Effective Bioremediation of Chlorinated Solvent Sites ...
Transcript of Effective Bioremediation of Chlorinated Solvent Sites ...
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Advances in EVO Deployment Using In Situ Alcoholysis
Part 1, Wednesday, April 28, 2021
Effective Bioremediation of Chlorinated Solvent Sites – Avoiding Pitfalls and
Maximizing Performance
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Agenda
01 02
03
05
04
06
Biological Reductive Dechlorination
Bioremediation
History and Advancements
Emulsified Vegetable Oils
Why do Wells Bio-Foul?
Bio-Fouling
Overview and Options
Electron Donors
Impact of pH on Dechlorination
pH
Method for Improved ROI and Fatty Acid Distribution
Subsurface Distribution
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How Does Bioremediation
Work?Energy
Electron
Donor
(Food)
Electron
Acceptor
(something to
breathe)
[O2, NO3, SO4,
TCE, etc.]
Waste Products
[CO2, N2, FeS2, Cl-]
+ +
(Drawing Modified from AFCEE and Wiedemeier)
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What is needed?
•Organic substrates that ferment to:oAcetateoHydrogen (H2)
•Strong reducing conditions•Right organohalide respiring bacteria•Nutrients
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O2
Ethene and other
degradation
products
DhbDhb
DhcDhc
Dhc
Dhb
Electron
Donor Fermented
Dhc
Dhc
Dhb
H2 (Energy)
TCE or Others
(Electron acceptor)
Cell GrowthDhc
Dhb
Dhb
Dhb
DhbDhc
Dhc
Dhc
Dhb
Slide Courtesy of SiREM
Biological Reductive Dechlorination
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Reductive Dechlorination by Dhc
PCE-reductase
TCE-reductase
cDCE-reductase
VC-reductase
PCE
TCE
cDCE
VC
TCE
cDCE
VC
Ethene
Cl
ClCl
Cl+ H2
Cl
ClH
Cl+ Cl
-
+ H+
Cl
ClH
Cl+ H2
Cl
HH
Cl+ Cl
-
+ H+
Cl
HH
Cl+ H2
H
HH
Cl+ Cl
-
+ H+
H
HH
Cl+ H2
H
HH
H+ Cl
-
+ H+
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Anaerobic Fermentation
Soybean oil ferments to acetic acid and hydrogen
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Electron Donors
Average Composition and Electrons Released During Anaerobic Fermentation
Electron
Donor
Atoms per Mole Substrate
Average
Molecular
Weight
H2 Released
per mole
Substrate
Moles H2
Released
per
gram
Substrate
Carbon Hydrogen Oxygen
Acetate 2 4 2 60.1 4 0.0666
Lactate 3 6 3 90.1 6 0.0666
Glucose 6 12 6 180.2 12 0.0666
Soybean Oil 56.3 99.5 6 873.1 156.5 0.1792
Ref: ESTCP, May 2006, Table 2.3
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A Historic Look at Soybean Oil Prices
COVID & TightGlobal Supplies
Dawn of Biodiesel
Supply Concerns
Recession
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Trade War Phase One Announcement Reopening Jitters/Election
COVID Lockdowns
Tight Supply
Concerns
Nearby Continuous Soybean Oil Chart (02.03.2021)
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Soybean Fatty Acid Distribution
Fatty Acid PercentC-16:0 Palmitic 11.0 %
C-18:0 Stearic 4.0 %
C-18:1 Oleic 24.0 %
C-18:2 Linoleic 54.0 %
C-18:3 Linolenic 7.0 %
𝐻2𝐶 − 𝑂 − 𝐶 − 𝑅𝑖
𝑂=
𝐻2𝐶 − 𝑂 − 𝐶 − 𝑅𝑖
𝑂=
𝐻2𝐶 − 𝑂 − 𝐶 − 𝑅𝑖
𝑂=
Alpha-Linolenic Acid
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Fatty Acid Oxidation
Linoleic Acid Multiple step metabolic process
• Removes two carbons from the chain
• Releases:• Four hydrogen atoms (H)
• Acetic Acid (C2H4O2)
Beta (β)
Alpha (α)
Carboxyl group
CnH2nO2 + 2 H2O ⇒ Cn-2H2n-4O2 + 2 H2 + C2H4O2
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Distribution of the Correct Type of Fatty Acids is EssentialAcetate
• Slow consumption
•Will migrate downgradient
• Stimulates PCE -> TCE -> cDCE
•Will not stimulate cDCE -> VC -> ethene
Hydrogen (H2)Produced from linolenic acid, propionate, butyrate, etc.
• Rapid consumption
• Does not migrate beyond injection zone
• Required for cDCE -> VC -> ethene
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pH Plays a Key Role in VFA Production
Systems under alkaline conditions
• Enhances the activity of fatty acid-producing bacteria
• Inhibits methanogens
• Increases production of VFAs
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Impact of pH on
Dechlorination
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6.0 8.55.0
No
Dechlorination
10
Complete
Dechlorination
7.5
• pH of 6.0-8.5 is generally required for dechlorination to ethene*
• pH 6.8-7.5 is considered optimal range, 7.5 is best*
• Sites with low pH more likely to accumulate cDCE/VC
Optimal
Dechlorination
6.8
No
Dechlorination
Incomplete/Slow
Dechlorination
Incomplete/Slow
Dechlorination
*Rowlands, 2004 (Slide Courtesy of SiREM)
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Why is low pH so Common?
