LNAPL Delineation and Remediation Utilizing UV Fluorescence/Hydrophobic Dye Field Screening and In-Situ Chemical Oxidation
James F. Spicer,ATOFINA Petrochemicals, Inc.
Montgomery S. Bennett, Groundwater & Environmental Services, Inc.
Eric M. Kovich, Groundwater & Environmental Services, Inc.

A Cost Effective Decision: Accelerated Cleanup Using Permanganate
Elizabeth Rasmussen, Raytheon Company
Richard W. Lewis, ERM
Robert Luhrs, Raytheon Company
Timothy Pac, ERM 
Ronald C. Slager,  Raytheon Company

Application of In-situ Oxidation (ISCO) at a Site With Multiple Diverse  Hydrogeologic Settings
Raymond Cadorette, Shaw Environmental, Hopkinton, MA
David Walker, Shaw Environmental, Hopkinton, MA
Lawrence Nesbitt, Shaw Environmental, Hopkinton, MA

Chemical Oxidation Delivery by EK
Christopher Athmer, Terran Corporation
Bernard Woody, United Technologies Corporation

Degradation of Volatile Organic Compounds with Thermally Activated Persulfate Oxidation
Dr. Kun-Chang Huang, University of Connecticut
Zhiqiang Zhao, University of Connecticut
Dr. George Hoag, University of Connecticut
Dr. Philip Block,FMC Corp

An Evaluation of In Situ Chemical Oxidation (ISCO) for MGP Impacted Soils and Ground Water
Michael C. Marley, Xpert Design and Diagnostics, LLC, Stratham, NH
Bruce L. Cliff, Xpert Design and Diagnostics, LLC, Stratham, NH
Kenneth L. Sperry, Xpert Design and Diagnostics, LLC, Stratham, NH
Jaydeep M. Parikh, Xpert Design and Diagnostics, LLC, Stratham, NH

LNAPL Delineation and Remediation Utilizing UV Fluorescence/Hydrophobic Dye Field Screening and In-Situ Chemical Oxidation

James F. Spicer,Remediation Project Manager, ATOFINA Petrochemicals, Inc., 15710 JFK Boulevard, Houston, TX, 77032, USA, Tel: 281-227-5052, Fax: 281-227-5055, Email: james.spicer@atofina.com
Montgomery S. Bennett, P.G., Senior Hydrogeologist, Groundwater & Environmental Services, Inc., 23 S. 13^th Street, Suite 201, Richmond, VA, 23219, USA, Tel: 804-343-0700, Fax: 804-343-0770, Email: mbennett@gesonline.com
Eric M. Kovich, E.I.T., Project Manager, Groundwater & Environmental Services, Inc., 410 Eagleview Boulevard, Suite 110, Exton, PA, 19341, USA, Tel: 610-458-1077 x101, Fax: 610-458-2300, Email: ekovich@gesonline.com

ATOFINA and GES have worked together to utilize an innovative light non-aqueous phase liquid (LNAPL) field-screening methodology to facilitate delineation of residual LNAPL at a former polystyrene manufacturing facility located in New Jersey.  The field screening approach utilized UV fluorescence and hydrophobic dye tests to identify the presence of residual LNAPL in vadose zone and saturated soils in multiple source areas at the site.  The results of the LNAPL delineation were used to design an aggressive in-situ chemical oxidation program focused on remediating the residual LNAPL to below regulatory levels required by the New Jersey Department of Environmental Protection (NJDEP).  GES and ATOFINA teamed with MEC^x, LLC and utilized their patented CleanOX^® chemical oxidation technology to complete a 14-day pilot injection program at the site.  During the 14-day pilot program, a total of approximately 59,000 gallons of 17.5% hydrogen peroxide were injected through a network of 28 stainless steel injection wells. A temperature monitoring program, utilizing downwell thermocouples, was conducted throughout the injection to ensure that subsurface temperatures remained below predetermined levels.  Additionally, field parameters such as dissolved oxygen (DO), oxidation/reduction potential (ORP), temperature, and pH were monitored at a downgradient monitoring well to determine the effect of the injection activities on groundwater geochemistry.  Following completion of the 14-day pilot program, a total of 19 soil borings were installed throughout the pilot injection area to determine the LNAPL removal effectiveness.  The data generated during the follow-up soil boring program indicated that the aerial extent of residual LNAPL in the pilot area was reduced approximately 66% and the vertical thickness was reduced by as much as 80%.  Currently, the second phase of injection well installation and chemical injection, which is designed to remediate all source areas of residual LNAPL at the site, is underway and will be completed in March 2003.

