In Situ Remediation at an Active Manufacturing Facility in Northern Italy

In Situ Remediation at an Active Manufacturing Facility in Northern Italy

Historic leakages at an active manufacturing facility in Northern Italy resulted in the underlying groundwater becoming impacted with hexavalent chromium (Cr(VI)) contamination of up to 2,000 μg/L, and chlorinated solvents (CHC) concentrations of up to 10,000 μg/L. 3-D Microemulsion® (3DMe) and Metals Remediation Compound (MRC®) were selected to remediate the site because of:Read More

Enhanced Reductive Dechlorination in a Fast Flowing Aerobic Aquifer

Enhanced Reductive Dechlorination in a Fast Flowing Aerobic Aquifer

Introduction

Enhanced Reductive Dechlorination (ERD) through biostimulation and redox manipulation is a well-established treatment method for chlorinated solvent contamination in groundwater. However, it is sometimes considered inappropriate where natural conditions are not already conducive to anaerobic attenuation, such as highly aerobic aquifers or fast-flowing groundwater. The use of microbial assays or PCR testing can potentially reinforce this view, when baseline sampling shows little or no evidence of the presence of dehalorespirators or active reductive dechlorination. However, ERD can be achieved in these situations through the creation and maintenance of the ideal redox conditions, coupled with a long term supply of terminal electron donors. Regenesis has successfully remediated many sites via ERD, where initial conditions appear unpromising, using Hydrogen Release Compound (HRC) and 3-D Microemulsion (3DMe) substrate technologies. This case study exemplifies this approach and presents data from a site where treatment is ongoing.


Fig. 1 Metal fabrication works

The Site

The groundwater under an active metal fabrication works in eastern France was impacted with tetrachloroethylene (also known as perchloroethylene (PCE)) following historic leaks and spillages at the facility. The underlying aquifer comprised a highly permeable sandy formation, which allowed a high groundwater seepage velocity of greater than 300 m/year. This had resulted in an extensive dissolved phase plume forming on the site. The contamination extended over 260 m, with concentrations of up to 1,300 μg/L and no obvious source, although multiple areas were suspected. The contamination also extended from the top of the groundwater at 3 m BGL to approximately 10 – 13 m BGL (chlorinated solvents, having a high specific gravity and a low viscosity, tend to move downwards through the water column). The groundwater in ux was also highly aerobic, hence very little natural biological attenuation of the PCE was occurring.

The main risk from the PCE plume was due to its migration beyond the site boundary into a nearby fishing lake. Where the contaminant concentrations could actually be measured in the lake water (32 μg/L PCE). The contamination also potentially posed a human health risk to site.


Fig. 2 Impacted nearby fishing lake

Remediation Strategy

Studio Maffezzoli and Regenesis designed, and Ortec implemented, a safe, economical and cost effective in situ ERD strategy, which was new to this part of France.

Although no site specific target values were set for the project, the intention of the remediation strategy is to prevent offsite migration of the plume, thereby mitigating the impact to the fishing lake and secondary, and to reduce the risk to human health onsite.

There are several potential spill locations at the site and as the high seepage velocity has created a large plume with low concentrations, it has proved difficult to accurately delineate the source areas. The buildings and activity on the site have also made access for site investigation, difficult in some areas. Therefore, a staged remedial strategy has been adopted, with a series of barriers used to treat as much of the plume as can be accessed in an economical manner. As monitoring continues, it may be the case that more recalcitrant areas may be observed, which will help to give better resolution on the source locations. Further site investigation during the validation period can also then be used to determine if a second locally tailored dose may then be completed in these areas.

The remedial approach was also intended to minimise the disturbance to this busy, active facility. It was therefore decided to use 3D Microemulsion (3DMe) as this stimulates ERD from a single application for up to 5 years (although it may be expected to be slightly less in a fast flowing site such as this), minimises the number of injection locations and avoids the use of any physical abstraction equipment at the site.


