PRESENTER: Eric Bueltel, P.E.

PRESENTER: Eric Bueltel, P.E.
Utilizing an In Situ Groundwater Recirculation Bioremediation Process to Remediate a Hydrocarbon Release on an Active Oil Production Pad, North Dakota PRESENTER: Eric Bueltel, P.E. PHONE: x104

Roadmap Introduction: Process Overview: ETEC, LLC Conceptual model
Bioremediation technologies Role in cleanup Process Overview: Conceptual model Equipment & products PHONE: x104 ETEC Bioremediation

Roadmap Continued Setup: Operation: Site Characteristics Flow rates
Infrastructure Mass balance Obstacles Operation: Process Data evaluation Treatment modifications PHONE: x104 ETEC Bioremediation

Introduction ETEC, LLC Providing bioremediation services since 1991
Started landfarming Exxon Valdez shoreline soil Been providing in situ treatments since 1997 Projects throughout North America include: Upstream Midstream Downstream Retail PHONE: x104 ETEC Bioremediation

Introduction - Technologies
For petroleum: Dissolved Oxygen In situ Treatment (DO-ITTM) Super-OxTM oxygenation equipment PetroBacTM biological products & CBNTM Nutrients PetroSolvTM biosurfactant For chlorinated solvents In Situ Delivery (ISDTM) groundwater recirculation equipment CarBstrateTM nutrient-amended, soluble substrate PHONE: x104 ETEC Bioremediation

Introduction – Role in Cleanups
Innovative Technology Provider ETEC is partner with remediation consultants Help provide setup & planning for remediation treatments Manufacture equipment & products for remediation Evaluate client-collected data Recommend treatment modifications Onsite assistance if requested ETEC is not An environmental consultant An installation contractor PHONE: x104 ETEC Bioremediation

Process Overview - Conceptual
Dissolved Oxygen In situ Treatment (DO-ITTM) The DO-ITTM system uses groundwater recirculation to distribute Dissolved oxygen Bioremediation amendments Nutrients & electron acceptors Surfactants Provide hydraulic control & capture Achieve mass balance requirements Combine multiple remediation technologies PHONE: x104 ETEC Bioremediation

3) Case Studies: Field applications of the technology/approach.
Roadmap Surfactants & Chemical Oxidants Oxygenated Water Nutrients Substrates (Electron Donors) REMEDIATION SUCCESS DEPENDS ON: Physical Contact Mass Balance 1) It’s All About Delivery!!! Why automated equipment systems provide powerful delivery platforms to support site-wide biological degradation of target contaminants. APPLICATION/ENGINEERING 2) Fundamentals of Enhanced In Situ Bioremediation: An overview of the laws that govern biological degradation of organic compounds. SCIENCE DIRECT CONTACT 3) Case Studies: Field applications of the technology/approach. RESULTS 8

Super-Ox ™ systems provide: 24/7 electron acceptor & amendment delivery Optimum contact via pore volume exchanges Managed in situ environment for accelerated microbial activity Hydraulic capture and plume control Gas Station UST UST Extraction well Bedrock Aerobic Bioremediation

Process Overview - Equipment
Super-OxTM Oxygenation Equipment Specifications 10-gpm recirculation rate 45-ppm dissolved oxygen process water Metering for biological products, nutrients, & surfactants Up to 12 customizable injection areas Up to 6 integrated groundwater pumps Activated carbon pre-treatment controls Fully weatherized 8’x10’ building 220V 100-amp PHONE: x104 ETEC Bioremediation

Super-OxTM Oxygenation Equipment PHONE: x104 ETEC Bioremediation

PHONE: x104 ETEC Bioremediation

Process Overview - Products
Biological Products PetroBacTM biological amendments Active cultures of hydrocarbon-degrading bacteria Enzyme enhancements to increase bioavailability CBNTM nutrients Supplies nitrogen, phosphorus & micronutrients Contains over 60% electron acceptors (nitrate, sulfate) PetroSolvTM Non-ionic surfactant for free-product & residual mobilization PHONE: x104 Surfactant-Enhanced Remediation

