Experience.

Reputation.

Results.

Geo-Cleanse International, Inc.

400 State Route 34, Suite B Matawan, NJ 07747 (732) 970-6696 www.geocleanse.com

Geo-Cleanse International, Inc.

Company Profile
Since 1995, Geo-Cleanse International, Inc. (Geo-Cleanse) has been dedicated exclusively to the design and implementation of in-situ chemical remediation technologies. We have completed well over 150 full-scale remediation programs across the United States, and have been active internationally since 1999, conducting the first in-situ chemical remediation application in Europe. We are a full-service remediation firm, offering a variety of chemical remediation services, including site-specific design and implementation of bench-, pilot-, and full-scale applications. Geo-Cleanse has consistently provided innovative remedial solutions to our diverse client network, and we continue to expand our services to incorporate the advances occurring within the industry. Our extensive field experience, together with independently published results of our work, and our knowledgeable staff of professionals, ensures that Geo-Cleanse continues to be one of the worlds top environmental remediation firms. Our experience includes the design and implementation of the two largest in-situ chemical oxidation (ISCO) projects ever performed, one of which included over 1,200 injection wells and over 3 million gallons of peroxide solution. Geo-Cleanse has been the leader in the in-situ chemical remediation field, completing the first ISCO treatment program to address chlorinated dense non-aqueous phase liquid contamination and manufactured gas plant contamination. We have experience remediating a wide range of contaminants including petroleum hydrocarbons, chlorinated solvents, manufactured gas plant constituents, energetics, chloromethanes, and pesticides.

Geo-Cleanse Experience
(States in blue)

Office Location:
400 State Route 34, Suite B Matawan, NJ 07747 Tel. 732.970.6696 Fax 732.970.6697 www.geocleanse.com

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Geo-Cleanse International, Inc.

Our Services
In-situ chemical remediation offers an efficient and effective way to eliminate organic contaminants in both saturated and unsaturated environments. The Geo-Cleanse Process, which patents both the methodology and injection equipment, can be utilized to distribute either catalyzed hydrogen peroxide solutions or other oxidant based reagents (permanganate and sodium persulfate) to the subsurface. A critical step in ensuring the success of a remedial design is selecting the appropriate chemical oxidant. Geo-Cleanse evaluates each of the oxidants strengths and weaknesses as they apply to the site and its relevant conditions, and then chooses the appropriate oxidant or oxidants. Once the oxidant or oxidants have been selected, Geo-Cleanse designs site-specific treatment program for our client. Treatment programs utilized by Geo-Cleanse are comprised of one or a combination of the following types:
Bench-Scale Treatability Studies Pilot-Scale Treatment Programs Full-Scale Treatment Programs Pay-for-Performance Treatment Programs

Because our patented injection equipment and methodology are equipped to deliver all types of oxidants and substrates to the subsurface, Geo-Cleanse evaluates each site to determine which oxidant provides the best fit, both chemically and economically. Geo-Cleanse initially researches the ability of each oxidant to destroy the type of contamination present. For example, at sites containing BTEX compounds, it is well known that permanganate cannot oxidize the benzene ring, thus eliminating permanganate as an oxidant choice at sites containing BTEX impacts. Next, Geo-Cleanse calculates the number of pounds of contaminant present at the site and corresponding number of pounds of oxidant necessary to destroy that amount of contamination. Using the calculated total amount of oxidant to be delivered, Geo-Cleanse then determines the rate of delivery of the oxidant solution by evaluating the lithologies. Finally, GeoCleanse looks at the cost of the oxidant and the timeframe associated with delivery. The oxidant package that is more effective and less expensive than the other is then selected.
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Geo-Cleanse International, Inc.

Oxidant Chemistry
Catalyzed Hydrogen Peroxide
The chemistry involved with catalyzed hydrogen peroxide (CHP) is based upon Fentons reagent. In 1894, H.J.H. Fenton reported that malic acid was rapidly oxidized by hydrogen peroxide in the presence of iron salts. Haber and Weiss (1934) identified the oxidation mechanism resulting from mixtures of hydrogen peroxide and ferrous iron (referred to as Fentons reagent) as a hydroxyl free radical (OH) formed by the reaction:
H 2 O 2 + Fe+2 OH + OH- + Fe+3 (1)

Where H 2 O 2 is hydrogen peroxide, Fe+2 is ferrous iron, OH is hydroxyl free radical, OH- is hydroxyl ion, and Fe+3 is ferric iron. CHP chemistry is complex, involving a number of additional reactions producing both oxidants and reductants that contribute to the destruction of the contaminant of concern (e.g., Watts et al., 1999a):
OH + Fe+2 OH- + Fe+3 Fe + H 2 O 2 H+ + HO 2 + Fe+2 Fe+2 + HO 2 Fe+3 + HO 2 Fe+3 + HO 2 Fe+2 + O 2 + H+ OH + H 2 O 2 H 2 O + HO 2 HO 2 H+ + O 2 +3

(2) (3) (4) (5) (6) (7)

Where HO 2 is hydroperoxyl radical, HO 2 - is hydroperoxyl anion, O 2 is molecular oxygen, O 2 - is superoxide radical, H+ is hydronium ion, and H 2 O is water. Additional reactions occur with organic compounds. The suite of reactions associated with CHP is complex, but very effective at destroying many organic compounds dissolved in groundwater, sorbed to soil, or existing as non-aqueous phase liquids in the subsurface. CHP is generally most efficient under acidic pH conditions (pH <5) because oxidation of iron (from Fe+2 to Fe+3) by other reactions is minimized, hydrous ferric iron oxides are less likely to precipitate and remove iron from solution, and bicarbonate (which competes with the organic compounds for hydroxyl radicals) is absent. However, an effective (although not chemically optimal) Fentons reagent system can be established at a pH >6 (e.g., Watts et al., 1999b; Lindsey and Tarr, 2000). The hydroxyl free radical is a powerful, non-selective oxidant. Oxidation of an organic compound by hydroxyl free radical is a rapid and exothermic (heat-producing) reaction. Rate constants for reactions of hydroxyl free radical with common environmental pollutants are typically in the range of 108 to 1010 M-1s-1 (e.g., Buxton et al., 1988; Haag and Yao, 1992), and 100% mineralization is generally complete in minutes. Intermediate compounds are primarily naturally occurring carboxylic acids, and the end products of oxidation are primarily carbon dioxide and water. None of the injected reagents pose an environmental hazard. Unconsumed H 2 O 2 naturally degrades to oxygen and water after injection.

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Geo-Cleanse International, Inc.

Sodium or Potassium Permanganate
Permanganate is supplied as a soluble salt, either as the potassium permanganate (KMnO 4 ) or sodium permanganate (NaMnO 4 ). The two salts differ primarily by solubility; however in aqueous solution both dissolve to release the cation (either Na+ or K+) and the anion (MnO 4 -):
NaMnO 4 Na+ + MnO 4 KMnO 4 K+ + MnO 4 (1) (2)

The active oxidant for either salt is the permanganate anion (MnO 4 -), which is a strong and persistent oxidant in the subsurface. The permanganate oxidation pathway for alkenes such as TCE begins with electrophilic attack on the carbon-carbon double bond, producing a cyclic hypomanganate diester as a reaction intermediate. There are two potential oxidation pathways for the diester intermediate, via either hydrolysis to glycol aldehyde or bond cleavage to formaldehyde. Both compounds continue to degrade to carboxylic acids.

Sodium Persulfate
Persulfates are strong oxidants that have a wide variety of industrial applications. Dissolution of a persulfate salt such as sodium persulfate (Na 2 S 2 O 8 ) in water liberates the persulfate anion (S 2 O 8 -2) which is an oxidizer:
Na 2 S 2 O 8 (solid) 2Na+ + S 2 O 8 -2 S 2 O 8 -2 + 2H+ + 2e- 2HSO 4 (1) (2)

The persulfate anion has an oxidation potential of 2.1 V. In addition to direct oxidation by the persulfate anion, the persulfate anion can be catalyzed to produce a persulfate radical (SO 4 -):
S 2 O 8 -2 + initiator SO 4 - + (SO 4 - or SO 4 -2) (3)

The persulfate radical is a more powerful oxidizer than the persulfate anion, and has an oxidation potential of 2.6 V. Commonly used activators to catalyze persulfate are heat, hydrogen peroxide, transition metals, and high pH. For economical and technical reasons the most commonly used activators in the environmental industry for ISCO are transition metals and high pH.

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Geo-Cleanse International, Inc.

