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Carus Remediation Technologies

Carus Remediation Technologies Simplified Science

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St Louis Tank Conference 2012

http://www.caruscorporation.com/

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Remediation is complex In Situ remediation is even more complex In life do we try to complicate or simplify? Carus Remediation

Technologies…Simplified Science

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Advances with in situ remediation

1970’s

Early Bioremediation Chemical Oxidation

Second Generation

Bioremediation

Site Delineation

Better Design

Metrics

Delivery Methodologies

Advanced Site Deliniation

2012

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Improvement in

• Delineation • In Situ Oxidation /

Reduction • In Situ Bioremediation

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On-site, Contaminant Characterization -Membrane Interface Probe

• Advanced with DPT at 1 ft/min

• The tool tip has a VOC permeable membrane

• The tool tip has a built-in heating element that can volatize VOCs

• A nitrogen carrier gas transports the VOCs through sealed tubing to above- ground detectors.

• Qualitative and quantitative concentrations

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Contaminant Mass Identification - Qualitative vs Extrapolated Data

http://ehsjournal.org/wp-content/uploads/2010/01/Fiacco-High-Resolution-Diagram.jpg

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Source Area 80% Mass

5% Plume Size

Core Plume Area 10% Mass

20% Plume Size

Dissolved Plume Area 10% Mass

75% Plume Size

Dig and Haul, Thermal, ISCO

Bioremediation, Natural Attenuation, ISCO (speed only)

ISCO, BioRemediation, Pump & Treat

GW Flow

http://www.geoanalysis.com/images/Plume_industrial_text.jpg

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Simplified ISCO

Advanced Oxidation Modified Fenton Slow Release ISCO

Simplified Bio

Aerobic IXPER STIMULOX Remediation Grade Bioremediation Products

Simplified Source

Reduction

EZVI Source Zone DNAPL Treatment

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Simplified ISCO

Advanced Oxidation Modified Fenton Slow Release Fenton

•Advanced Oxidative Process •pH adjustment to pH of 4 •Catalyzing of system with Iron •Inject oxidant sequentially or simultaneously

•Short circuiting •Heat and gas control

•Modified Fenton •pH adjustment in the 6 range •Catalyzing of system with Iron •Inject oxidant sequentially or simultaneously

•Reduce Short circuiting •Lower heat and gas production

•Slow Release Modified Fenton •Injection of stable solid peroxide compound •Catalyze with iron •As slowly H2O2 releases from solid peroxide it can both oxidize and create oxygen rich environment

SIMPLIFIED ISCO SCIENCE

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The Keys to Success with ISCO are:

•Choosing the correct oxidant

•Choosing the correct delivery mechanism

•Understanding the site specific oxidant demand

•Injecting enough oxidant

•Creating contact

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Basic ISCO Chemistry

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The common Petroleum ISCO Oxidants:

•Fenton Chemistry •Persulfate Chemistry •Ozone Chemistry

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Geology

• Sands • Silts • Clays • Glacial Till • Fractured Bedrock

Geochemical Concerns • Target Contaminants • Natural Oxidant Demand • Contaminant Phase • pH • Alkalinity • Heavy Metals

Oxidant Selection • Sodium Permanganate • Potassium Permanganate • Hydrogen Peroxide • Ozone • Sodium Persulfate • Fenton’s Reagent

Delivery Mechanisms • High or Low Pressure Injection • Hydraulic Fracturing • Pneumatic Fracturing • Recirculation Systems • Reactive Barriers

What Site Factors Need to be Considered

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•Contaminant Concentration in soil (mg/kg) •Contaminant Concentration in groundwater (ug/l) •Effective Porosity •Gallons Water To Be Treated •Yards of Soil To Be Treated •Stoichiometric requirements per pound of contaminant •Soil Oxidant Demand (g/kg) •Effective Soil Oxidant Demand % •Other Scavenging Reactions (g/kg) •Confidence Factor (contaminants, lithology, hydrogeology, distribution, contact delivery)

How Much Oxidant Do I Need?

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•CS = Contaminant Concentration in soil (mg/kg) • CGW = Contaminant Concentration in groundwater (ug/l) • CNPL = Contaminant Concentration in NAPL phase (mg/l) • PEb= Effective Porosity • G = Gallons Water To Be Treated (X*Y*Z*PE) • YS = Yards of Soil To Be Treated (X*Y*Z)

• S = Stoichiometric requirements per pound of contaminant • SOD = Soil Oxidant Demand (g/kg) • SODE = Effective Soil Oxidant Demand % • SR = Other Scavenging Reactions (g/kg) • CF = Confidence Factor (contaminants, lithology, hydrogeology, distribution, contact delivery) TR = Total Pounds of Oxidant required

Eliot Cooper

TR = { (CS+CGW+CNPL)*G*S + (SOD*SODE+SR)*Ys}* CF

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Pressurized Hydrogen Peroxide Injection

GW

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1,000 ppb

3,000 ppb

10,000

ppb

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http://www.insituoxidation.com/images/FAQ.pdf

http://www.insituoxidation.com/images/ISOTEC Treatability.xls

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Clean Sands Showing Radius of

Injection

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Advances in ISCO Technologies