Fig. 3 The buildings and activity on the site made access difficult in some areas


Fig. 4 3DMe Electron Donor Release Profile

3DMe provides three stages of electron donor release from a single concentrate of specially designed polar molecules. When mixed with water on site, 3DMe forms a high-volume microemulsion, without the requirement of emulsifiers. Upon injection into the groundwater, 3DMe initially moves out into the formation and adsorbs to the soil particles. As the molecule is designed to be appropriately soluble, it then gradually dissolves back into the groundwater, where it ferments to drive ERD, but also reaches its critical micelle concentration (300 ppm), reforms as a microemulsion and moves further out from the injection point.

This process repeats to ‘self-distribute’ the 3DMe over large distances within the subsurface, without it washing away. This mechanism allowed for wider injection spacing which reduced the number of injection locations. This then allowed both the cost and disruption to the site to be minimised. The ability of 3DMe to coat the subsurface without being washed away, whilst still being soluble enough to provide an effective terminal electron donor concentration in the groundwater, made it ideal for this fast flowing site.


Fig. 5 3DMe Molecular Structure


Fig. 6 Treatment zones (‘barrier’) locations

The first phase of the treatment was applied in March 2012. 3DMe was applied in six ‘barriers’ installed perpendicular to the flow of the groundwater. Each injection involved driving a direct push injection rod into the subsurface and applying the requisite dose across the vertical target zone. The injections were then repeated in a row across the width of the plume. The 3DMe then self-distributes from these locations to create a wide radii of influence (ROI), which interlock, creating an anaerobic treatment zone in which reductive dechlorinating bacteria can flourish.

As the groundwater flows through the treatment zones (or ‘barriers’, see Fig. 6), the dehalogenators biologically degrade the dissolved contamination through reductive dechlorination, enhanced through the creation and maintenance of ideal redox conditions and a continual supply of dissolved hydrogen. A barrier approach was chosen to minimize costs whilst still ensuring treatment of the entire plume, through migration of contamination between barriers into the next treatment zone downgradient. In order to remediate a plume of 12,000 m2 to a depth of 13 m BGL, the treatment comprised a single injection into 45 points, spaced 4 m apart within 6 barriers. The works took only 15 days to complete, with in situ treatment expected to last several years.

Results

Following the application, a rapid reduction in PCE concentrations was seen in all wells downgradient of the barriers across the site. In Fig. 7, it can be seen that concentrations of PCE are non-detect after only 5 months. The application resulted in the sequential production and breakdown of daughter products and an increase in ethene production showing that full reductive dechlorination is being achieved.

Ongoing low levels of DCE and VC downgradient of the barrier show that there is a small residual in ux of PCE/TCE into the barrier, which is being fully dechlorinated. Ortec are completing further SI in order to locate the source and target further treatment.

In Fig 8, it can be seen that the PCE concentrations in the fishing lake were rapidly reduced after the application and have remained low ever since. The breakdown products have also reduced to almost non-detect and remain at a very low level. With the onsite barriers remediating the contamination before it reaches the lake, the residual concentrations in the lake water may be expected to attenuate over time.

Conclusions

24 months after treatment, the concentration of PCE onsite has been dramatically reduced on the site and within the fishing lake, without the build- up of daughter products. In the monitoring locations downgradient of the onsite barriers, parent compound concentrations have been reduced to non detect, preventing any further contaminant egress from the site. With only 15 days of onsite works, two years of remediation has so far been achieved, overcoming challenging aquifer conditions to successfully create and maintain ERD treatment.

Further intrusive investigation has recently started to locate any residual source areas on the site, which can then be accurately targeted. In the meantime, the 3DMe product applied on the site will continue to remain active for many months/years to come, continuing to degrade any contaminant in ux and protect both the offsite environment and site personnel.

