KMnO₄ and Hydraulic Fracturing, An Innovative Technology Combination for Passive ISCO Destruction of Chlorinated Compounds

Montague W. Busbee, FRx Inc., 501-8 Old Greenville Hwy, Clemson, SC, 29631, Tel: 864-836-0116, Fax: 864-653-4868, Email: monty@frx-inc.com
William W. Slack, PhD, PE, FRx Inc., PO Box 498292, Cincinnati, OH, 45249-8292, Tel: 513-469-6040, Fax: 513-469-6041, Email: wslack@frx-inc.com
James R. Richardson, MS, FRx Inc., 501-8 Old Greenville Hwy, Clemson, SC, 29631, Tel: 864-356-8245, Fax: 864-653-4868, Email: jim@frx-inc.com

The delivery of solid potassium permanganate by hydraulic fracturing offers several benefits over other delivery mechanisms for low permeability media. Fracturing can exploit long recognized fundamental characteristics of solid permanganate – that it is an aggressive and easy to use oxidant, it operates over a wide range of soil conditions and it can persist in the subsurface for long periods of time following placement – to render a nearly ideal single–application, passive remediation program.   The advantages follow in at least four categories. First, large quantities of concentrated solid oxidizer can be delivered to the subsurface at one time.  This eliminates operation and maintenance costs associated with the operation of injection and extraction pumps and above ground oxidant handling equipment required for permanganate distribution via conventional wells.  Second, hydraulic fracturing technology is compatible with and indeed best employed via DPT allowing the creation of source zones of solid oxidizer at discrete depths via one direct push location.  This eliminates the costs associated with the installation of permanent injection wells and allows the oxidizer to be positioned vertically in the subsurface to best address varying vertical contaminant distributions which might remain untreated by injection through wells with long screen sections.  Third, the radius of influence of hydraulic fractures is vastly greater than that of conventional wells in LPM.  This means less injection locations are required than with conventional wells.  And fourth, the mechanism of mass transport of oxidizer through the treatment zone can be by diffusion away from the emplaced oxidant source zones, which should encourage the treatment of formation heterogeneities or regions of especially low groundwater flow in the treatment zone. Hydraulic fracture emplaced KMnO4 for ISCO degradation of chlorinated organic contaminants has been employed on three full scale commercial projects since the fourth quarter of 2003 and on at least one pilot scale project at a DoD site in 2004.

A Three Year Application of Bulk Quantities of Sodium Permanganate for In-Situ Chemical Oxidation (ISCO) of Chlorinated VOCs

Raymond J. Cadorette, BS in Bio-Resource Engineering, Shaw Environmental, Inc., 88C Elm Street, Hopkinton, MA  01748, Tel: 508-497-6102, Fax: 508-435-9641, Email: Raymond.Cadorette@shawgrp.com
Lawrence Nesbitt, PE, BS in Civil Engineering, MS Water Resources, MBA, Shaw Environmental, Inc., 88C Elm Street, Hopkinton, MA  01748, Tel: 508-497-6125, Fax: 508-435-9641, Email: Larry.Nesbitt@shawgrp.com

Shaw Environmental, Inc has completed the third year of implement a large, multi-year, in-situ chemical oxidation (ISCO) groundwater treatment program at an active manufacturing site located in New England.  The program was initiated as part of an effort to reach state cleanup goals and alleviate the need for continued source area hydraulic control.  TCE and PCE are the primary contaminants at the site.  An ISCO pilot test was conducted in the primary contaminant source area, and based on its initial success a full-scale ISCO system was designed and implemented.  The extent of impacts made injection of oxidant a viable alternative due to its potential to more quickly achieve cleanup objectives at a lower cost than implementing a traditional, full-scale groundwater pump and treat technology.

The topographic and geologic conditions vary widely at the site, from low permeability glacial tills with moderate groundwater gradients to highly permeable outwash deposits with low groundwater gradients.  Impacts extend into weathered bedrock with an irregular surface profile, and associated varying overburden thicknesses.  Sodium permanganate was chosen as the oxidant for its high concentration and suitability for bulk liquid delivery in tanker trucks. 