Setup – Site Characteristics
Active production pad - western North Dakota Older pad (est. 1989) with major release 2010 Site-wide LNAPL (0.01 – 1.9 feet) Operated LNAPL recovery system from Contaminant Concentrations LNAPL still present in 3 MWs (<0.2 feet) Benzene in groundwater (<500 µg/L to 5,000 µg/L) TPH up to 5 mg/L PHONE: x104 ETEC Bioremediation

Active production pad - western North Dakota Hydrogeology Silty clay from surface to 3-4 feet bgs Silty sand & gravelly sand from 9-15 feet bgs Lower confining unit Target Plume Zone Onsite infrastructure measures 250 feet x 175 feet Offsite infrastructure included MWs 100 feet downgradient Remediation Goals 5 µg/L benzene, 0.5 mg/L TPH PHONE: x104 ETEC Bioremediation

LNAPL Thickness PHONE: x104 ETEC Bioremediation

Benzene Concentrations PHONE: x104 ETEC Bioremediation

TPH Concentrations PHONE: x104 ETEC Bioremediation

Setup - Flow Rates Flow Rates Pilot study – 30 feet x 30 feet
1 well surfactant recirculation over 2 days RW-9 used for extraction Surrounding wells used for simultaneous injection Recirculated 3,000 gallons Flow rate observed was 3-gpm from one well Full-scale flow rate estimated to be 6- to 9-gpm (2 wells) PHONE: x104 ETEC Bioremediation

Setup - Infrastructure
Onsite Infrastructure Injection trenches Four 50-foot long injection trenches Gravel-lined & cover with impermeable barrier Installed 4-5 feet bgs (at top of the smear zone soil) Individually piped for flow control Recovery wells Utilized 2 existing recovery wells for process water Screened 3-15 feet bgs Originally used for LNAPL recovery system PHONE: x104 ETEC Bioremediation

Distal End 1st to treat offsite benzene, impacts to surface water Injection Trenches 50 ft long, 4-5 ft bgs. Retrofitted old recovery system piping/conduit 2 Extraction Wells Setup – Site Characteristics PHONE: x104 ETEC Bioremediation

Setup - Infrastructure

Setup - Mass Balance Contaminant Mass – Phase 1 area
TPH mass estimated at more than 500 lbs. TPH Using Contaminant Mass for Calculating Nutrient Needs Breakdown of 500 lb. of TPH requires 100 lb. nitrogen 25 lb. phosphorus Using Contaminant Mass for Calculating Electron Acceptor Needs 500 lb. TPH * 3 lb. O2 / 1 lb. TPH = 1,500 lb. oxygen 500 lb. TPH * 5 lb. NO3- / 1 lb. TPH = 2,500 lb. (nitrate/sulfate) PHONE: x104 ETEC Bioremediation

Setup - Obstacles Setup Obstacles
Miles of onsite piping for production activities Required compliance w/ Pipeline Corrosion Standard (4,000 µS/cm) ETEC installed metering system for biological products Testing to ensure injectate / groundwater did not exceed standard Limited infrastructure placement Inclement weather Robust weatherization Intermittent season operation PHONE: x104 ETEC Bioremediation

Operation - Process Startup 9/2014 Initial amendments applied
50 gallons of microbial consortium (PetroBacTM) 150 gallons of surfactant (PetroSolvTM) 500 lbs. nutrients (CBNTM) Monthly amendments applied 15 gallons of microbial consortium (PetroBacTM) 15 gallons of surfactant (PetroSolvTM) PHONE: x104 ETEC Bioremediation

Operation - Process Winter Shutdown 11/2014 Operated for 6 weeks
Average 3- to 5-gpm recirculation rate 225,000 gallons recirculated Added 85 lbs. dissolved oxygen Added 900 lbs. nitrate/sulfate Weekly site visits by consulting partner (1-2 hours) PHONE: x104 ETEC Bioremediation

