, PhD

April 13, 2015

Landfill Water Balance

Leachate (L)

Variables:
• Runoff/Infiltration
• Storage
• Evapotranspiration

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Landfill Water Balance

𝑳𝑳 ≈ 𝑰𝑰 = 𝑷𝑷 − 𝑬𝑬𝑬𝑬 − 𝑹𝑹𝑹𝑹 + ∆𝑺𝑺

Order-of-Magnitude Estimate:
Parameter Value
Precipitation (P) 40 in/yr
Evapo-transpiration (ET) ~1/3
Infiltration (I) ~1/3
Runoff (RO) ~1/3
Change in Storage (∆𝑺𝑺) 0
Leachate Generation (L) ~13 in/yr

Specific Leachate Generation: 365,000 gal/yr/acre

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Cost Comparisons
Treatment Process Technology Marginal Cost
(¢/gal)
Conventional Activated Sludge 3.3-7.5
Membrane Biological Reactor 3.3-4.0
Reverse Osmosis 4.3-6.4
Hauling & Disposal 4.5-9.5
Leachate Management ($/ac/yr): $12,000 - $35,000

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‘Typical’ Leachate Quality

Young Medium Old

Age (yr) <1 1-5 >5
pH <6.5 6.5-7.5 >7.5
COD (mg/l) >15,000 3,000-15,000 <3,000
BOD5/COD 0.5-1.0 0.1-0.5 <0.1
TOC/COD <0.3 0.3-0.5 >0.5
NH3-N (mg/l) <400 400 >400
Metals (mg/l) >2.0 <2.0 <2.0
Humic 80% Hp1 5-30% Hp1 5-10% Hp1
Compounds HA, FA HA, FA
Hp1 – hydrophilic acids: volatile fatty acids, sugar acids, and other unidentified acids
HA – Humic Acid
FA – Fulvic Acid

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Categorical Pretreatment Standards
for Leachate

Parameter Value
BOD5 (mg/l) 140
TSS (mg/l) 88
alpha-Terpineol (mg/l) 0.033
Benzoic Acid (mg/l) 0.12
p-Cresol (mg/l) 0.025
Total Phosphorus (mg/l) -
Oil & Grease (mg/l) 100
Ammonia-N (mg/l) 10
pH (Field) 6-9
Phenolics (mg/l) 0.026
Total Zinc (mg/l) 0.2

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Chemical Characteristics of Leachate
Parameter Range Comment on Treatment
pH 4.5 to 9.0 Can be easily adjusted
BOD5 (mg/l) 20 to 57,000 Removed by biological treatment
Volatile Organic Compounds, VOC Highly variable Removed by air stripping
Total dissolved solids, TDS (mg/L) 1,700 to 25,000 Conventional treatment ineffective
Chloride (mg/L) 150 to 1,400 Conventional treatment ineffective
Total organic carbon, TOC (mg/L) 30 to 29,000 Conventional treatment ineffective
Dissolved Organic Nitrogen (mg/L) 14 to 2,500 Conventional treatment ineffective
UV Transmittance Conventional treatment ineffective
Metals: Arsenic (mg/L) 0.01 to 1.0 Removal is highly variable
Cadmium (mg/L) 0.0001 to 0.4
Chromium (mg/L) 0.02 to 1.5
Copper (mg/L) 0.005 to 10
Lead (mg/L) 0.001 to 5
Nickel (mg/L) 0.015 to 13
Zinc (mg/L) 0.03 to 1000
Source: Christensen et al. Appl. Geochem. 2001, 16, 659-718.

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Dissolved Organic in Leachate Effluent
Effluent residual organic content
• Small, complex organic compounds, resistant to biological treatment:
Hydrophilic Acids, Fulvic and Humic Acids
• Size indicative that physico-chemical treatments will not be effective
• Ultra-filtration (UF) and Reverse Osmosis (RO) more likely to be effective

Effluent 1.5μm .45μm .22μm 100kDa 30kDa 10kDa 5kDa 3kDa 1kDa 500Da

Source: John T Novak, PhD

Virginia Polytechnic Institute

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UV Transmittance at POTWs

Source: John T Novak, PhD

Virginia Polytechnic Institute

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Effect of Humic Compounds on UV

Source: John T Novak, PhD

Virginia Polytechnic Institute

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rDON
Recalcitrant Dissolved Organic Nitrogen
• Fractions of the organic N resists biological treatment
• Residual N in wastewater - about 0.5-1.5 mg/l
• Quantification/speciation in landfill leachate – ongoing
• Effluent from leachate treatment: 30-40 mg/l organic N
• Additional DON from leachate is a problem for WWTP
• Specific problem for East Coast utilities
• Effluent total N: 3-4 mg/l, including rDON

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Leachate Treatment is Challenging

• Leachate age is important (older leachates are easier to treat)