Expanding on the results of the first year of treatment that were presented at the 2003 UMASS Soil, Sediment and Water Conference, this presentation will explain the continuing reductions in contaminant concentrations, over an increasingly larger area, resulting from the second and third year of treatment.  The presentation will review the monitoring methods and results, present a general overview of the ongoing success of the program, and a few notable lessons learned. 

USEPA Superfund Innovative Technology Evaluation (SITE) of Persulfate Oxidation for the Remediation of Chlorinated Solvents

M. Amine Dahmani, University of Connecticut, 270 Middle Turnpike, Longley Bldg., Box U-5210, Storrs, CT, 06269-5210, Tel: 860-486-2781, Fax: 860-486-5488, Email: adahmani@eri.uconn.edu
Kunchang Huang, University of Connecticut, 270 Middle Turnpike, Longley Bldg., Box U-5210, Storrs, CT, 06269-5210, Tel: 860-486-2781, Fax: 860-486-5488, Email: khuang@eri.uconn.edu
George E.Hoag, Hoag Environmental Systems, P.O. Box 275, Storrs, Connecticut 06268, Tel: 860-429-3798, Fax: 860-429-0437, Email: georgehoag@hoagenvsys.com

This study has been conducted by the Environmental Research Institute (ERI) at the University of Connecticut and the USEPA Superfund Innovative Technology Evaluation (SITE) program to evaluate persulfate-based chemical oxidation technologies developed at ERI.  Persulfate oxidation technologies utilize persulfate or a combination of persulfate with a catalyst to destroy contaminants and offer great promise toward economical and permanent solutions for many contaminated sites. These technologies rely on the complete destruction of the contaminants of concern and their breakdown products in soil and groundwater.

A protocol developed by University of Connecticut researchers to assess the efficacy of oxidation technologies at contaminated sites has been used.  This protocol, which consists of obtaining data from a treatability study, identified persulfate, Fe(II)-EDTA catalyzed persulfate, and potassium permanganate as oxidation technologies that can be used effectively to treat solvent-contaminated soil and groundwater at a site in Vernon, Connecticut.  Based on the treatability report results and additional field data collected at the site, the design for the field implementation of the chemical oxidation remediation was completed and the field application of the persulfate and catalyzed persulfate technologies is being implemented under the USEPA SITE program. Results of this demonstration project obtained thus far are presented here.

Aggressive Chemical Oxidation Using Ozone and Hydrogen Peroxide Injection to Address Significant LNAPL Plumes

Cullen Flanders, PE, Groundwater & Environmental Services, Inc., 290 Executive Dr, Suite 200, Cranberry Twp, PA 16066   Phone: 724-779-4614; Fax: 724-779-4617

The presentation will discuss how aggressive chemical oxidation processes using ozone and hydrogen peroxide injection can be utilized to address all phases of contaminants, including non-aqueous phase liquid (NAPL). 

The discussion will detail the aggressive processes which assist in breaking down NAPL, including the presence of three oxidation species (ozone, hydrogen peroxide, and hydroxyl radicals), mass-transfer mechanisms, volatilization, and bioremediation.  Case study data will be presented where the process was utilized in a significant LNAPL plume to aggressively remediate greater than two feet of weathered gasoline and diesel.  The case study also showed significant soil and groundwater remediation, in addition to the LNAPL reduction.  Other case study information will be discussed, including utilizing the process on heating oil and diesel releases for higher-chain hydrocarbons.

The presentation will discuss the changes in LNAPL chemical properties during operation and evaluation of the soil/groundwater oxidant demand.  Methods to enhance the distribution of oxidants to promote effective remediation will also be evaluated.