A Cost Effective Decision: Accelerated Cleanup Using Permanganate

Elizabeth Rasmussen, Raytheon Company, 528 Boston Post Road, Mail Stop 1880, Sudbury, MA 01776
Richard W. Lewis, CPG, Program Manager, ERM, 2 Commercial Drive, Sharon, MA 02067, Tel:  617-646-7811, Fax: 617-267-6447, Email: rick.lewis@erm.com
Robert Luhrs, LSP, Raytheon Company, 141 Spring Street, Mail Stop 1-2-303, Lexington, MA 02173
Timothy Pac, CPG, Sr. Project Manager, ERM, 2 Commercial Drive, Sharon, MA 02067 , Tel: 617-646-7862, Fax: 617-267-6447, Email: tim.pac@erm.com
Ronald C. Slager, Restoration Program Manager , Raytheon Company, 528 Boston Post Road,Mail Stop 1880, Sudbury, MA  01776

Raytheon Company has a former manufacturing facility in Quincy, Massachusetts that has on-going environmental restoration work for a release of chlorinated volatile organic compounds (VOCs) to soil and groundwater.  The site soil consists of 8 to10 feet of a granular fill with some peat still present intermittently.  Underlying the fill from 40 to 50 feet are interbedded fine sands, silts and clays. Groundwater is shallow at a depth of 2 to 8 feet. The highest VOC groundwater concentrations are generally immediately on top of the silt layer.

Raytheon installed a treatment system at the facility consisting of a groundwater/soil vapor extraction with air stripping of groundwater and thermal oxidation of stripper and soil vapor off-gasses from 1997-1999.   Consistent long-term operation of the thermal oxidizer was expected to be expensive with an anticipated utility bill of $150,000 per year. 

Raytheon sold the facility in 2001.  The new owner has redeveloped the site as a retail store.  Pending imminent site redevelopment, Raytheon considered the use of innovative remedial technologies that would save the company time and money.  As a result of this analysis and successful pilot testing, Raytheon used chemical oxidation at the site.

Applications of both sodium and potassium permanganate were selected for four target areas of the site (approximately 1-acre).  Permanganate was added into a network of temporary injection points, completed 12-14 feet below ground surface. A total of 44,680 pounds of permanganate was applied through 97 points during the 10 weeks of addition in 2001.

Post application monitoring indicates significantly decreased VOC concentrations indicating about an order of magnitude reduction in total VOCs at most locations.  Several small programs of treatment for residual areas have resulted in application of an additional 7,000 pounds of permanganate.  Raytheon anticipates continued monitoring of the groundwater until site closure can be achieved. 

Application of In-situ Oxidation (ISCO) at a Site with Multiple Diverse  Hydrogeologic Settings

Raymond Cadorette, Shaw Environmental, Inc., 88C Elm Street, Hopkinton, MA  01748, Tel: 508-497-6102, Fax: 508-435-9641, Email: Raymond.Cadorette@shawgrp.com
David Walker, Shaw Environmental, Inc., 88C Elm Street, Hopkinton, MA  01748, Tel; 508-497-6158, Fax: 508-435-9641, Email: David.Walker@shawgrp.com
Lawrence Nesbitt, PE, Shaw Environmental, Inc., 88C Elm Street, Hopkinton, MA  01748, Tel: 508-497-6158, Fax: 508-435-9641, Email: Larry.Nesbitt@Shawgrp.com

