Sponsored by Regenesis and Kerfoot Technologies, Inc.

Ozone, Hydrogen Peroxide, and Air Injection Systems for Aggressive Remediation
Charles B. Whisman, GES, Exton, PA

An Innovative Approach to Protecting a Municipal Supply Well – Air/Ozone Sparge Curtain Results
Kent Zenobia, URS Corporation, Sacramento, CA

Superoxidation Ozone Systems for Aquifer Restoration – A Michigan State Superfund Site
Andrew Brolowski, Kerfoot Technologies, Inc., Mashpee, MA

Ozone Oxidation for Source Reduction and a Prevention Barrier at a Fire Training Academy
Tom Cambareri and Scott Michaud, Cape Cod Commission, Barnstable, MA

Successful Closure of an Industrial Site Adjacent to an Ohio Municipal Well field
William B. Kerfoot, Kerfoot Technologies, Inc., Mashpee, MA

In Situ Chemical Oxidation of Manufactured Gas Plant (MGP) using Ozone  
Jeffrey C. Dey, Resource Control Corporation, Moorestown, NJ

Ozone, Hydrogen Peroxide, and Air Injection Systems for Aggressive Remediation

Charles B. Whisman, P.E., Groundwater & Environmental Services, Inc., 410 Eagleview Blvd., Suite 110, Exton, PA 19341, Tel: 610-458-1077, ext. 156, Fax: 610-458-2300, Email: cwhisman@gesonline.com

An Innovative Approach to Protecting a Municipal Supply Well — Air/Ozone Sparge Curtain Results

Kent Zenobia, PE, DEE, URS Corporation, 2870 Gateway Oaks Drive, Suite 150, Sacramento, CA  95833, Tel: 916-679-2210, Fax: 916-679-2900, Email:  Kent_Zenobia@URSCorp.com
Ed Tarter, PE, URS Corporation, 2870 Gateway Oaks Drive, Suite 150, Sacramento, CA  95833, Tel: 916-679-2055, Fax: 916-679-2900, Email:  Edmund_Tarter@URSCorp.com
Vern Elarth, PG, URS Corporation, 2870 Gateway Oaks Drive, Suite 150, Sacramento, CA 95833, Tel: 916-679-2299, Fax: 916-679-2299, Email:  Vernon_Elarth@URSCorp.com
Nicole Damin, Stanislaus County Department of Environmental Resources, 3800 Cornucopia Way, Suite C, Modesto, CA 95358-9492, Tel: 209-525-6725, Fax: 209-525-6774, Email: ndamin@envres.org

Petroleum contaminants released from a retail gasoline station in a California Central Valley town threatened a municipal supply well (muni well) immediately adjacent to the station. Methyl tert-butyl ether (MtBE) was present in groundwater at concentra­tions up to 30,000 micrograms per liter (mg/L) in the first encountered groundwater aquifer, between 30 to 45 feet below ground surface (bgs). The muni well is located approximately 200 feet downgradient from the source area. Quarterly groundwater monitoring results indicated MtBE had migrated off site, and remedial action would be required to protect the downgradient muni well. The project team designed an innovative remediation system comprising an aggressive source area treatment with soil vapor extraction (SVE) for impacted vadose zone soils and a downgradient in situ treatment barrier at the property boundary.

The in situ treatment barrier includes air/ozone sparge wells placed downgradient of the source area and upgradient of the municipal supply well. The barrier is intended to reduce/destroy the MtBE concentrations and other residual gasoline-range organic (GRO) contamination. The perimeter in situ treatment barrier—sparge curtain—comprises dual-completion air/ozone sparge points co-located in the aquifer’s deeper and shallow portions.

URS developed a pilot test protocol for this process and agreed to share results with the Regulatory Agency prior to full system operation. Test results showed monitoring well MtBE concentrations were 780 mg/L initially, 50 mg/L after 8 days, and 1.5 mg/L after 35 days. Tertiary compounds were not generated. The pilot test protocol included employing a downhole video camera to record the intercept on the monitoring well from the sparge point locations. Contaminant concentrations in wells downgradient have shown further improvement and the system continues to protect the muni well. The site is currently in monitoring status, and installation of new confirmation soil borings is scheduled so final closure can be requested.