Results Phase 1 - Downgradient Wells ETEC Bioremediation
Action Level 5 0.5 Date Benzene (µg/L) TPH-D (mg/L) MW-4 6/14/2012 1390 <0.21 12/5/2012 1280 <0.20 3/12/2013 1360 7/30/2013 857 NA Baseline 8/20/2014 344 <0.19 Shutdown 11/17/2014 <0.50 0.34 MW-11 617 974 199 8/21/2014 981 0.288 26.6 0.372 MW-12 3000 2870 6.7 0.52 0.279 PHONE: x104 ETEC Bioremediation

Phase 1 Implemented Phase 2 Implemented Phase 3 Planned Injection Trenches 50 ft long, 4-5 ft bgs. Retrofitted old recovery system piping/conduit 2 Extraction Wells Setup – Site Characteristics PHONE: x104 ETEC Bioremediation

Results Spring Startup 4/2015 Phase 1 & 2 implemented
Dewatered treatment zone due to dry conditions Operated when water was available Shutdown & weatherized 11/2015 Treatment will resume Spring 2016 PHONE: x104 ETEC Bioremediation

Summary Phase 1 – Excellent results in first 6 weeks of operation
Phase 2 in process Operation Successes Recirculated 225,000 gallons during 6 weeks operation Observed excellent distribution between injection/extraction wells Were able to add large masses of products while remaining below pipeline corrosion standard (µS/cm) Phase 1 & 2 will resume Spring 2016 PHONE: x104 ETEC Bioremediation

Summary Eric Bueltel, P.E. Project Manager - Colorado ETEC, LLC x104 PHONE: x104 Aerobic Bioremediation

Operation - Process Spring Startup 4/2015 Operated all summer
Dewatered treatment zone due to dry conditions Shutdown & weatherized 11/2015 Treatment will resume Spring 2016 PHONE: x104 ETEC Bioremediation

Bioremediation Setup e- Food (hydrocarbon) O2 CO2 H2O NO3- N2 Mn4+
Electron donor Electron acceptors: O2 NO3- Mn4+ Fe3+ SO42- CO2 CO2 H2O N2 MN2+ FE2+ H2S CH4 e- Respiration NUTRIENTS: N P K Trace Metals Biomass Mineralization

Bioremediation Setup Site Selection Geochemical ETEC Bioremediation
Field sampling – DO, ORP, pH, conductivity Nutrient sampling – Nitrogen, phosphorus, micronutrients Electron acceptor sampling – NO3-, SO42-, Mn2+, Fe2+ PHONE: x104 ETEC Bioremediation

Site Selection - Geochemistry
Dissolved Oxygen Typically 0-8 ppm depending upon temperature & organic material present Most preferred electron acceptor used by bacteria Usually 0-2 ppm at an un-enhanced sites PHONE: x104 ETEC Bioremediation

Oxidation-Reduction Potential (ORP) Varies from negative to positive Used to gauge electron acceptor presence & biological activity at impacted sites Usually < 0 mV at an un-enhanced sites PHONE: x104 ETEC Bioremediation

pH Determines if GW is acidic or basic Can vary at impacted sites depending upon geology Bacteria are most effective between SU pH can be adjusted prior to or during treatment PHONE: x104 ETEC Bioremediation

Conductivity A measure of ions present in solution High conductivity can inhibit growth Not common – bioremediation in ocean water (5 s/m) PHONE: x104 ETEC Bioremediation

Site Selection – Field Parameters Most important parameter - pH DO, ORP, & conductivity are good baseline measurements Initial measurements are useful for evaluation of treatment effectiveness PHONE: x104 ETEC Bioremediation

Site Selection - Nutrient Sampling Nitrogen Phosphorus Micro-nutrients PHONE: x104 ETEC Bioremediation

Nitrogen Used for building proteins & biomass Preferred form is ammonia-nitrogen Typically 0-1 mg/L at un-enhanced sites Makes up 20 % of bacterial biomass 1 lb. of N supports degradation of 5 lb. TPH PHONE: x104 ETEC Bioremediation

Phosphorus Used for building proteins & biomass Preferred form is ortho-phosphate Typically 0-1 mg/L at un-enhanced sites Makes up 5 % of bacterial biomass 1 lb. of P supports degradation of 40 lb. TPH PHONE: x104 ETEC Bioremediation

