Copyright VeruTEK 2010 - ATV - Jord og Grundvand
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Copyright VeruTEK 2010 - ATV - Jord og Grundvand

Surfactant Enhanced In Situ Chemical Oxidation• The focus of S‐ISCO ® is to treat Light and Dense Non AqueousPhase Liquids (NAPLs) & Sorbed Phase Contaminants‐ Chlorinated Solvents, Hydrocarbons, Coal Tars, FuelsPesticides, Hydraulic Oils, Heat Exchange Fluids, PCBs• Coupled Subsurface Coelution of Cosolvent/Surfactants toSolubilize and Free Radical Oxidants to Destroy NAPLsand Sorbed Residuals• Also Applicable for Ex Situ, Construction Materials, OilyWastewater, Oil Drilling CuttingsCopyright VeruTEK 2010 2010

Purpose of S‐ISCO®• Chemical Oxidation Reactions are Basically Aqueous PhaseReactions• Immiscible Organic Liquids by Definition Do Not Exist in theAqueous Phase• Aqueous Solubilities of NAPLs Varies Depending onHydrophobicities and Structure• For ISCO to be Effective on NAPLs and Source Areas Need toIncrease the Aqueous Solubility of Organic Compounds• Surfactants Increase Solubility of NAPLs in WaterBenzeneTetrachloroethyleneNaphthalenePyreneBenzo[a]pyrene2,2',4,4',5,5'‐Hexachlorobiphenyl1,780 mg/L150 mg/L31 mg/L0.13 mg/L0.002 mg/L0.009 mg/LCopyright VeruTEK 2010 2010

Key Factors to Make S‐ISCO® Work• Emulsify/Solubilize NAPL Phase and Desorb “Source Zone”Contaminants using Surfactants and Cosolvents• Make Free Radicals by Activating/Catalyzing Oxidants• Oxidize Solubilized Contaminants with Free Radicals• Do The Above by Simultaneous Subsurface Injections ofSurfactants, Oxidants and Catalysts• This is Called Reactive Transport or Co‐Elution• Monitor Surfactants, Oxidants and Catalysts DuringApplicationCopyright VeruTEK 2010 2010

TCE Column ExperimentISCO vs. S‐ISCO ®Alkaline Persulfate Treatment14 DaysS‐ISCO ® with Alkaline Persulfate Treatment14 DaysISCOS‐ISCO TMCopyright VeruTEK 2010 2010

Australia Chlorinated DNAPL Soil Column ExperimentColumn 1‐ ISCO – Alkaline PersulfateColumn 2‐ S‐ISCO with Alkaline Persulfate(DNAPL dyed red with Suidan IV)1 212 12Time = 0 daysPrior to InjectionsTime = 2 daysCopyright VeruTEK 2010 2010Time = 5 days

Winsor Type Lexicon• Winsor Type I Micelles have a Hydrophilic Exterior and aHydrophobic Interior – Water is the Continuous Phaseand the Oil (NAPL) is Inside the Micelle – Example MilkThis is What VeruTEK UsesOilLovingHydrophobicTailHydrophilicHeadWaterLoving• Winsor Type II Micelles have Hydrophobic Exterior and aHydrophilic Interior – Oil is the Continuous Phase andWater is Inside the Micelle – Example Butter• Winsor Type III – Middle Phase Emulsion Coinciding withUltralow IFT Causing a Third Mobile PhaseCopyright VeruTEK 2010 2010

Surfactants That Make Oil in Water Emulsions• Have Specific Balance of Hydrophilic and HydrophobicGroups Termed Hydrophile‐Lipophile Balance (HLB)• Are Non‐Ionic (not charged) – Do Not Sorb on Soils• Can be Made from Edible Oils• Can be Food Grade• Micelles can be in the Nanoemulsion Size RangeCleaning MovieCopyright VeruTEK 2010 2010

Our Premier Formulation ‐ VeruSOL®‐3• Mixture of Ethoxylated Castor Oil, Coconut Oils andCitrus Terpenes – and Other Minor Compounds• Surfactant and Cosolvent Mixture Enables ExcellentSolubilization of All Petroleum Distillates, IndustrialSolvents, MGP and Creosote DNAPLs, and Tar Sands• U.S. FDA Generally Recognized as Safe (GRAS)• Components Found in Fruit Juice, Various Foodsand Consumer Care Products such as Cosmetics,Fragrances, Air Deodorizers• These Plant‐Based Surfactants are NonionicCopyright VeruTEK 2010 2010

