Overview of FMC Soil and Groundwater Remediation Technologies

Ian Ross Ph.D. Business Manager, EMEA Health and Safety

• Always review and refer to appropriate MSDS • Material compatibility for delivery systems / design – for oxidants use stainless steel or plastics • Appropriate PPE for site and any other hazards should be worn (e.g. overalls, gloves, boots, safety glasses etc.) • Injecting any liquid under pressure creates a hazard to be risk assessed and controlled

FMC Soil and Groundwater Remediation Webinar Series

• Series of free webinars for the soil and groundwater remediation market • The educational webinars focus on the underlying science and application of chemical and biological remedial technologies • Highlight successful case studies • Demonstrate how our experienced team of technical professionals can assist with remedial design

September 12, 2013 Agenda

• Overview of FMC Soil and Groundwater Remediation and our comprehensive portfolio • cost effective, proven products that address a wide range of contaminants and site conditions • Chemical Oxidation Technologies • Aerobic Bioremediation Technologies • Chemical Reduction Technologies • Anaerobic Bioremediation Technologies • Summary

September 12, 2013 FMC Soil & Groundwater Remediation

• FMC is a global chemical company • FMC is a supplier of reagents to cause the destruction of organic contaminants and immobilisation of metals. • Success of remediation projects requires design expertise based on a technical understanding of: • contaminant chemistry • site geology and hydrogeology • the mechanisms by which the technology works • experience of successful applications of the techniques • FMC backs up its products with an experienced team, including 8 with Ph.D.’s, who also have decades of industry experience designing and implementing remediation projects • Our business model enables implementation of in situ / on site remediation technologies by provision of reagents and expertise.

September 12, 2013

Chemical Oxidation Soil and Groundwater Remediation Technologies

Klozur® Persulfate Technologies for Chemical Oxidation What is Chemical Oxidation?

• Addition of Oxidants into the subsurface to facilitate the

conversion of recalcitrant and toxic compounds to CO2 and H2O or less toxic / more biodegradable intermediates

• Chemical Oxidation reduces contaminant mass through the oxidation process

• Suitable for saturated and/or vadose zone source and plume treatment

• Chemical Oxidation maybe combined with other techniques (e.g. enhanced or monitored natural attenuation) Common Chemical Oxidants used for Remediation

• Ozone (O3) • Permanganate (MnO ) 4 – low solubility gas must be sparged – low solubility of K salt – short half life thus limited distribution – not strong enough to destroy – Radical mechanism benzene (no radical mechanism) – often an addition to AS/SVE so – can oxidise TCE unclear if oxidation mechanism is – forms solid residues “crust” on responsible for contaminant removal DNAPL

• Hydrogen Peroxide (H2O2) • Persulfate (S O ) (Fenton’s Reagent) 2 8 – high solubility – very reactive (creates heat and off gas) so potential safety issues – radical mechanism – short half life so limited distribution – variable half live hence longevity can be adjusted from hours to months – radical mechanism – Safe to handle and inject

Klozur ® Persulfate

• Oxidation mechanisms via direct oxidation (relatively strong) and production of radicals (sulphate SO4˙ and hydroxyl OH˙) • Thermodynamically very strong –can oxidise multiple organic compounds • Does not produce gaseous breakdown products or significant heat • High aqueous solubility (>40%) for diffusion and advection –large ROI • Can be activated over a wide range of geochemical conditions • Can be mixed into unsaturated soils to destroy a wide range of target organics • Ease of handling as oxidant is supplied as a granular solid • Leaves residual sulfate in formation to stimulation biodegradation

Purchase of FMC’s Klozur® Persulfate includes rights to practice the inventions covered by the patents in the purchase price of the Granular Persulfate product

Klozur Persulfate Chemistry – Activation

• Persulfate can produce radicals which are powerful and kinetically fast but activation is required • Engineered activation methods are designed based on: • specific contaminant(s) –their nature and distribution • site lithology hydrogeology • Activation is simple, as usually two liquids are mixed together – like adding milk to tea!

