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RegenOx® Treats Benzene in Low Permeability Soils
Introduction
Service station operations created a benzene contaminant plume in tight subsurface soils. A dual-phase extraction system (DPE) was installed and removed a total of 9,965 pounds of petroleum hydrocarbons over two 90-day operational periods. However, contaminant removal reached asymptotic levels and a more effective remedial strategy was needed to address the remaining benzene concentrations. The DPE system was shut down in December 2004 and RegenOx® was selected to evaluate the effectiveness of reducing benzene and MTBE concentrations in tight soil lithology.
Description of Activities
RegenOx was pilot tested around well DPRW-6 to evaluate its effectiveness in tight soil. A total of 1,439 pounds of RegenOx was applied near well DPRW-6 as a pilot test in August 2005 (510 lbs) and July 2006 (929 lbs). Benzene concentrations declined within 15 weeks by 76% and successfully reached the Site Specific Target Level (SSTL) (Graph 1), prompting a design for full scale implementation.
The objective of full-scale treatment was to provide rapid mass reduction of benzene concentrations and reach the SSTL of 20.1ppm across the 9,100 ft2 source area. Benzene rebound at DPRW-6 (the original pilot test well) six months post-injection suggested that a previously unidentified plume had re- contaminated that area. After additional site characterization was completed, 7,110 pounds of RegenOx were applied during six injection events over five treatment areas (Figure 1).
The RegenOx injections were performed over a 6 month period due to weather delays. Monitoring was conducted to observe potential contaminant rebound from areas requiring additional injections. The applications targeted a treatment thickness of 14-20 feet bgs into silty clay with intermittent sand “stringers”. RegenOx was injected using a top-down direct-push injection technique with 5-15 lbs of RegenOx injected per vertical foot.
Results
Prior to the full-scale application, benzene concentrations exceeded the SSTL of 20.1ppm in all wells. Monitoring over a 7 month period prior to remedial treatment indicated an increase in concentrations from 12 – 32ppm to 20.4 – 44.1ppm.
RegenOx was applied over six injection events as indicated in Table 2. Sampling conducted
after the final application event in December 2007 indicated a benzene reduction to at or below the SSTL in all wells (Graphs 2) including the original pilot test well DPRW-6. As monitoring continued, a decline in benzene concentrations persisted via natural attenuation and all wells sampled below 10ppm in August 2009. Based on the reducing trend observed over the past 12 months, the site was recommended for closure.
3-D Microemulsion® Bio-Barrier Rapidly Treats Cis-DCE and Vinyl Chloride Contamination and Maintains Reductive Dechlorination Over a 1,200-Day Period
CASE SUMMARY
Cis-1,2-dichloroethene (cis-DCE) and vinyl chloride (VC) were migrating off-site at this commercial facility. A pilot test of enhanced anaerobic bioremediation was performed to determine if a bio-barrier using 3-D Microemulsion, a form of HRC Advanced®, could effectively reduce the cis-DCE and VC contamination before it moved off-site. The remediation design included the subsurface injection of 3-D Microemulsion upgradient of contaminated well MW-9.
TECHNOLOGY DESCRIPTION
Reductive dechlorination is a process used to degrade certain contaminants in groundwater (e.g., cis-DCE and VC) to ethene. 3-D Microemulsion is a highly effective agent to facilitate this process. 3-D Microemulsion is composed of free lactic acid, controlled-release lactic acid (polylactate), and certain fatty acid components esterified to a carbon backbone molecule of glycerin. When injected into contaminated soil and groundwater, 3DMe produces a sequential, staged release of its electron donor components. The immediately available free lactic acid is fermented rapidly while the controlled-release lactic acid is metabolized at a more gradual rate. The fatty acids are converted to hydrogen over a mid- to long-range timeline giving 3DMe an exceptionally long electron donor release profile. This staged fermentation provides an immediate, mid-term, and very long-term controlled release supply of hydrogen (electron donor) to fuel the reductive dechlorination process.
REMEDIATION APPROACH
The objective at the site was to demonstrate the ability of 3-D Microemulsion to prevent the off-site migration of cis-DCE and VC by contaminant reduction. The reduction was to be achieved by the introduction of 3DMe into the subsurface through 8 injection points spaced 5 feet apart (Figure 1).
