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

September 12, 2013

• 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.

FMC Soil & Groundwater Remediation

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)

• Permanganate (MnO4) – low solubility of K salt

– not strong enough to destroy benzene (no radical mechanism)

– can oxidise TCE

– forms solid residues “crust” on DNAPL

• Hydrogen Peroxide (H2O2) (Fenton’s Reagent) – very reactive (creates heat and off

gas) so potential safety issues

– short half life so limited distribution

– radical mechanism

• Ozone (O3) – low solubility gas must be sparged

– short half life thus limited distribution

– Radical mechanism

– often an addition to AS/SVE so

unclear if oxidation mechanism is

responsible for contaminant removal

• Persulfate (S2O8) – high solubility

– radical mechanism

– variable half live hence longevity can

be adjusted from hours to months

– Safe to handle and inject

Common Chemical Oxidants used for Remediation

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

product

Granular Persulfate

• 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!

Klozur Persulfate Chemistry – Activation

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

-2)

Heat Iron H2O2 High pH

Sustainable Solution: FMC Manufactures Utilizing Hydroelectric Power

Klozur Activated Persulfate

Examples of contaminants destroyed

Chlorinated Solvents

PCE, TCE, DCE

TCA, DCA

Vinyl chloride

Carbon tetrachloride

Chloroform

Chloroethane

Chloromethane

Dichloropropane

Trichloropropane

Methylene chloride

TPH

BTEX

GRO

DRO

ORO

creosote

Oxygenates

MTBE

TBA

Chlorobenzenes

Chlorobenzene

Dichlorobenzene

trichlorobenzene

Phenols

phenol

Pentachlorophenol

nitrophenol

Freons

Pesticides

DDT

Chlordane

Heptachlor

Lindane

Toxaphene

MCPA

Bromoxynil

PAHs

Anthracene

Benzopyrene

Styrene

Naphthalene

Pyrene

Chrysene

trimethylbenzene

Others

Carbon disulfide

PFOS / PFOA

Aniline

PVA

TNT / DNT

1,4 Dioxane

Klozur® Activated Persulfate Application Methods

• Direct push

• Fixed well

• In situ soil mixing

• Ex situ soil mixing

Forming a persulfate solution

Fixed wells

Direct push rig

In situ mixing

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

Fixed Wells - H2O2 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

Klozur Persulfate Case Study

Soil Mixing - Alkaline Activation

In Situ Chemical Oxidation of Chlorobenzene using Klozur Activated Persulfate

• Design objective; maximize in situ destruction of COC in a

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

• Concentrations of chlorobenzene and dichlorobenzene reduced

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

continuous

flight auger rigs

Area A Area C Area E

Area B Area D

2008 Brownfield Briefing Remediation Innovative Award -“Best Conceptual Design”

Thornton, England

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

September 12, 2013

PermeOx Plus –Oxygen Release Profile

September 12, 2013

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

Aerobic Bioremediation Case Study

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)

September 12, 2013

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.

ß–Elimination: Main Pathway

Biogenolysis/Hydrogenolysis: Minor 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

Direct Chemical Reduction

cVOC Dechlorination Pathways with ZVI

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

Production of organic acids (VFAs):

• Serves as electron donor for microbial

reduction of CVOCs and other oxidized

species such as O2, NO3, SO4

• The release of acids keeps the pH down and

thereby serve to reduce precipitate formation

on ZVI surfaces to increase reactivity

• Increase rate of iron corrosion/H2 generation

Favorable thermodynamic conditions for

dechlorination:

• Combined oxygen consumption from carbon

fermentation and iron oxidation Strongly

reduced environment (-250 to -500 mV)

• High electron/H+ pressure

ZVI Reactions:

Fe0 Fe2+ + 2e-

2H2O 2H+ + 2OH-

2H+ + 2e- H2(g)

R-Cl + H+ + 2e- R-H + Cl-

Fe+2 generation

Material

Solid

Organic

Carbon

Iron

Metal

Oxide Film

Ferm

enta

tion

H+

VFA H2 generation

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

September 12, 2013

Waterfront Medieval Town Center, The Netherlands

• 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 Permeable Reactive Zone (PRZ)

Case Study

Plume Treatment CCl4

-50

-45

-40

-35

-30

-25

-20

-15

-10

-5

0

0 27 54 81 108 135 162 189 216 243 270

Distance from SBE [ft]

Inje

cti

on

de

pth

[ft

]

EHC PRZ – Plume

Treatment Injection Layout

44<1

<1

120067

25<1 <1

19

1575

16

72<1

5.825

<1

EHC Treatment Zone

Monitoring well andCT concentration (ug/L)

N

Property Line

0 300 600

SCALE IN FEET

May 2010

60<1

<1

57062

31<1 <1

21

1635

21

120<1

1334

<1

EHC Treatment Zone

Monitoring well andCT concentration (ug/L)