• Every technology appears to have some drawbacks
• Best approach:
• Know you local utility
• Understand the utility's treatment process
• Work with your local utility
• Work with your regulator

• Treat enough to avoid UV/rDON issues

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Treatment Options for Organics
Process Qualitative Effectiveness
Coagulation No
Anaerobic MBR promising
Adsoprtion PACT has shown promise
Ion Exchange Can work, expensive
Ultrafiltration MBR Works
Reverse Osmosis Works, expensive
How to manage rejects (25-30% for
treatment capacity)?
Oxidation Ozone
Perozone (O3 + H2O2)
TiO2/UV
Fenton’s Reagent (Fe2++ H2O2)
Non-thermal Plasma

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Plasma – the Fourth State of Matter

• 99% of the Observable Universe is comprised of plasma

• Created by stripping/adding electrons from a gas

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Non-Thermal Plasma (NPT)

NPT is not in thermodynamic

equilibrium: ion and electron
temperatures are different
• Applications:
• Antimicrobial treatment of foods
• Self-decontaminating filters
• Sterilization in dentistry
• Manufacture of nano-particles
• Properties
• No electrical current
• Non-contact electrodes Source: NASA/ISS Expedition 28, Re-entry
• Ambient temperatures (macro) of the Shuttle Atlantis as seen from ISS
• Partially ionized gas (approx. 1%)

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NPT Applications in Water Treatment

NPT can target a wide range of refractory pollutants with high

aqueous solubility and toxicity:
• Petrochemicals (e.g., MTBE, BTEX)
• Organic solvents (e.g., TCE, 1,4-dioxane)
• Organic Pollutants (e.g., endocrine disruptors)
Electric Demand
NPT does not: (kWh/1,000 gal)
TCE 1.21
• require chemicals or conditioning
MIB 1.67
• No moving or disposable parts NDMA 0.63
1,4-dioxane 1.24
• No dedicated pre- or post-treatment
MTBE 3.8

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Corona Discharge NPT

creates plasma discharge above the water, which

• Emits an ‘electron wind’
• Emits UV radiation
• Produces ozone (O3(g)), hydroxyl radicals (●OH)

Parameter Value

Pulse Generator 500-1,000 Hz

Output Voltage Amplitude 40 kV

Max. Pulse Energy 1J

Electrode Carbon Fiber

Source: Gerrity et al. (2009), doi:10.1016/j.waters.2009.09.029

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 Materials Courtesy of
Advanced Plasma Solutions
Pulsed Corona

Plasma in
Water

10kW Corona

Gliding Arc
Micro APG TORNADO
Floating Electrode DBD

Dielectric Barrier Discharge / Nanosecond DBD Magnetic Gliding Arc

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 Gliding Arc NPT
Reactor
• Various configurations
• Water electrodes
• Hollow electrodes
• Submerged Plasmatron
• Voltage
• Range – 800V to 10kV
• Preferred – 1,000 to 1,500 V
• Current
Electrodes
• Range – 2 to 50 A
Gas • Preferred – 5 to 30 A

H.V. Power
Ground Supply Source: Concentration of hydrogen peroxide
generated by gliding arc discharge and inactivation of
E. coli in water, Kim et al., December 30, 2012

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State of NPT Technology

• Efficient destruction of emerging contaminants

• Capable of meeting USEPA MCLs
• More efficient (energetically) than Advanced
Oxidation Processes (e.g., UV, H2O2)
• Generation of UV, O3, and ●OH without additives
• Technology/equipment development ongoing
• Insignificant generation of oxidation by-products
• Negligible volatilization of pollutants

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Microbial Fuel Cell (MFC)

• Bio-electrochemical System Leachate Treatment

• Resource Recovery
Load

e- e-

Fuel O2

H+

CO2 H2O
Anode Cathode

Produced Feeding Recircultation Aeration Total Net

kWh/m3
Energy Energy Energy Energy Consumed Energy
Leachate 0.0189 0.0002 0.0123 0.0410 0.0535 -0.0346
Source: Zhen (Jason) He, PhD, Virginia Polytechnic Institute

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Bio-electrochemical Systems (BES)

Opportunities
• Direct electricity generation from organic contaminants
• Low energy consumption
• H2, O2 and H2O production, NH3 recovery
Challenges
• Understanding of microbial/electrode interaction
• Lowering cost of electrodes and membranes
• System scale-up

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Emerging Contaminants

• recalcitrant Dissolved Organic Compounds (rDON, TOC)

• UV Transmittance inhibiting compounds (Hp1, HA, FA)
• Total Dissolved Solids (TDS)
• Pharmaceuticals;
• Nutritional supplements (‘nutraceuticals’);
• Personal care products, e.g., exfoliants;
• Xeno-hormones mimicking estrogens & androgens;

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Thank you.

Questions?
Comments?
Arie Kremen, PhD
845.695.0213
Arie.Kremen@CornerstoneEG.com

© 2014 Cornerstone. All rights reserved.