RESULTS
Within 60 days of the application of 3-D Microemulsion, concentrations of the target contaminants were significantly reduced (Table 1 and Figure 2). Over the 1,200-day monitoring period, cis-DCE was reduced by a magnitude of 3 from 4,300 to 3 micrograms per liter (μg/L). VC was reduced by 2 orders of magnitude from 7,300 to 24 μg/L, interrupted briefly by an anomalous spike likely to be laboratory error. As a result of this process, ethene concentrations increased by 102 percent, from 3,100 to 6,500 μg/L, after 130 days (a clear indication of complete dechlorination). Elevated levels of ethene were maintained for more than 300 days until ethene monitoring ended at Day 350 (Figure 2)
CONCLUSION
Overall, the results of this pilot test clearly show that when using 3-D Microemulsion, chlorinated ethene degradation via enhanced reductive dechlorination can be achieved both rapidly (60 days after injection) and successfully maintained over the long term.
PCE and TCE Remediation at a Dry Cleaning Facility
SITE SUMMARY
Subsurface investigations at this operating dry cleaner site revealed elevated levels of PCE and TCE in the site soils and groundwater (perched aquifer). Soil remediation was accomplished via over-excavation in June of 1998. Accelerated bioremediation using HRC was selected to treat the groundwater contamination. The HRC application approach was chosen because it minimized disturbance to site operations. Most importantly, the site was granted closure status 17 months after initial HRC treatment.
REMEDIATION APPROACH
- Remediation Objective: Reduce concentrations of chlorinated aliphatic hydrocarbons to target concentrations at the entire site. See Table 1.
- Application Type: Grid (Direct-Push Injection)
- Product: HRC
- Quantity Applied: 10,020
- Application Rate: 10.37 lb/ft
- Injection Spacing: 5 ft on-center
- Product Cost: $62,340
SITE CHARACTERISTICS
General
- Name: Arlington Strip Mall
- Location: Arlington, Texas
- Industry: Dry Cleaning
- Contaminants of Concern:
Hydrogeology
- Treatment Area: 3,000 ft2
- Soil Type: Clay
- Groundwater Velocity: 0.055 ft/day
- Groundwater Flow Direction: Southwest
- Depth to Groundwater: 7 ft
RESULTS
CONCLUSION
In an attempt to successfully treat the difficult to reach source area, directly beneath the facility, and to minimize building disturbance, 15 HRC injection points were installed on 30- degree angles (See site map). The site was granted closure approximately 17 months after the application due to the high degree of accelerated natural attenuation that resulted from the use of HRC at the site.
PCE and TCE Remediation at a Dry Cleaning Facility
SITE SUMMARY
A focused Site Investigation was completed for a dry cleaner site in Portland, OR. Results showed contamination levels of PCE as high as 120,000 ug/L in groundwater and 320,000 ug/L in soil. It is believed that the source of the contamination was a leaking sewer line beneath the facility. The high concentrations suggested the presence of Dense Non-Aqueous Phase Liquid (DNAPL) and a remedial technology was needed to address the distinctive contaminant concentrations. The HRC® application at this site is significant since it was the first time HRC-X® was injected, along with HRC, to treat VOCs. The extended life expectancy of HRC-X, 2 times-3 times that of HRC, made for a feasible option to reduce the high concentration of PCE. A pilot study was implemented using HRC to target the area near wells MW-1, MW-2, and MW-4 while HRC-X was injected near JEMW-4, the projected area of DNAPL.
REMEDIATION APPROACH
- Remediation Objective: Pilot Study to prove HRC applicability at the site.