Free Radical Production• Hydrogen Peroxide and Sodium Persulfate Generate FreeRadicals – but Requires Activation or Catalysis• Activation/Catalysis of Peroxide and Persulfate Essential– No Activation = No Free Radicals = No Destruction‐ Fe‐EDTA, Fe‐EDDS and other Fe‐Chelates‐Green Synthesized Nanoscale Zero Valent Iron(2 joint EPA/VeruTEK® Patents Pending)‐ Iron‐TAML® – Organometallic Catalyst – not a chelate(Exclusive Supply Agreement with GreenOX Catalysts)• Microemulsion Catalysis, pH, Heat and Peroxide‐PersulfateCopyright VeruTEK 2010 2010

Free Radical ISSUES• Hydrogen Peroxide – Unless Stabilized Well it Decomposes Quickly(Hours to a Day) in Soil and Groundwater• Hydrogen Peroxide Infrequently Monitored in Groundwater DuringRemediation – Is Hydrogen Peroxide Really There?• Must Be Catalyzed/Activated to Make Free Radicals– Is the Catalyst Really There?• Sodium Persulfate – Decomposes Slowly In Soils – Weeks to Months• Persulfate Infrequently Monitored in Groundwater During Remediation– Is it Really There?• Must Be Catalyzed/Activated to Make Free Radicals – Is the Catalyst ReallyThere? Does the Catalyst Last as Long as PersulfateProblem Solved! Don’t Be Fooled Again!Now You Can Easily Measure the Presence of FreeRadicals At Sites Where Advanced Oxidation Processare the Operative Destruction MethodCopyright VeruTEK 2010 2010

Sodium Persulfate Generated Free Radicals Measuredwith Bromothymol BlueCopyright VeruTEK 2010 2010

Bromothymol Blue Used as a Probe Compound to Measure MixtureStability of Persulfate with Na‐EDTA, Fe‐EDTA and Alkaline ConditionsWith and Without VeruSOL‐3Na-EDTAFe-EDTAAlkalineCopyright VeruTEK 2010 2010

Bromothymol Blue Used as a Probe Compound to MeasureStabilization of Alkaline Persulfate with VeruSOL‐3VS-3 = 0VS-3 = 5VS-3 = 10VS-3 = 10(g/L)Copyright VeruTEK 2010 2010ControlVS-3 = 20 g/LSP = 0

Copyright VeruTEK 2010 2010

MGP DNAPL VeruSOL‐3 TM SolubilizationDissolvedDNAPLDNAPLMGP DNAPL Dyed with Suidan IV and Near CompleteDissolution in VeruSOL TMCopyright VeruTEK 2010 2010

Microemulsion of Solubilized MGP DNAPLTypical ConcentrationRange of OperationsDoes Not Mobilize MGP DNAPL Even atConcentrations Greater Than Appliedin FieldCopyright VeruTEK 2010 2010

VeruSOL‐3 TM Effect on Interfacial TensionAs the VeruSOL‐3 Dose is Increased, the InterfacialTension Between the Two Liquids DecreasesCopyright VeruTEK 2010 2010

VeruSOL‐3 TM MGP SolubilityAs the VeruSOL‐3 Dose is Increased, the MGP DNAPL SolubilityIncreases Because of Creating Oil in Water EmulsionsCopyright VeruTEK 2010 2010

MGP Emulsion Particle SizeAs the VeruSOL‐3 Dose is Increased, the MGP Emulsion ParticleSize Decreases – Inflection at Critical Micelle ConcentrationCopyright VeruTEK 2010 2010

Chlorinated Solvent DNAPL Dyed with Suidan IVand Complete Dissolution in VeruSOL‐3 ®DissolvedDNAPLDNAPLCopyright VeruTEK 2010 2010

Chlorinated Hydrocarbon Dissolution ExampleEffect of VeruSOL TM on DNAPL Solubilization(Concentration VeruSOL TM vs. Solubilized VOCs)Carbon Tetrachloride (CTC) Tetrachloroethene (PCE) Hexachlorobutadiene (HCBD) Total VOCs40Solubilized Contaminants (g/L) .353025201510500 10 20 30 40 50 60 70 80 90VeruSOL TM (g/L)Copyright VeruTEK 2010 2010

VOCChlorinated Hydrocarbon Dissolution ExampleSolubility EnhancementlogKow@ 0.8 g/LVeruSOLSolubility Enhancement Factor@ 4.2 g/LVeruSOL@16.7 g/LVeruSOL@ 83.3 g/LVeruSOLCTC 2.83 2.79 9.29 54.29 62.86PCE 3.40 7.50 24.00 160.00 250.00HCBD 4.90 17.86 70.71 571.43 857.140 hr 8 hr 24 hrß i = C w,i, (VS) /C w,iCopyright VeruTEK 2010 2010