-2 - - -2 S2O8 + activator  SO4• + (SO4• or SO4 )

Heat Iron H2O2 High pH

Sustainable Solution: FMC Manufactures Utilizing Hydroelectric Power Klozur Activated Persulfate Examples of contaminants destroyed

Chlorinated Solvents TPH Chlorobenzenes Pesticides PCE, TCE, DCE BTEX Chlorobenzene DDT TCA, DCA GRO Dichlorobenzene Chlordane Vinyl chloride DRO trichlorobenzene Heptachlor Carbon tetrachloride ORO Lindane Chloroform creosote Phenols Toxaphene Chloroethane phenol MCPA Chloromethane Pentachlorophenol Bromoxynil Oxygenates Dichloropropane nitrophenol MTBE Trichloropropane TBA PAHs Methylene chloride Anthracene Benzopyrene Others Freons Carbon disulfide Styrene PFOS / PFOA Naphthalene Aniline Pyrene PVA Chrysene TNT / DNT trimethylbenzene 1,4 Dioxane Klozur® Activated Persulfate Application Methods Forming a persulfate solution • Direct push Fixed wells • Fixed well • In situ soil mixing • Ex situ soil mixing

In situ mixing Direct push rig Klozur Persulfate Case Study

Fixed Wells - H2O2 Activation

Site: Leaking UST at Former Chemical Plant

Contaminant: Dichloromethane Lowest Conc. 910 ppb Highest Conc. 12,000 ppb

Treatment: Six Years - Pump Treat System Two Years - Soil Vapor Extraction System Soil & GW Did Not Meet LA RWQCB Closure Level Injected Hydrogen Peroxide Activated Klozur®

Target GW Zone 40-48 ft bgs 1,600 ft2 Under Bldg & 800 ft2 Outside Bldg Geology: Silty Clays/Narrow Silty Sand Layers 23 Application Wells (16 inside the bldg) ROI = 8-12 ft

Results: 1. Levels Reduced 94 - 97% within 61 Days of Monitoring Following Treatment 2. Site Closure Accepted by LA RWQCB after Two Years of Monitoring Klozur Persulfate Case Study Soil Mixing - Alkaline Activation

• 5,000 tons Treated in 2 days • Depth to Groundwater – 1 foot • Treatment Interval – 1 to 11 feet bgs • 10 gram Klozur / 1 gram Hydrated Lime Applied per Kilogram of Soil • Concentrations Dropped from 100 – 200 ppm Total VOCs in Groundwater to Less than 0.1 ppm in One Week In Situ Chemical Oxidation of Chlorobenzene using Klozur Activated Persulfate

• Design objective; maximize in situ destruction of COC in a continuous flight auger rigs single round of intensive treatment • 7,317 m2 (all 5 Hotspots) treated Sept 07 – Feb 08 • Most impacted areas in Hotspots were treated twice • Persulfate injection concentrations; 20 and 40% wt/wt (mostly 40% wt/wt) • Lime activation resulted in enhanced mobilization of COC from sorbed and NAPL phases • Estimated that 11,304 kg of COC’s were oxidized in the soil phase • Calculated that 189 kg of COC was oxidized in dissolved phase Thornton, England

• Concentrations of chlorobenzene and dichlorobenzene reduced Area B Area D at least ten fold since completion of the ISCO treatment • Latest samples; all COC’s are significantly below EQS (Envl Quality Std’s) • June 2008; Site “closed” acceptance letter by The Environment Agency

Area A Area C Area E 2008 Brownfield Briefing Remediation Innovative Award -“Best Conceptual Design” Aerobic Bioremediation Soil and Groundwater Remediation Technologies

Aerobic Bioremediation Using PermeOx® Plus, Calcium Peroxide and Terramend®

What is Aerobic Bioremediation? • Addition of oxygen and nutrients to allow microbial biodegradation of organic contaminants

• Facilitate the conversion of biodegradable

compounds to CO2 and H2O

• Aerobic bioremediation reduces contaminant mass through natural biological processes, which are often limited by the availability of oxygen or nutrients

• The solubility of oxygen in water in very low (10 mg/L) so a continuing source of oxygen can promote aerobic biodegradation in groundwater

• For unsaturated soils oxygen can be provided from air (21% oxygen), and the moisture content managed, so a source of nutrients containing N & P will stimulate biodegradation PermeOx® Plus and Calcium Peroxide

CaO2 + 2H2O → Ca(OH)2 + H2O2 2H2O2 → O2 + 2H2O

• PermeOx Plus is Engineered calcium peroxide for very slow release of oxygen • Calcium Peroxide is a standard (food) grade with a faster oxygen release profile

Both products provide oxygen for enhanced aerobic bioremediation

• For the treatment of readily biodegradable organic compounds such as petroleum hydrocarbons • 18% Active Oxygen • Applied as a slurry • PermeOx Plus provides long-term oxygen release up to one year • Calcium Peroxide gives oxygen release over multiple months • Priced very competitively