Ohio Brownfield Site Receives “No Further Action” Status within One Year of Implementation

Project Highlights

  • Combined remedy approach allowed for immediate redevelopment within same year of implementation.
  • Efficiencies resulted in vapor intrusion mitigation cost of $3.34 per sq. ft., with no long term operation and maintenance required.
  • Cost for groundwater treatment approximately $10 per cubic yard (product + application).

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Project Summary

A former industrial magnet manufacturing facility in Ohio received a $2.34 million Clean Ohio Revitalization Fund (CORF) grant through the Ohio Department of Development in 2011. Site investigation activities identified chlorinated VOC’s in groundwater and vapors above the state standards, requiring remediation. Enhanced Reductive Dechlorination, using 3D Micro-Emulsion®, and BDI-Plus® were implemented within the defined 24,000 sq. ft. treatment area via direct push injection.

This work was conducted in the Spring of 2012. In the Fall of 2012, the Geo-Seal Vapor barrier system was installed below a 15,522 sq. ft. apartment complex raised at the site. Utilizing a combined approach of enhanced reductive dechlorination with vapor mitigation addressed the immediate risk of vapor intrusion, in addition to the long term risk of groundwater impacts. By implementing this strategy, the site was allowed to be redeveloped as an apartment complex roughly 6 months following the groundwater treatment. The cost for groundwater treatment was approximately $10/cy (product + application) and Geo-Seal® was $3.34/sq. ft. (product + installation).

Technology Description

BDI Plus is an enriched, natural microbial consortium containing species of Dehalococcoides sp. (DHC) which are capable of completely dechlorinating contaminants during in situ anaerobic bioremediation processes.

3-D Microemulsion is a wide-area distribution, staged release, electron donor emulsion for the optimized enhanced anaerobic biodegradation of chlorinated compounds.

Geo-Seal is a composite system that creates the ideal blend between constructability and chemical resistance by using both high density polyethylene (HDPE) and spray-applied asphalt latex.

Results

Housing developers face many considerations, including approvals for land excavation and required building permits. By implementing a combined remedy approach, consisting of enhanced reductive dechlorination with vapor mitigation, this site was able to qualify for NFA status in less than a year, allowing the developer to begin new construction without further delay.

Successful Bioremediation at a Former Air Force Base Fire Training Area

Project Highlights

  • Air Force Base contaminated with high levels of carbon tetrachloride due to on-site firefighting training
  • 97% reduction in contaminant within three months
  • Carbon tetrachloride reduced to below detection limits

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Project Summary

Training exercises at Texas Air Force Base resulted in an impact to soil and groundwater by trichloroethylene (TCE) and carbon tetrachloride. A monitored natural attenuation study conducted indicated that chlorinated solvents at the plume would naturally decline to acceptable levels after 30 years of monitoring.

After over 14 years of monitoring, contaminant reductions were not proceeding as quickly as predicted and additional remediation was advised. It was determined that limited anaerobic activity was present and biostimulation was a viable option. A pilot test was conducted on-site.

The objective of the test was to determine the feasibility of injection into the shallow, discontinuous groundwater unit. The pilot test was also designed to determine if the residual TCE and carbon tetrachloride could be biodegraded through enhanced bioremediation and reduced to below 5 ppb (the Texas Risk Reduction Program limit). Follow-up injections were applied downgradient of the source area and also in a barrier configuration several hundred feet dowgradient of the source were implemented about 6 months after the pilot test.

Technology Description

3-D Microemulsion® is an engineered electron donor material that offers a novel 3-stage electron donor release profile, pH neutral chemistry, and is delivered on-site as a factory-emulsified product.

Results

The combination of the pilot test and full-scale application resulted in a 97.8% reduction in carbon tetrachloride 8 months post-injection, with chloroform, methylene chloride, and chloromethane remediation daughter products on a downward trend. High TCE concentrations were effectively treated as well with TCE peaking after injections to 126 ppb within a 3-month period to 0.2 ppb.