Micro-nutrients Used for building proteins & specialty functions Include sulfur, magnesium, copper, & other metals Typically <1 mg/L at un-enhanced sites Only a small amount is required Usually present at sufficient quantities PHONE: x104 ETEC Bioremediation

Electron Acceptors Used for bacterial respiration Bacteria are facultative, meaning they can use: Oxygen – O2 Nitrate – NO3- Sulfate – SO42- Manganese – Mn4+ Iron – Fe3+ Chromium & other metals PHONE: x104 ETEC Bioremediation

Dissolved Oxygen Most preferred for bacterial respiration Bacteria require 3 lb. of O2 to degrade 1 lb. TPH Difficult to provide large masses of O2 to GW Example: A site 100 ft. x 100 ft., with 10 ft. thickness contains 224,000 gallons At 8 ppm, 15 lb. of DO is present PHONE: x104 ETEC Bioremediation

Nitrate-nitrogen Second most preferred for bacterial respiration Typically depleted at impacted sites 0-2 mg/L Usually not naturally-occurring Bacteria require 5 lb. of NO3- to degrade 1 lb. TPH PHONE: x104 ETEC Bioremediation

Sulfate Less preferred for bacterial respiration Typically depleted at impacted sites 0-10 mg/L Naturally present within geology Bacteria require 5 lb. of SO42- to degrade 1 lb. TPH If sulfate is low, electron acceptors are being utilized & ORP < 0 If sulfate is high, electron acceptors are in abundance & ORP > 0 PHONE: x104 ETEC Bioremediation

Manganese Less preferred for bacterial respiration Soluble manganese is elevated at impacted sites 2-10 mg/L Naturally present within geology Insoluble manganese (Mn4+) is converted to soluble manganese (Mn2+) If soluble manganese is high, electron acceptors are being utilized & ORP < 0 If soluble manganese is low, electron acceptors are in abundance & ORP > 0 PHONE: x104 ETEC Bioremediation

Iron Less preferred for bacterial respiration Soluble iron is elevated at impacted sites mg/L Naturally present within geology Insoluble iron (Fe3+) is converted to soluble iron (Fe2+) If soluble iron is high, electron acceptors are being utilized & ORP < 0 If soluble iron is low, electron acceptors are in abundance & ORP > 0 PHONE: x104 ETEC Bioremediation

Site Selection - Geology
Needs to have some porosity – Its All About Delivery! Acceptable geology – from boring logs Clay mixtures Silt Sand Bedrock When in doubt, field test! Injection / extraction testing - 8+ hour PHONE: x104 ETEC Bioremediation

Site Selection - Contaminant Location
Determines the contaminant mass Site Maps Calculate the treatment area Used in contaminant mass calculation Helps plan for injection / extraction well locations Depth-to-water data Fluctuations determine smear zone thickness Helps plan for injection / extraction well screens PHONE: x104 ETEC Bioremediation

Site Selection - Contaminant Mass
Accurate TPH mass estimates determine nutrient & electron acceptor requirements TPH is important – represents the total contaminant mass (not just BTEX sampling!) Soil TPH sampling preferred - Total TPH mass can be inferred from GW sampling Must include groundwater & soil estimates Groundwater estimate example: 100 ft. * 100 ft. * 10 ft. = 100,000 ft3 soil/groundwater 100,000 cubic feet * 0.3 (porosity) * 28.4 L/ft3 = 852,000 L groundwater 852,000 L * 10 mg/L TPH / 454,000 mg/lb. = 19 lb. dissolved TPH PHONE: x104 ETEC Bioremediation

Soil estimate example: 100 ft. * 100 ft. * 10 ft. = 100,000 ft3 soil/groundwater 100,000 ft3 * 45 kg/ ft3 = 45,000,000 kg soil Koc * Foc * Cwater = Csoil (using Koc = 191 for gasoline, Foc = 0.01 soil organic content) 191 * 0.01 * 10 mg/L = 19.1 mg/kg 19.1 mg/kg * 45,000,000 kg soil / 454,000 mg/lb = 1,893 lb. adsorbed TPH PHONE: x104 ETEC Bioremediation