- Application Type: Grid (Direct-Push Injection) for both applications
- Product: HRC and HRC-X
- Quantity Applied: 1,920 lb of HRC and 1,680 lb of HRC-X
- Application Rate: HRC – 6 lb/ft; HRC-X – 9 lb/ft
- Injection Spacing: Variable distances, see site map
- Product Cost: $11,520 HRC; $11,760 HRC-X
SITE CHARACTERISTICS
General
- Name: Springdale Cleaners
- Location: Portland, OR
- Industry: Dry Cleaning
Hydrogeology
- Treatment Area: 9,100 ft2
- Soil Type: silty clay and silty sand
- Groundwater Velocity: 0.68 ft/day
- Groundwater Flow Direction: Southwest
- Depth to Groundwater: Variable
RESULTS
CONCLUSION
HRC performance in MW-2 produced sustained degradation of PCE and TCE as well as their breakdown products over roughly a two year period (Graph 1). HRC metabolic acids peaked around 1300 mg/L after a year then tapered off over time (Graph 2). HRC-X performance in JEMW-4 and JEMW-5 indicates unprecedented performance in terms of contaminant reduction and total metabolic acid production and longevity. JEMW-4 shows significant reductions in high concentrations of 100,000 ug/L PCE to near non-detect (ND) levels in approximately 300 days (Graph 3). PCE levels continue to remain at very low levels for greater than 5 years after HRC-X application. TCE was also reduced significantly from 90,000 ug/L to approximately 35,000 ug/L in close to 4 years. Daughter products such as cis-DCE and VC have been produced as a result of the parent product breakdown and are eventually expected to dissipate. Metabolic acids remain high (1000 mg/L) as a result of the HRC-X application. HRC-X continues to reduce high concentration PCE and daughter products TCE, cis-DCE, and VC more than 5 years after injection.
Replacement of P&T with ORC Advanced® Reduces Cost to Closure
CASE SUMMARY
Two leaking underground storage tanks (USTs) resulted in soil and groundwater contamination at a service station in Michigan. Naphthalene, trimethylbenzene (TMB) and benzene, toluene, ethylbenzene, and xylenes (BTEX) contamination were discovered in the subsurface prompting the need for remedial cleanup. Michigan DEQ began remediation via UST removal and soil excavation. A total of 4,000 cubic yards of contaminated soil was removed. A pump and treat (P&T) system was installed and operated for 8 years through November 2003. The system removed 1,575 pounds of BTEX and significantly lowered contaminant concentrations. However, the P&T system reached asymptotic conditions and would not be effective in achieving site closure goals. Regulators began looking into new ways of accelerating the remediation process and reducing the overall cost of cleanup. Enhanced aerobic bioremediation using ORC Advanced® was deployed to replace the P&T system and degrade the remaining contamination.
REMEDIATION APPROACH
The remediation objective was to continue the reduction of petroleum hydrocarbons in the subsurface and reduce the cost to closure. Three months after the P&T was shutdown an ORC Advanced application took place. The ORC Advanced injection included 43 injection points in a grid design within the contaminated area surrounding well MW-9 (Figure 1).
RESULTS
Pump & Treat Results
An increase in rainfall during certain parts of the remedial period contributed to some of the increases observed in Graph 1. During wet periods, an increase in concentrations resulted from the mobilization of contaminants within the capillary fringe smear zone. An infiltration gallery was installed to flush the contamination into the dissolved-phase where it was available for P&T removal.
Prior to shutdown in November 2003, O&M costs were increasing and low-level dissolved- phase concentrations were still elevated indicating the system was not effective at reaching the required low cleanup levels.
ORC Advanced Injection Results
ORC Advanced Injection Results
Within 60 days of the ORC Advanced application, low-level concentrations were significantly reduced below post-P&T levels. Reduction continued throughout the monitoring period and a 99% mass reduction was achieved approximately 13 months after the initial injection. In well MW-9, concentrations in all contaminants were reduced to below the cleanup goals.
The ORC Advanced application eliminated increasing O&M costs of an aging P&T system and allowed the site to be closed years ahead of projections.
High Benzene Concentrations Reduced Using ORC Advanced
SITE SUMMARY
Elevated levels of petroleum hydrocarbons were discovered near the former dispenser island at a former service station in Sheboygan, WI. In hopes of reducing concentrations, soil excavation activities took place in June 2003. A total of 500 tons of hydrocarbon-impacted soils were removed and transported to a landfill for disposal. However, residual contamination continued to affect the groundwater after the excavation. By March 2004, benzene and ethylbenzene had risen to 2,500 ug/L and 1,300 ug/L, respectively. In Situ bioremediation using ORC Advanced was chosen to reduce BTEX, naphthalene, and trimethylbenzenes. In the northwest corner of the site, the location of the former UST basin, a total of 480 pounds of ORC Advanced was injected. In the southeast corner, the area of highest contamination, a total of 2,370 pounds of ORC Advanced was injected.
