Surfactant Enhanced Remediation Technologies and Case Studies. Dan Socci EthicalChem. SMART Remediation Ottawa, ON February 4, 2016

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1 Surfactant Enhanced Remediation Technologies and Case Studies Dan Socci EthicalChem SMART Remediation Ottawa, ON February 4, 2016 SMART is Powered by:

2 A division of Ethical Solutions LLC Surfactant Enhanced Remediation Technologies and Case Studies Dan Socci, CEO Green Chemical Solutions for Environmental Remediation ETHICALCHEM BACKGROUND 1

3 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 2

4 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 3

5 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 4

6 Emulsification and Surface Area Emulsions increase interface area between oxidant and contaminant by several orders of magnitude NAPL Groundwater 10 Volume: 50 cubic feet Surface area: 220 square feet Volume: 50 cubic feet Emulsion Diameter: 1 millimeter Surface area: 91,440 square feet Approximately 2.5 orders of magnitude higher Volume: 50 cubic feet Emulsion Diameter: 1 micrometer Surface area: 91,493,000 square feet Approximately 5 orders of magnitude higher 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 5

7 CASE STUDY EXAMPLES SEPR & S ISCO Treatment of Creosote Site Former Wood Treatment Facility, Bridgeville, DE Contaminants of Concern Creosote DNAPL Objectives Full scale soil remediation Remedial Implementation SEPR & S ISCO 6

8 SEPR & S ISCO Treatment of Creosote Site Background Lumber Treating Facility ( ) 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 DNAPL o S ISCO to remove residual contamination 7

9 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 ( g/l) SEPR & S ISCO Treatment of Creosote Pre SEPR No Product Recovery; Clear Samples Day 1 Product + Emulsion Recovered Day 2 Increased Product Recovery Day 3 Product Flow 8

10 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 Volume Creosote (gal) Pre and Post Treatment Creosote Volumes 85% 86% 95% 73% Depth Interval (ft) Pre Treatment Creosote Volume (gal) Post Treatment Creosote Volume (gal) 58% 18% 81% 9

11 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 10

12 MGP Coal Tar Remediation in NYC Site Former Roofing Products Manufacturer Contaminants of Concern BTEX, PAHs, & naphthalene Objectives Reduce 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 NAPL Northern edge of site boundary ~ 100 ft from high rise, luxury residential building 11

13 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 RemMetrik SM process 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 12

14 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 qns.com Photo Courtesy stevenholl.com 13

15 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 14

16 FAQs: Mobilization S ISCO chemistry travels together Data from an on site monitoring well during and after injections Persulfate (g/l) / VeruSOL (g/l) S ISCO Chemistry Tracking at a Monitoring Well within Injection Area Maximum SP detected = 27 g/l Maximum TPH detected = 215 mg/l Maximum VeruSOL detected = 18 g/l VeruSOL Persulfate TPH TPH (mg/l) 0.0 9/29/10 11/18/10 1/7/11 2/26/11 4/17/11 6/6/11 7/26/11 0 Injection Period Post Injection Monitoring Monitoring Well Data S ISCO Chemistry Tracking at a Monitoring Well Down gradient Persulfate (g/l) / VeruSOL (g/l) Maximum VeruSOL detected = 1.1 g/l Maximum SP detected = 2.9 g/l VeruSOL Persulfate TPH Maximum TPH detected = 24 mg/l TPH (mg/l) 0 9/29/10 11/18/10 1/7/11 2/26/11 4/17/11 6/6/11 7/26/11 0 Injection Period Post Injection Monitoring Period 15

17 FAQs: Mobilization Projection of two emulsions, traveling vs. destruction 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 TPH (mg/l) mg/l by 43 ft 10 mg/l by 51.5 ft Groundwater Movement (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 IFT (mn/m) Evaluation of Surfactant Over Time During Oxidation With and Without Contaminant Interfacial Tension (IFT) Over Time VeruSOL with SP VeruSOL, SP, and NAPL Increase in IFT indicates destruction of surfactant /22 12/12 1/1 1/21 2/10 3/2 3/22 4/11 5/1 5/21 Stable, low IFT indicates stable presence of surfactant 16

18 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. EthicalChem USA 17