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• Some sites have intrinsic groundwater pH in the 5.0-6.0 range
• Reductive dechlorination produces hydrochloric acid
PCE
Cl
ClCl
Cl
TCE
Cl
ClH
Cl
cDCE VC Ethene
Cl
HH
Cl H
HH
Cl H
HH
H
2H HCl 2H HCl 2H HCl 2H HCl
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Fermentation of electron donors generates acidic byproducts
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Lactic Acid
• 2H2 + Acetate + CO2
• CO2 dissolves in water forming carbonic acid
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BiofoulingNutrients in the vicinity of aerobic wells promote excessive biomass growth that reduce permeability
Bacterial growth within delivery wells
Hard Soap and Soap Scum
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SaponificationThe Process of Making Soap
+ =Acid(Oil)
Base(Lye)
Salt(Soap)
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Hard Water
• Water that contains salts of calcium and magnesium principally as:
oBicarbonates
oChlorides
o Sulfates
• Ferrous iron may also be present
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Hard Water
Calcium and Magnesium Ions
• React with the fatty acids to form an insoluble gelatinous curd
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Treated Samples
Co-solvent liquifies soap scum
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Alkaline Groundwater
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Bench test to liquify viscous material
• Samples mixed with co-solvent liquifies insoluble gelatinous curd
• Addition of water, forms an EVO
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Field Mixing• TASK™ EVO Self-
Emulsifier
• RBD Soybean Oil
EVO Deployment Using In Situ Alcoholysis
Emulsified Vegetable Oil(EVO)
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Anaerobic Bioremediation Deploying Electron Donor Via In Situ Alcoholysis
EDS-Activator™
𝐻2𝐶 − 𝑂𝐻
𝐻2𝐶 − 𝑂𝐻
𝐻2𝐶 − 𝑂𝐻
+
Mixture ofFatty Acid Esters
EDS-QR™Salts of the
Carboxylic Acids+ +
In Situ Generation of Slowly Fermenting and Soluble Electron Donors
+
EDS-Advanced™
TASK™ MicroEVO™Self-Emulsifier &Substrate Shuttle
Vegetable Oil
𝐻2𝐶 − 𝑂 − 𝐶 − 𝑅𝑖
𝑂=
𝐻2𝐶 − 𝑂 − 𝐶 − 𝑅𝑖
𝑂=
𝐻2𝐶 − 𝑂 − 𝐶 − 𝑅𝑖
𝑂=
+ 𝑅𝑖 − 𝐶 − 𝑂−
𝑂=
𝑅𝑖𝑖 − 𝑂 − 𝐶 − 𝑅𝑖
𝑂=
+ 𝑅𝑖 − 𝐶 − 𝑂−
𝑂=𝑅𝑖𝑖 − 𝑂 − 𝐶 − 𝑅𝑖
𝑂=
+ 𝑅𝑖 − 𝐶 − 𝑂−
𝑂=
𝑅𝑖𝑖 − 𝑂 − 𝐶 − 𝑅𝑖
𝑂=
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Activator Options
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• Homogeneous Alkaline Catalysto Alkyl oxides (RO−)
• Heato Steam hydrolysiso Electrical resistance heatingo Thermal conduction heatingo Gas thermal heatingo Residual heat from an in-situ thermal remediation project
• Biocatalysto Enzyme (triglyceride lipases)
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EDS-Advanced™Unrestricted Electron Donor Subsurface Distribution for Anaerobic Bioremediation
• Improved subsurface distribution of a vegetable oil-based electron donor
• Improved ROI, fatty acid distribution and TOC when compared to EVO
• Eliminates dependence on EVO droplet size
• Aids in reducing cVOC inhibitory concentrations by sequestering DNAPL
• High alcohol content and high solubility reduces injection well biofouling risk
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Typical Application Rates
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EDS-ER™ (Soybean Oil and TASK™MicroEVO™ Self-Emulsifier
2 to 8 g/L
EDS-Activator™ 16 to 20% of EDS-ER Dose
EDS Substrate Shuttle (Co-Solvent) 0 to 0.4 g/L
mZVI Suspension 4 to 6 g/L
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Case Study
ZVI with Biostimulationand Bioaugmentation
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Former Dry Cleaner Site
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Former Dry Cleaner Site
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PCE Isoconcentration
Contours
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140 Injection Points
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• MW5A total CVOCs dropped from 1016 to 4 ppb in 5 months
• MW14 PCE dropped from 451 to 97 ppb in 5 months
Former Dry Cleaner
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Field Mixing
TASK™ EVO Self-Emulsifier totes Bulk tanker delivery of soybean oil
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Quality Control Testing
Field prepared EDS-ER™ Field prepared EVO
Add Water
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Distribution Centers
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PRODUCTSANDSERVICES
ISCO
Modulated TersOx™ LiquidActivated and Controlled Exothermic (ACE)
AEROBIC BIOREMEDIATION
TersOx™ Family of Products
ELECTRON ACCEPTORS FORANEROBIC BIOREMEDIATIONSulfate Enhanced In Situ Remediation ofPetroleum Hydrocarbons using Nuristulfate®and NutriBind®
ELECTRON DONORS
Enhanced Anerobic Bioremediation of Chlorinated Solvents
PERFORMANCE MONITORING
Compound Specific Isotope Analysis (CSIA) and Molecular Diagnostic Tools (MDT)
NAPL REMEDIATION
Tersus Advanced Surface Kinetics (TASK™) liberates NAPL and captures them with enhanced recovery techniques
EQUIPMENT
Subsurface Delivery SystemsAdditive injection and groundwater recirculation trailers available for short- or long-term leases
TECHNICAL SUPPORT
Professional technical services
ZVI AND ISCR
ZVI Powders, mZVI, & ISR-Cl
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Gary M. Birk, P.E. (NC, VA, & FL) T. 919.453.5577 x2001 | M. 919.638.7892 [email protected] www.tersusenv.com | www.surbec.com
Course Code ISNC