Highly Successful ERD Pilot Evaluation

Utilizing a Simple Additive Delivery Approach

Kent C. Armstrong – BioStryke® Remediation Products, LLCP.O. Box 254, Andover, NH USA; Brampton, Ontario CDN

James Romeo PG – Partner Engineering & Science, Inc.Altamonte Springs, FloridaInternational Petroleum Environmental ConferenceDenver, Colorado November 2015

Stennis Space Center (SSC), Hancock County, Mississippi

Southern Edge of the Gulf Coastal Plain Approximately 55 miles NE of New Orleans, Louisiana Approximately 36 miles West of Biloxi, Mississippi

Historical equipment cleaning and disposal practices contributed to groundwater contamination at SSC

10 Contaminant-of-Concern (COC) Trichloroethylene (TCE)

Concentrations of [TCE] exceeding compliance standards detected at 5-separate locations

Performed on-site PRS Based and microcosm evaluations

Project Background

Evaluations to determine efficacy and feasibility of biostimulation as a residual source mass site strategy [TCE] at depths ranging from 7 to over 90-ft bgs Four Pump-and-Treat (P&T) systems currently operating NASA estimates cleanup timelines to exceed 20-years

P&T systems currently reaching asymptotic conditions Unable to remove remaining residual contaminant mass effectively Recent independent evaluations determined little to no-effect over

last 5-years of operations NASA and independent consultant believe both cleanup duration

and costs of current P&T grossly underestimated

Project Background

Pro’s & Con’s of Bioremediation

Ideal Situation Accessible impact zone Time constraints minimal Homogeneous stratigraphic conditions

Appropriate with Remedial Design Considerations Heterogeneous matrix, silty/clay soil, fractured bedrock Residual DNAPL, cVOC and non-cVOC mixture Highly aerobic overburden

Inappropriate without Physical Removal Pooled DNAPL Source Zone Time is of the essence

Nourishes, stimulates native microbial populations

Eliminates above ground support equipment

Minimizes off-site removal, fuel and energy costs

Eliminates nuisance noise, emissions and vapors

Expedites residual source mass solubilization

Increases contaminant bioavailability

Facilitates cost-effective Long-Term Compliance

Benefits to Biostimulation

minimize the impact of remediation

cVOC Biotransformation Pathway

NASA and independent consultant (ITB, Inc.) desire alternative remedial strategy to optimize current cleanup strategies at SSC

Conduct field based biostimulation demonstration Utilize additive filled Passive Release Sock (PRS) deployment units Amended Area D Water Bearing Unit 3 (WBZ 3)

Evaluation ObjectivesField Evaluation

Utilized Monitoring Well 06-12MW 4-inch OD test well; depth to water

≈27ft Total depth of well ≈92-ft w/10-ft

screened interval at bottom Determine potential for native

microbial populations to degrade TCE effectively

Data gathered assists other NASA sites

Performed independent microcosm evaluation (CB&I)

Confirm field results supported by laboratory results Compare two additives efficacy as sole electron donor Included augmentation and amendment addition

Evaluation ObjectivesMicrocosm Evaluation

Compared ERDENHANCED™ to Lactate Each microcosm started with additive

concentration of 1.35 g/L Augmented with SDC-9 Dehalococcoides sp.

at 1 x 107 cells/ml Site groundwater spiked with ≈45 mg/L

[TCE] 10-day evaluation period

Pilot Study Microcosm EvaluationERDENHANCED®

NASA Stennis Space Station - Mississippi

• Evaluation performed by CB&I, Lawrenceville, NJ

Pilot Study Microcosm Evaluation OneERDENHANCED™

NASA Stennis Space Station - Mississippi

Lactate did not yield complete biotransformation during evaluation period

Day 1 Day 3 Day 5 Day 7 Day 100

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Lactate

TCE DCE VC

µg/L

• ≈97.8%REDUCTION by day-10

• An increase to 17,000 ug/L [cis-DCE] by day-7; followed by,

• 19.0%REDUCTION [cis-DCE] from peak bioavailability at evaluation end

• Increases in [VC] start at day-7 with continued upward trend at evaluation end

• Increases in [VC] without reduction may result in 20 contaminant and compliance issues

Lactate amended microcosm realized:

Pilot Study Microcosm EvaluationERDENHANCED™

NASA Stennis Space Station - Mississippi

µg/L

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BioStryke® Faster, Safer Biotransformation of cVOC contaminants

• BioStryke® ERDENHANCED® realized:

• >99.99% REDUCTION [TCE] by day 5

• Overall >93.3% reduction in [cis-DCE]

• Initial 2,300% increase at day 5

• >71% than lactate microcosm

• >99.7% reduction from peak bioavailability at evaluation end

• A four order-of-magnitude increase [VC] at day-7 of the evaluation

• >99.99% reduction in [VC] at day-10

• Complete parent destruction with twice the daughter production and subsequent complete destruction

Over 10-day microcosm study

NASA and independent consultant (ITB, Inc.) desire alternative remedial strategy to optimize current cleanup strategies at SSC

Conduct field based biostimulation demonstration Utilize additive filled Passive Release Sock (PRS) deployment units Amended Area D Water Bearing Unit 3 (WBZ 3)

Evaluation ObjectivesField Evaluation

Utilized Monitoring Well 06-12MW 4-inch OD test well; depth to water

≈27ft Total depth of well ≈92-ft w/10-ft

screened interval at bottom Determine potential for native

microbial populations to degrade TCE effectively

Data gathered assists other NASA sites

Site Plan – Area D

Direction of GW

Background ConditionsStennis Space Station Area D: 06-12MW

Deep Groundwater Bearing Unit Historical non-compliant [TCE]