Using Contaminant Mass for Calculating Nutrient Needs Breakdown of 1,900 lb. of TPH requires 380 lb. nitrogen 95 lb. phosphorus Using Contaminant Mass for Calculating Electron Acceptor Needs 1,900 lb. TPH * 3 lb. O2 / 1 lb. TPH = 5,700 lb. oxygen 1,900 lb. TPH * 5 lb. NO3- / 1 lb. TPH = 9,500 lb. nitrate-nitrogen 1,900 lb. TPH * 5 lb. SO42- / 1 lb. TPH = 9,500 lb. sulfate PHONE: x104 ETEC Bioremediation

Site Selection – Site Restrictions
Physical Restrictions - buildings, utilities Determine what injection/extraction infrastructure to use Determine equipment type & operation Activity Restrictions – operating hours, traffic Determine time available onsite Funding Restrictions – A lot, a little, or none Determine pretty much everything else PHONE: x104 ETEC Bioremediation

Bioremediation Monitoring
Biological Monitoring Field data DO, ORP, pH DTW Nutrients Ammonia-nitrogen, ortho-phosphate Electron acceptors DO, nitrate-nitrogen, sulfate, manganese, iron Bacterial plate counts Heterotrophic Hydrocarbon-degrading PHONE: x104 ETEC Bioremediation

Field Data As an aerobic or oxidative treatment progresses DO Should increase on the periphery ( > 2 mg/L) May not increase in heavily impacted areas ORP Should become positive as electron acceptors are applied Increases represent an abundance of electron acceptors pH Should remain between SU PHONE: x104 ETEC Bioremediation

Nutrients As an biological enhancement treatment progresses Ammonia-nitrogen Should be increasing in periodic sampling ( > 2 mg/L) May be used rapidly in heavily impacted areas Used as a tracer to show nutrient transport Ortho-phosphate Should be present in periodic sampling ( > 0 mg/L) PHONE: x104 ETEC Bioremediation

Electron Acceptors As an aerobic / oxidative treatment progresses Nitrate-nitrogen Should be increasing in periodic sampling ( > 10 mg/L) May be used rapidly in heavily impacted areas Used as a tracer to show nutrient transport Sulfate Should be increasing in periodic sampling ( > 5 mg/L) Trend indicates the abundance or depletion of electron acceptors PHONE: x104 ETEC Bioremediation

Electron Acceptors As an aerobic / oxidative treatment progresses Soluble manganese Should be decreasing in periodic sampling ( < 2 mg/L) Reductions indicate an abundance of electron acceptors Soluble iron Should be decreasing in periodic sampling ( < 10 mg/L) PHONE: x104 ETEC Bioremediation

Bacterial Plate Counts As an aerobic / oxidative treatment progresses Heterotrophic plate counts Should be high in periodic sampling ( > 1,000 CFU/mL) Used as a qualitative measurement Grown on a 0.1% gasoline media, 14 day incubation PHONE: x104 ETEC Bioremediation

Bioremediation Adjustments
Field Data As an aerobic / oxidative treatment progresses Dissolved oxygen If low, apply more air, oxygen, or oxygenated water to area If high, continue application or redistribute to depleted areas ORP pH If > 8, apply acid to area (phosphoric acid) If < 5.5, apply base to area (sodium bicarbonate) PHONE: x104 ETEC Bioremediation

Nutrients As a biological enhancement treatment progresses Ammonia-nitrogen If low, apply more nutrients to area If high, continue application or redistribute to depleted areas Ortho-phosphate PHONE: x104 ETEC Bioremediation

Electron Acceptors As an aerobic / oxidative treatment progresses Nitrate-nitrogen If low, apply more nitrate-nitrogen or electron acceptors to area If high, continue application or redistribute to depleted areas Sulfate If low, apply more electron acceptors to area PHONE: x104 ETEC Bioremediation