Injection Well Installation
Injection wells can either be temporary or permanent injection points. Geo-Cleanse requires that permanent injection points are installed by direct push or sonic methods by a licensed driller. The spacing between injection wells is typically a conservatively small spacing appropriate to distribute the reagents across the target treatment zone. Our permanent injection wells are constructed with material this is compatible with the injected reagents and elevated temperatures if CHP is applied. When applying CHP, permanent injection wells, in contrast to temporary (direct push) injection points, is preferred for several reasons: 1. Direct push drill rigs and crews are only mobilized once for well installation. If additional injection phases are necessary, wells can be reoccupied. In contrast, if additional injection is necessary with temporary well points, drilling crews must also be remobilized. 2. Adjacent injection wells provide a dense network of process monitoring locations. These wells allow close monitoring of treatment progress to ensure that appropriate chemical conditions are established, treatment is occurring effectively, and to determine the actual radius of influence. The process monitoring data are critical for daily optimization of the injection to ensure the most efficient treatment program. Process monitoring and optimization are not possible with temporary injection points. 3. Installation is relatively inexpensive. Injection and vent wells are installed using direct push drilling technology and are constructed of CPVC. 4. Geo-Cleanse can establish a larger radius using permanent injection wells in conjunction with our patented equipment. Temporary injection locations, due to the nature of that type of delivery, can generally only distribute reagents a few feet from each location. 5. Multiple injection wells can be treated simultaneously. Geo-Cleanse mobile treatment units can each independently treat between four and 12 injection wells simultaneously.

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Geo-Cleanse International, Inc.

Injection Equipment
The Geo-Cleanse Process utilizes a specialized mobile treatment vehicle and patented injection heads to deliver reagents to the subsurface. The treatment unit includes tanks, pumps, gauges and flow controls to prepare and deliver injection solutions safely and effectively to the injection wells. The mobility of the Geo-Cleanse Process allows effective remediation with no permanent structures, no need to remove pavement or buildings, no need to close facilities, and no disruption of operations. Geo-Cleanse has small and large rigs, depending on the size of the site. We also have specially designed injection boxes, that we can be used within tighter areas (e.g., inside a building). The view of the injection vehicle shows the control board, which allows the operator to independently control the

flow of reagents and injection pressures to each of the four mixing heads. The mixing heads are specifically designed to control and mix the reagents used during the Geo-Cleanse Process. The figure to the right shows the general design of an injection head. The specially designed mixing heads are designed with redundant safety features including check valves, pressure gauges and flow control ball valves which are all constructed of material compatible with all of the reagents. The mixing head has a duplicate set of ball valves to control the flow of catalyst, oxidant, and air as a secondary and backup control. The mixing heads are constructed of polypropylene and CPVC for chemical compatibility, and have a pressure relief valve at the base for added safety. The ability to monitor the flow of reagents is present at the control board of the injection vehicle, the control valves of the mixing heads, and the control valves of the reagent storage tanks. The redundant control is established for health and safety reasons. The Geo-Cleanse mobile treatment unit is powered by a 60-kW generator.
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Geo-Cleanse International, Inc.

Daily Process Optimization-CHP
requires characteristic pH and iron concentration ranges in order to be most effective, and the nature of a CHP injection allows constant monitoring to ensure the treatment is occurring effectively. Geo-Cleanse conducts routine process monitoring sampling and data analysis each day to ensure that subsurface conditions within an active injection area are optimal for an effective and efficient CHP treatment. These data are evaluated daily to assess the treatment progress and to optimize the injection. This optimization includes an assessment of the catalyst formulation and target injection volumes, to ensure treatment progresses efficiently.
CHP

Geo-Cleanse monitors pH, alkalinity, dissolved iron, hydrogen peroxide and chloride concentrations, PID headspace, and temperature taken from groundwater samples obtained daily from the injection and monitoring wells within the treatment area. These field parameters monitor the reaction progress and ensure that appropriate subsurface conditions exist for an efficient reaction. They also assist Geo-Cleanse in proportioning additional reagents into areas onsite where contamination still exists. Monitoring of the offgas concentrations, from the injection and the monitoring wells within the treatment area, also occurs during injection. These offgas parameters, coupled with the groundwater measurements are effective in determining the progress of a treatment program in the field.
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Geo-Cleanse International, Inc.

Case Studies
A few case studies and our most recent newsletters are included as Attachment B. Additional case studies and past newsletters are located on our website. The case studies give an overview of the site conditions and treatment program design. If requested, Geo-Cleanse can provide additional information regarding our past and current projects in the US and abroad.

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Geo-Cleanse International, Inc.

Site Data Desired for Project Design
The site information desired for final Geo-Cleanse project design is typically included in a very thorough remedial investigation report. Specifically, we search for the following information: I. General Site Information. A. Map(s) with buildings, overhead or underground utilities, sample locations, etc. B. Topographic map. C. Site history, especially regarding the plume origin, previous remediation, etc. D. Site hazards and access for drill rig, Geo-Cleanse treatment rig, etc. II. Soil Data. A. Detailed lithologic descriptions and geologic cross sections. B. Soil density. C. All soil boring logs from the site. D. All soil analytical data in tabular form. E. Contaminant isopleth maps (by compound and by discrete depth intervals). III. Groundwater Data. A. Detailed lithologic descriptions of the aquifer (boring logs). B. Depths of aquiclude/aquitard intervals. C. Depth to groundwater and seasonal variations. D. Hydraulic conductivity. E. Porosity. F. Water quality (pH, alkalinity and iron concentration). G. All groundwater analytical data in tabular form. H. Observations/thickness of free product layers. I. Contaminant isopleth maps (by compound and by aquifer if more than one). J. Groundwater piezometric surface map. IV. Bedrock Data (if applicable). A. All groundwater quality data described in Section III. B. Depth to bedrock, and unconsolidated soil data described in Section II. C. Depth to water and seasonal variations. D. Distribution, strike and dip of fracture sets and discrete zones. E. Packer testing results (pump tests, temperature, resistivity, etc.).

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Attachment A References

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Geo-Cleanse International, Inc.

References Cited
Buxton, G., Greenstock, C.L., Helman, W.P., and Ross, A.B. 1988. Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (OH/O-) in aqueous solutions. Journal of Physical Chemistry Reference Data, v. 17, pp. 513-886. Haag, W. W. R., Yao, C. C. D. 1992. Rate constants for reaction of hydroxyl radicals with several drinking water contaminants. Environmental Science and Technology, v. 26, pp. 1005-1013. Haber, F., and Weiss, J. 1934. The catalytic decomposition of hydrogen peroxide by iron salts. Proceedings of the Royal Society of London, Series A, v. 147, pp. 332-351. Lindsey, M. E., and Tarr, M. A. 2000. Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter. Environmental Science & Technology, v. 34, pp. 444-449. Watts, R. J., Bottenberg, B. C., Hess, T. F., Jensen, M. D., and Teel, A. L. 1999a. Role of reductants in the enhanced desorption and transformation of chloroaliphatic compounds by modified Fenton's reactions. Environmental Science and Technology, v. 33, pp. 3432-3437. Watts, R. J., Foget, M. K., Kong, S.-H., Teel, A. L. 1999b. Hydrogen peroxide decomposition in model subsurface systems. Journal of Hazardous Materials, v. B69, pp. 229-243.

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Attachment B Newsletters & Case Studies

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A New Approach Combining ISCO with Chemical Reduction to Destroy Carbon Tetrachloride DNAPL and Mixed Plumes
In-situ chemical oxidation with catalyzed hydrogen peroxide (CHP) or sodium persulfate (CSP) are generally optimized to produce oxidants such as hydroxyl radicals and sulfate radicals. Although these powerful oxidants are capable of destroying a wide range of contaminants, there are common soil and groundwater contaminants that cannot be oxidized. These contaminants, such as carbon tetrachloride (CT), must instead be reduced in order to be degraded. As a result, in-situ treatment of such compounds, particularly in the presence of DNAPL or as part of mixed plumes with compounds that can be oxidized, has presented a challenging problem. CHP and CSP are known to produce superoxide radicals (O2-, a chemical reductant) as part of the chain of reactions associated with these reagents. Destruction of CT by CHP and CSP has been reported, however O2- production generally appears to have been very inefficient. Recent reports have found that under certain conditions, hydrogen peroxide (H2O2) could be efficiently catalyzed to produce O2-, resulting in degradation of CT including DNAPL. In light of these results, GeoCleanse undertook extensive research of catalysts to produce O2- in response to a client seeking a rapid, cost-effective solution for a site impacted with CT and a suite of other compounds. The chemicals of concern included compounds that react well with oxidants (e.g., chlorobenzene and ethylbenzene), and compounds that cannot be oxidized or do not react well with oxidants (e.g., CT and related chloromethanes), including a DNAPL phase. The result of this effort is a new catalytic system for H2O2, which produces both superoxide and hydroxyl radicals efficiently for insitu destruction of a mixed contaminant plume and DNAPL. Previous research by Watts and coworkers has shown that O2is produced by catalyzing H2O2 with Mn+4 at a pH of about 6.8 or higher. Applying this approach in the field, however, would be challenging because Mn+4 forms an insoluble precipitate (MnO2) at circumneutral pH; thus application would require manipulating large pH shifts within an aquifer to maintain Mn in solution for distribution and subsequent precipitation of MnO2, or perhaps fracture emplacement of solid MnO2. Thus an approach was developed to more efficiently distribute the MnO2 catalyst, and then controllably react the catalyst with H2O2 to produce O2- in-situ. The approach developed by GeoCleanse comprises the following steps: (1) First inject sodium permanganate solution. Permanganate is an oxidant that can destroy certain organic compounds; but most importantly for this approach, the permanganate anion is reduced and manganese is precipitated throughout the aquifer as MnO2. The manganese in MnO2 is predominantly in the Mn+4 valence state. (2) Permanganate reduction to MnO2 preferentially occurs in zones with the highest organic mass, such as the portion of the treatment area impacted with DNAPL and associated highly elevated soil concentrations. Thus this catalyst is preferentially precipitated in the zones requiring treatment.