As part of an effort to reach state cleanup goals and alleviate the continued need for source area hydraulic control, the largest known in-situ oxidation (ISCO) effort was implemented at this manufacturing facility site located in New England. TCE and PCE are the primary contaminants at the site.  Groundwater extraction and treatment was conducted in the primary contaminant source areas at the site for a period of eleven years. Over the course of the pumping and treatment program, dissolved concentrations of total chlorinated organic compounds (CVOCs) in the most impacted recovery well averaged 457 mg/L.  An ISCO pilot test was conducted in the primary contaminant source area, which reduced the average (over 12 months) dissolved concentration of total CVOCs to 63 mg/L in the most impacted recovery well, a sustained decrease of over 85%.  Based on this initial successful application of ISCO technology, a full-scale ISCO system was designed and implemented.  One key to successful ISCO is to achieve intimate contact between the contaminant and the oxidant.  To achieve this contact and account for the varying depths of the targeted CVOCs and the multiple diverse hydrogeologic settings at the site, various permanganate application methods were employed at different depths in the full-scale ISCO system.  Application methods utilized at this site included gravity addition through vertical and horizontal wells and pressurized application through vertical wells to a maximum depth of 160 feet.  This ISCO full-scale treatment program used a 20% sodium permanganate solution in 28 injection locations in the primary contaminant source area and downgradient locations.  This paper summarizes the various application methods employed at this site, the safety measures employed and the results of the first year’s application of over 75,000 gallons of sodium permanganate solution. This dosage is part of the largest ISCO application of permanganate to be applied to date. 

Chemical Oxidation Delivery by EK

Christopher Athmer,PE., Terran Corporation, 4080 Executive Dr., Beavercreek, OH  45430, Tel: 937-320-3601, Email: cjathmer@terrancorp.com
Bernard Woody,United Technologies Corporation, 1 Financial Plaza, MS 503, Hartford, CT 06101 Email: bernard.woody@corphq.utc.com

In-situ chemical oxidation has become a standard tool for the treatment of volatile organic contaminants in soil and groundwater.  In-situ chemical oxidation requires the delivery of a chemical oxidant, such as potassium permanganate, through the soil to contact the target contaminant.  However, in heterogeneous or low permeability soils, the delivery can be difficult if not impossible by normal hydraulic means due to the development preferential pathways.   Electrokinetics (EK), a potential solution to this problem, has been explored. EK can be used to move ionic oxidants, such as permanganate, through soil regardless of soil type, hydraulic conductivity or, to a certain extent, saturation level.  Negatively charged permanganate will move from the cathode region toward the anode in a uniform and predictable manner while the pore water and contaminant migrate toward the cathode.  The entire soil area can become saturated with permanganate ions.  Based on the known utility of potassium permanganate and electrokinetics, the integration of these two processes can become an extremely powerful remediation tool. 

Experiments have been performed to show that permanganate ions can be delivered through clay soil by electrokinetics to treat TCE contaminated soil.  In a laboratory size cell, a zone of potassium permanganate was emplaced near, but not in, the cathode zone.  The applied DC voltage gradient causes migration of the dissolved permanganate ions toward the anode, contacting the soil and contaminants as it travels.  Tests were operated at ambient and elevated temperatures to simulate actual field conditions caused by EK.

The manganese reached the anode in all experiments after roughly three days, traveling a distance of 17 centimeters.  The runs with TCE contaminated soils showed destruction of at least 99% and no daughter products were detected.  Based on the results of these experiments, it appears permanganate can be delivered through clay soils effectively using electrokinetics. 