Use of Novel Chemical Oxidation Program to Remediate Petroleum Hydrocarbons at an Active Gasoline Station

Joseph Hayes, P.G Environmental Compliance Services, 65 Millet Street Richmond, VT  05477, Tel: 802-434-4500, Fax: 802-434-6076, Email: jhayes@ecsconsult.com
Steven A. Peck, P.E., Regenesis, 3268 Shadowtree Drive, Oceanside, CA 92054, Tel: 760-231-5092, Fax: 760-231-5093, Email: speck@regenesis.com

A site remediation program was implemented at an active gasoline station located in Barre, Vermont under Vermont’s Pay for Performance Program.  The remedial design incorporated several technologies including multiphase extraction, ORC® and chemical oxidation to remediate both free phase and dissolved phase gasoline contaminants.  The multiphase extraction system operated over a 24 month period and significant reductions in the concentration of gasoline constituents were observed across the site.  However, a small area on the site remained above the remedial target levels and chemical oxidation was used to address the residual gasoline contamination.   The chemical oxidation process employed at this site was REGENOX^TM.  The REGENOX^TM product uses a solid alkaline oxidant that is activated through the action of a proprietary dual catalytic system.  The chemical oxidant was applied twice using 8 foot on center spacing across an injection grid.  Data were collected to evaluate the performance of the chemical oxidant.  Data from both the multiphase and chemical oxidation phases of the program will be presented.

Field Results with an Alkaline In-Situ Chemical Oxidation Process

Stephen S. Koenigsberg, Regenesis, 1011 Calle Sombra, San Clemente, CA  92673; Tel: 949-366-8000, Fax: 949-366-8090, Email: skoenigsberg@regenesis.com
Steve Peck, Regenesis, 3268 Shadowtree Drive, Oceanside, CA  92054, Tel: 760-231-5092, Fax: 760-231-5093, Email: stevepeck@regenesis.com
Michelle Von Arb, Regenesis, 1011 Calle Sombra, San Clemente, CA  92673, Tel: 949-366-8000, Fax: 949-366-8090, Email: mvonarb@regenesis.com
Maryam Azad, Applied Power Concepts, 411 Julianna Street, Anaheim, CA  92801, Tel: 714-502-1150, Fax: 714-502-2450, Email:  mazad@appliedpowerconcepts.com
William A. Farone, Applied Power Concepts, 411 Julianna Street, Anaheim, CA  92801, Tel: 714-502-1150, Fax: 714-502-2450, Email:  farone@appliedpowerconcepts.com

Regenesis has recently developed an in situ chemical oxidation process designed to treat organic contaminants.  As with other chemical oxidation products, this product is used to target high concentration source areas in the saturated and vadose zones, often followed by treatment technologies such as bioremediation as a polishing step.  The RegenOx™ product uses a solid oxidant that is activated to a very high performance level through the action of a proprietary dual catalytic complex and which operates under alkaline conditions with certain advantages.

Regenesis initiated a field test program in conjunction with several engineering consulting firms.  RegenOx was tested at various sites throughout the United States, including gasoline stations, dry cleaning facilities, former manufactured gas plants and a chemical packaging facility among others.

The typical field test was conducted using direct injection points in a defined area.  After the initial injection event, monitoring wells within and adjacent to the test area were monitored for oxidation-reduction potential (ORP), pH, dissolved oxygen (DO), the contaminants of concern (COCs), the RegenOx oxidant, anions, and cations.  As scheduled, a second and some cases third injection event were conducted at the sites and monitoring was continued.  The wells were monitored just prior to injection and at daily, weekly and monthly intervals.

This presentation discusses the basic technology and laboratory data, in addition to the design of the field test program and the evaluation of the data collected from the tests.  

Low-cost Chemical Oxidation at Gasoline Release Sites via air Hydrogen Peroxide, Ozone, and Air Injection (HypeAir)

Jennifer Roushey, Groundwater & Environmental Services, Inc., 410 Eagleview Blvd., suite 110, Exton, PA 19341, Tel: 610-458 1077x156, Fax: 610-458-2300, Email:  jroushey@gesonline.com
Charles B. Whisman, P.E. Groundwater & Environmental Services, Inc., 410 Eagleview Blvd., suite 110, Exton, PA 19341, Tel: 610-458 1077x156, Fax: 610-458-2300, Email:  cwhisman@gesonline.com

Case studies will be presented where BTEX and MTBE impact in soil and groundwater remediated through the combination of short-term hydrogen peroxide and air/ozone injection events.  The technology will be presented in detail and case studies will be shown where contaminated soil and groundwater was aggressively remediated through short-term (daily/weekly) remediation solutions.  Sites to be discussed include both active and inactive gasoline service stations. 