PermeOx Plus –Oxygen Release Profile

September 12, 2013 Aerobic Bioremediation Case Study Active Petrol Retail Station - Germany

• Groundwater remediation via stimulation of aerobic bioremediation via slow release of oxygen from modified calcium peroxide • Two Direct Push slurry injections • Two and a half years of site monitoring

September 12, 2013 Terramend®

• Terramend comprises nutrients containing N and P sources to allow microbial growth on biodegradable organic compounds in soils • Specific Terramend formulations may also allow co-metabolic induction of PAH degrading enzymes via addition of plant fibres

September 12, 2013 Chemical Reduction Soil and Groundwater Remediation Technologies

Chemical Reduction Using Daramend® and EHC® (Carbohydrate & ZVI) What is chemical reduction?

• Chemical reduction involves transfer of electrons to contaminants from reduced metals (ZVI, ferrous iron) or reduced minerals (magnetite, pyrite) • The major dechlorination pathway promoted by ISCR technology is β-elimination, which supports complete dechlorination of TCE and PCE with less accumulation of metabolites such as cis-DCE and VC than pure enzymatic systems • Permeable reactive barriers, known as PRBs, constructed using ZVI are probably the most well- know and broadly applied example of ISCR.

September 12, 2013 Direct Chemical Reduction cVOC Dechlorination Pathways with ZVI

Biogenolysis/Hydrogenolysis: Minor Pathway

ß–Elimination: Main Pathway • Reaction is abiotic reductive dehalogenation; minimizes/eliminates DCE/VC

• Requires direct contact with ZVI surface

• β-elimination is the dominant pathway (~90%); ZVI generates hydrogen so some biotic reductive reactions are supported Contaminants Treated via Chemical Reduction

EHC® / Daramend® • Chlorinated Solvents o PCE, TCE, cDCE, 11DCE, VC o 1122TeCA, 111TCA, 12DCA o CT, CF, DCM, CM • Pesticides o Toxaphene, Chlordane, Dieldrin, Pentachlorophenol • Energetics o TNT, DNT, RDX, HMX, Perchlorate

EHC® Metals ISCR Reagent • Heavy Metals including As, Cr, Pb, Zn, Cd EHC In Situ Chemical Reduction (ISCR) Reagent Composition EHC is for application to groundwater

EHC is delivered as a dry powder and includes the following:

• Micro-scale zero valent iron (standard ~40%)

• Controlled-release, food grade, complex carbohydrate (plant fibres) (standard ~60%)

• Major, minor, and micronutrients

• Food grade organic binding agent

• Sustainable Solution o scrap metal o food production by-products

EHC® ISCR Installation Methods

Injection Methods • Direct injection • Hydraulic fracturing • Pneumatic fracturing • Well injections (EHC-L)

Direct Placement • Trenching • Excavations • Deep soil mixing

59-01-EIT-DL Chemical Reduction of Contaminants in Soil – Daramend

• Patented combination of slow-release carbohydrate and nutrients with micro- scale ZVI (20% to 50% w/w) • Stimulates indigenous bacteria by providing carbon and nutrients • Generate very strong reducing conditions that promote reductive dehalogenation reactions • 2% to 5% by weight required to treat most soils to remedial goals • More than 10,000,000 tons of soil, sediment, and other wastes have been successfully treated to date. Carbon Fermentation + ZVI Corrosion: Multiple Dechlorination Mechanisms

Material Oxide Film ZVI Reactions:

Fe+2 generation Solid Fe0  Fe2+ + 2e- Organic VFA Carbon + - H2 generation 2H O  2H + 2OH H+ 2

Fermentation + - 2H + 2e  H2(g) R-Cl + H+ + 2e-  R-H + Cl-

Iron Production of organic acids (VFAs): Metal • Serves as electron donor for microbial reduction of CVOCs and other oxidized species such as O2, NO3, SO4 Favorable thermodynamic conditions for • The release of acids keeps the pH down and dechlorination: thereby serve to reduce precipitate formation • Combined oxygen consumption from carbon on ZVI surfaces to increase reactivity fermentation and iron oxidation  Strongly • Increase rate of iron corrosion/H2 generation reduced environment (-250 to -500 mV) • High electron/H+ pressure

59-01-EIT-DL Downtown Urban Setting Former Dry Cleaner – Site Remediation Using Direct Injection of EHC