REMEDIATION APPROACH
- Remediation Objective: Reduce concentrations of Benzene to cleanup goals at the entire site. See Table 1.
- Application Type: Grid
- Product: ORC Advanced
- Quantity Applied: 2,850 lbs
- Application Rate: NW Corner–4 lbs/ft; SE Corner-11.9 lbs/ft
- Injection Spacing: 10 ft
- Product Cost: $24,225
SITE CHARACTERISTICS
- Name: Former Marathon Unit #3697
- Location: Sheboygan, WI
- Industry: Service Station
- Contaminants of Concern:
Hydrogeology
- Treatment Area: NW Corner 1,200 ft2; SE Corner 1,800 ft2
- Soil Type: Silty sand lenses in clay matrix
- Groundwater Flow Direction: Southeast
- Depth to Groundwater: 12-15 ft
RESULTS
CONCLUSION
Groundwater sampling results after excavation activities show an increasing trend of contamination. On average, concentrations continued to increase up until the ORC Advanced application due to residual contamination. Concentrations peaked before ORC Advanced injection followed by a significant reduction across the plume. In well MW-5, benzene spiked to 160 ug/L while naphthalene rose to 170 ug/L and in well MW-4 BTEX, naphthalene and trimethylbenzenes all increased. Significant decreases of all contaminants were seen shortly after ORC Advanced injection. In well MW-8 total BTEX was reduced from 6,720 ug/L to 168.8 ug/L, a 97% reduction. Naphthalene concentrations were above the MCL of 20 ug/L in wells MW-1, MW-4, MW-5. ORC Advanced reduced concentrations to non-detect in wells MW-4 and MW-5, leaving 38 ug/L in well MW-1. Monitoring is on-going as concentrations continue to decrease towards MCLs.
Surgical Site Closure – 30 Sites in Indiana Receive Closure using ORC
CASE SUMMARY
Surgical Site Closure
The “Surgical Site Closure” strategy was developed by Mr. Steve Sittler, an employee of KERAMIDA in Indianapolis, Indiana. The method is an innovative remedial strategy designed to intelligently integrate natural attenuation, risk-based cleanup goals and focused source removal/treatment to cost-effectively remediate contaminated areas. This approach is best applied at sites where released materials are amenable to biodegradation and where long-term, natural attenuation-type strategies are not suitable for reasons of property transfer or potential off-site liability. This strategy was performed at 30 sites in Indiana for a major oil company.
Service Stations/Bulk Storage Terminals – Indiana
From 1998-2008, a total of 30 service station/bulk storage terminal sites were targeted for Surgical Site Closure in Indiana. The subsurface matrix consisted of unconsolidated sediments ranging from low-permeability silty clays with sand stringers to sand and gravel formations. The contaminants of concern were primarily gasoline and diesel fuel. A combination of source removal via excavation coupled with enhanced in situ bioremediation using Oxygen Release Compound (ORC®) was performed at most sites.
REMEDIATION APPROACH
The remediation approach included focused soil excavation of the source area and/or ORC direct-push injection. At some sites ORC was applied to the base of the excavation prior to backfilling. Shortly afterwards, a direct-push injection of ORC was completed over the remainder of the plume. The amount of ORC needed at each site location was determined using various site characteristics including contaminant concentration, seepage velocity, and treatment area.
The majority of the sites were successfully treated using only one injection of ORC; however, a handful of sites received multiple applications. Most of these sites indicated that high levels of BTEX were present prior to treatment (>1,000ppb to <50,000ppb) and required additional applications to sustain aerobic bioremediation.
