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“The Good, the Bad, and the Ugly” Experiences of Chemical Oxidation and Why Presented “The Good, the Bad, and the Ugly” Experiences of Chemical Oxidation and Why Presented by: Larry Kinsman ORIN Remediation Technologies

Overview • • • Site Evaluation Bench Testing Implementation The Chemistries and Case Studies Overview • • • Site Evaluation Bench Testing Implementation The Chemistries and Case Studies Health and Safety Pricing

Site Evaluation • Determining if the site is a good fit for treatment – Site Evaluation • Determining if the site is a good fit for treatment – Type of soils – Type of contaminant – Type of subsurface conditions (geochemistry, anaerobic or aerobic) – Which approach is best? (bioremediation, chemical oxidation) – Type of implementation (in-situ, ex-situ, or a combination)

Conditions that Require Special Consideration • • Low permeable soils Deep aquifers and very Conditions that Require Special Consideration • • Low permeable soils Deep aquifers and very shallow aquifers LNAPL / DNAPL Confined formations High organic soils Old landfills and dumps River embankments Under buildings Source: ITRC's In Situ Chemical Oxidation of Contaminated Soil and Groundwater Second Edition (ISCO -2, 2005) available from www. itrcweb. org

Implementation The Keys to Success ! Delineation! – Leads to the Right chemistry – Implementation The Keys to Success ! Delineation! – Leads to the Right chemistry – Leads to the Proper Implementation

Bench Testing • Verify contaminant removal • Test natural oxidant demand (NOD) requirement • Bench Testing • Verify contaminant removal • Test natural oxidant demand (NOD) requirement • Assess effect of treatment on secondary water quality (e. g. p. H, dissolved iron, mobilization of metals) • Assess attenuation of secondary parameters

Column Tests Column Tests

Fenton’s and Persulfate Test Setup Fenton’s and Persulfate Test Setup

What Lab Testing Cannot Do • Perfectly simulate field conditions – Can’t determine exact What Lab Testing Cannot Do • Perfectly simulate field conditions – Can’t determine exact amount of reagent needed – Can’t predict the exact degree of change in a secondary parameter – Predict exactly how long secondary effects will last • Promise perfect results in the field – Applicability of bench test results depends upon how well test soil / groundwater represents the site – Success of ISCO depends upon skill and experience of field remediation team

Implementation Processes Ex-situ - Above ground treatment of contaminants In-situ - In place treatment Implementation Processes Ex-situ - Above ground treatment of contaminants In-situ - In place treatment of contaminants

Ex-Situ Applications Backhoe mixing Ex-Situ Applications Backhoe mixing

TROMMEL SCREENER Used for: - Soil screening and addition of soil amendments - Best TROMMEL SCREENER Used for: - Soil screening and addition of soil amendments - Best suited for large scale jobs

Mixing Head Mixing Head

Types of subsurface in-situ techniques • Grouted in injection points • Backhoe mixing • Types of subsurface in-situ techniques • Grouted in injection points • Backhoe mixing • Auger/ Grinder mixing • Direct Push

High Pressure Activated Injection Point High Pressure Activated Injection Point

Injection Rod With Disposable Point Injection Rod With Disposable Point

Side Injection Point Side Injection Point

Injection screen point Injection screen point

Specialized Injection Trailer Specialized Injection Trailer

Delivery Systems Batch vs. Recirculation Batch Oxidant Injection Oxidant Recirculation 20 Source: ITRC's In Delivery Systems Batch vs. Recirculation Batch Oxidant Injection Oxidant Recirculation 20 Source: ITRC's In Situ Chemical Oxidation of Contaminated Soil and Groundwater Second Edition

Treatment Approaches • Chemical Oxidation • Reductive Dechlorination • Bioremediation Treatment Approaches • Chemical Oxidation • Reductive Dechlorination • Bioremediation

The Oxidation Chemistries • Hydrogen Peroxide with Acid Water (p. H dependent) • Klozur® The Oxidation Chemistries • Hydrogen Peroxide with Acid Water (p. H dependent) • Klozur® Sodium Persulfate • Ozone • Calcium Peroxide • Permanganate (not p. H dependent) • Fenton’s Reagent (p. H dependent)