• Site: Waterfront Medieval Town Center, The Netherlands • Solution Provider: Groundwater Technology B.V., Rotterdam, The Netherlands • Geotechnically sensitive subsoil (some peat / clay) • P&T virtually impossible (low permeability) • Busy street – services, sewers etc • Recreational shopping – boutiques, café. bars

Waterfront Medieval Town Center, The Netherlands

September 12, 2013 EHC Permeable Reactive Zone (PRZ) Case Study

Plume Treatment CCl4 • Plume extends 2,600 ft / 800 m from grain elevators. • Discharges into small creek. • The bedrock rises to an elevation of ca 9 ft / 3 m above the present day water table at the presumed source area. • PRZ installed down-gradient of suspected source area in April 2005. • The PRZ is installed as a line of injection points spaced approximately 10 ft / 3 m apart. • The PRZ extends across the width of the plume and measures ca 270 ft / 90 m long. EHC PRZ – Plume Treatment Injection Layout

0 -5 0 27 54 81 108 135 162 189 216 243 270 -10 -15 -20 -25 -30 -35 Injection depth [ft] depth Injection -40 -45 -50 Distance from SBE [ft] EHC PRZ - Plume Treatment Results

<1<1

<1<1 15082983660704447

1400160027001200570620770 1303001706201406267 100057273349312925<111 <1<1

FebruaryMayOctoberAprilMarchAprilAugust 2010 2009 2008 2005 2007200920072008 140191314173721

150490151621199412 140380754654351767 380610110280162162 NN <16.4 12026065054041049046072

EHCEHC TreatmentTreatment ZoneZone MonitoringMonitoring wellwell andand CT concentration (ug/L) CTCT concentrationconcentration (ug/L)(ug/L) 2801901702534898598 PropertyProperty LineLine 5.82.4131525822837

SCALESCALE ININ FEETFEET

00 300300 600600 <1<1 EHC® Permeable Reactive Zone Plume Treatment Economics

• A total of 21,800 kg of EHC was used to create the 90 m long PRB at a product cost of less than € 80,000  €330/m2 of PRB cross-section. • The installation was completed in 12 days using direct injection. • So far, the PRB has treated a total of 73,000 m3 of groundwater during its life-time at a product cost of (€1/m3). Treatment of Pesticides in Soils with Daramend

• Former agricultural chemical manufacturing facility • Approximately 4,500 tons of soil and sediment from drainage ditch contaminated with DDT, DDE, DDD, and Toxaphene • Applied and incorporated 2% (w/w) DARAMEND amendments • Irrigate amended soil to 90% of soil water holding capacity and leave for 7 days • Aerate by tilling for 2 or 3 days • Repeat process if required

Treatment of Pesticides

Toxaphene 200 DDT DDE 150 DDD 100

50 Concentration (mg/kg) Concentration

0 0 2 4 6 8 10 12 14 Time (cycles) EHC Metals ISCR Treated and Mechanisms

EHC Metal is controlled-release carbohydrate with sulfide, nutrients & micro-scale ZVI Treatment Mechanisms in the ZVI- Contaminant Carbohydrate zone Reductive precipitation with oxidized iron As (III, V) minerals. Precipitation as As sulfide and mixed Fe-As sulfide Cr(VI), Mo(VI), Reductive precipitation with oxidized iron Se(IV,VI), minerals and adsorption to iron oxides. U(VI) Metal cations precipitate as sulfides, following stimulated heterotrophic Me2+ (Cu, Zn, microbial sulfate reduction to sulfide. Pb, Cd, Ni) Adsorption to iron corrosion products (e.g.; iron oxides and oxyhydroxides).

• Puls and Su, EPA Research Lab, OK:, Reductive precipitation of chromium and arsenic treatment with ZVI PRBs. • Blowes et al., University of Waterloo: Organic substrate PRBs for sulfate reduction and trace metals treatment in acid mine drainage.