N

Property Line

0 300 600

SCALE IN FEET

October 2009

70<1

<1

1400130

29<1 <1

21

2117

62

260<1

1589

<1

EHC Treatment Zone

Monitoring well andCT concentration (ug/L)

N

Property Line

0 300 600

SCALE IN FEET

April 2009

150<1

<1

620170

49<1 <1

37

1254

110

490<1

28170

<1

EHC Treatment Zone

Monitoring well andCT concentration (ug/L)

N

Property Line

0 300 600

SCALE IN FEET

October 2008

82<1

<1

1400300

57<1 <1

13

1946

380

650<1

25280

<1

EHC Treatment Zone

Monitoring well andCT concentration (ug/L)

N

Property Line

0 300 600

SCALE IN FEET

April 2008

98<1

<1

1600170

27<1 <1

14

94140

610

540<1

82190

<1

EHC Treatment Zone

Monitoring well andCT concentration (ug/L)

N

Property Line

0 300 600

SCALE IN FEET

August 2007

36<1

<1

2700620

33<1 <1

17

150380

610

410<1

2.485

<1

EHC Treatment Zone

Monitoring well andCT concentration (ug/L)

N

Property Line

0 300 600

SCALE IN FEET

February 2007

47<1

<1

770140

100011 <1

140

49067

280

4606.4

3798

<1

EHC Treatment Zone

Monitoring well andCT concentration (ug/L)

N

Property Line

0 300 600

SCALE IN FEET

March 2005

EHC PRZ - Plume Treatment Results

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

0

50

100

150

200

0 2 4 6 8 10 12 14

Time (cycles)

Co

nc

en

tra

tio

n (

mg

/kg

)

Toxaphene

DDT

DDE

DDD

EHC Metals ISCR Treated and Mechanisms

Contaminant Treatment Mechanisms in the ZVI-

Carbohydrate zone

As (III, V) Reductive precipitation with oxidized iron

minerals. Precipitation as As sulfide and mixed Fe-As sulfide

Cr(VI), Mo(VI), Se(IV,VI),

U(VI)

Reductive precipitation with oxidized iron minerals and adsorption to iron oxides.

Me2+ (Cu, Zn, Pb, Cd, Ni)

Metal cations precipitate as sulfides, following stimulated heterotrophic

microbial sulfate reduction to sulfide. 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 Metal is controlled-release carbohydrate with sulfide, nutrients &

micro-scale ZVI

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

-200

-100

0

100

200

300

400

0

3

6

9

12

15

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

Po

ten

cia

l R

ed

ox

(m

V)

pH

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

pH

ORP (mV)

Results

• Pb concentration

reduced to <10 ppb in

six months

• Full-scale remediation

in progress

EHC Metals injection 11/11/07 59-01-EIT-DL

EHC Metals Case Study – Pb Treatment

Battery Recycling Facility

Anaerobic

Bioremediation

Soil an Groundwater

Remediation

Technologies

ELS™ for in situ Bioremediation

via Enhanced Reductive

Dechlorination

September 12, 2013

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

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)

• Efficient source of hydrogen:

• High yield of H2

produced/gram substrate

• Long lasting:

• Extended release profile of

2 to 3 years

Superior transport in the subsurface

(hydrophilic nature of phospholipids

eliminates need for chase water)

Hydrogen Yield from Organic Electron Donors

Product

Product Concentration

(%)

Theoretical Hydrogen yield * (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

* Source ESTCP Project ER-0627, 2010

• Hydrogen utilization by bacteria is influenced by other factors including:

• Biodegradation rate (longevity)

• Substrate distribution

• Availability of nutrients

• pH

ELS Longevity (Column effluent TOC at 20 °C)

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

0

100

200

300

400

500

600

700

0 100 200 300 400 500

To

tal O

rgan

ic C

arb

on

(m

g/L

)

Time (Days)

Feed

EHC-L

20 mg/L TOC

ELS – Applicability

Target Compounds: • Chlorinated ethenes • Chlorinated methanes • Chlorinated ethanes • Some heavy metals • Some pesticides & herbicides • Some organic explosives

Suitable Site Conditions & Objectives:

• Wide range of permeability • Moderate to slow groundwater flow • Plume treatment • Diffuse source zone treatment

Contaminant Levels: • Wide range subject to target

compound identity and site conditions

Longevity: • Typically 2 to 3 years

Application Methods: • Direct push • Gravity feed through existing wells or

well points • Low or high pressure injection; subject

to site conditions • 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

September 12, 2013

©2013 FMC Corporation. FMC, DARAMEND, EHC, ELS, PermeOx and Teramend are trademarks of FMC Corporation or its

subsidiaries. HRC is a trademark of Regenesis. All rights reserved

FMC Soil and Groundwater Remediation - Europe

Technical Support

Dr. Ian Ross (UK) ian.ross@fmc.com

+44 7855 745531

General Enquiries

Mike Mueller (Austria) mike.mueller@fmc.com

+43 664 1803060