Combining Chemical and Biological Technologies for Soil and Groundwater Remediation

Sponsored by Regenesis

Integration Chemical and Biological Technologies for Remediation of Contaminated Soil and Groundwater
Ben Mork, Regenesis, San Clemente, CA

Combined Physical and Biological Processes for Remediation of Contaminated Sites.
Maureen Dooley, Regenesis, Wakefield, MA

Former Manufactured Gas Plant (MGP) Remediation using Surfactant-Enhanced In-Situ Chemical Oxidation (S-ISCO®)
John Collins, Ph.D., VeruTEK Technologies, Inc., Glastonbury, CT

Evaluation of In-Situ Biostimulation Effects Related to Sodium Persulfate Injections
Edward Sullivan, P.G., The Whitman Companies, Inc., East Brunswick, NJ

Bioremediation of TCE and TCA using SDC-9TM after Sodium Permanganate Treatment
Raymond J. Cadorette, Shaw Environmental, Inc., Hopkinton, MA 

Biodegradation of Anthracene in Presence of Humid Acid and Biosurfactants
Hui Chen, Northwest Normal University, Lanzhou, Gansu, P.R. China
 

Integration Chemical and Biological Technologies for Remediation of Contaminated Soil and Groundwater

Ben Mork, Ph.D. and Bob Kelley, Ph.D., Regenesis, 1011 Calle Sombra, San Clemente, CA, 92673 USA, Tel: 949-366-8000, Fax: 949-366-8090, Email: bmork@regenesis.com

While environmental remediation literature has contained references to 'treatment trains' for decades, the last 3-5 years have seen a significant increase in actual field deployments to address contaminated groundwater.  ISCO and enhanced bioremediation are promising technologies for the treatment of source areas.  Several field demonstrations were recently completed to demonstrate the efficacy of coupling in situ chemical oxidation (ISCO) to rapidly remove accessible mass with in situ enhanced bioremediation to degrade and contain the remaining mass. 

Two case studies will be discussed in detail.  The first was a former retail gasoline station in which chemical oxidation (RegenOx™) was followed sequentially with enhanced bioremediation (ORC-Advanced®) were used to remediate BTEX contamination in and round a excavation resulting from a tank removal. The initial concentrations were in the 50ppm range, and treatment goals were achieved within 2 months.  Mass flux calculations based on groundwater measurement indicate significant reduction in contaminant mass. In a second field demonstration, similar BTEX removal (96%) was seen with a simultaneous application of RegenOx™ and ORC Advanced®.  Treatment goals were reached in 4 months

This presentation will provide an overview of the results from these field demonstrations, draw conclusions for the applicability of the technology for groundwater remediation and provide recommendations for a best-practice approach for future work with the combined chemical oxidation and enhanced bioremediation technologies.

Combined Physical and Biological Processes for Remediation of Contaminated Sites

Maureen Dooley, Regenesis, 19 Belmont Road, Wakefield, MA 01880, USA, Tel: 781-245-1320, Fax: 781-245-1329, Email: mdooley@regenesis.com
Bob Kelley, Ph.D., Regenesis, 1011 Calle Sombra, San Clemente, California, 92673 USA, Tel: 949-366-8000, Fax: 949-366-8090, Email: bmork@regenesis.com

Distribution of electron donor substrates is a key factor in the successful in situ reductive dechlorination of contaminants in aquifers. Transport in the subsurface is governed by hydrogeologic characteristics of the aquifer under treatment and, equally important, by the characteristics of the electron donor substrate itself.

As electron donor technology has evolved away from simple sugar substrates that rapidly ferment and require continuous application, complex electron donor substrates have emerged allowing for a range of hydrogen release rates from a single application.  Many of these products contain slower releasing components of very low solubility.  The aqueous solubility and oil/water partitioning of substrates is governed by the specific hydrophile/lipophile balance index (HLB) of the compound considered. 

The HLB of the electron donor substrate governs its ability to form emulsions when preparing the material for subsurface application, as well as the requirement for chemical emulsifiers to aid in stabilization of the product.  Additionally, and perhaps most importantly, the HLB indicates the propensity for the substrate to spontaneously form micelles (sub-micron size colloids) that advance the forward movement of the substrate through the contaminated aquifer.

This paper reviews the impact of substrate HLB on subsurface adhesion to aquifer matrices, micro-emulsion formation, and micro-emulsion/micelle movement in the subsurface.  Data is presented from laboratory studies involving aquifer simulation columns (20’ in length) which demonstrate the positive impact of spontaneous micelle formation on the advancement of electron donors in aquifer materials.   Data is also presented from full-scale field applications of an electron donor substrate designed to cost effectively achieve broad aquifer distribution through micellar transport.

Data is presented from full-scale projects in the field where HRC Advanced has been applied for the treatment of the DNAPLcomtaminant showing wide distribution compared to typical controlled release electron donors and excellent biostimulation.  Results from a variety of geologic conditions where chlorinated ethenes have been treated indicate performance.  Cost data is presented and compared with the use of other commercially available controlled release electron donors indicating the wide cost advantage of employing this state-of-the-art product.