ISCO TECHNOLOGY REVIEW

Volume 4

Inside this Issue of ISCO Technology Review

Cover Story (continued) Current Geo-Cleanse projects
Geo-Cleanse International, Inc. 400 State Route 34, Suite B Matawan, NJ 07747

2 2 3 3

State of the Art - Comparing Contaminant Oxidant Demand among ISCO Reagents Upcoming Conferences

www.geocleanse.com

Cover Story (Continued from Page 1)

(3) A phosphate buffer at pH of 6.8 to 7.0 is injected next. The phosphate forms a ligand with colloidal MnO2 and MnO2 surfaces, thus stabilizing the very rapid catalytic reaction with H2O2. The phosphate solution also buffers the pH within the desired range. (4) H2O2 solution is added next. The H2O2 reacts with MnO2 to produce O2-. The O2- degrades the CT and other chloromethanes. (5) The H2O2 solution also reacts with native iron in the formation, and/or with Mn+2 produced by manganese redox cycling, to produce hydroxyl radicals. This is important for degradation of other COCs such as ethylbenzene, which are destroyed by hydroxyl radicals but not reactive with O2-. Laboratory bench tests were conducted with soil and groundwater from an industrial site in New Jersey. The soil and groundwater were impacted with CT, chloroform, methylene chloride, chlorobenzene, ethylbenzene, and methoxychlor, including a visible DNAPL phase. Batch reactor tests controlling all phases (soil, groundwater, and volatilization; volatilization was measured using absorbent cartridges) were performed to optimize and test the approach. Results for CT, chloroform, and chlorobenzene from a representative series of tests are shown in Figures 1 & 2. Results for the aqueous phase (Figure 1) show that baseline VOC concentrations were reduced by 99.99% for CT and chloroform, and 94.6% for chlorobenzene. The approach was also found to be extremely effective for the soil-sorbed and DNAPL phase; this was evaluated by calculating the total contaminant mass in each reactor. The contaminant mass results (Figure 2) show that VOC mass (excluding volatilized fraction) was reduced by very similar magnitudes, indicating destruction of soilsorbed and DNAPL phases in similar proportions to the aqueous phase. Experiments demonstrated that all of the compounds, including compounds destroyed only by reduction (e.g., CT) and compounds destroyed only by oxidation (e.g., chlorobenzene), were degraded effecPage 2

tively. Overall destruction ranged from 84% to a nominal 100% relative to control samples. The compounds destroyed by O2- reduction were destroyed slightly more efficiently than compounds destroyed by hydroxyl radical oxidation, but the efficient destruction of all Figure 1. compounds indicates that this approach can be used effectively for sites impacted with a wide range of oxidizable and reducible compounds. Analyses also included sampling for intermediate and final oxidation products to elucidate the degradation pathways. No hazardous intermediate or final compounds were detected, including negative analyses for phosgene (a potential reduction product of CT).

Aqueous VOC Concentrations

Figure 2. VOC Mass

Based upon these results, a field pilot test is anticipated to be complete in the spring of 2010.

Current Geo-Cleanse International, Inc. Projects

Phase Bench Pilot Pilot Full Full Full Full Contaminants Coal Tar Carbon Tetrachloride 1,4-Dioxane Petroleum / Coal Tar Chlorobenzene Petroleum 1,1-Biphenyl, 1,4-Diphenyl Ether, Toluene Location Confidential NJ NC FL NJ GA NJ

ISCO TECHNOLOGY REVIEW

State of the Art ISCO Insights from Geo-Cleanse Comparing Contaminant Oxidant Demand among ISCO Reagents
Table 1: Comparison of Oxidant Requirements and Cost Many factors must be considered when evaluat- Factor TCE Benzene Naphthalene ing a site and assessing Formula Weight 131.4 78.11 128.2 potential ISCO approaches. One of the Moles of Oxidant Required to Destory Contaminant 6 30 48 fundamental decisions to Pounds of H O per 1 mole of Contaminant 0.45 2.25 3.60 2 2 be made is which oxidant 3.15 15.74 25.19 to utilize. An important Pounds of Na2 S2O8 per 1 mole of Contaminant factor in this decision, H2 O2 Cost per 1 lb (including catalyst; 100% basis) $1.10 which is often overNa 2S2 O8 Cost per 1 lb (including caustic catalyst) $2.25 looked, is how much H2 O2 Cost to Destroy 1 mole of Contaminant $0.49 $2.47 $3.96 oxidant is required to Na2S2 O8 Cost to Destroy 1 mole of Contaminant $7.08 $35.42 $56.68 destroy target contaminant mass and the correoxide and persulfate, one mole of oxidant contaminant) is very different. This is besponding impact on cost. At sites with accepts one mole of electrons and produces cause the formula weight of each oxidant relatively low contaminant concentraone mole of radicals. The number of radiis different. Sodium persulfate has a fortions, the natural oxidant demand is usucals required (or electrons removed) from a mula weight of 238 grams per mole, while ally larger than the contaminant oxidant target contaminant can also be calculated hydrogen peroxide has a formula weight of demand; however at more heavily imfrom oxidation half-reactions. Reactions for 34.0 grams per mole. For example, oxidapacted sites, the contaminant oxidant several common contaminants are as foltion of 1 mole of TCE requires 0.45 lbs of demand is generally much larger than the peroxide or 3.15 lbs of persulfate. Calculalows: natural oxidant demand. At sites with tions for benzene and naphthalene are provery high contaminant mass, such as coal vided in Table 1. Due to the difference in tar or DNAPL sites, the overall project TCE: oxidant formula weights, contaminant oxi+ cost is heavily influenced by the cost of C2HCl3 + 4H2O 2CO2 + 3Cl + 9H + 6e dation requires approximately 7 times the oxidant required to destroy the conmore persulfate by mass than peroxide. taminant. Thus the objective of this article Benzene: is to show how contaminant oxidant deC6H6 + 12H2O 6CO2 + 30H+ + 30eThe oxidants also have a significant differmand can affect project costs. ence in cost. Hydrogen peroxide, on a

For comparison purposes, oxidant demand is compared on a stoichiometric basis. The radical-initiating oxidation half -reactions for catalyzed persulfate and catalyzed peroxide are as follows:
Persulfate: S2O8-2 + e- SO4- + SO4-2 Peroxide: H2O2 + e- OH + OH-

Naphthalene: C10H8 + 20H2O 10CO2 + 48H+ +48e-

Thus on a stoichiometric basis, oxidation of one mole of TCE produces six moles of electrons, or in other words requires six moles of radicals and, therefore, six moles of oxidant. Similarly, one mole of benzene requires 30 moles of oxidant, and one mole of naphthalene requires 48 moles of oxidant. While the number of moles of peroxide or persulfate required to oxidize a contaminant is identical, the weight ratio (in terms of pounds of oxidant required per pound of

100% concentration basis and including ferrous iron catalyst, costs approximately $1.10 per pound. Sodium persulfate, also on a 100% concentration basis and including caustic catalyst to overcome the oxidant and soil caustic demand, costs approximately $2.25 per pound. The corresponding costs to destroy one pound of contaminant are shown at the bottom of Table 1. Overall, persulfate costs about 14 times more than peroxide to destroy the same contaminant mass. The potential impact of the reagent cost on overall project cost will vary with the overall contaminant mass. At sites with low contaminant concentrations, the overall impact on cost may not be large, and other technical factors may have greater weight in determining oxidant choice. But at large sites with relatively high contaminant concentrations, such as a manufactured gas plant or DNAPL sites where contaminant mass is measured in tens of thousands of pounds or more, the difference in reagent costs can be tremendous. In these cases, catalyzed peroxide ISCO provides a much better choice from the perspective of reagent cost.