Superoxidation Ozone Systems for Aquifer Restoration – A Michigan State Superfund Site

Andrew Brolowski, Kerfoot Technologies, Inc., 766-B Falmouth Road, Mashpee, MA  02649, Tel:  508-539-3002, Fax:  508-539-3566, Email: andrewbrolowski@kerfoottech.com
William B. Kerfoot, Kerfoot Technologies, Inc., 766-B Falmouth Road, Mashpee, MA  02649, Tel:  508-539-3002, Fax:  508-539-3566, Email: wbkerfoot@kerfoottech.com

The term “superoxidation” refers to the combination of oxidative gases and liquids in such a manner as to maintain high oxidative states despite rapid reduction of target organics.  Coatings of peroxides and perates on ozone microbubbles can continuously generate hydroxyl,  perhydroxyl radicals, and persulfate.  With fine microbubbles volatile organics are drawn into the gas bubbles, reacting with the hydroxyl radicals.  The variety of organics which can be treated is substantially broadened over normal ozone to include alkanes, ethers,  aromatics, and polyaromatics (PAHs).  Even though the PAHs are poorly soluble semi-volatile compounds, the reactions with these compounds generate acetone and alcohols which serve to increase their solubility and reactivity.  Although easy to isolate in the laboratory, monitoring during field remediation has shown low or nondetectable acetone or alcohol presence.  This occurs because of reactivity with excess ozone and likely bacteriological activity.

An example of “super-oxidation” involves the case study of the former Thomas Solvents Company site, Ypsilanti Township, a Michigan Department of Environmental Quality (MDEQ) remediation cleanup which began in January, 2004.  With treatment area soil consisting primarily of fine to medium and coarse sand, the remediation system was designed with ozone gas with a peroxide coating (Perozone™) to treat the following wide variety of source area and outlying organic ground water contamination exceeding applicable regulatory cleanup standards: ketones (including acetone and butanone), chloroethanes (CE, MC, CTC, and TCA), chloroethenes (PCE, TCE, DCE, and VC), and aromatics (BTEX, isopropylbenzene, trimethylbenzene, butylbenzenes, naphthalenes).  Following 24 months of operation, with source area dissolved ground water total VOCs ranging in average above 20,000 ppb, total VOC ground water mass had been reduced greater than 93%.

Ozone Oxidation for Source Removal and a Prevention Barrier at a Fire Training Academy

Thomas C Cambareri and Scott Michaud, Cape Cod Commission, 3225 Main Street, PO Box 226, Barnstable, MA 0263, Tel: 508-362-3828, Fax: 508-362-3136 

The Barnstable Fire Training Academy is a multi-plume site resulting from chronic releases of petroleum hydrocarbons during simulated fire-fighting conditions over several decades as an “industrial/commercial” use in a Zone II public water-supply area.  Use of petroleum at the site was ceased in 1986.  Multiple source removals were conducted over the last 20 years. A pump and treat containment system was successful in reducing the down-gradient extent of petroleum, a release of MTBE from a leaking gasoline tank and a chloroform plume from another up-gradient site.  Although contamination migrating down-gradient of the site does not present an imminent threat or substantial hazard to public health due to natural attenuation, the smear zone continues to release slugs of contamination to groundwater. The site is located in a highly permeable aquifer suitable for an air-sparging system.  The Kerfoot Technologies “C-Sparge/Perozone™” system was selected as the preferred remedy to treat the residual smear zone.  The system consists of 12 sparge points capable of delivering air/ozone and peroxide to the smear zones and was configured with a secondary purpose of forming a barrier against unforeseeable events related to on-going training activities.  Sparge points are duel-stacked in source/smear-zone areas in recognition that deep sparge points treat a wider lateral area, while the shallow sparge points concentrate treatment close to the source.  The system was brought on line in April 2006 and continuous peroxide injection commenced in June 2006 following monitoring, repairs, adjustments and optimization of the system.  Sparge times for each well are set to optimize the duration of ozone/air and peroxide delivery to each well.  Initial results indicate a range of groundwater dissolved-oxygen concentrations around each sparge well up to supersaturated conditions.  Concentrations of BTEX, naphthalene and associated volatile organics in groundwater samples collected in June 2006 remain within concentration ranges observed since 2002-3.  Additional groundwater samples scheduled to be collected in August 2006 will provide further opportunity to evaluate system performance.