Former Manufactured Gas Plant (MGP) Remediation using Surfactant-Enhanced In-Situ Chemical Oxidation (S-ISCO®)

John Collins, Ph.D., VeruTEK Technologies, Inc., 628-2 Hebron Avenue, Suite 505, Glastonbury, CT 06033

, Tel:  860-633-4900, Fax:  860-633-6501, Email: Jcollins@VeruTEK.com
George E. Hoag, Ph.D., VeruTEK Technologies, Inc., 628-2 Hebron Avenue, Suite 505, Glastonbury, CT  06033, Tel:  860-633-4900, Fax:  860-633-6501, Email: ghoag@VeruTEK.com

A treatability study and a field verification pilot study were conducted to test the efficiency of a new type of Coelution Technology®, Surfactant-Enhanced In-Situ Chemical Oxidation (S-ISCO®), in reducing the amount of source coal tar DNAPL in soils and reducing the flux of groundwater constituents associated with a former Manufactured Gas Plant Site (MGP).

Both laboratory column studies and a large field pilot test confirm that the S-ISCO® process effectively degrades MGP tar-saturated soils without any significant increases of groundwater contaminant flux.  Persulfate-Fe-EDTA mixtures persisted in solution and effectively destroyed solubilized COCs in laboratory column tests.  Batch tests revealed that VeruSOL®-3, a proprietary cosolvent/surfactant mixture of FDA approved chemicals, was able to resist activated persulfate oxidation and maintain low IFT conditions while maintaining the ability to dissolve COC from coal tar saturated soils. The Pilot Test consisted of four injection phases and three post-injection monitoring Phases.  A total of 72,674 kg persulfate, 475 kg Fe(II)-EDTA, and 3,314 kg of VeruSOL®-3) were injected during the Pilot Test. Both the field and laboratory treatability studies found that VeruSOL®-3 treatment was able to solubilize both high and low molecular weight PAHs.  Soils mass destruction analysis from more than 50 soil sampling locations collected before and after the S-ISCO® Pilot Test indicates that at least 954 kg of polycyclic aromatic hydrocarbons (PAHs) and at least 3,636 kg of medium weight petroleum hydrocarbons (MPH) were removed in the Pilot Test area.  Thirty days after the termination of S-ISCO® injection and 75 feet downgradient of injection wells, the mass flux was less than the pre-Pilot Test mass flux for PAH and MPH compounds and slightly greater for BTEX compounds.

Evaluation of In-Situ Biostimulation Effects Related to Sodium Persulfate Injections

Edward Sullivan, P.G., The Whitman Companies, Inc., 116 Tices Lane, Unit B-1, East Brunswick, NJ 08816, Tel: 732-390-5858, Fax: 732-390-9496, Email: esullivan@whitmanco.com
Eric C. Hince, P.G., Geovation Consultants, Inc., 468 Route 17A, Florida, NY, 10021, Tel:  845-651-4141, Fax: 845-651-0040, Email: echince@geovation.com
Greg Davis, and Dora Ogles, Microbial Insights, Inc., 2340 Stock Creek Blvd., Rockford, TN  37853-3044, Tel: 865-573-8188, Fax: 865- 573-8133, Email: gdavis@microbe.com; dogles@microbe.com
Kerry Sublette, Jennifer Busch-Harris and Eleanor Jennings, University of Tulsa, Center for Applied Biogeosciences, 600 S. College Ave, Tulsa, OK  74104, Tel: 918-631-3085, Fax: 865- 573-8133, Email:  kerry-sublette@utulsa.edu, jennifer-busch@utulsa.edu, eleanor-jennings@utulsa.edu

In recent years there has been increased interest in combined chemical oxidation and bioremediation approaches to site remediation.  At a site contaminated with 1,2-dichlorobenzene DCB), a chemical oxidation remedy was implemented in the fall of 2006 using sodium persulfate persulfate).  Geochemical parameter and DAPI cell count data were collected prior to the initial persulfate injection and approximately one month post-injection.  DAPI cell counts one month after the first injection indicated microbial counts had not decreased, which was contrary to expectations.  Post-injection cell counts ranged from 3 x 105 to over 2.5 x 107 cells/ml.  The highest cell counts were observed in the most highly contaminated source area well.   This unexpected trend in cell counts prompted the additional investigations outlined herein. 

Dissolution of injected sodium persulfate Na2S2O8-results in the formation of sulfate ions SO4--upon reaction. Additional oxidation and decomposition reactions could result in the formation of bioavailable ferric iron and oxygen.  All of the above could theoretically be used by native microbes as electron acceptors. 

