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A Semi-Passive Permeable Reactive Barrier (PRB) Remediation Technology Using Membrane-Attached Biofilms. Lee Clapp Bala Veerasekaran Vipin Sumani February 5, 2003. Chlorinated solvents (e.g., PCE & TCE) are used for industrial vapor degreasing. Problem:
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A Semi-Passive Permeable Reactive Barrier (PRB) Remediation Technology Using Membrane-Attached Biofilms Lee Clapp Bala Veerasekaran Vipin Sumani February 5, 2003
Chlorinated solvents (e.g., PCE & TCE) are used for industrial vapor degreasing
Problem: Improper disposal of chlorinated solvents
Magnitude of Problem: • DoD • 22,089 identified contaminated sites (1995) • 49% contaminated with chlorinated solvents. • Estimated cost of remediation - $28.6 billion. • DOE • 10,500 identified contaminated sites (1996) • 25% contaminated with chlorinated solvents. • Estimated cost of remediation - $63 billion • Estimated time for remediation - 75 years NEED - Development of technologies to reduce remediation costs. (Ref: EPA-542-R-96-005)
Hollow-Fiber Membrane Semi-Passive Permeable Reactive Barrier DCE CO2 + Cl- VC CO2 + Cl- CH4 Water Table CH4 Groundwater flow CH4 Confining Contaminant Biofilm Bacterium Layer Plume Hollow Fiber Membrane Overall Research Goal To develop a semi-passive membrane permeable reactive barrier (PRB) remediation technology that fosters biological destruction of chlorinated organic compounds by the controlled delivery of soluble methane & oxygen gas into the subsurface.
DNAPL Contamination EPA, 2003
Recovery of “Free Product” EPA, 2003
Pump & Treat EPA, 2003
Wells loaded with HRC or ORC Permeable Reactive Barrier (PRB) Remediation Technology Regenesis, 2003
hydrogen added to these wells H2initially detected in these wells & a sampling well 6 ft downstream direction of groundwater flow Passive Membrane PRB System at TCAAP Superfund Site
H2 HCl H2 HCl H2 HCl H2 HCl PCE TCE cis-DCE VC ETH O2 TCE CO2 + Cl- CH4 Two processes for chlorinated solvent biodegradation • (1) Reductive dechlorination removes one chlorine at a time (anaerobic). • (2) Cometabolic oxidation results in >99% mineralization (aerobic).
(1) Previous research with reductive dechlorination processes
H2 gas 4H2 2H2O Geoprobe well H2 HCl H2 HCl hollow-fiber membranes PCE plume CO2 CH4 CH4 H2 DCE VC PCE TCE TCE DCE VC ETH ~ 4 cm Using hollow-fiber membranes to supply H2 to contaminated aquifers flow aquaclude
Problems with enhanced reductive dechlorination for CAH remediation. • Accumulation of intermediate transformation products (DCE & VC). • Microbial competition for H2. • MCLs below threshold concentrations required for dechlorinator growth. • Aquifer biofouling. • Adverse impact on groundwater quality.
soil column reactors
Concentrations of PCE & byproducts in test column (H2 added) after ~1 year
Concentrations of PCE & byproducts in control column (no H2) after ~1 year
Concentrations of PCE & byproducts in test column after ~1 year
Previous research with cometabolic (aerobic) degradation processes
atmospheric discharge blower air compressor vapor treatment compressed CH4 tank CH4 explosion hazard, vapor-phase TCE gas extraction well TCE Cl- TCE plume gas-channeling thru porous media CH4 CO2
air compressor compressed CH4 tank TCE Cl- TCE plume CH4 CO2 CH4 O2 What if CH4-utilizing bacteria grew as biofilms on surface of membranes?
growing cells utilizing CH4 non-growing cells cometabolizing TCE inactivated cells CH4 & O2 continuous flux of new cells erosion Biofilm stratification membrane
flux of new cells SEM of biofilm cross-section
cells with compromised membranes stained red with propidium iodide viable cells stained green with “Syto 9” Biofilm viability staining
Other modeling studies • Olaf Cirpka at Stanford has modeled different strategies for minimizing biofouling in aquifers.
Two obstacles • How can “capture zone” for each well be increased? - Bala • Will presence of copper in groundwater repress expression of operative TCE-degrading enzyme (sMMO)? - Vipin
Research Topic: • Characterizing effect of superimposed transverse flow on well capture zone.
Decreasing CH4 “zone of influence” due to microbial accumulation GW flow
Research Objectives • Phase 1: Characterize relationship between well-spacing, inter-well pumping rate, and capture zone. • Phase 2: Characterize relationship between well-spacing, inter-well pumping rate, and DCE removal efficiency.
Modeling Methods: • GMS (Groundwater Modeling System) • ModFlow • ModPath • RT3D
Basic Concepts in Groundwater Flow • Darcy’s Law: Qx = -KxA (h2 – h1)/L • Time taken for a particle to travelt = LnA/Q • t-Time ,L-Length of the Sample, n-Aquifer porosity, A-Area, Q-Flow Rate
Capture Zone: The capture zone defines the area of an aquifer that will contribute water to an extraction well within a specified time period.
Assumed Parameter Values • Grid: 20 ft 20 ft. • Aquifer Hydraulic Conductivity =8.42ft/day • Head: Left=10ft , Right=9.57ft • Aquifer Porosity=0.35 • Well Hydraulic Conductivity=842 ft/day • Well Porosity=1.0 • Unconfined Aquifer ref: Wilson & MacKay, 1997.
Capture zone without pumping Unpumped Well Unpumped Well
Capture zone with pumping injection well extraction well injection well extraction well
Conceptualized flow field % capture vs. # of wells & pumping rate
Research Topic: • Characterizing effect of copper loading on sMMO expression in membrane-attached methanotrophic biofilms.
Copper Loading Effect on sMMO Expression in Membrane-Attached Methanotrophic Biofilms • Methanotrophs - methane oxidizing bacteria. • They are of two types – Type 1 and Type 2. • Methane is oxidized by methanotrophs to CO2 via intermediates like methanol and formaldehyde. • Two enzymes sMMO and pMMO play an important role for the oxidation of CH4. • sMMO co-oxidizes a wide range of alkanes & alkenes, including chlorinated hydrocarbons. • Cu inhibits sMMO activity.