surfactant enhanced in situ chemical oxidation (s isco®) · copyright verutek 2010copyright...

Copyright VeruTEK 2010Copyright VeruTEK 2010

Surfactant EnhancedIn Situ Chemical Oxidation (S‐ISCO®)

Presented by

George E. Hoag, Ph.D.Senior Vice‐President

VeruTEK Technologies, Inc.Bloomfield, Connecticut

USA

8 Marts 2010

‐1.0

0.0

1.0

2.0

3.0

4.0

5.0

200.0 300.0 400.0 500.0 600.0

Abs

orba

nce

Wavelength (nm)

Free Radical Screening Assay 2B39

Day 0

Day 1

Day 3

Day 7


Presentation Outline

• Purpose – Balance Scientific Fundamentals with Applications

• Introduction

‐ Overview of Surfactant Behavior

‐ Reactions of Surfactants and Oxidants

• Laboratory‐Scale Results

• Full‐Scale Applications

• Conclusions


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, Oily Wastewater, Oil Drilling Cuttings


Purpose of S‐ISCO®

• Chemical Oxidation Reactions are Basically Aqueous Phase Reactions

• Immiscible Organic Liquids by Definition Do Not Exist in the Aqueous Phase

• Aqueous Solubilities of NAPLs Varies Depending on Hydrophobicities and Structure

• For ISCO to be Effective on NAPLs and Source Areas Need to Increase the Aqueous Solubility of Organic Compounds

• Surfactants Increase Solubility of NAPLs in WaterBenzene 1,780 mg/LTetrachloroethylene 150 mg/LNaphthalene 31 mg/LPyrene 0.13 mg/LBenzo[a]pyrene 0.002 mg/L2,2',4,4',5,5'‐Hexachlorobiphenyl 0.009 mg/L


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 of Surfactants, Oxidants and Catalysts

• This is Called Reactive Transport or Co‐Elution

• Monitor Surfactants, Oxidants and Catalysts During

Application


S‐ISCOTM Technology

Nonionic SurfactantWater Soluble Head

Oil Soluble Tail

Sand ParticleDNAPL

DNAPL SaturatedSoil Zone

Injected SInjected S--ISCOISCO®®

Chemical MixtureChemical MixtureDNAPL DNAPL

Contaminated SoilContaminated Soil

Oxidant‐Surfactant MixtureDNAPL Solubilization

AndDNAPL Destruction Zone

Remediated Clean Soil

=Nonionic Surfactant

DNAPL+

Solubilized DNAPL

+ ChemicalOxidant

=Destroyed

Contaminant+

Destroyed Surfactant

Treated Soil and GroundwaterTreated Soil and Groundwater

Mol

ecul

ar

Mol

ecul

ar

Leve

lLe

vel

Proc

ess

Proc

ess

Leve

lLe

vel

Ingr

edie

nts

Ingr

edie

nts


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

DNAPLDissolvedDNAPL


TCE Column ExperimentISCO vs. S‐ISCO®

S‐ISCOTMISCO

Alkaline Persulfate Treatment14 Days

S‐ISCO® with Alkaline Persulfate Treatment14 Days


1 2

Time = 0 daysPrior to Injections

Time = 2 days Time = 5 days

Australia Chlorinated DNAPL Soil Column Experiment

Column 1‐ ISCO – Alkaline PersulfateColumn 2‐ S‐ISCO with Alkaline Persulfate

(DNAPL dyed red with Suidan IV)

1 2 1 2


Surfactants

Oil in Water EmulsionsUsed to Solubilize Oils

Water in Oil EmulsionsUsed to Mobilize Oils

Surfactants are Surface Active Agents that Lower the Surface Tension of aLiquid and Decrease the Interfacial Tension between Two Liquids

Surfactants are Amphiphilic – they have Hydrophobic Groups (tails)and Hydrophilic Groups (heads)

Surfactants Form Micelles


Winsor Type Lexicon

• Winsor Type I Micelles have a Hydrophilic Exterior and a Hydrophobic Interior – Water is the Continuous Phase and the Oil (NAPL) is Inside the Micelle – Example MilkThis is What VeruTEK Uses

• Winsor Type II Micelles have Hydrophobic Exterior and a Hydrophilic Interior – Oil is the Continuous Phase and Water is Inside the Micelle – Example Butter