Electron Acceptors As an aerobic / oxidative treatment progresses Soluble manganese If high, apply more electron acceptors to area If low, continue application or redistribute amendments to depleted areas Soluble iron PHONE: x104 ETEC Bioremediation

Bacterial Population As a biological enhancement treatment progresses Hydrocarbon-degrading plate counts If low ( < 1,000 CFU/mL), apply more oxygen, electron acceptors, nutrients, and possibly active cultures to area May be low due to low pH If the area is now clean, plate counts will be low (Yeah!) PHONE: x104 ETEC Bioremediation

Bioremediation Treatments
Activated Carbon with Bioremediation Supplies carbon to adsorb contaminants from GW Can capture 1-35% by weight TPH Granular, insoluble Treats groundwater as it contacts the carbon Simple application – inject & monitor Mass balance To adsorb 1,900 lb. TPH 1,900 lb. TPH / 1% adsorption = 190,000 lb. carbon 1,900 lb. TPH / 35% adsorption = 5,400 lb. carbon PHONE: x104 ETEC Bioremediation

Activated Carbon with Bioremediation Limitations “If we rely entirely on the adsorptive capacity of AC to remediation NAPLs, we see that it may be impractical to inject enough CBI (carbon-based injectates) to fully adsorb free-phase liquids.” – Thomas B. Lewis, P.E. Does not destroy contaminants, only adsorbs Limited by amount that can be applied in initial application Does not distribute away from the injection points Absolutely must contact contaminants in GW Does not actively treat the large mass of soil adsorbed contamination Does not contain nitrogen or phosphorus PHONE: x104 ETEC Bioremediation

Activated Carbon with Bioremediation Mass balance Contains 19% gypsum (calcium sulfate) Calcium sulfate contains 56% sulfate Activated carbon/gypsum products contain 11% sulfate To biologically treat 1,900 lb. TPH 1,900 lb. TPH * 5 lb. sulfate / 1 lb. TPH = 9,500 lb. sulfate 9,500 lb. sulfate / 11% sulfate in product = 86,000 lb. product Calcium sulfate solubility is very low (0.24 g/100 mL) indicating much of the sulfate mass is not bioavailable This would require much more product to biologically degrade the TPH mass Product composition information provided from RPI Boss 200 MSDS PHONE: x104 ETEC Bioremediation

Direct Injection Supplies electron acceptors, nutrients, & cultures Can apply large masses of nitrate or sulfate Minimal site disturbance Geoprobe can be used – dedicated injection wells preferred for ongoing injections Limitations ROI of wells may be limited May require many injections to provide the correct mass balance PHONE: x104 ETEC Bioremediation

Direct Injection PetroBacTM Product Bundle Hydrocarbon-degrading consortium reduces lag-phase growth period, nuisance bacteria 3-strain consortium designed for oil, diesel, BTEX, and MTBE Also contains enzyme enhancements CBNTM Custom Blend NutrientsTM Contains ~60% electron acceptors (nitrate and sulfate) N, P, K, and micronutrient blend in correct microbial ratio (100:20:5) Fully Soluble Aerobic Bioremediation

Direct Injection Mass balance Contains 60% NO3-SO4 along with N, P, & bacterial cultures To biologically treat 1,900 lb. TPH 1,900 lb. TPH * 5 lb. NO3-SO4 / 1 lb. TPH = 9,500 lb. NO3-SO4 9,500 lb. NO3-SO4 / 60% NO3-SO4 in CBNTM = 15,800 lb. CBNTM ETEC’s CBNTM Nutrient is 100% soluble Provides all the necessary nutrients & enhancements PHONE: x104 ETEC Bioremediation

Air Sparging / Biosparging Supplies oxygen to the groundwater & vadose soil Can apply large masses of dissolved oxygen Simple equipment operation Couples with biological enhancement for efficient bioremediation Limitations ROI of wells may be limited Preferential pathways will form PHONE: x104 ETEC Bioremediation