The key observation is that, for both per-

Upcoming Conferences
Come visit Geo-Cleanse at the following conferences:
20th Annual Conference on Soils, Sediments, Water, and Energy San Diego, CA TCEQs Annual Environmental Trade Fair and Conference Austin, TX

Remediation of Chlorinated & Recalcitrant Compounds Conference, Battelle Monterey, CA

26th International Conference on Soils, Sediments, and Water Amherst, MA

VOLUME 4

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Geo-Cleanse International, Inc.

400 State Route 34, Suite B Matawan, NJ 07747

About Geo-Cleanse International, Inc.

experience, together with independently published results of our work, and an experienced staff of professionals, keeps Geo-Cleanse at the top of the industry. As the chemical oxidation field continues to evolve, GeoCleanse has expanded our services to incorporate the advances occurring within the industry. The Geo-Cleanse Process can effectively treat a wide range of contaminants and has successfully been applied in many different litholoGeo-Cleanse Field Experience (Blue States) gies. To date, Geo-Cleanse has situ chemical oxidation company. Geofield experience on well over 100 sites Cleanse consistently provides quality in 28 states, Canada, and Europe. service and ensures that the goals of our treatment programs are achieved. Please visit our website for addiWe have the most experience of any tional information or a free site chemical oxidation firm and were the evaluation: first to commercially apply oxidants for geocleanse.com a successful NAPL remediation. Our Since 1995, Geo-Cleanse International, Inc. (Geo-Cleanse) has established a reputation as the premier in-

We Adapt to the SiteSpecific Conditions

Oxidants: Peroxide, Permanganate, Persulfate Additives: Surfactants, Chelating Agents, Stabilizers Novel Application Methods In-Situ Reduction Site-Specific Treatment Goals Coupling with: Bioremediation Extraction Other Technologies

TheVolume 3, Issue 2 Chemical Oxidation Experts I S C O T E C HN O L O G Y

R E V I EW

Innovative Coupling of ISCO Technologies Proves Successful in Orlando

Soil and groundwater contaminated by chlorinated solvents posed a potential delay to construction of the Orlando Events Center, the future home of the Orlando Magic basketball team. Rapid remediation of a perchloroethylene (PCE) source area was required in order to prevent construction delays. After a competitive public bid, the City of Orlando contracted Geo-Cleanse International, Inc. (Geo-Cleanse) to provide turnkey in-situ chemical oxidation (ISCO) remediation at site. GeoCleanse subcontracted MACTEC Engineering and Consulting, Inc. to provide local support, including acting as regulatory liaison for the project team, securing approval of a Limited Scope Remedial Action Work Plan from the Florida Department of Environmental Protection (FDEP), and overseeing certain field construction activities. Challenges to be addressed as part of the treatment program were:

Very short time frame Nov.

2007 award to July 2008 completion, including six months of post-remediation groundwater monitoring.

Presence of potential dense

nonaqueous phase liquid (DNAPL) source, with groundwater concentrations greater than 14,000 g/L of PCE.

ISCO TECHNOLOGY REVIEW

Basal clay aquitard could

pose rebound problem with back-diffusion of PCE into groundwater.

Figure 2: Our Patented Mixing Head

GEO-CLEANSE INTERNATIONAL, INC.

Pay for performance contract

- The City of Orlando was not obligated to make payments over the initial 50% of contract unless Geo-Cleanse achieved and maintained Cleanup Target Levels (CTLs) of 3 g/L PCE, 3 g/ L of trichloroethylene (TCE), and 70 g/L of cis-1,2dichloroethylene (DCE) in groundwater, and soil leachability criteria of 0.03 mg/kg for PCE. After careful review of the site background investigation data, GeoCleanse designed a phased treatment program to meet the CTLs in the timeframe neces-

sary to avoid development delays. The remediation program incorporated a treatment train consisting of three remediation phases:

Phase 1 consisted of injection

of catalyzed hydrogen peroxide (CHP) for primary source reduction.

Phase 2 consisted of injection

of sodium permanganate to achieve the CTLs and prevent back-diffusion from the underlying clay aquitard.

Phase 3 consisted of excavation of shallow vadose zone soil impacts. The ISCO component called for 72 injection wells installed across three depth intervals between approximately 10-40 feet below grade, in an approximate 130 feet x 80 feet area (Figure 1). The aquifer lithology consists of sand to silty sand with an underlying

Figure 1: Treatment Area Map

Inside this issue of ITR

Cover Story (continued) State of the Art - Acidification During Catalyzed Hydrogen Peroxide ISCO Current Geo-Cleanse Projects Upcoming Conferences About Geo-Cleanse 2 3 3 3 4

Cover Story (Continued from Page 1)

jection consisted of collecting groundwater samples for visual analysis to ensure uniform distribution of the permanganate reagent. Permanganate (recognized by its characteristic purple color) was found throughout the treatment area following the injection. The post-injection groundwater monitoring period began after completion of the permanganate injection. The third phase of remediation consisted of soil removal from two areas at which PCE was deFigure 3: Monitoring Well Headspace PID tected at concentrations exceedclay aquitard at a depth of 40 feet. Injecing the soil leachability criterion of 0.03 mg/ tion well installation was completed during kg. A total of approximately 94 tons of soil the period of November 27 to December was removed from two areas over the period 15, 2007. The injection wells were then from February 25-27, 2008. During the reallowed to cure for two weeks. moval action, a PVC pipe attached to an apThe first phase of remediation consisted of parent floor drain system was discovered at injecting 85,000 gallons of CHP solution over the period from January 2-26, 2008 (Figure 2). Geo-Cleanse conducted intensive groundwater and offgas sampling to ensure appropriate geochemical conditions for an effective CHP injection existed in the treatment area, and to evaluate treatment progress. Measurements of volatile organic compounds (VOCs) in the headspace over a groundwater sample, as taken with a photoionization detector (PID), provide a semi-quantitative measure of VOC concentration in the groundwater. Figure 3 Figure 4: Presumed Source of PCE Contamination is a chart of the PID readings of groundwater samples from the four monitoring wells in the source area. The PID readings show the site (Figure 4). The pipe was found to an initial spike in headspace PID measure- contain residual sludge and exhibited elements related to desorption of VOCs from vated PID readings, and was located directly the aquifer matrix, followed by subsequent over the groundwater source areas, and thus degradation of the PID measurements to is the presumed source. The pipnon-detectable levels over the treatment ing and associated bedding was, period. These data confirm that the CHP therefore, also removed from component was complete, and the next accessible portions of the site. After receipt of post-excavation remediation phase was initiated. sampling results, the excavation One week was allowed for residual hydrowas backfilled on March 7, 2008. gen peroxide to degrade after completing the CHP injection before beginning the The post-treatment performance permanganate injection. The same network sampling program consisted of of injection wells installed for the CHP three groundwater sampling injection was also utilized for the perman- events, conducted on February ganate. This second phase of remediation 14, 2008 (4 days after injection), consisted of injecting 21,000 gallons of 4% April 23, 2008 (73 days after sodium permanganate solution over the injection), and July 23, 2008 (164 period from February 4-10, 2008. Field days) after injection, with a supmonitoring for sodium permanganate in- plemental sampling event on
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August 5, 2008 (177 days after injection). With one exception, the VOC concentrations in all five of the performance monitoring wells have been reduced to below the CTLs. The total VOC concentration (consisting of the summed PCE, TCE and DCE concentrations) is plotted in Figure 5 for the two monitoring wells exhibiting the highest preinjection VOC concentrations. During the July 23rd event, PCE was detected at 11 mg/L in MW-5 and was confirmed with a second analysis. MW-5 is a shallow well located adjacent to the soil excavation area, thus the VOC detection is likely associated with the soil removal. Additional treatment was focused in the area of MW-5, and a new sample was collected on August 5, 2008. All VOCs were below CTLs. The injection and monitoring wells were then abandoned in accordance with Florida regulations by August 8, 2008 to allow construction. This treatment program was successful in obtaining Florida CTLs for the target compounds and was completed in a timeframe in order to avoid delays in construction. All preconstruction permitting and field work to achieve the CTLs in all media, including LSRAP submittal, regulatory approval, drilling, injection, soil removal, and backfill, was completed by March 7, 2008, approximately 4.5 months after contract execution. The FDEP has approved the results and construction has begun. This project demonstrates how DNAPL sites can be successfully remediated with a treatment train approach utilizing ISCO. Rarely can one single technology provide a complete remedy. As this case study demonstrates, Geo-Cleanse has the experience and capability to couple technologies, and to undertake innovative approaches, to achieve cleanup goals.

