BARRIER IMPLANTS FOR THE ACCELERATED BIO-ATTENUATION OF TCE Jack K. Sheldon (MWH, Des Moines, Iowa) Kevin G.

Armstrong (MWH, Des Moines, Iowa) ABSTRACT: A manufacturing facility located in the central United States, showing evidence of reductive dechlorination of TCE, was selected for a pilot study that was designed to evaluate a barrier implant technology. The concept of a barrier implant utilizes chemicals that can accelerate bio-attenuation and that have a long-term release profile. The compound used in this study was a polylactate ester (HRC) that slowly releases fermentable lactic acid for reductive dechlorination. The semi-solid material was introduced in a series of four 4-foot (1.2-m) long perforated canister implants that were suspended inside a well. This constituted one unit of a potential barrier implant series. A previously existing monitoring well and a series of monitoring points were established in a 250-sq. foot (23.2-sq. m) study area. This area was located in a distal portion of the plume screened in a sand aquifer at a depth of approximately 30 to 45 feet (9.1 to 13.7 m) below ground surface. During the study, a monitoring well, located approximately 5 feet (1.5 m) downgradient of the barrier implant well, showed the greatest change in TCE concentration of any of the locations sampled during the pilot study. Lactic acid was observed in that well six months after implant installation, indicating that the substrate had migrated into the aquifer from groundwater flow through the area. This coincided with a decrease in the sulfate concentration and an increase in sulfide. Dissolved oxygen (DO) concentration in the well decreased during the study to below 0.1 mg/L. Redox fell to -206 mV. A 70% reduction in TCE with a corresponding increase in daughter products was observed in that well, which showed that this method could produce the desired long-term enhancement of natural attenuation. INTRODUCTION HRC is a polylactate ester where the lactic acid moiety is hydrolyzed off the molecule and degraded through pyruvic acid to acetic acid. The hydrogen available at each step is then used by a specific population of microorganisms to drive the reductive dechlorination of trichloroethene (TCE) at an accelerated rate. The product is delivered to the subsurface through direct injection or through perforated canisters or barrier implants suspended inside a well. Delivery of HRC , because it is a source of organic carbon, helps to consume existing oxygen and electron acceptors. A typical application for HRC would be a site showing evidence of natural attenuation due to biodegradation where a site owner would benefit from an increased rate of degradation. HRC was selected for the pilot study because TCE breakdown products had been detected in the groundwater, field measurements showed low oxygen conditions

(<0.5 mg/L) existed in the groundwater, and the groundwater flow velocity and site geology were favorable. The HRC product used at the site was a first generation version, a semi-solid material contained in perforated canisters. Based on laboratory studies by the manufacturer (Regenesis, San Clemente, CA), it was initially estimated that a minimum of six months would be required to see the effects of HRC . MATERIALS AND METHODS The pilot test area consists of a single Delivery Well, a previously existing monitoring well, and a series of monitoring points. The 4-inch (10.2-cm) inner diameter (ID) Delivery Well and the previously installed 2 -inch (5.1-cm) ID m onitoring well, MW-14D, were installed using standard hollow-stem auger drilling techniques. The monitoring point network (MP-1 through MP-6) was established at a distal portion of the plume based on the groundwater flow system that was previously characterized. The 1-inch (2.5-cm) ID monitoring points were installed using direct push technology. All of the wells and monitoring points were constructed of polyvinyl chloride (PVC) risers and screens. The pilot test wells and monitoring points are screened in a sand aquifer at a depth of approximately 30 to 45 feet (9.1 to 13.7 m) below grade; plan and cross sectional views of the pilot test area are provided in Figure 1. Pilot study activities were implemented according to the schedule outlined in Table 1. TABLE 1. Schedule of field activities for the barrier implant pilot study. Weeks Elapsed Since Placement of Activity Date HRC Monitoring/Delivery Well Network February 9-11, 1998 Week -1 Installation Background Groundwater Sampling February 19, 1998 Week 0 (Round 1) Installation of HRC Canisters February 19, 1998 Week 0 Round 2 Groundwater Sampling March 3, 1998 Week 2 Round 3 Groundwater Sampling March 19, 1998 Week 4 Round 4 Groundwater Sampling April 14, 1998 Week 8 Round 5 Groundwater Sampling May 8, 1998 Week 11 Round 6 Groundwater Sampling August 4, 1998 Week 24 Round 7 Groundwater Sampling October 21, 1998 Week 35 Groundwater purging and sampling were conducted using dedicated inertial pumps installed in each well. Purge water was analyzed using a multiparameter water quality meter with a flow-through-cell, monitoring temperature, pH, conductivity, DO, and redox. Samples were collected both pre- and post-purging for the February through May samples. Only post-purge samples were collected for August through October sampling, since data from the pre-purge samples did not yield significantly

different information. Post-purge samples were collected after stabilization of the field parameters to within approximately 10 percent over three consecutive readings. Samples were analyzed for the parameters outlined in Table 2. Table 2. Monitoring parameters for the barrier implant study. Parameter Sampling Schedule Chlorinated Volatile Organic Compounds All Monitoring Events Methane, Ethane, and Ethene Degradation Gases; Ammonia Nitrogen; Nitrate; Phosphorus; Sulfate; Sulfide; Iron (total and dissolved); Manganese; Chloride; Alkalinity; Total Organic Carbon (TOC); and Volatile Fatty Acids (lactic, propionic, pyruvic, and acetic) Aerobic and Anaerobic Microbial Counts All Monitoring Events Except Weeks 2 and 8