Successful Closure of an Industrial Site Adjacent to an Ohio Municipal Wellfield

William B. Kerfoot, Kerfoot Technologies, Inc., 766-B Falmouth Road, Mashpee, MA  02649
Tel:  508-539-3002, Fax:  508-539-3566, Email:  wbkerfoot@kerfoottech.com
Bruce E. Ehleringer, Washington Group International, Inc., 1500 West 3^rd Street, Cleveland, OH  44113, Tel:  216-523-5286, Fax:  216-523-5201, Email:  bruce.ehleringer@wgint.com
John Muncy, REM Investments, P. O. Box 266, Enon, OH  45323, Tel:  937-882-6158

Ozone sparging using the KTI C-Sparge™ process was performed on an industrial site adjacent to a major water supply well site. Ozone sparging was initiated in February, 2000, and groundwater volatile organic compound (VOC) concentrations in downgradient wells decreased as much as 95% by the end of 2001.  From 2003 to closure in 2006, the responsible party continued treatment with monitored attenuation and combined source treatment with a barrier region rather than more aggressively attack plant source areas.  There were three reasons:  1) initial treatment showed reductions to near MCLs at the well site and boundary, and reductions were continuing; 2)  monitoring costs were projected to closure at substantially less than addition of capital equipment; and 3)  the current plant owner was separate from the responsible party, so access was limited, and interruption of work unacceptable.

The site geology consisted of a fluvial sand and gravel aquifer with discontinuous silt lenses, where near surface caused perched water conditions.  Initial remedial actions included source excavation (1996), a Fenton’s Reagent flood (1998), followed by ozone sparging.

The regulatory agency accepted ozone sparging for source treatment and temporary barrier as the most desirable alternative.  Monitored attenuation was not acceptable without source reduction and elimination.  Continued operation of the facility progressed during remedial treatment.  Closure was obtained with the region achieving MCLs at the operational water supply wells and on the industrial site boundary.  Final groundwater removal was in excess of 99%.  No adverse water quality impacts were found during treatment at the water supply wellheads.

In Situ Chemical Oxidation of Manufactured Gas Plant (MGP) using Ozone

Jeffrey C. Dey, The Resource Companies, 1274 N. Church Street, Moorestown, NJ 08057, Tel: (856) 273-1009, Fax: 856-273-1012, Email: jeffd@rcc-net.com
Imtiyaz Kahn, The Resource Companies, 1274 N. Church Street, Moorestown, NJ 08057, Tel: 856-273-1009, Fax: 856-273-1012, Email: imtiyazk@rcc-net.com

A comprehensive pilot-scale field test of in situ chemical oxidation with ozone as a potential in situ remedial approach for Manufactured Gas Production (MGP) related contamination was conducted at an MGP site in the Northeastern United States.

The targeted treatment area occupies 2500 sq. feet, located 10 to 15 feet below grade.. Residual MGP impact in subsurface soil and groundwater at the site included coal tar, coal fragments, Non Aqueous Phase Liquid (NAPL), TPH-DRO including elevated concentrations of polynuclear aromatic hydrocarbons (PAHs), and TPH-GRO with elevated concentrations of benzene, toluene, ethylbenzene, and xylenes (BTEX).

Injection activities were conducted for 90 days.  Baseline, mid-treatment, and post treatment soil and groundwater sampling and analysis were completed as part of the pilot study. Post treatment sampling and analysis was conducted immediately after the completion of ozone injection and also 30 days after cessation. In monitoring well MW-103 (located within targeted area), a comparison of post test groundwater analytical results with the baseline analytical results indicated a reduction of total BTEX concentrations by 95% (from 10.99 to 0.56 ppm), total PAHs concentrations by 92% (from 7.93 to 0.62 ppm), TPH-DRO concentrations by 55% (from 20 to 9.0 ppm) and TPH-GRO concentrations by 93% (from 25 to 1.8 ppm). 

Comparisons of soil sampling analytical results with the baseline analytical results were varied. The post test soil results (samples taken 30 days after cessation of ozone treatment) indicated that BTEX concentrations increased by 8% (an increase from 93 to 101 mg/kg) in samples collected from 10 to 15 ft depth , but show reduction of BTEX concentrations by 7% (from 145 to 134 mg/kg) in samples when depth varies, PAHs concentrations were reduced by 38% (from 4,069 to 2,531 mg/kg), C-PAHs concentrations were reduced by 39% (from 417 to 253 ppm), TPH-DRO concentrations were reduced by 22% (from 6,329 to 4,910 ppm), and TPH-GRO concentrations were reduced by 81% (from 922 to 179 ppm). The observed increase in BTEX concentration is due to abnormal variation of BTEX concentrations observed in preliminary samples.  The SVE data indicated a total vapor phase VOC mass recovery of 78.94 lbs, and an average recovery rate of 0.021 lbs/hr. 

Destruction of COCs within the test area indicated the viability of using ozone as a feasible approach to remediation of the MGP related COCs.  However, as the post –remediation soil data suggests treatment activities should be conducted for a period greater than 90 days.

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