Figure 5: Post-Treatment Groundwater Results

I S C O T E C HN O L O G Y R E V I E W

State of the Art - ISCO insights from Geo-Cleanse:

Acidification during Catalyzed Hydrogen Peroxide ISCO

cals. Thus when a chelated metal is added, are kept in solution rather than precipitating often at a concentration much higher than as oxyhydroxides. Naturally occurring tranthe target contaminant, the chelating agent sition metals are also released from the aqbecomes a hydroxyl radical scavenger and uifer matrix, thus the amount of transition contaminant treatmetals that must be added is ment efficiency is reduced under acidic conditions. Bicarbonate interference is re- Our goal is to provide the most reduced. At neutral pH, radical scavengeffective treatment, and will duced. Hydroxyl radicals react ing from dissolved with dissolved bicarbonate in always optimize the catalyst to and groundwater. The reaction rate best fit the site-specific conditions bicarbonate chelators will sigof the hydroxyl radical with a and treatment objectives. nificantly reduce bicarbonate is slower than for treatment efficiency. reaction of hydroxyl radical with common contaminants; however, if Many commonly used chelating agents may also be considered environmental hazards if dissolved bicarbonate is present at relatively not fully destroyed by the catalyzed peroxhigh concentrations (200 400 mg/L), then ide. For example, EDTA does not readily radicals may be hundreds or thousands of biodegrade in groundwater, and has been times more likely to react with bicarbonate linked to mobilization of metals; and NTA than with the contaminants, and thus may is a suspected carcinogen. significantly reduce treatment effectiveness. Bicarbonate is eliminated at a pH of about Transition metal injection must be sustained Hydroxyl radicals (which are the primary 5.4, thus the hydroxyl radicals are utilized throughout the treatment. At circumneutral reactants with CHP) can be generated at more efficiently for contaminant destruction pH, once the chelating agent is destroyed nearly any pH. Thus important considerations under mildly acidic pH conditions. and the transition metal has reacted with are how pH affects, or is affected by, (1) peroxide, the metal is oxidized and will lithology of the At circumneutral pH, transiprecipitate as an insoluble oxyhydroxide. soil and aquifer tion metals are typically Additional transition metal injection is matrix, (2) the ...important considerations are how pH added in a chelated form. therefore required in order to continue to affects, or is affected by, (1) lithology This offers both advantages catalyst system, catalyze the peroxide. and (3) scavenof the soil and aquifer matrix, (2) the and disadvantages: gers that affect catalyst system, and (3) scavengers that The decision to utilize an acidic pH catalyst Treatment can be accom- system or a circumneutral, chelated metal treatment effiaffect treatment efficiency. These ciency. These factors are interrelated, and should not plished in carbonate-rich catalyst system requires consideration of siteaquifers. Under heavily im- specific issues. Both catalyst systems have factors are be considered independently. pacted (NAPL) conditions, advantages and disadvantages, and there is no interrelated, the contaminant concentra- best catalyst system applicable to all sites. and should not tions are typically high enough that bicar- Geo-Cleanse has considerable experience with be considered independently. bonate interference is less significant. This both acidic and circumneutral catalyst sysThe advantages of an acidic pH catalyst sysmay remain as an advantage until dissolved tems. Our goal is to provide the most effective tem over a circumneutral pH catalyst system contaminant concentrations are reduced (for treatment, and will always optimize the catainclude: example, to the 1-10 mg/L range), and bi- lyst to best fit the site-specific conditions and carbonate interference again becomes sig Transition metals are required to catalyze treatment objectives. nificant. peroxide to produce hydroxyl radicals. Under acidic conditions, transition metals Chelating agents react with hydroxyl radiThere are many choices today regarding selection of oxidants and catalytic systems. Catalyzed hydrogen peroxide (CHP) is arguably the most versatile oxidant, and an important question to be addressed during system design is whether acidification is necessary as part of the treatment. Studies of classical Fentons reagent systems found that treatment was generally most effective at acidic pH conditions, typically at a pH of 3-4. Some practitioners try to differentiate themselves as using neutral or cool CHP as opposed to an acidified CHP approach, and claim more efficient treatment than an acidified approach. However the answer to the which is best? question lies with consideration of site-specific conditions and treatment objectives. This article explores some of the advantages and disadvantages of acidification as part of CHP ISCO.

Current Geo-Cleanse Projects

Scale Bench Bench Pilot Pilot Full Full Full Oxidant CHP CHP CHP CHP CHP CHP CHP Contaminant Carbon Tetrachloride Coal Tar TCE, BCEE Dioxane Petroleum / Coal tar Chlorobenzene Petroleum Location NJ NJ NJ NC FL NJ NJ

Upcoming Conferences
Come visit Geo-Cleanse at the following conferences:
Remediation of Chlorinated & Recalcitrant Compounds Monterey, CA Conference on Soil, Sediments, and Water San Diego, CA

Environmental Trade Fair and Conference Austin, TX.

Annual Florida Brownfields Conference Florida International Conference on Soils, Sediments, & Water Amherst, MA.

Florida Remediation Conference Orlando, Fl

VOLUME 3, ISSUE 2

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Geo-Cleanse International, Inc.

400 State Route 34, Suite B Matawan, NJ 07747

The Chemical Oxidation Experts

About Geo-Cleanse ...

a successful NAPL remediation. Our experience, together with independently published results of our work, and an experienced staff of professionals, keeps Geo-Cleanse at the top of the industry. As the chemical oxidation field continues to evolve, GeoCleanse has expanded our services to incorporate the advances occurring within the industry. The Geo-Cleanse Process can effectively treat a wide range of contaminants and has successfully been applied in many different lithologies. To date, Geo-Cleanse has field exGeo-Cleanse Field Experience (Blue States) perience on well over 100 sites Cleanse consistently provides quality in 28 states, Canada, and Europe. service and ensures that the goals of our treatment programs are achieved. Please visit our website We have the most experience of any www.geocleanse.com to view our case chemical oxidation firm and were the studies or for a free site evaluation. first to commercially apply oxidants for Since 1995, Geo-Cleanse International, Inc. (Geo-Cleanse) has established a reputation as the premier insitu chemical oxidation company. Geo-

We Adapt to the Specific Site Conditions

Oxidants: Peroxide, Permanganate, Persulfate Additives: Surfactants, Chelating Agents, Stabilizers Novel Application Methods In-Situ Reduction Coupling with:

Bioremediation Extraction Other Technologies

Geo-Cleanse Remediation Summary Augusta, GA Former MGP Plant Coal Tar

Overview: Geo-Cleanse International, Inc. (Geo-Cleanse) was contracted to perform an in-situ chemical oxidation (ISCO) full-scale treatment program to remediate by-product like material (BPLM) on the on- and off-site properties surrounding a former manufactured gas plant (MGP) facility in Augusta, Georgia. BPLM is identified as free phase coal tar residuals measured as BTEX (benzene, toluene, ethylbenzene and xylenes) and PAHs (polycyclic aromatic hydrocarbons), which are MGP-specific constituents. Results from the pilot ISCO treatment program indicated these constituents were amenable to chemical oxidation using Fentons reagent. Site Background Characteristics: This site was a former MGP located in Augusta, Georgia. From the early 1800s until the 1950s, the MGP site was used to produce gas from coal, coke, or oil. During the gas productions process, various residuals such as tars, liquors, sludges, coal fragments and gas purifying wastes were produced, some of which were released into the soil and groundwater. Treatment Program Design: The full-scale ISCO treatment program was designed to remediate BPLM mass to the extent practicable. Treatment to the extent practicable was defined as the point where no significant BPLM reduction will occur with further treatment. Activities at the site consisted of four main phases of implementation: injection well installation; mass calculations and hydrogen peroxide proportioning; injection; and post-treatment sampling. Each phase of the treatment program was specifically designed to attain the overall goal of the treatment program and to meet the criteria for closure at this site. Injection Well Installation: Injection well installation for the full-scale treatment program at the Augusta site began on July 6, 2004 and was completed on October 27, 2004. The installation phase consisted of approximately 88 days of active installation. Over this time period, 686 injection wells were installed across the site in a maximum of three vertical treatment intervals. In addition, the 43 injection wells installed for the pilot treatment program at this site were utilized as active injection points for the full-scale, equating to a total of 729 injection wells. The injection wells were placed on an approximate 15-ft x 15-ft grid pattern across the majority of the site. In addition to the injection wells, 33 vent wells were installed at this site. The depths and amounts of injection well layers varied based on the presence of BPLM. Injection wells were installed and screened where BPLM was observed. The entire treatment area was subdivided into 39 blocks, which each consisted of 43 injection wells or less. These divisions were implemented to simplify the sampling, injection and data management activities for the site. Baseline Sampling and Mass Calculations: During injection well installation, several injection well locations were continuously cored and sampled. Soil samples were obtained in 5-ft increments from several locations across the site. A minimum of 20% of the injection wells were sampled in order to define the lateral and vertical extent of the contaminant mass present at the site. These samples were analyzed by STLs Mobile

