CRT CRT - NEIWPCC

CRT CRT Carus Remediation Technologies Carus Remediation Technologies

Carus Remediation Technologies Simplified Science St Louis Tank Conference 2012

CRT Carus Remediation Technologies

Remediation is complex

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


Advances with in situ remediation

1970’s Early Bioremediation

2012 Chemical Oxidation

Site Delineation

Delivery Methodologies

Second Generation Bioremediation

Better Design Metrics

Advanced Site Deliniation


Improvement in • Delineation • In Situ Oxidation / Reduction • In Situ Bioremediation



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


Contaminant Mass Identification - Qualitative vs Extrapolated Data


GW Flow

Dissolved Plume Area 10% Mass

Core Plume Area 10% Mass

75% Plume Size

20% Plume Size

Bioremediation, Natural Attenuation, ISCO (speed only)

ISCO, BioRemediation, Pump & Treat

Source Area 80% Mass 5% Plume Size Dig and Haul, Thermal, ISCO


Simplified ISCO

Advanced Oxidation

Simplified Bio

Aerobic IXPER STIMULOX

Simplified Source Reduction EZVI

Modified Fenton Remediation Grade Bioremediation Products

Slow Release ISCO Source Zone DNAPL Treatment


SIMPLIFIED ISCO SCIENCE •Advanced Oxidative Process

Simplified ISCO

Advanced Oxidation Modified Fenton Slow Release Fenton

•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


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


Basic ISCO Chemistry


The common Petroleum ISCO Oxidants: •Fenton Chemistry •Persulfate Chemistry

•Ozone Chemistry


What Site Factors Need to be Considered 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


How Much Oxidant Do I Need? •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)


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




Pressurized Hydrogen Peroxide Injection

GW


10,000 ppb

1,000 ppb 3,000 ppb





Clean Sands Showing Radius of Injection


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


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


Simplified Simplified ISCO Bio

Aerobic RemOx S RemOx IXPER SD RemOx STIMULOX L RemOx LD Anaerobic RemOx SR CAP 18 Remediation Grade CAP 18Products ME Permanganate Remediation Grade Bioremediation Products

SIMPLIFIED BIO SCIENCE •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


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 peroxide

higher AO content (10%) lower cost

ORC Advanced

calcium peroxide


EHC-O

calcium peroxide zeolite


PermeOx Plus

calcium peroxide

higher AO content (17%)

calcium peroxide

long term O2 source higher AO (16.6%) lower cost

IXPER 70C & 75C

consumed faster higher pH no nutrients no ISCO consumed faster higher pH no nutrients no ISCO consumed faster higher pH no nutrients no ISCO consumed faster higher pH no nutrients no ISCO higher pH no nutrients no ISCO

$5.00 - $7.00 / lb

$5.00 - $7.00 / lb

$5.23/lb

$4.00-$6.00/lb

$3.00 - $4.00 / lb


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

CRT

How Does IXPER Work

Carus Remediation Technologies

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

CaO2 Remaining (%)

90 80

PermeOx Plus

70

IXPER 75C

60

IXPER 70C granules

50 40 30 20 10 0 0

1% Suspention

6

12

18

24

30

Time (weeks)

36

42

48

54

CRT

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

13 12

pH

11 10 PermeOx Plus

9

IXPER 75C 8

IXPER 70C granules

7 0

6

1% Suspension

12

18

24

30

Time (weeks)

36

42

48

54

CRT

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

CRT

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

CRT

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 25 Dissolved Oxygen (mg/L)

23 21 19 17 15

13 STIMULOX ORC MgO2

11 9 0

5

10

15 Days

20

25

30


Application with STIMULOX

CRT

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