All Monitoring Events Except Weeks 2, 4, and 8

The HRC product was delivered to the subsurface by four 4-foot (1.2-m) long perforated polycarbonate canister implants. The perforations were approximately 1 mm in diameter and went completely around the canisters, spaced approximately 1 inch (2.5 cm) apart, and spanned the entire length of the canisters. The canister implants were linked together using carabiners and were lowered by a rope attached to the top canister implant so that the bottom canister implant was suspended approximately 3 feet (0.9 m) from the bottom of the well. RESULTS Following installation of the HRC canister implants, groundwater samples were collected from the monitoring array for selected parameters to monitor delivery of the HRC to the subsurface and ultimately the reductive dechlorination of the contaminants of concern. Groundwater sampling results from the pilot test are provided in Table 3. Table 3. Summary of pilot test data (all units in mg/L).
Parameter Trichloroethylen e Cis -1,2-DCE Trans-1,2-DCE Vinyl Chloride Lactic Acid Pyruvic Acid Week 0 Feb. 19, 1998 2.23 5.03 0.0674 0.134 <200 <2 Week 2 Mar. 3, 1998 2.05 4.82 0.0781 0.147 Week 4 Mar. 19, 1998 2.1 4.89 0.0786 0.141 <1 <1 Week 8 Apr. 14, 1998 2.02 4.29 0.0705 0.127 Week 11 May 8, 1998 1.4 3.39 0.0403 0.0906 <1 <1 Week 24 Aug. 4, 1998 0.290 1.36 0.0361 0.0337 2 <1 Week 35 Oct. 21, 1998 0.557 1.71 <0.001 <0.001 <1 <1

Acetic Acid Sulfate Sulfide

<10 25.9 <0.1

<1 25.3 <0.1

<1 33 <0.1

<1 19.9 0.14

<1 21.4 0.11

Well MW-14D, located approximately 5 feet (1.5 m) downgradient of the delivery well, shows the greatest change in TCE concentration of any of the locations sampled during the pilot study. Lactic acid is observed during the sixth month of the study, indicating that HRC has migrated into the aquifer. This coincides with a decrease in the sulfate concentration and an increase in sulfide. Sulfate is an electron acceptor used in the reductive dechlorination of chlorinated compounds. An increase in sulfide is evidence of sulfate utilization and concentrations of sulfide in excess of 0.1 mg/L are considered significant indicators of biological activity. Also, the DO concentration in MW-14D decreased during the study to nearly 0.1 mg/L. Redox fell to -206 mV during the study. These measurements suggest the strongly reducing conditions necessary for degradation of TCE have been achieved at MW-14D. A graph (Figure 2) of the Total VOCs and Percent TCE removed in the downgradient monitoring well, MW-14D, shows the most significant effects of HRC over the 8-month study. Cis-1,2-DCE was accumulating and was shown to degrade more than 75% during the study. Vinyl chloride began to accumulate early in the study, but its degradation also became apparent over the final half of the pilot study.
9.0 40%

8.0

35%

7.0

30%

6.0 Total VOCs (mg/L) 25% 5.0 20% 4.0 15% 3.0 10% Percent TCE Total VOCs %TCE

2.0

1.0

5%

0.0 Oct-96 Jan-97 Apr-97 Jul-97

0% Oct-97 Jan-98 Apr-98 Sample Date Jul-98 Oct-98

Figure 2. Changes in Total VOCs and Percent TCE during pilot study.

CONCLUSIONS While clear evidence of biodegradation of TCE was observed at only one well during the pilot study, the pilot study did show that the HRC barrier implants could produce the desired enhancement of natural attenuation in the field. It was also determined from the study that the effects of HRC would last greater than six months, consistent with earlier laboratory tests. Based on the analytical results, it appears that the HRC barrier implants had a significant effect in close proximity to the delivery well. The analytical results indicate that HRC may have traveled along a preferential flow path within the deep sand aquifer, resulting in increased reductive dechlorination and the detection of lactic acid at MW-14D, but not monitoring points closer to the delivery well. ACKNOWLEDGEMENTS This work was partially supported by Regenesis (San Clemente, CA) as a development activity for the new HRC bioremediation product. REFERENCES Koenigsberg, S.S. and C.A. Sandefur. The Use of Hydrogen Release Compound for the Accelerated Bioremediation of Anaerobically Degradable Contaminants: The Advent of Time-Release Electron Donors. Remediation. 10(1): 31-53. Sheldon, J.K., S.S. Koengisberg, K.J. Quinn, and C.A. Sandefur. Field Application of a Lactic Acid Ester for PCE Bioremediation. In B.C. Alleman and A. Leeson (Eds.), Engineered Approaches for In Situ Bioremediation of Chlorinated Solvent Contamination, pp.61-66. Battelle Press, Columbus, OH.