Reductive Dechlorination • • Zero Valent Iron Lactic Acid Soy Bean Oil Combinations Reductive Dechlorination • • Zero Valent Iron Lactic Acid Soy Bean Oil Combinations

Bioremediation • Perme. Ox® Plus , EHC-O, Regenesis ORC ® Advanced “Slow release oxygenating Bioremediation • Perme. Ox® Plus , EHC-O, Regenesis ORC ® Advanced “Slow release oxygenating compound” • Combination of oxidants - Klozur® ENA • ISOC’s gas diffusion devices

Case Histories: Bench-, Pilot- and Full-Scale Case Histories: Bench-, Pilot- and Full-Scale

Case Studies - Background • The case studies presented here represent both petroleum hydrocarbons Case Studies - Background • The case studies presented here represent both petroleum hydrocarbons and chlorinated solvents. • While this trend for Chemox of petroleum hydrocarbons exists, these following case studies offer reasons why scale-up testing can be valuable and should be considered as a useful, cost-effective step in scaling up the design of Chemox systems targeting petroleum.

Case Study #1 Property Redevelopment Pilot-Scale Case Study #1 Property Redevelopment Pilot-Scale

General Information • Successful bench and pilot scale project – Bench-scale soil tested for General Information • Successful bench and pilot scale project – Bench-scale soil tested for TOD – Pilot-scale testing parameters, based upon TOD, was implemented: • • Old dumping area Soil: Sand with trace silts Depth of contamination: 20 to 55 feet Contaminants: Creosote, BTEX, and Naphthalene Oxidant injected 25% Klozur® Sodium Persulfate Number of injection points: 8 Number of days of injecting: 2

Groundwater Results Units ppb Groundwater Results Units ppb

Case Study # 2 Site Redevelopment Case Study # 2 Site Redevelopment

General Information • Unsuccessful pilot-scale testing – Bench-scale testing of soil for TOD successfully General Information • Unsuccessful pilot-scale testing – Bench-scale testing of soil for TOD successfully completed, and design criteria established for pilot-scale test • • • Abandon Manufacturing Facility Soil: Clay Depth of contamination: 20 to 35 feet Contaminants: PCE and TCE Chemical injected : Hydrogen Peroxide and Sodium Persulfate • Number of injection points: 16

Groundwater Results Groundwater Results

Case Study # 3 Property Transaction Site Case Study # 3 Property Transaction Site

General Information • Successful field implementation -Bench test successfully completed • Oil Refinery (pipeline General Information • Successful field implementation -Bench test successfully completed • Oil Refinery (pipeline leak) • Soil: silty clay • Depth of contamination: 4 to 13 feet • Contaminants: BTEX • Calcium Peroxide and Sodium Persulfate injected 15% to 40% (Klozur® ENA) • Number of injection points: 35 • Number of days on injecting: 3

Groundwater Results Units ppm Groundwater Results Units ppm

Case Study # 4 • Successful bench-scale testing of soil containing petroleum hydrocarbons and Case Study # 4 • Successful bench-scale testing of soil containing petroleum hydrocarbons and lead – Soil sample was tested for TOD – Successful treatment of lead noted, but natural oxidant demand was high, resulting in the need for multiple oxidant injections to overcome the oxidant demand to achieve satisfactory petroleum hydrocarbon reductions • Due to background oxidant demand needing to be overcome in order to reduce COC levels, Chemox at this site was not a costs-effective option – Dig & haul was a more cost-effective option offering assurance that all COC were removed from the site

Case Study #5 Industrial Clean-up Pilot-Scale Case Study #5 Industrial Clean-up Pilot-Scale

General Information • Mixed results for pilot scale activities – Successful reduction under the General Information • Mixed results for pilot scale activities – Successful reduction under the building – Currently, no reduction down-gradient injection area • • Plume over 1 mile in length (injection areas ½ mile apart) Soil: Fine to medium sands with silt and clay lenses Depth of contamination: 15 to 30 feet Contaminants: TCE, DCE, VC (exhibited reducing conditions at both areas) • Chemistry: EOS® • Number of injection points: 22 DPT points outside and seven 4” PVC recovery wells inside building • Number of days of injecting: 3