Air Sparging / Biosparging Setup Make sure DO is present in monitoring wells Check screen intervals of AS/SVE wells Incorporate dedicated injection wells screened across the smear zone Ensure adequate volumes of product can be applied Mass balance If AS is setup well, O2 will be the abundant electron acceptor To biologically treat 1,900 lb. TPH 1,900 lb. TPH * 0.2 lb. nitrogen / 1 lb. TPH = 380 lb. nitrogen 1,900 lb. TPH * 0.05 lb. phosphorus / 1 lb. TPH = 95 lb. phosphorus PHONE: x104 ETEC Bioremediation

Product injection using existing infrastructure Combines physical removal w/ biological treatment (polishing) GW & smear-zone treatment Cheap addition – breathes new life into old systems! Soluble products are a MUST! Product Mixing Tank Vapor Treatment System Blower / compressor Vacuum pump / blower Aerobic Bioremediation

Biological enhancement period w/ air sparging

Surfactants, or surface-active agents, are chemical compounds that have the potential to alter the properties of fluid interfaces. Surfactant usage dates back to the 1960s when sulfonate surfactants attained widespread use for enhanced oil recovery efforts. Use in environmental applications dates to the 1980s. Surfactants are composed of a strongly hydrophilic (water loving) group, and a strongly hydrophobic (water fearing) group Hydrophilic “head” group Hydrophobic “tail” group PHONE: x104 Surfactant-Enhanced Remediation

Surfactant-flushing Key Activities GW Elevation Surfactant injection when smear zone is submerged Optimum contact with sorbed fuel & trapped NAPL Subsurface Agitation & Pressure Injection Vigorous surging (surge block) forces surfactant thru NAPL-saturated soil Localized soil washing = larger and larger contact ROI for surfactant Hydraulic Control Fluid Recovered > Fluid Injected Active GW extraction = capture zone, enhanced in situ distribution Post-injection Bioremediation Provides long-term remediation process, abates 5-25 equiv. gallons of fuel Minimal Cost (less than 10% of overall injection event cost) PHONE: x104 Surfactant-Enhanced Remediation

PetroSolv™ BioSurfactant Biodegradable, non-ionic Concentrated, applied at 1-10% concentrations Effective on gasoline, diesel, and fuel oils Available in small quantities or large bulk quantities (5-gal, drums, totes) PHONE: x104 Surfactant-Enhanced Remediation

GW/Surfactant/NAPL Holding Tank Nutrient Solution Mixing Tank N, P, K Electron Acceptors Surfactant Solution Mixing Tank Ground Surface VADOSE ZONE N,P,K Emulsion Emulsion SATURATED ZONE

HISTORY: Diesel Fuel in UST Cavity DIESEL NAPL THICKNESS : ’ in UST OWs & 1-2’ in dwngrdt. MWs LITHOLOGY: Silty Clay & Clayey Silt underlain by fractured bedrock DTW: ’ bgs PLUME: 60’ x 50’ GOALS: Remove NAPL to < 0.01’ in all site wells Surfactant-Enhanced Remediation

NAPL fully removed from all site wells with 1 pilot- scale and 2 full- scale events No NAPL rebound No residual dissolved VOC/PAH constituents Site Received NFA in 2011 ft.

3) Case Studies: Field applications of the technology/approach.
Roadmap Surfactants & Chemical Oxidants Oxygenated Water Nutrients Substrates (Electron Donors) REMEDIATION SUCCESS DEPENDS ON: Physical Contact Mass Balance 1) It’s All About Delivery!!! Why automated equipment systems provide powerful delivery platforms to support site-wide biological degradation of target contaminants. APPLICATION/ENGINEERING 2) Fundamentals of Enhanced In Situ Bioremediation: An overview of the laws that govern biological degradation of organic compounds. SCIENCE DIRECT CONTACT 3) Case Studies: Field applications of the technology/approach. RESULTS 84

Dissolved Oxygen In situ TreatmentTM – DO-ITTM Advantages of Groundwater Recirculation: Direct hydraulic influence & capture Facilitate distribution of tons of enhancements Programmable automation = constant delivery Remediate under roads/buildings Retrofit P&T/MPE systems - utilize existing wells Shorter remedial timeframes (1-3 years) via rapid contact PHONE: x104 ETEC Bioremediation