• Winsor Type III – Middle Phase Emulsion Coinciding with Ultralow IFT Causing a Third Mobile Phase

HydrophilicHead

HydrophobicTail

WaterLoving

OilLoving


Cleaning Movie

Surfactants That Make Oil in Water Emulsions

• Have Specific Balance of Hydrophilic and Hydrophobic Groups 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 Range


Our Premier Formulation ‐ VeruSOL®‐3

• Mixture of Ethoxylated Castor Oil, Coconut Oils and Citrus Terpenes – and Other Minor Compounds

• Surfactant and Cosolvent Mixture Enables Excellent Solubilization of All Petroleum Distillates, Industrial Solvents, MGP and Creosote DNAPLs, and Tar Sands

• U.S. FDA Generally Recognized as Safe (GRAS)

• Components Found in Fruit Juice, Various Foods and Consumer Care Products such as Cosmetics, Fragrances, Air Deodorizers

• These Plant‐Based Surfactants are Nonionic


• Hydrogen Peroxide and Sodium Persulfate Generate Free Radicals – 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‐Persulfate

Free Radical Production


Free Radical Production


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 During

Remediation – 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 Really

There? Does the Catalyst Last as Long as Persulfate

Problem Solved! Don’t Be Fooled Again!Now You Can Easily Measure the Presence of Free

Radicals At Sites Where Advanced Oxidation Process are the Operative Destruction Method


New Method to Measure Presence of Free Radicals in Groundwater

Acidic pH Range Bromothymol Blue

pH<6 pH=7 pH>7.6

• Probe Compound• Only Degrades by

Free Radical Pathway


Sodium Persulfate Generated Free Radicals Measured with Bromothymol Blue


Bromothymol Blue Used as a Probe Compound to Measure MixtureStability of Persulfate with Na‐EDTA, Fe‐EDTA and Alkaline Conditions

With and Without VeruSOL‐3

Na-EDTA

Fe-EDTA

Alkaline


Bromothymol Blue Used as a Probe Compound to MeasureStabilization of Alkaline Persulfate with VeruSOL‐3

VS-3 = 0VS-3 = 5VS-3 = 10VS-3 = 10

(g/L)

ControlVS-3 = 20 g/LSP = 0


MGP DNAPL Dyed with Suidan IV and Near Complete Dissolution in VeruSOLTM

DNAPL

DissolvedDNAPL

MGP DNAPL VeruSOL‐3TM Solubilization


Microemulsion of Solubilized MGP DNAPL

Typical ConcentrationRange of Operations

Does Not Mobilize MGP DNAPL Even at Concentrations Greater Than Applied

in Field


As the VeruSOL‐3 Dose is Increased, the Interfacial Tension Between the Two Liquids Decreases

VeruSOL‐3TM Effect on Interfacial Tension


As the VeruSOL‐3 Dose is Increased, the MGP DNAPL Solubility Increases Because of Creating Oil in Water Emulsions

VeruSOL‐3TM MGP Solubility


As the VeruSOL‐3 Dose is Increased, the MGP Emulsion Particle Size Decreases – Inflection at Critical Micelle Concentration

MGP Emulsion Particle Size


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

DNAPLDissolvedDNAPL


0

5

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35

40

0 10 20 30 40 50 60 70 80 90

Solu

biliz

ed C

onta

min

ants

(g/L

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.

VeruSOLTM (g/L)

Effect of VeruSOLTM on DNAPL Solubilization(Concentration VeruSOLTM vs. Solubilized VOCs)

Carbon Tetrachloride (CTC) Tetrachloroethene (PCE) Hexachlorobutadiene (HCBD) Total VOCs

Chlorinated Hydrocarbon Dissolution Example


@ 0.8 g/L VeruSOL

@ 4.2 g/L VeruSOL

@16.7 g/L VeruSOL

@ 83.3 g/L VeruSOL

CTC 2.83 2.79 9.29 54.29 62.86PCE 3.40 7.50 24.00 160.00 250.00HCBD 4.90 17.86 70.71 571.43 857.14

Solubility Enhancement FactorVOC log

Kow

ßi = Cw,i, (VS)/Cw,i

0 hr 8 hr 24 hr

Chlorinated Hydrocarbon Dissolution ExampleSolubility Enhancement


13,600 14,80063,120 56,000 68,320

14,484

107,500

156,824

263,840

347,640

0

50,000

100,000

150,000

200,000

250,000

300,000

350,000

400,000

450,000

T2-I1 (Control) T2-I2 (1.0 g/LVeruSOL-3)