EHC Metals Case Study – Pb Treatment Battery Recycling Facility

Contaminants •Lead – 360 - 86 μg/L

Approach • Create sulfate reducing conditions • Conditions by Injecting EHC-M • 0.05% EHC-M by wt. application rate • 0.25% by wt. Dolomite • Direct push, Direct Placement

59-01-EIT-DL EHC Metals Case Study – Pb Treatment Battery Recycling Facility

Gráfico 2 - Potencial Redox e pH no poço PB-01

11/7/07 11/9/07 11/11/07 11/1/08 11/3/08 11/5/08

15 400

12 300 200 9 pH

pH ORP (mV) 100 6 Results 0 • Pb concentration 3 -100 Potencial Redox(mV) Potencial reduced to <10 ppb in 0 -200 six months

• Full-scale remediation in progress

EHC Metals injection 11/11/07

59-01-EIT-DL Anaerobic Bioremediation Soil an Groundwater Remediation Technologies

ELS™ for in situ Bioremediation via Enhanced Reductive Dechlorination What is Anaerobic Bioremediation? • Anaerobic bioremediation of chlorinated solvents involves the use of the contaminants as the terminal electron acceptor (respiratory substrate) i.e. instead of oxygen, nitrate, sulfate etc. • This process may also be termed dehalorespiration or enhanced reductive dechlorination. • The process involves sequential dechlorination of chlorinated solvents where cis-DCE and VC are common daughter products, before ethene / ethane is formed. • The process is mediated by Dehalococoides sp. which are relatively ubiquitous but need to increase in population density (grow) to allow rapid sequential biotransformations

September 12, 2013 ELS™ emulsified lecithin substrate

• Applications: • Enhanced reductive dechlorination including both biostimulation and bioaugmentation • Composition: • Food-grade lecithin, including: • Phospholipids for long-term release of organic carbohydrate • Slow-release nitrogen & phosphorus • Polysaccharides and sugars to support rapid creation of reducing conditions

• Availability: • 25% emulsion and 100% concentrate • Packaging: • 5-gal. pail, 55-gal. drum, 275-gal. tote (25% emulsion only)

ELS Advantages • Easy to use: • Stable emulsion • No chase water needed

• Slow release nutrients: • Provides both organic nitrogen and phosphorus

• Good distribution: • Hydrophilic for enhanced distribution • Small droplet size (60% <1µm and 85% <2μm) Superior transport in the subsurface • Efficient source of hydrogen: (hydrophilic nature of phospholipids eliminates need for chase water) • High yield of H2 produced/gram substrate • Long lasting: • Extended release profile of 2 to 3 years

Hydrogen Yield from Organic Electron Donors

Product Theoretical Hydrogen yield *

Product Concentration (g H2/g substrate, estimate, (%) as delivered)

ELS™ Concentrate 100 0.324 Emulsified Vegetable Oil 100 0.359

HRC® 100 0.141 Sodium Lactate Solution 100 0.075

• Hydrogen utilization by bacteria is influenced by other factors including: • Biodegradation rate (longevity) • Substrate distribution • Availability of nutrients • pH

* Source ESTCP Project ER-0627, 2010

ELS Longevity (Column effluent TOC at 20 °C) 700

600 Feed

EHC-L 500 20 mg/L TOC

400

300

200 Total Organic Carbon (mg/L) Carbon Organic Total 100

0 0 100 200 300 400 500 Time (Days)

15cm/day gw flow TOC remained above the 20 mg/L threshold needed to support ERD for more than 365 days. Column test run at RT (20±2 °C); Given the Q10 for carbohydrate fermentation is 2.0 we estimate ELS longevity in groundwater at a typical temperature of 10±2 °C will be between 2 and 3 years ELS – Applicability

Target Compounds: Suitable Site Conditions & • Chlorinated ethenes Objectives: • Chlorinated methanes • Wide range of permeability • Chlorinated ethanes • Moderate to slow groundwater flow • Some heavy metals • Plume treatment • Some pesticides & herbicides • Diffuse source zone treatment • Some organic explosives Contaminant Levels: Application Methods: • Wide range subject to target • Direct push compound identity and site • Gravity feed through existing wells or conditions well points • Low or high pressure injection; subject Longevity: to site conditions • Typically 2 to 3 years • Recirculation systems FMC Soil & Groundwater Remediation

• A comprehensive portfolio of cost effective proven products to address a wide range of contaminants and site conditions • Unsurpassed technical support • An experienced team of environmental professionals focused on remedial strategies; including 8 Ph.D. level remediation specialists • Remedial design and field support • Other Services • Laboratories focused on research and treatability studies • Support services including site test kits • Upcoming Events • Technical webinars • The application of In Situ Chemical Reduction (ISCR) Groundwater Remediation Technologies • Destruction organic contaminants in soil and groundwater using Chemical Oxidation • November conferences in London, Paris and Milan

FMC Soil and Groundwater Remediation - Europe

Technical Support Dr. Ian Ross (UK) [email protected] +44 7855 745531

General Enquiries Mike Mueller (Austria) [email protected] +43 664 1803060

September 12, 2013