surfactant enhanced remediation technologies and · sepr & s‐isco treatment of creosote site...

Dan SocciEthicalChem

Surfactant Enhanced Remediation Technologies and Case Studies

www.vertexenvironmental.ca

SMART RemediationOttawa, ON

February 4, 2016

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Surfactant Enhanced Remediation Technologies and Case Studies

Dan Socci, CEO

A division of Ethical Solutions LLC

ETHICALCHEM BACKGROUNDGreen Chemical Solutions for Environmental Remediation

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EthicalChem Background

Optimized plant‐based surfactants for enhanced in situ remediation technologies

Surfactant Enhanced Product Recovery

(SEPR)

Surfactant‐enhanced In Situ Chemical Oxidation

(S‐ISCO)

Bulk free phase removal – creosote,DNAPL, LNAPL

Oxidation of heavy hydrocarbon contamination on soil

EthicalChem Background

• EthicalChem –

– Chemical company serving environmental and oil production industries

– Flexible business model provides any or all of:

• Chemical products

• Treatability studies

• Treatment design

• Implementation assistance

• Implementation prime contracting

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SEPR Technology

Surfactant Enhanced Product Recovery (SEPR)

– Proprietary plant based surfactant blend with low doses of hydrogen peroxide

– Bubbles generated from peroxide decomposition provide physical agitation to loosen NAPL

– Enables efficient recovery of Non‐Aqueous Phase Liquid (NAPL) contamination, including creosote

SEPR Performance

• Bulk, free phase NAPL present in subsurface

• SEPR fluid injected

• Surfactants desorb and emulsify NAPL

• Gas bubbles generated from peroxide

• Help facilitate movement to recovery wells

• Residual contamination may remain

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S‐ISCO Technology

Surfactant‐enhanced In Situ Chemical Oxidation (S‐ISCO)

– Combined proprietary surfactant blend & oxidant injection

– Use of the oxidant best suited for site (Klozur, peroxide, etc)

– Addresses contamination sorbed on soil

– Provides clean soil and groundwater

– Avoids contaminant rebound

S‐ISCO Performance

• Sorbed contaminants on soil and in soil pores

• Surfactant and oxidant introduced into groundwater

• Sorbed contaminants are emulsified into aqueous phase

• Thorough removal of contamination – no rebound

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Emulsification and Surface Area

Volume: 50 cubic feetSurface area: 220 square feet

10’

0.5’

10’

Volume: 50 cubic feetEmulsion Diameter: 1 millimeterSurface area: 91,440 square feetApproximately 2.5 orders of magnitude higher

Volume: 50 cubic feetEmulsion Diameter: 1 micrometerSurface area: 91,493,000 square feetApproximately 5 orders of magnitude higher

Emulsions increase interface area between oxidant andcontaminant by several orders of magnitude

Groundwater

NAPL

Combined SEPR/S‐ISCO Technology

• NAPL contamination • Proprietary surfactant blend and low doses of peroxide are injected• Surfactant desorbs and lowers viscosity of NAPL• Gas generated from peroxide helps loosen NAPL for extraction

• VeruSOL® and oxidant are injected simultaneously• VeruSOL® emulsifies residual NAPL into fine particles, increasing surface area exposed for oxidation

• Clean soil and groundwater

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CASE STUDY EXAMPLES

SEPR & S‐ISCO Treatment of Creosote

SiteFormer Wood Treatment Facility, Bridgeville, DE

Contaminants of ConcernCreosote DNAPL

ObjectivesFull‐scale soil remediation

Remedial Implementation SEPR & S‐ISCO

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Site Background

• Lumber Treating Facility (1963 – 1986)

• DNREC‐Hazardous Substances Cleanup Act (HSCA) Program

• Creosote waste oil & condensate water was gravity‐fed into unlined waste lagoon

• Lagoon was excavated in 1986 but the vertical extent of NAPL was greater than originally reported


Remedial Design

Observations of free product and/or residual DNAPL in soil borings were used to define the area of the DNAPL plume in each 1‐ft interval from 6 to 15 ft below ground surface (bgs).

• Target Treatment Area:

o 4,000+ gal of creosote DNAPL o 200 ft X 60 ft X 15 ft bgs.

• Treatment:

o SEPR to remove DNAPLo S‐ISCO to remove residual contamination

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Implementation:

• SEPR – 8 weeks• Hydrogen Peroxide (up to 4%)• Surfactant (5 – 30 g/L)• Extraction of 8,000 gal of DNAPL and fluid

• S‐ISCO – 8 weeks• VeruSOL (5 – 10 g/L)• Hydrogen Peroxide (4 – 8%) • Klozur Sodium Persulfate (50 – 100 g/L)


Pre SEPRNo Product

Recovery; Clear Samples

Day 1 Product + Emulsion Recovered

Day 2 Increased Product Recovery

Day 3 Product Flow

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Late Stage of SEPR Treatment / Pre‐S‐ISCO Treatment

End of S‐ISCO Treatment


0

200

400

600

800

1000

1200

1400

1600

1800

6‐7 7‐8 8‐9 9‐10 10‐11 11‐12 12‐15

Volume Creosote (gal)

Depth Interval (ft)

Pre‐ and Post‐Treatment Creosote Volumes

Pre‐Treatment CreosoteVolume (gal)

Post‐Treatment CreosoteVolume (gal)

85% 86%

95%

73%

58% 18% 81%

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Result Summary

• 81% of DNAPL was removed from treatment area

• Site objective achieved and closure expected

• Cost of remediation <$100/cubic yard• Less than 1/3 the cost of CA identified alternative ‐

thermal desorption followed by bioremediation.