Laboratory. The samples were analyzed for BTEX using EPA Method 8260B and PAHs using EPA Method 8270C. Using the analytical data from these samples, a target volume was calculated for each injection well at the site, which was based on a 22:1 ratio of hydrogen peroxide to contaminant mass. Every injection well was assigned a BPLM mass and a corresponding volume of hydrogen peroxide was calculated. If the mass volume calculated was less than the minimum amount required to establish an effective radius of influence (ROI), then a volume of 400 gallons of 12.5% hydrogen peroxide was used for that injection well. Remediation Operations: The injection activities implemented during the full-scale treatment program took place in the following stages: 22:1 Ratio/Minimum Injection (Target Volumes) Photoionization Detector (PID) Headspace Chasing Peroxide Stability 21-Day Post-Treatment Monitoring Long Term Monitoring These stages of injection were developed to demonstrate that the performance criteria for treating BPLM to the extent practicable were achieved. A description of the treatment criteria is described in more detail below. Each day prior to oxidant injection, groundwater samples were obtained from all of the injection wells within an active treatment block and analyzed for pH, alkalinity, iron, and hydrogen peroxide concentrations, temperature and PID headspace. This process continued throughout the program on a daily basis to monitor the changes in groundwater chemistry and volatile constituents. Once the delivery of the target volume to each injection well was complete in an active block, treatment focused on the injection well locations with PID headspace readings in groundwater greater than 50 ppm. Results from the pilot ISCO treatment demonstrated that PID headspace in groundwater was directly proportional to remaining VOC concentrations. Treatment to the extent practicable was achieved when every injection well within an active block had headspace readings below 50 ppm, thus oxidant delivery refocused on the locations that did not meet this criteria. Once all injection wells within an active treatment block were all below 50 ppm, Geo-Cleanse conducted a hydrogen peroxide stability test. This test involved injecting hydrogen peroxide over the course of one day to obtain a concentration of peroxide equal to or greater than 250 ppm at each injection well for 8 hours. The following day groundwater samples verified that sufficient hydrogen peroxide concentrations existed in each injection well within the treatment block. After the concentration of hydrogen peroxide decreased to 2.5 ppm or below in every injection well, 21-day post-treatment monitoring began, which consisted of obtaining daily PID headspace readings. If headspaces remained below 50 ppm during this 21-day period, the final treatment criterion was effectively met and the block was considered closed. However, select locations within each treatment block were still monitored weekly until active treatment in all the blocks across the site was complete. The long-term monitoring served as an assessment of BPLM rebound and as a final check that the block was treated to the extent practicable. Including the standard ISCO remediation operations, Geo-Cleanse also implemented other innovative remedial technologies and procedures to increase the efficiency of the overall ISCO program. Geo-Cleanse created an above ground piping network designed to contain all fluids

generated during the treatment program. As injection activities proceeded, off-gases created from the reaction caused fluids to mound from the subsurface through the injection wells. In order to manage these mounding fluids, controls were placed on each injection well to direct the groundwater into pipes of the water collection system. At the end of the system, the groundwater was directed through an oil water separator and then into a frac tank. Geo-Cleanse personnel treated and discharged the groundwater on-site eliminating many of the transport, treatment and disposal costs. Geo-Cleanse personnel also used vacuum extraction to reduce the coal tar mass, influence the direction of injected oxidant solution and create larger pathways for oxidant migration. During the treatment program, Geo-Cleanse harnessed the exothermic nature of Fentons reagent to desorb and extract some of the free phase and residual product. Geo-Cleanse used a vacuum truck equipped with a multiple port manifold system to extract the liberated contaminants, using the injection wells as extraction points. These collected materials were then discharged into the frac tank portion of the water collection system and treated. This system helped to remove the free phase and residual product and opened up the site for better oxidant delivery. Treatment Results: The full-scale treatment program conducted at the former MGP site in Augusta, Georgia met the criteria required to establish that the BPLM mass at the site was treated to the extent practicable. Based on the injection activities and groundwater quality data, the full-scale treatment program conducted by Geo-Cleanse obtained closure in each of the 39 blocks on the site. Therefore, the criteria for treating BPLM mass to the extent practicable was achieved and maintained for the length of the treatment program. Summary: Injection at the site began in Block A on November 3, 2004, where the pilot was originally conducted. Injection activities were completed in Block AH on September 14, 2005. The entire treatment program from start to finish included the injection of approximately 2.1 million gallons of 12.5% hydrogen peroxide and a site-specific catalyst solution. The full-scale treatment program at the former MGP site in Augusta, Georgia was completed on October 9, 2005.

This summary sheet is intended to provide a general overview of the referenced site. For more detailed information, please contact us at (732) 970-6696.

Geo-Cleanse Remediation Summary Savannah, GA Former MGP Coal Tar

Overview: Geo-Cleanse International, Inc. (Geo-Cleanse) was contracted to perform a full-scale in-situ chemical oxidation (ISCO) treatment program to treat by-product like material (BPLM), which is a manufactured gas plant (MGP) specific constituent. BPLM is identified as free phase coal tar residuals measured as BTEX (benzene, toluene, ethylbenzene and xylenes) and PAH (polycyclic aromatic hydrocarbons). Results from the pilot ISCO treatment program indicated these constituents were amenable to chemical oxidation using Fentons reagent. Site Background Characteristics: This site was a former MGP located in Savannah, Georgia. From the early 1800s until the 1950s, the MGP site was used to produce gas from coal, coke, or oil. During the gas productions process, various residuals such as tars, liquors, sludges, coal fragments and gas purifying wastes were produced, some of which were released into the soil and groundwater. Program Goals: The goal of the treatment program was to reduce the BPLM contamination in the groundwater and soil within the targeted depth intervals to the extent practicable. Treatment to the extent practicable is defined as the point where no significant BPLM reduction will occur with further treatment. Activities at the site consisted of four main phases of implementation: injection well installation; mass calculations and hydrogen peroxide proportioning; injection; and post-treatment sampling. Each phase of the treatment program was specifically designed to attain the overall goal of meeting the criteria for closure at this site. Injection Well Installation: The injection well installation for the full-scale treatment program at the site began on January 6, 2005 and was complete on April 30, 2005. This phase consisted of approximately 95 days of active installation. Over this time period, 1,238 injection wells were installed on an approximate 15-foot by 15-foot grid pattern, across a maximum of five vertical treatment intervals (see attached map). In addition, the 45 injection wells that were installed for the pilot treatment program at this site were utilized as active injection points for the full-scale. 74 vent wells were also installed at this site. The depths and amounts of injection well layers varied based on the presence of BPLM. Injection wells were installed and screened where BPLM was observed. Once an injection well was installed, four adjacent injection wells were installed in the same screened interval to ensure sufficient oxidant solution contact with the contaminated area. The entire treatment area was subdivided into 28 blocks, with each consisting of 91 injection wells or less. These divisions were implemented to simplify the sampling, injection and data management activities for the site. Baseline Sampling and Mass Calculations: During installation, several injection wells were continuously cored and sampled. Soil samples were obtained in 5-foot increments from approximately 20% of the injection wells across the site, in order to define the lateral and vertical extent of the contaminant mass present at the site. The

samples were analyzed for BTEX using EPA Method 8260B and PAHs using EPA Method 8270C. Using the analytical data from these samples, injection wells were assigned a contaminant mass and a target volume of hydrogen peroxide for each injection well was calculated. The volume of hydrogen peroxide required was based on a 22:1 ratio of hydrogen peroxide to contaminant mass. This ratio was proven to be effective during the pilot ISCO treatment program. If the mass volume calculation was less than the minimum amount of hydrogen peroxide required to be injected to establish the radius of influence, a minimum volume of 480 gallons of 12.5% hydrogen peroxide was used for that injection well. Once mass volume calculations were achieved, the injection activities were implemented and the full-scale treatment program took place in the following stages: 22:1 Ratio/Minimum Injection (Target Volumes) Photoionization Detector (PID) Headspace Chasing Peroxide Stability 21-Day Post-Treatment Monitoring Long Term Monitoring

These stages of injection were developed to demonstrate that the performance criteria for treating BPLM to the extent practicable were achieved. Remediation Operations: Each day prior to oxidant injection, groundwater samples were obtained from all of the injection wells within an active treatment block and analyzed for pH, alkalinity, iron and hydrogen peroxide concentrations, temperature, and PID headspace. This process continued throughout the program on a daily basis to monitor the changes in groundwater chemistry and volatile constituents. Once the delivery of target volume to each injection well was complete in an active block, treatment focused on the locations with PID headspace readings in groundwater greater than 50 ppm. Results from the pilot ISCO treatment demonstrated that PID headspace in groundwater was directly proportional to remaining VOC concentrations. Treatment to the extent practicable was achieved when every injection well within an active block had a headspace reading below 50 ppm, thus oxidant delivery refocused on the locations that did not meet this criteria. Once all injection wells within an active treatment block were all below 50 ppm, Geo-Cleanse conducted a hydrogen peroxide stability test. This test involved injecting hydrogen peroxide over the course of one day to obtain a concentration of peroxide equal to or greater than 250 ppm at each injection well for 8 hours. The following day groundwater samples verified that sufficient hydrogen peroxide concentrations existed in each injection well within the treatment block. After the concentration of hydrogen peroxide decreased to 2.5 ppm or below in every injection well, 21-day post-treatment monitoring began, which consisted of obtaining daily PID headspace readings. If headspaces remained below 50 ppm during this 21-day period, the final treatment criterion was effectively met and the block was considered closed, however select locations within each treatment block were still monitored weekly until active treatment in all the blocks across the site was complete. The long-term monitoring served as an assessment of BPLM rebound and as a final check that the block was treated to the extent practicable.