Creosote DNAPL Solubilization450,00014.81xEnhancement400,000350,00011.39xEnhancementVOCs andSVOCsCOC concentration (ug/L)300,000250,000200,000150,0004.35xEnhancement7.83xEnhancement156,824263,840347,640SVOCsVOCs100,00050,0000107,50014,48413,600 14,80063,120 56,000 68,320T2-I1 (Control)T2-I2 (1.0 g/LVeruSOL-3)T2-I3 (2.5 g/LVeruSOL-3)T2-I4 (5.0 g/LVeruSOL-3)T2-I5 (10 g/LVeruSOL-3)TPH8,0007,0006,3807,598TPH (ppm)6,0005,0004,0003,0002,0001,00002.1 g TPH Dissolved/1.0 g VeruSOL‐31172,14418.3xEnhancement3,64831.2xEnhancement54.5xEnhancement64.9xEnhancementT2-I1 (Control)T2-I2 (1.0 g/LVeruSOL-3)T2-I3 (2.5 g/LVeruSOL-3)Copyright VeruTEK 2010 2010T2-I4 (5.0 g/LVeruSOL-3)T2-I5 (10 g/LVeruSOL-3)

Solubilization and Oxidation of Chlorinated DNAPLAlkaline PersulfateCopyright VeruTEK 2010 2010

Oxidation of Emulsified/Solubilized NAPLsCopyright VeruTEK 2010 2010

Activated Persulfate Oxidation of Solubilized MGP DNAPLContaminant Concentration (mg/L).1600014000120001000080006000400020000TPH Solubilization and Oxidation of MGP DNAPL with VeruSOL TM -1TPHSOLUBILIZATIONT2-2 T2-4 T2-6 T2-2VS-1VS-1 VS-1 (oxidation)2 g/L 10 g/L 50 g/LTPH Percent RemovalCopyright VeruTEK 2010 2010OXIDATIONT2-4(oxidation)T2-6(oxidation)Notes: (1) Solubilized TPH concentration were estimated based on estimates relationship between T-64 concentration and TPH solubilized fromTest 1.(2) Oxidized with 200 g/l sodium persulfate activated with pH>12 using NaOH.100%90%80%70%60%50%40%30%20%10%0%Percent Removal (%) .

Large Landfill CVOC Site– Soil Column Test ResultsSoil Column Experiments ‐COC Destruction of Treated Soils350,000318,880300,000250,000259,200COC Concentration (ug/L)200,000150,000130,713VOCsSVOCsArsenic100,00089,12050,0000Initial Soil27,59017,6485,900 10,1251,159 4,550 4,250 3,550Column 1 ‐ 30 Day TreatedSoilColumn SoilColumn 2 ‐ 14 Day TreatedSoilColumn 3 ‐ 14 Day TreatedSoilColumn 1 – Sodium Persulfate – 50 g/L, pH> 11, VeruSOL‐3 ‐ 5 g/L, 10oC, 30 daysColumn 2 – Sodium Persulfate – 100 g/L, pH> 11, VeruSOL‐3 ‐ 5 g/L, 10oC, 14 daysColumn 3 – Sodium Persulfate – 100 g/L, pH> 8, Fe‐TAML‐ 0.1 µMm VeruSOL‐3 ‐ 5 g/L, 14 daysAll Columns run at 10 o CCopyright VeruTEK 2010 2010

Large Landfill CVOC Site– Soil Column Test Results120,000Soil Column Experiments ‐Destruction of Target Compounds100,000100,000COC Concentration (ug/L)80,00060,00040,00079,00044,00041,00020,000017,000Initial Soil6,70014,05010,3505,9505,5003,3505,0002,90067 425 8 295375 1,500 2,3600 0101,900Column 1 ‐ 30 Day Treated Soil Column 2 ‐ 14 Day Treated Soil Column 3 ‐ 14 Day Treated SoilColumn SoilToluene Total Xylenes TCE PCE Hexachlorobenzene NaphthaleneCopyright VeruTEK 2010 2010