ABOUT THE CONSULTANT
KERAMIDA Inc. is an engineering and consulting firm that serves industries, businesses, cities, and governments worldwide. They provide strategy and implementation services in: Sustainability, Green House Gases, Energy, Environmental Compliance, Remediation, Environmental Due Diligence, Brownfield Redevelopment, Plant Decommissioning, Health & Safety, Training, Risk Management, and ISO Management Systems. Established in 1988, KERAMIDA is headquartered in the historic Lockerbie Square district of Indianapolis, Indiana. The firm employs over 70 technical experts and support personnel in offices throughout the U.S., including Chicago, IL; Pittsburgh, PA; New York, NY; Los Angeles, CA, Sacramento, CA. KERAMIDA’s many principals have worked for over 25 years in the sustainability, environmental, health & safety, and remediation arenas, and are recognized leaders in their fields. Their engineers, scientists, and planners are renowned for delivering creative, integrated EHS solutions to a broad range of clients throughout the U.S. and abroad.
CONCLUSION
The Surgical Site Closure method was successful in reaching site closure at 30 petroleum-impacted sites over a nine-year period. The average time to reach site closure was ~3 years and the average cost to implement the remedial strategy was ~$70,000. Cost analyses indicated that a traditional remediation approach would have ranged from at least $100,000 to potentially $1 million. Actual implementation costs for the Surgical Site Closure approach ranged from approximately $25,000 to $75,000 plus monitoring costs.
Successful Pilot Test Results in Full-Scale Treatment of Large BTEX Plume
CASE SUMMARY
Refueling Station – Algonquin, IL
Leaking underground storage tanks at a refueling station resulted in a benzene, toluene, ethylbenzene and xylene (BTEX) plume in the underlying sand/gravel aquifer. The plume covered 1-acre and extended 390 feet downgradient from the source area, with a total BTEX concentration exceeding 24,000 parts per billion (ppb). In an effort to mitigate the source, 795 cubic yards of contaminated soil was excavated; however, further groundwater monitoring revealed that BTEX concentrations still exceeded the Illinois EPA cleanup levels. To address the remaining contamination and reduce concentrations to the state cleanup goal, a remediation plan was implemented using Oxygen Release Compound (ORC®) and ORC Advanced®.
REMEDIATION APPROACH
The remediation objective was to reduce petroleum hydrocarbon contamination, mainly benzene, to the state cleanup goal. A pilot test was performed using ORC to observe the effectiveness of reducing BTEX concentrations. Successful reduction was achieved within 4 months and a full-scale application was implemented. The full-scale application was focused near the source area as well as within the mid-plume area (near MW-7 & MW-8). Two applications followed within the mid- and lower plume areas to continue BTEX reduction.
- Application Type: Grid & Barrier Application
- Soil Type: Clay above Sand/Gravel
- Groundwater Velocity: 0.25 ft/day
- Treatment Area: 43,500 ft2
- Injection Spacing: 10–20 feet
- Product Cost: $171,600
Five of the ten contaminated monitoring wells achieved the remedial objective for benzene as well as all other contaminants following the ORC and ORC Advanced injection. Benzene reduction for those wells that have not yet achieved the cleanup goal are listed in Table 3. Overall, a benzene mass reduction of over 95% was achieved. It is expected that the remaining contaminant concentrations will reach cleanup goals as monitoring continues.
Site Closure Sought after using ORC® Biobarrier to Enhance Aerobic Biodegradation of MTBE and TPHg
CASE SUMMARY
Former Service Station – Bishop, CA
Extensive methyl tertiary-butyl ether (MTBE) and total petroleum hydrocarbons as gasoline (TPHg) contamination was discovered within the subsurface as a result of leaking underground storage tanks (USTs) at a former service station. Following the removal of the leaking USTs, a total of 1,192 cubic yards of gasoline- impacted soil in the source area was excavated and transported off-site for treatment. Monitoring following the excavation activities revealed residual source contamination found in the capillary fringe immediately downgradient near Wells MW-6 and MW-7. Concentrations in Well MW-6 exceeded 7 parts per million (ppm) MTBE and approximately 11 ppm TPHg. Efforts to further delineate the plume revealed petroleum contamination extending 1,700 feet downgradient from the source. Early efforts were made to treat the downgradient plume utilizing an air sparging/vapor extraction system placed 800 feet downgradient from the site of the original release. This approach proved to be effective as MTBE and TPHg were reduced to non-detect levels downgradient from where it was installed. However, the source area continued to reveal MTBE and TPHg concentrations above the cleanup goals enforced by the California Regional Water Quality Board. To treat the source area and bring the site to closure, an enhanced bioremediation barrier (biobarrier) was designed and implemented using Oxygen Release Compound (ORC®).