Summary and Treatment Results: Injection at the site began on February 6, 2004 and injection activities were completed on January 17, 2005. A total of 7 injection rigs were used throughout the duration of the injection program. The entire treatment program from start to finish included the injection of approximately 3.1 million gallons of 8% hydrogen peroxide and a site-specific catalyst solution. The treatment criteria for treating BPLM mass to the extent practicable was achieved and maintained for the length of the treatment program across the entire site. Based on the injection activities and groundwater quality data, the full-scale treatment program conducted by Geo-Cleanse obtained closure in each of the 28 blocks on the site. The full-scale treatment program at the former MGP site in Savannah, Georgia was completed on February 17, 2005.

This summary sheet is intended to provide a general overview of the referenced site. For more detailed information, please contact us at (732) 970-6696.

Edwards AFB Abstract

Permanganate In-Situ Chemical Oxidation of TCE at Edwards Air Force Base, California Todd Battey, Earth Tech, 100 Contractor Hill Road, Edwards AFB, CA 93523 Telephone: (661) 258-7720; Fax: (661) 258-7725; E-mail: todd_battey@earthtech.com Kimberly Coleman, Earth Tech, 695 River Oaks Parkway, San Jose, CA 95134 Telephone: (408) 232-2872; Fax: (408) 000-0000; E-mail: kimberly_coleman@earthtech.com Dan Bryant, Geo-Cleanse International, Inc., 400 State Route 34, Suite B, Matawan, NJ 07747 Telephone: (732) 970-6696; Fax (732) 970-6697; E-mail: dbryant@geocleanse.com ABSTRACT A treatability study of in-situ chemical oxidation (ISCO) using permanganate was conducted in a bedrock aquifer at Site N7, NASA Dryden Flight Research Center, Edwards Air Force Base. The objectives were to achieve contaminant destruction, determine the injection radius of influence, optimize injection methods for bedrock, monitor persistence of permanganate, and evaluate groundwater quality effects. The study area was approximately 100 ft by 50 ft and 100 ft deep. 7,450 gallons of 1.8% potassium permanganate solution were injected into 8 screened wells and 2 boreholes over 5 days. Groundwater samples collected periodically for 60 days following treatment were analyzed for permanganate, metals, and volatile organic compound concentrations. Trichloroethylene and cis-1,2-dichloreothylene remained below detection (from a pre-injection cumulative concentration of 7,210 ug/L). Acetone (presumably an oxidation product) was detected at up to 3,000 u following injection and has attenuated to <460 ug/L. g/L Elevated metal concentrations following treatment have decreased to <80% of their postinjection maxima, with the exception of chromium and nickel. Permanganate degradation rates yield an average half-life of 19 days, and permanganate should degrade below visible concentrations (<0.5 mg/L) in approximately 283 days. Permanganate ISCO appears effective and viable for treatment of chlorinated hydrocarbons at Edwards Air Force Base. Introduction NASA Dryden is located at Edwards Air Force Base, approximately 60 miles north-northeast of Los Angeles, California. NASA Dryden occupies approximately 800 acres on the northwestern edge of Rogers Dry Lake, and consists of administrative, research, laboratory, service, hangar, and storage buildings for support of aeronautical research operations. Site N7 contains two former drum storage areas used by various facility management contractors and a paint shop. Site N7 has approximately 5 feet of silty sand overlying granitic bedrock. The first approximately 10 feet of bedrock is moderately weathered with progressively greater competence with increasing depth. Primary fractures strike northwesterly/southeasterly with a southwesterly dip, and secondary fractures strike north-northeasterly/south-southeasterly with a northwesterly dip. The dip magnitudes are typically 60 to 90 degrees. Apertures generally range from 0.08 to 0.77 inches. Depth to groundwater is approximately 10 feet. Groundwater flow is easterly. Geophysical and hydraulic tests conducted at Site N7 yielded hydraulic conductivity estimates ranging from 8.7 x 10-8 to 1.3 x 10-4 cm/sec, with no consistent trends with depth. Pump tests yielded average transmissivity of 0.004 to 0.035 ft 2 /min. Groundwater quality at Site N7 is alkaline and slightly saline, with groundwater pH ranging from 7.6 to 8.5, total alkalinity ranging from 383 to 552 mg/L, and chloride concentration ranging from 465 to 1,610 mg/L.

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Edwards AFB Abstract

Trichloroethylene (TCE) and its natural degradation product cis-1,2-dichloroethylene (CIS) were detected at Site N7 with maximum baseline concentrations of 6,500 ug/L and 710 ug/L, respectively. Packer tests indicate that TCE and CIS concentrations decreased with depth, with maxima of 45 ug/L TCE and 120 ug/L CIS at depths deeper than 100 ft below grade. Treatability Study Approach, Implementation and Monitoring Six existing screened wells and 2 new wells were used as injection points. The new wells were left as open boreholes (except for shallow casing to prevent overburden collapse) to provide maximum injection flexibility. Packer testing and geophysical logging were conducted on each new borehole to evaluate the vertical distribution of contaminants and potential transmissive zones within the bedrock aquifer. Project design included an injection volume of approximately 1,000 gallons of 2% KMnO4 solution to each of the 8 locations. This volume was based upon dissolved VOC concentrations and corresponding estimate of VOC mass within the treatment area, plus a conservative excess for inefficiencies. Based upon oxidation stoichiometry and a weighted average ratio of KMnO4 mass to VOC mass of 2.6:1 (based upon observed TCE and CIS concentrations), the minimum mass of solid KMnO 4 required was estimated at approximately 31.4 lbs. This estimate assumed perfect reaction efficiency and did not allow for natural inefficiencies due to competing reactions and delivery. A ratio of 40:1 was considered a conservative estimate to ensure complete delivery and oxidation, thus a KMnO4 mass of 1,256 lbs was estimated. A mobile treatment unit was staged at the site, with tanks, pumps, gauges and flow control valves to prepare and deliver reagents safely and effectively. Specially designed mixing heads were attached to the riser pipe of packers installed in the injection wells. The injection process was dynamic and several variables (including injection rate, pressure, and use of air to enhance reagent dispersion) were modified to evaluate optimal injection conditions. Injection rate ranged from <0.25 gpm to > 2 gpm, injection pressure (at which liquid reagents are delivered) ranged from 5 psi to 70 psi, and air was also introduced at pressures ranging up to 70 psi and flow rates ranging up to 4 cfm. Treatment Operations and Results Field injection operations were conducted from August 21-25, 2000. A total of 7,450 gallons of 1.8% potassium permanganate solution (equivalent to 1,102 lbs of solid KMnO 4 ) were injected. Field monitoring during the injection indicated that offgases were not produced in measurable quantities, and thus offgas monitoring for CO2 , O2 , volatile organics, and LEL were discontinued. Groundwater samples collected each morning were analyzed for manganese, chloride, pH, and permanganate, of which only permanganate concentrations were found to be useful field indicators of reaction or reagent distribution. Groundwater samples for VOC and metals analyses were collected at three stages during the treatability study: during packer testing to evaluate the vertical distribution of VOCs, prior to injection to establish baseline conditions, and 3 post-injection in three rounds (at 5 days, 30 days, and 60 days) to evaluate performance. Destruction of the TCE and CIS at the site was complete, and TCE and CIS have remained below detection for at least 60 days. Acetone, however, appeared at up to 3,000 ug/L following injection, suggesting formation as an oxidation product. Acetone has not been reported as a
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Edwards AFB Abstract