T2-I3 (2.5 g/LVeruSOL-3)


T2-I5 (10 g/LVeruSOL-3)

CO

C c

once

ntra

tion

(ug/

L)

SVOCsVOCs

7.83x Enhancement

11.39x Enhancement

14.81x Enhancement

4.35x Enhancement

117

2,144

3,648

6,380

7,598

0

1,000

2,000

3,000

4,000

5,000

6,000

7,000

8,000

T2-I1 (Control) T2-I2 (1.0 g/LVeruSOL-3)



T2-I5 (10 g/LVeruSOL-3)

TPH

(ppm

)

18.3x Enhancement

31.2x Enhancement

54.5x Enhancement

64.9x Enhancement

VOCs and SVOCs

TPH

Creosote DNAPL Solubilization

2.1 g TPH Dissolved/1.0 g VeruSOL‐3


Solubilization and Oxidation of Chlorinated DNAPLAlkaline Persulfate


Oxidation of Emulsified/Solubilized NAPLs


Activated Persulfate Oxidation of Solubilized MGP DNAPL

TPH Solubilization and Oxidation of MGP DNAPL with VeruSOLTM-1

0

2000

4000

6000

8000

10000

12000

14000

16000

T2-2 T2-4 T2-6 T2-2(oxidation)

T2-4(oxidation)

T2-6(oxidation)

Con

tam

inan

t Con

cent

ratio

n (m

g/L)

.

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Perc

ent R

emov

al (%

)

.

TPH TPH Percent RemovalSOLUBILIZATION OXIDATION

Notes: (1) Solubilized TPH concentration were estimated based on estimates relationship between T-64 concentration and TPH solubilized from Test 1. (2) Oxidized with 200 g/l sodium persulfate activated with pH>12 using NaOH.

VS-1 2 g/L

VS-110 g/L

VS-150 g/L


259,200

1,159

27,590

10,125

318,880

17,648

130,713

89,120

5,900 4,550 4,250 3,5500

50,000

100,000

150,000

200,000

250,000

300,000

350,000

Initial Soil Column 1 ‐ 30 Day Treated Soil

Column 2 ‐ 14 Day Treated Soil

Column 3 ‐ 14 Day Treated Soil

COC

Conc

entr

atio

n (u

g/L)

Column Soil

Soil Column Experiments ‐COC Destruction of Treated Soils

VOCs

SVOCs

Arsenic

Column 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 10oC

Large Landfill CVOC Site– Soil Column Test Results


79,000

673,350 1,500

100,000

425

14,050

5,500

17,000

8 375 10

44,000

2955,950

2,3606,700

02,900 1,900

41,000

0

10,3505,000

0

20,000

40,000

60,000

80,000

100,000

120,000

Initial Soil Column 1 ‐ 30 Day Treated Soil Column 2 ‐ 14 Day Treated Soil Column 3 ‐ 14 Day Treated Soil

COC

Conc

entr

atio

n (u

g/L)

Column Soil

Soil Column Experiments ‐Destruction of Target Compounds

Toluene Total Xylenes TCE PCE Hexachlorobenzene Naphthalene

Large Landfill CVOC Site– Soil Column Test Results


58,900

24 26 3

47,250

5,555

0

10,000

20,000

30,000

40,000

50,000

60,000

70,000

Column 100SP 20 g/L + VSOL 5 g/L

+ Fe-EDTA 250 mg/L


+ Fe-EDTA 250 mg/L


+ Fe-EDTA 250 mg/L

TPH

(mg/

kg)

Before After

99.9% Destruction

99.9% Destruction

99.9% Destruction

Notes: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 the column7)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 TPH 9)Experiments were run for 28 days10)Flow rates for each column were 0.5 ml/min

Column MGP S‐ISCO® Treatment


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 Surface over 0.33 ha

• Extensive Coal Tar Saturated Soils Present in Lenses(Shallower, Deeper and Upgradient Contamination Discovered After Project Started)

• Fine to Medium Sand – 1.0 m to Water Table – 21 m to Aquitard

• Required Targeting Upper 10 m



• 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, <5 g/L VeruSOL‐3 and 250 mg/L of Fe‐EDTA as Fe