REMEDIATION APPROACH
To address the source area, a total of 950 pounds of ORC was mixed with water to form a slurry and injected via direct-push technology. The 3 row ORC biobarrier was applied immediately downgradient from the release area (Figure 1). Wells MW-6 and MW-7 were monitored to observe the effectiveness of ORC.
RESULTS
The post-ORC injection monitoring results show an effective reduction of MTBE and TPHg within one year. Well MW-6 indicates two MTBE concentration spikes likely caused by residual contamination from the soil entering into the groundwater (Graph 1). However, an MTBE reduction of 94% occurred between day 210 and 300 and concentrations reached non-detect shortly afterwards. TPHg concentrations declined by 70% within the first 30 days and continued on a downward trend, reaching non-detect levels approximately one year after the application.
In Well MW-7, reduction occurred immediately after injection with an MTBE decrease of 88% by day 120 (Graph 2). Concentrations reached non-detect less than a year after the ORC application. TPHg levels declined similarly to MTBE and reached non-detect in less than one year.
The effective treatment of MTBE and TPHg using ORC resulted in non-detect levels of both contaminants and has allowed the consultant to seek site closure status from the regulatory agency.
In Situ Aerobic Bioremediation vs. AS/SVE Cost Comparison at UST Site
REGENESIS® Demonstrates Effective Cost-Savings Using ORC®
Project Highlights
- An in situ aerobic bioremediation pilot test demonstrates a cost-effective treatment option vs. traditional Air Sparge and Soil Vapor Extraction (AS/SVE) system
- Within one month, benzene concentrations were reduced from baseline concentrations of 200 ug/L to non-detect (>5 ug/L)
- Approach using ORC® resulted in a $79K savings vs. traditional mechanical treatment option
Project Summary
The site of a former gas station with leaking underground storage tanks (LUSTs) was chosen for a pilot test to demonstrate the effectiveness of ORC® in treating the existing benzene (BTEX) and MTBE concentrations. In addition to the pilot test, a cost-comparison was also prepared to illustrate the potential for cost-savings associated with the use of a passive, innovative technology like ORC vs. a traditional AS/SVE remediation system.
For the pilot test a 20 ft. x 20 ft. area, with the highest concentrations of BTEX and MTBE, was treated with 180 lbs of ORC. BTEX concentrations within this area varied from 200 ug/L to 2100 ug/L from low and high groundwater elevation, respectively. ORC was injected into 10 points from 8-14 ft bgs to ensure ample coverage of the sand layer and some of the smear zone.
Technology Description
Oxygen Release Compound (ORC) is an engineered, oxygen release compound designed specifically for enhanced, in situ aerobic bioremediation of petroleum hydrocarbons in groundwater or saturated soils.
Cost Comparison Analysis
A cost comparison analysis was prepared by the consultant for the Indiana Department of Environmental Management (IDEM) to show a comprehensive cost savings using ORC versus the AS/SVE system for full-scale treatment of benzene and MTBE. This cost comparison is illustrated in Table 2 and includes the initial full-scale ORC application costs as well as a second application at 50% of the initial application cost. This second application is shown as an “insurance policy” in the event that more ORC is needed to complete the remediation. The AS/SVE costs are reflective of the design, installation, and operation of such a system for two years. Based on the analysis, the use of ORC represents ~59% of the cost of the AS/SVE option or a potential savings of $79,451. If a second insurance application is avoided, then the savings are $79,451 (initial saving) plus $39,1529 (cost for re-application) equaling $118,603.
Results
Within one month, benzene concentrations in the low groundwater elevation were reduced from baseline concentrations of 200 ug/L to non-detect (<5 ug/L). Dissolved oxygen content also increased dramatically from <0.5 ppm (baseline) to >20 ppm post application. A successful full-scale application was designed using 4,000 pounds of ORC, which will save the client >$79K versus a traditional AS/SVE system.