Degradation of Volatile Organic Compounds with Thermally Activated Persulfate Oxidation

Kun-Chang Huang, Environmental Research Institute, University of Connecticut, 270 Middle Turnpike, U-5210, Storrs, CT 06269, Tel: 860-486-5893, Email:khuang@eri.uconn.edu
Zhiqiang Zhao, George E. Hoag and Amine Dahmani, Department of Environmental & Civil Engineering, University of Connecticut, 270 Middle Turnpike, U-5210, Storrs, CT 06269 Tel.: 860-486-2781, Fax: 860-486-5488
Philip A. Block, FMC Corp. P.O. Box 8, Route 1 and Plainsboro Rd., Princeton, NJ 08543 , Tel.: 609-951-3279, Fax:  609-951-3688              

Sodium persulfate is an alternative oxidant for site remediation with chemical oxidation processes.  At relatively high temperature (e.g., 40°C), persulfate (a radical-driven oxidant) is capable of degrading a wide variety of organic contaminants.  To facilitate the application of persulfate oxides for site remediation, laboratory-scale experiments were conducted.  The primary goal was to examine the extent and tendency of degradation of 60 volatile organic compounds (VOCs) listed in the EPA SW-846 Method 8260B with thermally activated persulfate oxidation. Experiments (in triplicate) were conducted using 43-mL volatile organic analysis vials under isothermal and zero headspace conditions.  Data on the degradation of VOCs (in mixture) with persulfate at three temperatures (i.e., 20°C, 30°C and 40°C) and in two oxidant doses (i.e., 1 g/L and 5 g/L) were obtained.  In addition, reaction parameters including the persulfate concentration, oxidation-reduction potential and pH were monitored in the experiments.  The experimental results indicate that the thermally activated persulfate oxidation process is effective in degrading many VOC contaminants that are commonly detected in the subsurface.  Most of the study VOCs were rapidly degraded under the experimental conditions while some, however, showed high persistent to persulfate oxidation.  Compounds with “C=C” bonds or with benzene rings bonding with reactive functional groups were readily degraded.  Saturated hydrocarbons and halogenated alkanes were much stable and difficult to degrade.  For most of the degradable VOCs, degradation was well predicted with a first-order decay equation.  The degradation rates increased with increasing temperature and oxidant concentration; the oxidant dose determined the extent of degradation of VOCs.

An Evaluation of In Situ Chemical Oxidation (ISCO) for MGP Impacted Soils and Ground Water

Michael C. Marley, Bruce L. Cliff, Kenneth L. Sperry, and Jaydeep M. Parikh, Xpert Design and Diagnostics, LLC, 22 Marin Way, Stratham, NH 03885, Tel: 603-778-1100, Fax 603-778-2121 

Both MGP site owners and the regulatory community are rapidly developing interest in situ chemical oxidation (ISCO) as a potential, cost effective remediation technology for MGP impacted soils and ground water.  ISCO and ISCO in combination with in situ bioremediation are gaining recognition and an experience database for application to BTEX and PAH constituents. Several field trials and many bench scale studies have been performed for MGP sites. Xpert Design and Diagnostics, LLC (XDD) in association with the University of Massachusetts – Lowell and Washington State University has performed a number of these studies.  Daughter products of the MGP constituents treated through the ISCO process are considered to be benign dihydrodiols, organic alcohols and acids that are readily biodegraded.

The primary oxidants evaluated for this presentation are Fenton’s reagent, persulfate, ozone and permanganate. The chemistry, advantages and disadvantages of each of the oxidants with respect to treatment of MGP impacted soils and ground water will be described.  Shortcomings of batch laboratory studies with respect to field applications are discussed. One very important oxidant property that dictates the potential success and / or need for multiple applications in the field is the oxidant stability or persistence. It is the stability / persistence of the oxidant that dictates its ability to transport in the subsurface and to sustain concentrations that are needed to treat the low solubility MGP constituents. Desorption and dissolution of the PAH constituents, even under the enhanced rates created in the present of an oxidant, are relatively slow processes and must be considered in the design and application of ISCO at MGP sites.  These physical - chemical characteristics also limit the cost effectiveness and practicality of the application of ISCO for DNAPL pools of significant thickness.

This presentation will also provide an update on both field and bench scale studies that have been performed on MGP impacted soils and ground water. An evaluation of a site closure objective of mass flux  / risk reduction as an alternative to achieving soil or ground water numerical standards, and costs of implementation of ISCO will be discussed.

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