Column MGP S‐ISCO® TreatmentBeforeAfterTPH (mg/kg)70,00060,00050,00040,00030,00020,00010,000047,250Column 100SP 20 g/L + VSOL 5 g/L+ Fe-EDTA 250 mg/L58,90099.9%99.9%99.9%DestructionDestructionDestruction5,55524 26 3Column 101SP 50 g/L + VSOL 10 g/L+ Fe-EDTA 250 mg/LColumn 102SP 10 g/L + VSOL 2 g/L+ Fe-EDTA 250 mg/LNotes:1)DNAPL spiked soil was prepared using hexane to dissolve the DNAPL and uniformly contaminate the soil, followed by evaporation of the hexane prior to treatment.2)1kg of AFS 50-70 sand (200 µ to 300 µ particle size) was used in each of Columns 100 and 101.3)1kg of AFS 20-40 sand was used in Column 102.4)5 g MGP DNAPL was dissolved in 100 mL hexane for Columns 100 and 101 and 1 g MGP DNAPL was dissolved in 100 mL hexane for Column 1025)For each column the DNAPL-hexane mixture was poured into the sand and periodically mixed in a pan and allowed to evaporate over a 24 hour period6)Each column was then packed in the columns in small lifts by place the sand in standing water then vibrating to consolidate sand. This procedure was repeated until 1kg was placed in thecolumn7)Columns effluents were sampled daily (complete composite) for persulfate, pH, ORP, conductivity, turbidity, flow rate, interfacial tension and TPH8)After completion of tests each column was sacrificed, composited into three aliquots (top, middle and bottom) and analyze for TPH9)Experiments were run for 28 days10)Flow rates for each column were 0.5 ml/minCopyright VeruTEK 2010 2010

Full‐Scale MGP Gasworks SiteCopyright VeruTEK 2010 2010

Full‐Scale MGP Gasworks Site• Gasworks Contamination at Large Site• This Portion of Site Received Process Wastewater and Coal Tar• Contamination from 1.2 m to ~ 9.0 m Below Ground Surfaceover 0.33 ha• Extensive Coal Tar Saturated Soils Present in Lenses(Shallower, Deeper and Upgradient ContaminationDiscovered After Project Started)• Fine to Medium Sand – 1.0 m to Water Table – 21 m toAquitard• Required Targeting Upper 10 mCopyright VeruTEK 2010 2010

Full‐Scale MGP Gasworks Site• Injected Chemicals – May 2009 to November 2009‐ 160,000 kg Sodium Persulfate‐ 45,000 kg Fe‐EDTA‐ 13,000 kg VeruSOL‐3• 42 Monitoring Wells in 18 Clusters• 12 Injection Wells – Typically 15 g/L to 25 g/L Persulfate,

Full‐Scale MGP Gasworks Site• Continuous Chemical Feed System – 29 Chemical Feed PumpsInjecting into 9 Injection Wells, Batch Water FromHydrantFed to Large Water Equilization Tank• 1 Metric Ton Batching of Persulfate• More than 3,000 hours of Operation without a ReportableSafety IncidentCopyright VeruTEK 2010 2010

Full‐Scale MGP Gasworks Site – 75% Injection CompletedCopyright VeruTEK 2010 2010

Full‐Scale MGP Gasworks Site – 75% Injection CompletedHighest Coal Tar DNAPL Contamination atSiteCopyright VeruTEK 2010 2010

Full‐Scale MGP Gasworks Site – Typical Monitoring ResultsElectrolytic Conductivity and Persulfate ConcentrationsElectrolytic Conductivity (mS/cm)‐16SElectrolytic Conductivity (mS/cm) and PersulfateConcentration (g/L)3/28 5/17 7/6 8/25 10/14 12/3 1/22 3/130.6 – 3.7 mScreened Interval9.1 – 10.7 mScreened IntervalDateElectrolytic Conductivity (mS/cm) (mS/cm)Persulfate Conc. (g/L)14121086420Persulfate Concentration (g/L)Electrolytic Conductivity (mS/cm)WCMW‐16I2Electrolytic Conductivity (mS/cm) and PersulfateConcentration (g/L)3/28 5/17 7/6 8/25 10/14 12/3 1/22 3/13DateCopyright VeruTEK 2010 201021.‐16IElectrolytic Conductivity (mS/cm) and PersulfateConcentration (g/L)3/28 5/17 7/6 8/25 10/14 12/3 1/22 3/13Cond. (mS/cm)Persulfate Conc. (g/L)14121086420Persulfate Concentration (g/L)DateCond. (mS/cm)Persulfate Conc. (g/L)14121086420Persulfate Concentration (g/L)6.1 – 7.6 mScreened Interval