Case studies will be presented where short-term mobile hydrogen peroxide and air/ozone (“HypeAir”) injection systems were utilized to remediate soil and groundwater impacted with BTEX and MTBE at relatively low life-cycle remediation costs ($15,000 to $100,000). 

The discussion will also explain how the processes have been modified to enhance the radial influence at injection points and to maximize the distribution of the oxidants.  The technology to be discussed utilizes numerous aggressive remediation processes together (chemical oxidation with three oxidizing species, mass-transfer from air injection, enhance bioremediation, and soil vapor extraction). 

TCE in Fractured Bedrock Groundwater Remediation via Sodium Permanganate Injection and Re-circulation

William F. Simons, P.G., Mabbett & Associates, Inc., 5 Alfred Circle, Bedford, MA 01730.  Tel: 781-275-6050, Fax: 781-275-5651, Email: simons@mabbett.com. 
Paul D. Steinberg, P.E., L.S.P, Mabbett & Associates, Inc., 5 Alfred Circle, Bedford, MA 01730.  Tel: 781-275-6050, Fax: 781-275-5651, Email: steinberg@mabbett.com.

In situ chemical oxidation (ISCO) is an emergent remedial technology where organic contaminants are degraded in the subsurface via contact with chemical oxidants.  Successful implementation of ISCO has been documented in overburden applications where the delivery mechanism provided sufficient oxidant-contaminant contact.  The objective of this pilot study was to field test the application of sodium permanganate solution injection and re-circulation (I&R) for remediation of dissolved trichloroethene (TCE) in fractured bedrock ground water.  The study entailed the intermittent injection and re-circulation of a sodium permanganate solution through bedrock fractures expressed in open bedrock boreholes and bedrock monitoring wells.  Extracted groundwater was initially dosed with sodium permanganate to create a solution with a 5% concentration that was re-injected back into the fractured bedrock at the contaminant source area.  The injected permanganate solution replaced ground water with high concentrations of dissolved TCE (100,000 to 200,000 ug/L), thus allowing continued TCE and permanganate contact via natural advection, dispersion, and diffusion under natural hydraulic gradients.  Injected solution was left in the bedrock fracture system until the permanganate was degraded and rebound was observed.

Post I&R groundwater sampling data indicated concentrations of TCE were reduced from between 100,000 to 150,000 ug/L and to below 1 ug/L in the injection well.  Concentrations in monitoring wells were reduced from approximately 150,000 ug/L to less than 1 ug/L initially and to between 30,000 and 50,000 ug/L once rebound occurred.  Post I&R monitoring did not indicate uncontrolled migration of the permanganate solution.  A larger scale source area implementation is currently in progress and is comprised of two additional open bedrock boreholes, injection and extraction manifolds with flow monitoring devices and pressure gauges, and permanganate dosing and injection equipment.  Ongoing ISCO implementation and monitoring is projected to occur over the next two years.

The Use of Permanganate for the Oxidation of Pentachlorophenol Part 2

Kelly A. Frasco, Carus Chemical Company, 1500 Eighth St., LaSalle, IL  61301, Tel: 815-224-6852, Fax: 815-224-6869, Email: kelly.frasco@caruschem.com
Dr. Clifford E. Harris, Albion College/Ecosynthetics, Albion, MI 49224, Tel: 517-629-0253, Email: charris@albion.edu 
Dr. Michael W. Osborne, Carus Chemical Company, 1500 Eighth St., LaSalle, IL  61301, Tel:  815-224-6852, Fax: 815-224-6869, Email: mike.osborne@caruschem.com 
Dr. Philip A. Vella, Carus Chemical Company, 1500 Eighth St., LaSalle, IL  61301, Tel: 815-224-6852, Fax: 815-224-6869, Email: phil.vella@caruschem.com

Pentachlorophenol (PCP), a chlorinated hydrocarbon, has been widely used as an insecticide, pesticide and a wood preservative until 1987 when its use was restricted to certified applicators in the wood preservative industry. PCP is listed in EPA toxicity class II, meaning it is considered moderately toxic.  In 1983 the production of PCP was 45 million lbs. According to the EPA, PCP is found at 313 of the 1,585 National Priorities List sites.  Potassium permanganate (KMnO₄) has been an effective technology for the oxidation of many organic compounds including chlorinated organics and phenolic compounds.