permanganate oxidation product of chlorinated ethenes and was not detected in pre-injection bench scale studies of TCE oxidation in groundwater from other sites at Edwards AFB. Determination of the radius of influence (ROI) was one of the primary objectives. The best ROI indicator was presence or absence of permanganate, which is readily detected in nearby wells. The second constraint is groundwater mounding, indicating connectivity between an injection well and nearby monitoring wells. During the treatability study, the first evidence of groundwater mounding was followed within a few hours by the appearance of permanganate in the well. Monitoring results indicated a horizontal ROI between 30 and 55 feet and a vertical ROI of at least 28 feet. The permanganate concentration data were utilized to determine the rate of permanganate degradation at the site. An initial rates method was utilized to calculate an average rate constant (k) of 0.036 day-1 (assuming a pseudo-first-order reaction), with a corresponding average halflife of approximately 19 days. The long-term persistence of permanganate was estimated from the rate constant using a first-order decay law. The point at which permanganate is no longer visible (approximately 0.5 mg/L) was taken as the final concentration, and the average maximum permanganate concentration (13,509 mg/L) was taken as the initial concentration, yielding an estimate of 283 days until permanganate is no longer visible. Concentrations of most metals were elevated following treatment, but all except chromium and nickel have decreased significantly (>80%) over the 60-day sampling interval relative to the post-injection maximum concentrations. Chromium concentrations in the injection wells doubled from averages of 14,300 to 29,320 ug/L between the 5 -day and 30-day post-injection sampling rounds, but then subsequently decreased by 29% to 20,804 ug/L in the 60-day round. Nickel, in contrast, has been variable but remained elevated. Regardless of the mechanism that resulted in the elevated metals (colloidal materials associated with the permanganate or liberated from the formation), the heavy metal concentrations within the treatment area are only anticipated to remain elevated above background concentrations as long as the permanganate persists. Chromium in particular, which may exist in the most soluble hexavalent state, will reduce and precipitate under the alkaline groundwater conditions at Edwards AFB. Overall Conclusions After a 5-day injection period, TCE and CIS have remained non-detectable (reduced from 7,210 ug/L) for 60 days following treatment. Temporary acetone and metals increases observed in groundwater following treatment attenuated rapidly. Only chromium and nickel have remained elevated 60 days after treatment, however neither are stable in alkaline aquifers and are anticipated to attenuate as the permanganate degrades. The purple color imparted to groundwater by permanganate will persist as long as permanganate concentrations remain >0.5 mg/L, which is anticipated to be approximately 283 days based upon permanganate degradation measurements. Overall, permanganate treatment appears to offer an effective and viable remedial alternative for chlorinated solvents dissolved in groundwater at Edwards AFB.

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The True ISCO Innovators for over 16 years

Geo-Cleanse International, Inc.

Site Summary: Garfield Chemical Site
Site Background: For over 100 years, this site was a chemical company located in Garfield, NJ. The 2,025 sq ft area is covered by a concrete cap and the geology of the treatment area consists of fine to medium grained sand. Depth to groundwater is approximately 10 feet below ground surface (ft bgs). During site investigations, toluene, 1,1biphenyl, and diphenyl ether were detected exceeding the applicable NJDEP soil and groundwater remediation standards. The goal of the in-situ chemical oxidation (ISCO) treatment program was to achieve source reduction without any negative impact to the groundwater.

Design & Treatment: Geo-Cleanse International, Inc. (Geo-Cleanse) was contracted to design and implement the ISCO field treatment program. Due to site-specific conditions, Geo-Cleanse determined that catalyzed hydrogen peroxide (CHP) would be the most appropriate oxidant. The primary field treatment area was approximately 45 ft x 45 ft, 6 ft thick, at a depth interval from 6 to 12 ft bgs. A total of 11 injection wells and 4 vent wells were installed utilizing direct push technology. Soil borings were also collected for visual soil characterization and to confirm the depth of the treatment interval. During soil boring collection and baseline sampling, light non-aqueous phase liquids (LNAPL) were present. A total of approximately 29,150 gallons of 8 % hydrogen peroxide and catalyst were injected during a course of 14 days.

Pre-Treatment Soil Borings

Treatment Results: Our routine process monitoring and sampling ensured a safe and efficient process. Groundwater data collected during active injection showed that conditions conducive to a CHP treatment were established. Offgas monitoring data indicated that oxidation was occurring, resulting in elevated carbon dioxide levels. Following the treatment program, LNAPL was eliminated and the soil and groundwater goals were achieved. Based on the success of the treatment program, a No Further Action (NFA) letter for the soil is expected in the near future. Monitored natural attenuation of groundwater will be used to achieve final groundwater goals.

400 STATE ROUTE 34, SUITE B MATAWAN, NEW JERSEY 07747 PHONE: (732) 970-6696 FAX: (732) 970-6697 WWW.GEOCLEANSE.COM

The True ISCO Innovators for over 16 years

Geo-Cleanse International, Inc.

Site Summary: Residential NJ Home
Site Background: Geo-Cleanse International, Inc. (Geo-Cleanse) was contracted to perform a full-scale in-situ chemical oxidation (ISCO) treatment program at a residential home in New Jersey. After the removal of an underground storage tank, post-treatment samples revealed residual vadose zone soil contamination. The contaminants of concern were total petroleum hydrocarbons (TPH), which were above the New Jersey Department of Environmental Protection Soil Cleanup Criteria (NJDEP SCC) of 10,000 mg/kg. Following excavation activities, soil data indicated that contaminant concentrations were still above the NJDEP SCC, at approximately 38,000 mg/kg. In order to protect the foundation of the house and reach final cleanup goals, an in-situ chemical oxidation treatment program was implemented. Design & Treatment: Based on the site access limitations and the contaminants present, GeoCleanse determined that catalyzed hydrogen peroxide (CHP) would be the most appropriate oxidant for the site to reach the cleanup goals in the desired time frame. The treatment program targeted an interval from approximately 10 to 19 feet below ground surface (ft-bgs). A total of 8 permanent injection wells were installed utilizing direct-push technology. The injection wells were installed as nested points, where each point contained two wells per bore hole. The nested points helped to reduce well locations and drilling costs. The injection program consisted of eight days of active injection and a total of 12,000 gallons of 10.5% concentration of CHP was injected across the site. Summary: Daily process monitoring was conducted during the injection program to ensure a safe and efficient process. Off gas monitoring data indicated that oxidation was occurring, resulting in elevated carbon dioxide concentrations. The reagents were successfully distributed throughout the targeted treatment intervals, and the structures on-site were not compromised. Performance monitoring indicated that the contaminant concentrations were below the NJDEP SSC and the property owner received a No Further Action letter.

400 STATE ROUTE 34, SUITE B MATAWAN, NEW JERSEY 07747 PHONE: (732) 970-6696 FAX: (732) 970-6697 WWW.GEOCLEANSE.COM

The True ISCO Innovators for over 16 years

Geo-Cleanse International, Inc.

Site Summary: Confidential Rochelle, Illinois Project
Site Background: Due to inclement weather, an accident occurred along Route 64 in Rochelle, Illinois involving a tanker truck. The tanker truck was carrying over 8,500 gallons of gasoline, and approximately 534 gallons were lost on the shoulder and into a drainage ditch. Approximately 558 tons of impacted soil was excavated from the drainage ditch and disposed of off-site. Additional investigation concluded that residual soil and groundwater contamination from approximately 2 to 7 feet below ground surface (ft-bgs) was present adjacent to the excavated area. The soil matrix of the impacted area consists of silty clay from 2 to 4 ft-bgs and sand from 4 to 7 ft-bgs. The depth of groundwater was estimated to be approximately 4.5 ft-bgs. The primary contaminant of concern was benzene, which was present above the Class I groundwater standards of 0.005 mg/L. Design & Treatment: Geo-Cleanse International, Inc. (Geo-Cleanse) was contracted to design and implement a full-scale in-situ chemical oxidation (ISCO) treatment program, utilizing activated sodium persulfate (ASP). A total of 12 temporary injection points were installed, with a 6-ft lateral spacing, over a 500 ft2 area. Temporary injection points were advanced via direct push technology using a truck mounted Geoprobe. The Geoprobe advanced the casing to 7 ft-bgs, then extracted the casing to 3.5-ft. Although there are impacts above 3.5 ft-bgs, injection directly into this interval was not possible due to the tight clay formation at a shallow depth and the likelihood of short-circuiting reagents to the surface. Geo-Cleanse expected that the water table would locally mound upward around the active injection point creating contact with the shallow soil interval. A total of approximately 2,050 gallons of ASP was applied to the target area.

Site Map

Mixing Tanks
Treatment Results: The treatment program was conducted on May 3rd and 4th, 2010. Post-treatment groundwater analytical results confirmed benzene reductions to below the Class I standard of 0.005 mg/L. Furthermore, all reagents were injected in a safe and efficient manner, injection occurred at the shallow target depths, and target injection volumes were delivered to each injection point.
Not to Scale
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Temporary Injection Point

Based on these conclusions, a successful treatment program was implemented.

400 STATE ROUTE 34, SUITE B MATAWAN, NEW JERSEY 07747 PHONE: (732) 970-6696 FAX: (732) 970-6697 WWW.GEOCLEANSE.COM