Subsequently, DGGE and mFISH data was collected to identify and quantify the important microbial consortia that had developed in response to the persulfate injections.  Prior to the 2nd injection planned for late February-and at various post-injection intervals, additional data will be collected including an expanded list of geochemical parameters, DAPI cell counts and mFISH.  In addition, Bio-trapTM samplers supplied by Microbial Insights, Inc., will be installed in the source area well.  The Bio-trapTM samplers will contain Bio-sepTM beads loaded with 13C labeled chlorobenzene and DCFB a fluorinated analog of DCB).  Stable carbon isotope profiles 13C/12C-of the phospholipid fatty acid PLFA-biomarkers from the microbial biomass will be measured to quantify approximate DCB aerobic/anaerobic oxidation biodegradation rates.  DCFB will be used to evaluate the reductive dechlorination pathway.  The combined geochemical and microbiological data will be used to compare 1-the amount of DCB mass reduction achieved by the direct chemical oxidation and secondary biodegradation and 2-the relative rates of anaerobic oxidation and reductive dechlorination to determine which biological process is dominant.

Bioremediation of TCE and TCA using SDC-9TM after Sodium Permanganate Treatment

Raymond J. Cadorette, BS in Bio-Resource Engineering, Shaw Environmental, Inc., 88C Elm Street, Hopkinton, MA  01748, Tel: 508-497-6102, Fax: 508-435-9641, Email: Raymond.Cadorette@shawgrp.com
Lawrence Nesbitt, PE, BS in Civil Engineering, MS Water Resources, MBA, Shaw Environmental, Inc., 88C Elm Street, Hopkinton, MA  01748, Tel: 508-497-6125, Fax: 508-435-9641, Email: Larry.Nesbitt@shawgrp.com
Tarek Ladaa, BA Chemistry, MS Environmental Engineering, Shaw Environmental, Inc., 312 Directors Drive, Knoxville, TN  37923, Tel: 865-670-2708, Fax 865-690-3626, Email: Tarek.Ladaa@shawgrp.com

Shaw has conducted a highly successful sodium permanganate treatment program at a manufacturing site in New England.  The permanganate treatment program involved the injection of over 177,000 gallons of a 20% sodium permanganate solution into the shallow overburden, deep overburden and bedrock aquifers at the site over four years.  The sodium permanganate applications have resulted in significant reductions in TCE concentrations across the site.

Subsequent to the sodium permanganate treatment, an enhanced bioaugmentation treatment program was conducted using sodium lactate, Shaw’s SDC-9TM culture and a TCA reducing bacteria also developed by Shaw.  The bioremediation program targeted TCE contamination adjacent to an on-site stream where permanganate injection was not feasible, and residual TCA impacts in the deep overburden that are not amenable to treatment via permanganate.  This presentation will discuss the additional steps needed to successfully complete an enhanced bioaugmentation program following permanganate treatment and will provide results of the initial application.  In particular, the presentation will focus on the technical aspects of implementing bioaugmentation in an area previously targeted with permanganate, such as the quenching of residual permanganate concentrations with lactate, the potential for solubilizing manganese under reducing conditions, and the ability to achieve complete dechlorination of TCE and TCA via bioaugmentation.

Biodegradation of Anthracene in Presence of Humid Acid and Biosurfactants

Hui Chen, College of Chemistry & Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, P.R. China, Email: lzchenh@sina.com.cn
Yingqin Wu,
Mingguang Ma, Yuan Zhang, College of Chemistry & Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, P.R. China

The fate of hydrophobic organic compounds, i.e., their transport and bioavailablity in the environment, is strongly affected by their interactions with dissolved humid acids(DHA), Saponin - a kind of biosufactants and a non-ionic surfactant Tween80. The biodegradation of anthracene was studied in aqueous system in present of HA, saponin and Tween-80, respectively. By using anthracene as the sole carbon source, a strain of bacterium that had the high degrading capacity for anthracene, was isolated and purified from petroleum-polluted soil in Yumen oil-field, China. Then it was incubated in the specific nutrients media at pH 7.2. The experimental results showed that HA, Saponin and Tween80 could significantly increase the degradation bacterial durability concentration on anthracene, shorten the retention time of bacterium, promote the growth of degradation bacteria and greatly accelerate the degradation of anthracene. The onset time for the biodegradation of anthracene needed 7days without surfactant, however, the time was shortened to 5d and 4d respectively If adding Tween-80 and Saponin. The bio-surfactants and humic acids (HAs) that have the surfactant-like micellar microstructure, were thought to accelerate the degradation of PAHs by enhancing PAH solubility, thereby increasing the PAH bioavailability to microorganisms. The HA exhibited more excellent efficacy than Tween80 and Saponin, which dramatically shortened the biodegradation time from 7 days to 1 day. The rate of biodegradation for anthrancene reached 93.5% after 1 day in the presence of HA. After 6 days, the corresponding concentration of anthracene was reduced from initial 50.00 mg.L-1 to 0.055 mg.L-1 if adding HA , 0.089 mg.L-1 for adding Saponin, and 3.426 mg.L-1 for adding Tween80. Therefore, HA and biosurfactents showed strongly capability to increase anthracene solubility and the relevant bioavailability. Regarding the toxicity of the synthetic surfactants to natural microorganisms, a potential alternative might be applied in the remediation by using the natural HA and biosurfactants to accelerate the biodegratation of PAHs in the soil environments.

Keywords: anthracene, biodegradation, dissolved humic acids, saponin

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