Preliminary studies have confirmed the ability of permanganate to oxidize PCP in an efficient manner and have been reported previously.  It has been shown that the reaction produces two possible intermediates tetrachloro-1,4 benzoquinone or tetrachlorophenol.  The goals of this study were: 1) confirm the true nature of the observed intermediate through GC/MS analysis, 2) determine the reaction kinetics of the intermediate with permanganate, and 3) determine the mass balance of the PCP/permanganate reaction by monitoring chloride formation and TOC reduction. Possible reaction mechanisms will be discussed based on confirmed intermediate formation along with final reaction by-products.  Data from a recent field evaluation will also be presented.

In-situ Chemical Oxidation of Pentachlorophenol Using Microbubble Perozone Technology

Christopher Watt, LACO ASSOCIATES, 21 West Fourth Street, CA, 95501, Tel: 707-443-5054, Fax: 707-443-0553, Email: wattc@lacoassociates.us

A proprietary ozone and hydrogen peroxide sparging system was operated for 10 months at a former lumber mill located on the margin of an estuarine environment.  Target compounds, intrinsic groundwater parameters, and chloride ion were monitored in the area groundwater.  In addition, pre and post-treatment intrinsic soil conditions were documented.

The strongly poised (up to 1% organic carbon and 2.5% ferric iron by weight) water-logged sediments resisted change in electron pressure (oxidation-reduction potential) during oxidant sparging.  This elevated reduction capacity appeared to limit effective distribution of the oxidants. Increased injection times and installation of additional sparge points allowed for sufficient oxidant distribution.

After nearly one year of treatment, dissolved chlorophenol concentrations were reduced 95% and soil sampling has confirmed the gradual destruction of sorbed-phase chlorophenols.

Short-term “Max-Ox” Ozone, Hydrogen Peroxide, and Air Injection Systems for Aggressive BTEX and MTBE Remediation (Including Fractured/Weathered Bedrock Sites)

Charles Whisman, P.E., Groundwater & Environmental Services, Inc., 410 Eagleview Blvd., suite 110, Exton, PA 19341, E-mail: cwhisman@gesonline.com, Phone: (610) 458 1077x156, Fax: 610 458-2300
Peter Herlihy, Eastern Region Manager, Applied Process Technology, Inc. 3333 Vincent Road, Suite 222, Pleasant Hill, CA, 94523, USA, E-mail: pherlihy@aptwater.com, Telephone: (925) 977-1811, Fax: (925) 977-1818

This presentation will explore recent advances in aggressive patent-pending “Max-Ox” chemical oxidation technologies that combine liquid oxidants (such as hydrogen peroxide) and a gas (such as ozone, oxygen, or air) for aggressive injection in soil and groundwater to address significant source reduction in all contaminant phases (adsorbed, dissolved, and LNAPL).  Case studies will include remediating thousands of pounds of contaminant mass (such as BTEX, MTBE, and TBA) in soil and groundwater through the injection of ozone, oxygen, air, and hydrogen peroxide. 

The technology uses three chemical oxidation species (ozone, hydrogen peroxide, and hydroxyl radicals) aggressively remediating contaminated soil and groundwater.  The technology can be applied to varying lithologies and at sites with significant contaminant mass, as case studies will show.  Case studies to be presented include recent success stories in weathered/fractured bedrock.  The discussion will evaluate the various remedial processes combined into the Max-Ox process, including: chemical oxidation (via three different oxidation species – ozone, hydrogen peroxide, and the hydroxyl radical); enhanced air sparging (scrubbing, mixing, washing effect in addition to mass transfer via air movement); enhanced bioremediation (via increased dissolve oxygen levels outside of injection area);  and soil vapor extraction (for off-gas control and unsaturated soil pact).

The discussion will also evaluate different methods available to perform on-site feasibility tests which can be utilized to evaluate the potential effectiveness of in-situ chemical oxidation using ozone and hydrogen peroxide injection.  Case study data has indicated that downgradient dissolved MTBE impact can be addressed via aggressive source area remediation and without requiring off-site remediation (due to enhanced bioremediation through elevated dissolved oxygen concentrations).

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