Full‐Scale MGP Gasworks Site – Typical Monitoring ResultsOxidation‐Reduction Potential and pHCopyright VeruTEK 2010 2010

Full‐Scale MGP Gasworks Site – MW‐1 PAH GroundwaterCopyright VeruTEK 2010 2010

Conclusions MGP Gasworks Site• Significant Mass Reduction After Only 50% Chemical Reacted‐ 49,000 kg TPH Removed• Groundwater Reductions Last to Be Observed Based on theProcess, but Reductions are Taking Place• No Groundwater PAH Increases Downgradient in the NextGasworks Contaminated Property• Rigorous Monitoring Shows Reactants and Reaction FrontPassing Through the Treatment Zones• Able to Target Upper 10 m of Saturated Zone• More Contamination Initially Present than Estimated byConsultants – Upgradient and Shallow• Costs for Design, Implementation, Project Management andMonitoring ~ 215DKK/Metric Ton – 28.8€/Metric TonCopyright VeruTEK 2010 2010

Residential No.2 Heating Oil Remedation• Treatment ‐ VeruSOLVE – 5, Hydrogen Peroxide (5.1%) , VeruSOL‐3 (30 g/L)• Total Injected Liquid 4076 Liters and 121 kg VeruSOL‐3 in 2 Days withDirect Geoprobe Injection• Initial Mass of No.2 Heating Oil Present – 1,600 kg as TPH/DRO• Cost – 337 DKK/Metric Ton (45.4€/Metric Ton)• Clean‐Up Criteria Met, NJDEP Site Closure Letter GivenCopyright VeruTEK 2010 2010

Pharmaceutical Chlorinated Solvent Site• 2,807 Metric Tons Soil Treated , 584 m 3 soil in November 2008• Contaminants ‐ 1‐1‐dichloroethene, 1,2‐dichloroethane, benzene andchlorobenzene• Total Contaminant Mass – 227 kg• Soils were Silty Sand with Clay with Significant Contamination of the BackfillAround Many Utility Trenches in Clay with Sand/Clay Backfill• 80,533 L liquid Injected with 13.2 kg Fe‐EDTA, 609 kg VeruSOL‐3• Injection Over a 18 days of Injection During 4 Week Period• CTDEP Criteria Met for All Contaminants 1,1‐dichloroethene (6 ug/L),benzene (530 ug/L), chlorobenzene (6150 ug/L), and 1,2‐dichloroethane (90 ug/L)• Site Closed in August 2009Copyright VeruTEK 2010 2010

Area III, Skuldelev Site Denmark• Full‐Scale Application Presented by Lotte Rasmussen, NIRAS• Summary Laboratory Treatability Test Presented Here• Significant Pure Phase Tetrachloroethylene (PCE) DNAPL PresentLower Concentrations of TCE, cis‐1,2‐DCE and Vinyl Chloride• Treatment using S‐ISCO with Alkaline Persulfate• Laboratory Treatability Test Completed in January 2008‐ PCE DNAPL Solubilization Tests‐ Emulsion Oxidation Tests‐ Soil Oxidant Demand TestsCopyright VeruTEK 2010 2010

PCE Solubility Enhancement Tests – Skuldelev Area III• Solubility Enhancement Factor = 13.7• Interfacial Tension = 39.4 mN/m• 5 g PCE, 2.5 g VeruSOL‐3 in 500 mL Reactor• Solubility Yield = 1.04 g PCE Solubilized/g VeruSOL‐3Copyright VeruTEK 2010 2010

Persulfate Soil Oxidant Demand Tests• Persulfate SOD TestConditions and ResultsCopyright VeruTEK 2010 2010

Persulfate Soil Oxidant Demand Tests• Control with Groundwater Only Had Significant Degradation of Persulfate• System was Not Buffered at Alkaline Conditions• The SOD Exerted with Soil was 11% Greater than in Groundwater AloneCopyright VeruTEK 2010 2010

Full‐ Scale Design Area III Skuldelev Site• Treatment Area ~75 m2 – Treat Larger Area to Ensure Contact• Treatment Soil Volume ‐ 375 m 3• Estimated Contaminant Mass ‐ 1,102 kg DNAPL• Design Soil Oxidant Demand (with DNAPL included) – 15 g/kg• VeruSOL‐3 Dose – 800 kg• NaOH Dose – 800 kg (based on Soil Titration Curve)• Design Injection Flow – 5 gpm (Sandy Site)• Design Injection Concentration of Persulfate – 100 g/L(Used 25 to 50 g/L to Avoid Density Driven Transport)Copyright VeruTEK 2010 2010

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