S‐ISCO Remediation of Coal Tar

NYC Brownfield Site

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MGP Coal Tar Remediation in NYC

SiteFormer Roofing Products Manufacturer

Contaminants of ConcernBTEX, PAHs, & naphthalene

ObjectivesReduce contaminant mass to enable issuance of Certificate of Completion

Remedial Implementation S‐ISCO


• Site Conditions: – Former roofing manufacture site

– ~41,000 lb contamination

– BTEX, PAHs, naphthalene

– NAPL

– Heterogeneous subsurface

• Challenges:– Adjacent to East River

– Dense urban neighborhood

– Weather

– NAPLNorthern edge of site boundary ~ 100 ft from high‐rise, luxury residential building

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Treatment Details:

• S‐ISCO Implementation

VeruSOL

Klozur Sodium Persulfate

Sodium Hydroxide

Total injected volume = 1,201,900 gal

100 days of injections

• RemMetrikSMprocess to quantify & target contamination

• Wavefront Technology’s Primawave Pressure‐Pulsing Sidewinder


Implementation Monitoring:

Weekly Monitoring Results:

• No NAPL mobilization

• No vapor pressure increases

• Reduced soil gas concentrations

• No nuisance complaints

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Results

• Soil: EXCEEDED CLEANUP OBJECTIVE– Destroyed > 90% Contaminant Mass (PAHs + BTEX)

• Groundwater: EXCEEDED CLEANUP OBJECTIVE– Reduced GW Concentrations;

• 91% BTEX

• Soil Gas: FULLY REDUCED SOIL GAS CONTAMINANTS

– 100% of benzene, ethylbenzene, naphthalene


Certificate of Completion, New York State DEC, • Construction of a 22,000 square foot

community library has begun at the site and is anticipated to be completed in 2017

Photo Courtesy – stevenholl.com

Photo Courtesy –qns.com

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FREQUENTLY ASKED QUESTIONS

FAQs: Mobilization

Question: How is contaminant mobilization managed during S‐ISCO treatments?

Answer:• During S‐ISCO the surfactant and oxidant are injected together as a homogeneous solution

• Injected chemistry travels together through subsurface• Emulsification and oxidation take place simultaneously• Average groundwater speeds do not carry emulsion offsite prior to

destruction

• Monitoring plans & contingency measures provide added protection for sensitive receptors

Question: How is contaminant mobilization managed during S‐ISCO treatments?

Answer:• During S‐ISCO the surfactant and oxidant are injected together as a homogeneous solution

• Injected chemistry travels together through subsurface• Emulsification and oxidation take place simultaneously• Average groundwater speeds do not carry emulsion offsite prior to

destruction

• Monitoring plans & contingency measures provide added protection for sensitive receptors

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FAQs: Mobilization

• S‐ISCO chemistry travels together• Data from an on site monitoring well during and after injections• S‐ISCO chemistry travels together• Data from an on site monitoring well during and after injections

0

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0.0

5.0

10.0

15.0

20.0

25.0

30.0

9/29/10 11/18/10 1/7/11 2/26/11 4/17/11 6/6/11 7/26/11

TPH (mg/L)

Persulfate (g/L) / VeruSO

L (g/L)

S‐ISCO Chemistry Tracking at a Monitoring Well within Injection Area

VeruSOL

Persulfate

TPH

Maximum SP detected = 27 g/L

Maximum TPH detected = 215 mg/L

Maximum VeruSOL detected = 18 g/L

Injection Period Post Injection Monitoring

Monitoring Well Data

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50

100

150

200

250

300

0

5

10

15

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25

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9/29/10 11/18/10 1/7/11 2/26/11 4/17/11 6/6/11 7/26/11

TPH (mg/L)

Persulfate (g/L) / VeruSO

L (g/L)

S‐ISCO Chemistry Tracking at a Monitoring WellDown‐gradient

VeruSOL

Persulfate

TPH

Maximum TPH detected = 24 mg/L

Maximum VeruSOL detected = 1.1 g/L

Maximum SP detected = 2.9 g/L

Injection Period Post Injection Monitoring Period

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FAQs: Mobilization

Projection of two emulsions, traveling vs. destructionProjection of two emulsions, traveling vs. destruction

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500

1000

1500

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2500

3000

3500

0 10 20 30 40 50 60

TPH (m

g/L)

Groundwater Movement (ft)

Theoretical Projection of Potential Emulsified Contaminant Movement During Oxidation with 0.5 ft/day Seepage Velocity

Emulsion oxidation of coal tar contamination

Emulsion oxidation of MGP Contamination

10mg/L by 43 ft

10mg/L by 51.5 ft

FAQs: Surfactant/Oxidant Interaction

Question: Do the surfactants compete with contaminants to consume oxidants?

Answer:

o Contaminants oxidized first

o Surfactant oxidation is minimal while contaminant is present

Question: Do the surfactants compete with contaminants to consume oxidants?

Answer:

o Contaminants oxidized first

o Surfactant oxidation is minimal while contaminant is present

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30

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11/22 12/12 1/1 1/21 2/10 3/2 3/22 4/11 5/1 5/21

IFT (m

N/m

)

Evaluation of Surfactant Over Time During Oxidation With and Without ContaminantInterfacial Tension (IFT) Over Time

VeruSOL with SP

VeruSOL, SP, and NAPL Increase in IFT indicates destruction of surfactant

Stable, low IFT indicates stable presence of surfactant

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S‐ISCO/SEPR Summary

• Optimized Surfactant/Oxidant Treatments Provide:

– Clean soil & groundwater

– Avoid rebound

– Are effective for a broad range of organic contaminants

Thank you.

EthicalChemUSA

www.ethicalchem.com

surfactant enhanced remediation technologies and · sepr & s‐isco treatment of creosote site...

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