DO-IT™ System Layouts: GW Extraction: Sub. Pumps or DPE/MPE Pre- Treatment: OWS, GAC, Air Stripper Holding Tank Super-OxTM Unit Injection Wells Large-Scale Recirc. Units w/ Walk-in Enclosures (10-, 20, & 40-gpm systems) Small-Scale/Short –Term Recirculation Systems Recirculation Systems

Super-Ox ™ systems provide: 24/7 electron acceptor & amendment delivery Optimum contact via pore volume exchanges Managed in situ environment for accelerated microbial activity Hydraulic capture and plume control Gas Station UST UST Extraction well Bedrock Aerobic Bioremediation

In situ “banded” zones: Aerobic degradation Nitrate- reducing conditions Sulfate- reducing conditions Controlled environment with nutrient availability Aerobic Bioremediation

Dissolved Oxygen In situ TreatmentTM – DO-ITTM Requirements for success Adequate injection & extraction infrastructure 1- to 40-gpm extraction rate Incorporate dedicated injection wells screened across the smear zone Ensure adequate volumes of product can be applied Mass balance If recirculation rate is high, O2 will be the abundant electron acceptor If recirculation rate is low, O2 & NO3- will be the electron acceptors PHONE: x104 ETEC Bioremediation

Dissolved Oxygen In situ TreatmentTM – DO-ITTM Mass balance Uses O2 & NO3- as the electron acceptors At 10-gpm flowrate, 500 lbs. CBNTM per month 162 lb. DO per month (54 lb. TPH degradation) 300 lb. NO3- per month (60 lb. TPH degradation) To biologically treat 1,900 lb. TPH 1,900 lb. TPH / 114 lb. TPH / month = 17 months Requires 7 million gallons water, 8,500 lb. CBNTM, 200 gallons PetroBacTM product This treatment also applies nutrients, active cultures, & surfactants PHONE: x104 ETEC Bioremediation

GW BTEX: Free- product gasoline (MW-33, MW-34) GW BENZENE: 35,000 ppb (MW-13) LITHOLOGY: silty sand with semi-confining silt/clay horizons DTW: 13-18’ bgs PLUME: 250’ x 100’ GOALS: BTEX/Benzene reductions INFRASTRUCTURE: Existing MPE Network 12 Injection wells Extraction wells Injection Area #3 Injection Area #1 Injection Area #2 Aerobic Bioremediation

Groundwater Recirculation – Case Study System operation 24-Month system operation Electron acceptor delivery: 3 million gallons of 45 ppm DO = 1,200 lbs. of O2 from Super-OxTM 1,000 lbs. Initial lbs x 23 mo. = 12,500 lbs. CBN™ (7,500 lbs. NO3-SO4) TPH Degradation: Aerobic degradation via DO = 400 lbs. Anaerobic degradation via nitrate/sulfate = 1,500 lbs. TOTAL: 2,900 lbs. in 24 months Costs: Super-OxTM Installation & Rental: $72,000 Amendment Costs: $61,000 PHONE: x104 ETEC Bioremediation

Startup Shutdown Restart

Observations from the Treatment MW-34 99% BTEX reduction MW-13 92% BTEX reduction 98% benzene reduction Appeased stakeholder with minimal disturbance Stream locations were below 50 ppb benzene in 21 months PHONE: x104 Aerobic Bioremediation

In situ “banded” zones: Aerobic degradation Nitrate- reducing conditions Sulfate- reducing conditions Controlled environment with nutrient availability Aerobic Bioremediation

Quality products (and correct masses) + The right application GW recirculation Direct injection Air sparge enhancement Excavation / pit application Landfarming / biopiles Biosurfactants / chem-ox + Ongoing data interpretation Treatment modifications = Successful Cleanups! Eric Bueltel, P.E. Project Manager ETEC, LLC x104 PHONE: x104 Aerobic Bioremediation

PRESENTER: Eric Bueltel, P.E.

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