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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SEPR & S‐ISCO Treatment of Creosote
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
SEPR & S‐ISCO Treatment of Creosote
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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SEPR & S‐ISCO Treatment of Creosote
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)
SEPR & S‐ISCO Treatment of Creosote
Pre SEPRNo Product
Recovery; Clear Samples
Day 1 Product + Emulsion Recovered
Day 2 Increased Product Recovery
Day 3 Product Flow
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SEPR & S‐ISCO Treatment of Creosote
Late Stage of SEPR Treatment / Pre‐S‐ISCO Treatment
End of S‐ISCO Treatment
SEPR & S‐ISCO Treatment of Creosote
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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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SEPR & S‐ISCO Treatment of Creosote
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
MGP Coal Tar Remediation in NYC
• 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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MGP Coal Tar Remediation in NYC
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
MGP Coal Tar Remediation in NYC
Implementation Monitoring:
Weekly Monitoring Results:
• No NAPL mobilization
• No vapor pressure increases
• Reduced soil gas concentrations
• No nuisance complaints
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MGP Coal Tar Remediation in NYC
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
MGP Coal Tar Remediation in NYC
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
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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 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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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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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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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