•Use of SVE in conjunction with ISCO

•Draw and control off gas from ISCO

•Lowers Temprature

•Use of low temperature ISCO

•CoolOx and Drill Ox

•Use of solid oxidants with passive release mechanisms

•New Methodologies to treat more recalcitrant compounds with Super Oxides

•Permanganate and Modified Fenton used as a treatment train

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How To Ensure a Successful ISCO Project

•Be confident in you site data

•MIPS or more sampling

•Inject enough oxidant

•Know your PNOD

•Know your goals

•Establish a sampling plan

•Make sure there are enough sample locations to prove goals

•Design for at least two injections

•Be flexible in the field

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Simplified ISCO

RemOx S RemOx SD RemOx L RemOx LD RemOx SR Remediation Grade Permanganate Products

•Aerobic Bioremediation •IXPER 75C & IXPER 70C

•Single Component •Longer lifespan

•STIMULOX •IXPER 75C with Nutrients and buffers included

•Anaerobic Bioremediation •CAP18 & CAP18 ME

•Complex mixing and emulsion of multiple compounds not necessary •Total volume of fluids injected reduced

•Potential reduced injection costs •Single injection lasts years

SIMPLIFIED BIO SCIENCE

Simplified Bio

Aerobic IXPER STIMULOX Anaerobic CAP 18 CAP 18 ME Remediation Grade Bioremediation Products

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Oxygen Releasing

Compounds

Comparison

Ingredients Advantages Disadvantages Price

STIMULOX

calcium peroxide

magnesium peroxide

ammonia persulfate

potassium persulfate

dicalcium phosphate

ST & LT release of O2

slightly lower pH

nutrients

passive ISCO

lower AO content

(9.7%) more

expensive

metals content

$7.00/lb

ORC magnesium peroxidehigher AO content (10%)

lower cost

consumed faster

higher pH

no nutrients

no ISCO

$5.00 - $7.00 / lb

ORC Advanced calcium peroxidehigher AO content (17%)

lower cost

consumed faster

higher pH

no nutrients

no ISCO

$5.00 - $7.00 / lb

EHC-Ocalcium peroxide

zeolite

higher AO content (17%)

lower cost

consumed faster

higher pH

no nutrients

no ISCO

$5.23/lb

PermeOx Plus calcium peroxide higher AO content (17%)

consumed faster

higher pH

no nutrients

no ISCO

$4.00-$6.00/lb

IXPER 70C & 75C calcium peroxide

long term O2 source

higher AO (16.6%)

lower cost

higher pH

no nutrients

no ISCO

$3.00 - $4.00 / lb

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Calcium Peroxide •IXPER 75C ~75% CaO2 by weight

•Dry powder average size 15µ (Talc powder) •Typical Injection product •~17% active oxygen by weight •Food grade

•IXPER 70C ~70% CaO2 by weight •Granular material average size 500-2,000µ •Typical trench or excavation product •Slower oxygen release profile due to surface area •~15.5% active oxygen by weight •Food grade quality

Product Use

•Long term oxygen source for aerobic degradation of petroleum hydrocarbons

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How Does IXPER Work

Onset of Action •Slowly decomposes in water generating oxygen •Slowest release of all competitors in studies conduction by Western Michigan University

CaO2 Remaining in Water

IXPER 70C granules slowest O2 release

0

10

20

30

40

50

60

70

80

90

0 6 12 18 24 30 36 42 48 54

Time (weeks)

Ca

O2 R

em

ain

ing

(%

) PermeOx Plus

IXPER 75C

IXPER 70C granules

1% Suspention

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7

8

9

10

11

12

13

0 6 12 18 24 30 36 42 48 54

Time (weeks)

pH

PermeOx Plus

IXPER 75C

IXPER 70C granules

How Does IXPER Work

Onset of Action •Higher pH allows for slower release mechanism as H2O2 not being produced pH in Water

PermeOx Plus lower than IXPER

1% Suspension

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IXPER Summary

• Longer Lasting oxygen release •Natural pH: Extends release of oxygen •Two grades to match application use •IXPER 75C price per pound

•$3.11 - $3.51 depending on volume

•IXPER 70C price per pound •$3.91

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What is STIMULOX®

A blend of five separate components designed to produce optimum aerobic bioremediation conditions

•IXPER 75C Calcium Permangnate

•Provides a long term oxygen source •Magnesium Peroxide

•Provides short and long term oxygen source •Ammonia Persulphate

•Provides fixed nitrogen and nutrients •Potassium Persulphate

•Provides potassium and pH adjustment •Dicalcium Phosphate

•Nutrients

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How Does STIMULOX Work

Onset of Action •Active ingredients decompose in water generating oxygen at different rates providing short and long term oxygen release •pH buffering and nutrients released over time to provide optimum conditions for bioremediation

Oxygen released in Water

9

11

13

15

17

19

21

23

25

0 5 10 15 20 25 30

Dis

solv

ed

Ox

yg

en

(m

g/L

)

Days

STIMULOX

ORC

MgO2

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Application with STIMULOX

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STIMULOX Summary

• Multiple oxygen release rates quick onset as well as long term oxygen •pH buffering •Nutrients •Fixed Nitrogen

•STIMULOX price per pound

•$7.00

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