• Interim Soil Samples Taken After 75% of Chemical Injected (10/09) (Represents 50% of S‐ISCO Chemicals Reacted)

• 56,000 Metric Tons Soils (29,250 m3) Treated

• 49,000 kg TPH Destroyed – 79% Reduction 50% Chemical Reacted

• ~2.9 g Persulfate/kg Soil Applied to Treatment Zone




• Continuous Chemical Feed System – 29 Chemical Feed PumpsInjecting into 9 Injection Wells, Batch Water From

HydrantFed to Large Water Equilization Tank

• 1 Metric Ton Batching of Persulfate• More than 3,000 hours of Operation without a Reportable

Safety Incident


Full‐Scale MGP Gasworks Site – 75% Injection Completed


Highest Coal Tar DNAPL Contamination at Site

Full‐Scale MGP Gasworks Site – 75% Injection Completed


0

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3/28 5/17 7/6 8/25 10/14 12/3 1/22 3/13

Pers

ulfa

te C

once

ntra

tion

(g/L

)

Elec

trol

ytic

Con

duct

ivit

y (m

S/cm

)

Date

WCMW‐16IElectrolytic Conductivity (mS/cm) and Persulfate

Concentration (g/L)

Cond. (mS/cm)

Persulfate Conc. (g/L)

0

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4

6

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14

0

0.2

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3/28 5/17 7/6 8/25 10/14 12/3 1/22 3/13

Pers

ulfa

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(g/L

)

Elec

trol

ytic

Con

duct

ivit

y (m

S/cm

)

Date

WCMW‐16SElectrolytic Conductivity (mS/cm) and Persulfate

Concentration (g/L)

Cond. (mS/cm)


0

2

4

6

8

10

12

14

0

0.2

0.4

0.6

0.8

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1.2

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3/28 5/17 7/6 8/25 10/14 12/3 1/22 3/13Pe

rsul

fate

Con

cent

rati

on (g

/L)

Elec

trol

ytic

Con

duct

ivit

y (m

S/cm

)

Date

WCMW‐16I2Electrolytic Conductivity (mS/cm) and Persulfate

Concentration (g/L)

Cond. (mS/cm)


0.6 – 3.7 mScreened Interval



Full‐Scale MGP Gasworks Site – Typical Monitoring ResultsElectrolytic Conductivity and Persulfate Concentrations


Full‐Scale MGP Gasworks Site – Typical Monitoring ResultsOxidation‐Reduction Potential and pH


Full‐Scale MGP Gasworks Site – MW‐1 PAH Groundwater


• Significant Mass Reduction After Only 50% Chemical Reacted‐ 49,000 kg TPH Removed

• Groundwater Reductions Last to Be Observed Based on the Process, but Reductions are Taking Place

• No Groundwater PAH Increases Downgradient in the Next Gasworks 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 by Consultants – Upgradient and Shallow

• Costs for Design, Implementation, Project Management and Monitoring ~ 215DKK/Metric Ton – 28.8€/Metric Ton

Conclusions MGP Gasworks Site


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 with Direct 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 Given


Pharmaceutical Chlorinated Solvent Site• 2,807 Metric Tons Soil Treated , 584 m3 soil in November 2008• Contaminants ‐ 1‐1‐dichloroethene, 1,2‐dichloroethane, benzene and

chlorobenzene• Total Contaminant Mass – 227 kg• Soils were Silty Sand with Clay with Significant Contamination of the Backfill

Around 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 2009


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 Tests


• 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‐3

PCE Solubility Enhancement Tests – Skuldelev Area III


Alkaline Persulfate Oxidation of Solubilized PCE

Initial IFT = 40.1 mN/mFinal IFT = 60.8 mN/mInitial Persulfate = 50.0 g/LFinal Persulfate= 30.6 g/LInitial pH = 12.81 Final pH = 12.58Initial PCE = 2,200 mg/LFinal PCE = 85 mg/L


Persulfate Soil Oxidant Demand Tests

• Persulfate SOD TestConditions and Results


• 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 Alone

Persulfate Soil Oxidant Demand Tests


• Treatment Area ~75 m2 – Treat Larger Area to Ensure Contact

• Treatment Soil Volume ‐ 375 m3

• 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)

Full‐ Scale Design Area III Skuldelev Site

surfactant enhanced in situ chemical oxidation (s isco®) · copyright verutek 2010copyright...

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