Ranging from >50 ug/L to ≈2,000 ug/L

Asymptotic over time

Indicative of residual source mass

Limited daughter production

No [Vinyl chloride] or [Ethene] recorded over entire period

P&T systems effectiveness limited

In terms of performance In terms of long-term cost

Well-ID Date [TCE][cis-DCE]

[VC]

06-12MW

2007 69 12 ND

2008 1,201 233 ND

2009 186 16 ND

2010 1,259 177 ND

2011 1,893 331 ND

2012 1,017 99 ND

2013 154 13 ND

MCL (µg/L) 5 70 2

PRS Evaluation ProcessDetermine Additive Efficacy Under Real Biogeochemical

Conditions

Utilize Passive Release Sock (PRS) deployment units

Low-Risk, Low-Cost alternative to lab based evaluations

Performed under actual Site biogeochemical conditions

ORP, DO, pH, Temp, Cond; NO3, SO4, diss. Mn/Fe Ethane, Methane, Ethene, and Contaminants of Concern

Field indicator parameters monitored and recorded each replacement event

Provides Representative ‘Go-no-Go’ on-Site Evaluation

Baseline & Performance Monitoring/Sampling

PRS replacement events every 6-8 weeks 7 replacement events over 15 month evaluation Performance sample collection/analysis each event Non-purge, low-flow sampling protocols

Well withdeployed PRS

Ground surface

Groundwater Flow Direction

Additive slowly dissolves into casing volume of test well

PRS unit acts as a wicking agent to manage additive delivery

Pilot Study ProgramBenefits - Limitations

Non-Scalable, PRS Pilot Study Generates Limited AOI

Typically < 2 meters

Confirm Additive Efficacy prior to Full-Scale Commitment

Confirms presence/absence dehalorespiring bacteria

Easily combined with BioTrap® and/or other evaluation tools

Non-purge sampling otherwise skews results

Removes amended groundwater Removes enhanced microbial populations

Helps identify presence/absence of residual mass and, provides go no-go based results

Utilizes casing volume of well as ‘laboratory microsm’

Overall 94.8%REDUCTION [TCE] over 15-month evaluation

>99.99% continuous reductions in [TCE] from months T7-T10

Overall 79.3%REDUCTION [cis-DCE] over 15-month evaluation

Initial 85.7% reduction at month 4

>1,530% increase by month 8

>91.1%REDUCTION [CIS-DCE] from peak bioavailability at end

Consistent decrease in ORP values (from +69 to -191mV)

No [VC] or [Ethene] recorded

Changes in concentrations of cVOC contaminants

ERDENHANCED™ PRS Pilot StudyNASA Stennis Space Station - Mississippi

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[TCE] [cis-DCE] ORP

Moles/L P:D Ratio

Final PRS Deployment

As TCE molecules are respired, moles TCE drop 100% in ≈8

mos.

Similarly, moles DCE drop 86% in ≈4 months; afterwards,

>1,500% increase moles DCE next 4 months

Moles DCE decrease 91% from peak bioavailability

Overall molar decrease TCE 94.8% DCE 79.3%

Parent Daughter Ratio Confirms biotransformation of

cVOC contaminants

NASA ERDenhanced™ Field Evaluation Results

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Moles TCE Moles DCE

P:D Ratio Linear (P:D Ratio)

ERDENHANCED™ PRS Pilot StudyNASA Stennis Space Station - Mississippi

Final PRS Deployment

Contaminant Reduction but NO Destruction?

The importance of molar comparisons

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g-13

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%Moles TCE vs. Sulfate and [TCE]

[TCE] P:D Ratio Sulfate

Potential Start of Biotic Activity

Period of No Biotransformation of Parent TCE Contaminant

Parent Daughter Ratio No Change in P:D Ration Regardless of [SO4] or [TCE]

ERDENHANCED™ PRS Pilot StudyNASA Stennis Space Station - Mississippi

1-Jul-13 1-Aug-13 1-Sep-13 1-Oct-13 1-Nov-13 1-Dec-13 1-Jan-14 1-Feb-14 1-Mar-14 1-Apr-14 1-May-14 1-Jun-140

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Diss Fe ORP Diss Mn

mg/L mV• 4 Order-of-Magnitude

increase in [dissolved Fe]

• >98.3% decrease [diss. Fe] from peak availability

• >3,000% increase [dissolved Manganese] at month

• >85.7% decrease [diss. Mn] by evaluation end

• 30,000% increase [Sulfate] by month 6; complete depletion by end of evaluation period

• Sustained decrease in ORP, general increases [Methane]

Geochemistry; 20 lines of evidence supporting biotic reductive

dechlorination

Conclusions

Demonstrated biostimulation cost-effective strategy

ERDENHANCED® amended microcosm superior performance

Field evaluation data supported complete cVOC biotransformation

Current estimations place biostimulation capable of obtaining sustainable reducing conditions and 3-5 year compliance timeline

From results of Treatability evaluation determine full-scale loading and site requirements

PRS study proved effective as ‘Go no-Go’ evaluation process

2016 proposed on-site treatability evaluation

DPT injection of ERDenhanced about performance well Confirm subsurface distribution capabilities Determine transferability of PRS and Microcosm

studies

Site currently undergoing additional characterization

Thank You ?? Questions ??

BioStryke Remediation Products, LLCP.O. Box 254, Andover NH

www.biostryke.com603.731.3159 karmstrong@biostryke.net