Groundwater Results • Reducing conditions under building – Adequate bacteria count – 85% reduction Groundwater Results • Reducing conditions under building – Adequate bacteria count – 85% reduction of TCE – Ethene observed post injection at 24 X original concentration • Reducing conditions under building – – Low to non-detect bacteria count little reduction of TCE Ethene observed non-detect pre- and post-injection Low fatty acid count (only acetic acid detected)

Groundwater Results Units ug/L Groundwater Results Units ug/L

Dissolved Gases Results Dissolved Gases Results

Health and Safety • Review of site conditions (utility corridor, constituents, surrounding land use) Health and Safety • Review of site conditions (utility corridor, constituents, surrounding land use) • Site-specific Health and Safety Plan • Subsurface mixing of reactive chemicals • Health and Safety audits

Oxidizing Chemistries: Health, Safety & Environment (HSE) Concerns • Read & understand material safety Oxidizing Chemistries: Health, Safety & Environment (HSE) Concerns • Read & understand material safety datasheets (MSDS) prior to material handling (reference MSDS websites as needed) • Potential hazard risks to mitigate and avoid: – extreme contact risk, especially to eyes • Personal protective equipment (PPE) is a must • Readily available eyewash / shower – inhalation and dermal contact • Ensure oxidants compatibility with equipment and materials • Store and protect oxidants (heat/cold & sun/rain, as appropriate) • Develop site-specific Health and Safety Plans (HASPs) in accordance with 29 CFR 1910. 120 guidance • Enforce HASP requirements for everyone on-site!

Oxidizing Chemistries: HSE Concerns Investigate, characterize and understand your site and surrounding area! – Oxidizing Chemistries: HSE Concerns Investigate, characterize and understand your site and surrounding area! – Complete a competent receptor survey – Evaluate potential migration pathways • Utility corridors, particularly underground • Potential conduits for vapors & liquids transport • Geologic/Hydrogeologic fractures – Consider surface runoff discharge points & ultimate discharge • Weather patterns • Precipitation collection basins & run-off routes – Infrastructure concerns • • Buildings, roadways, underground piping, sewers, wells UST systems and underground piping/pumps Overhead hazards Evaluate current infrastructure elements’ integrity

Oxidizing Chemistries: HSE Concerns – Available on-site space • Working space for remediation equipment Oxidizing Chemistries: HSE Concerns – Available on-site space • Working space for remediation equipment – Traffic patterns • People • Vehicles – Site accessibility • On-site personnel, public, visitors • Emergency vehicles • Ingress/Egress routes, primary and alternates – Hospital options & routes • All on-site personal should have up-to-date OSHA, First Aid, and First. Responder training • On-site HASP read, communicated, and signed by all on-site personnel and visitors

LAGGING INJURY REACTIVE LOSSES DAMAGE LEADING NEAR MISS HAZARD ID’s BEHAVIOR OBSERVATIONS PROACTIVE LAGGING INJURY REACTIVE LOSSES DAMAGE LEADING NEAR MISS HAZARD ID’s BEHAVIOR OBSERVATIONS PROACTIVE

Look at Total Recordable Incidents of the Contractors During their Operating Existence before Hiring Look at Total Recordable Incidents of the Contractors During their Operating Existence before Hiring

Implementation The Keys to Success ! • Delineation! • Leads to the Right chemistry Implementation The Keys to Success ! • Delineation! • Leads to the Right chemistry • Leads to the Proper Implementation

ORIN’s Services • In-house Treatability laboratory • Remediation Services – Construction Management – UV/Vis ORIN’s Services • In-house Treatability laboratory • Remediation Services – Construction Management – UV/Vis Spectroscopy – In-situ and Ex-situ treatment – Total Oxidant Demand Test – Product Recovery with – Bench Scale Feasibility Oxidant Flooding Studies – Organic and Inorganic

Question and Answers Relating to Chemical Treatment Question and Answers Relating to Chemical Treatment

Contact Information: Larry Kinsman ORIN Remediation Technologies Office: 608 -838 -6699 Cell: 608 -445 Contact Information: Larry Kinsman ORIN Remediation Technologies Office: 608 -838 -6699 Cell: 608 -445 -7707 “Offering you the finest environmental contracting services, products & remedial technologies available” Craig Marlow 8248 Hidden Forest Drive, Holland, Ohio 43528 Phone 419. 867. 8966 Fax 419. 867. 8976 Cell 419. 349. 7970 Email [email protected] net