Simplified Science St Louis Tank Conference 2012
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 2012 Early Bioremediation 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 75% Plume Size Bioremediation, Natural Attenuation, ISCO (speed only) Core Plume Area 10% Mass 20% Plume Size ISCO, BioRemediation, Pump & Treat Source Area 80% Mass 5% Plume Size Dig and Haul, Thermal, ISCO
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
Simplified ISCO Advanced Oxidation Modified Fenton Slow Release Fenton SIMPLIFIED ISCO SCIENCE 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
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)
T R = { (C S +C GW +C NPL )*G*S + (SOD*SOD E +S R )*Y s }* C F C S = Contaminant Concentration in soil (mg/kg) C GW = Contaminant Concentration in groundwater (ug/l) C NPL = Contaminant Concentration in NAPL phase (mg/l) P Eb = Effective Porosity G = Gallons Water To Be Treated (X*Y*Z*P E ) Y S = Yards of Soil To Be Treated (X*Y*Z) S = Stoichiometric requirements per pound of contaminant SOD = Soil Oxidant Demand (g/kg) SOD E = Effective Soil Oxidant Demand % S R = Other Scavenging Reactions (g/kg) C F = Confidence Factor (contaminants, lithology, hydrogeology, distribution, contact delivery) T R = Total Pounds of Oxidant required Eliot Cooper
Pressurized Hydrogen Peroxide Injection GW
10,000 ppb 3,000 ppb 1,000 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 ISCO Bio Aerobic RemOx S RemOx IXPER SD RemOx STIMULOX L RemOx LD Anaerobic RemOx SR CAP 18 Remediation Grade CAP 18 ME Permanganate Products 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 ORC ORC Advanced EHC-O calcium peroxide magnesium peroxide ammonia persulfate potassium persulfate dicalcium phosphate magnesium peroxide calcium peroxide calcium peroxide zeolite ST & LT release of O2 slightly lower ph nutrients passive ISCO higher AO content (10%) lower cost higher AO content (17%) lower cost higher AO content (17%) lower cost PermeOx Plus calcium peroxide higher AO content (17%) IXPER 70C & 75C calcium peroxide long term O2 source higher AO (16.6%) lower cost lower AO content (9.7%) more expensive metals content 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 $7.00/lb $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% CaO 2 by weight Dry powder average size 15µ (Talc powder) Typical Injection product ~17% active oxygen by weight Food grade IXPER 70C ~70% CaO 2 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
CaO2 Remaining (%) 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 CaO 2 Remaining in Water IXPER 70C granules slowest O 2 release 90 80 70 60 50 40 30 20 10 0 PermeOx Plus IXPER 75C IXPER 70C granules 0 6 12 18 24 30 36 42 48 54 1% Suspention Time (weeks)
ph How Does IXPER Work Onset of Action Higher ph allows for slower release mechanism as H2O2 not being produced ph in Water 13 12 11 PermeOx Plus lower than IXPER 10 9 8 7 PermeOx Plus IXPER 75C IXPER 70C granules 0 6 12 18 24 30 36 42 48 54 1% Suspension Time (weeks)
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
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
Dissolved Oxygen (mg/l) 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 25 23 21 19 17 15 Oxygen released in Water 13 11 9 0 5 10 15 20 25 30 Days STIMULOX ORC MgO2
Application with STIMULOX
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