Paper A-01, in: V.S. Magar and M.E. Kelley (Eds.), In Situ and On-Site Bioremediation2003.

Proceedings of the Seventh International In Situ and On-Site Bioremediation Symposium (Orlando, FL; June 2003). ISBN 1-57477-139-6, published by Battelle Press, Columbus, OH, www.battelle.org/bookstore.

CONSTRUCTION OF A SEQUENTIAL ANAEROBIC/AEROBIC IN SITU BIOREMEDIATION SYSTEM Benjamin L. Porter (bporter@theitgroup.com) and Daniel P. Leigh (Shaw Environmental & Infrastructure, Inc., Concord, California, USA) Christian D. Johnson and Michael J. Truex (Battelle Pacific Northwest Division, Richland, Washington, USA) Steve Granade (Naval Base Ventura County, Point Mugu, California, USA) ABSTRACT: A pilot-scale test was conducted to evaluate in situ bioremediation (ISB) of chlorinated solvent-contaminated groundwater at Naval Base Ventura County, Point Mugu, California. Initially the pilot-scale ISB test was for anaerobic dechlorination of trichloroethene (TCE). TCE and its daughter product, dichloroethene (DCE), were rapidly dechlorinated. However, the DCE dechlorination product, vinyl chloride (VC), was transformed at a much slower rate. With the intent of accelerating destruction of the remaining VC, a pilot-scale demonstration of cometabolic aerobic in situ biodegradation was performed and was successful in destroying VC. This paper discusses the selection and implementation of the equipment required for operation, monitoring, and control of this sequential treatment process. The anaerobic ISB pilot-scale test used a two-well groundwater recirculation cell to distribute periodic high concentration pulses of lactic acid to stimulate anaerobic microbial activity. An automated process control/data collection system was used to operate the nutrient injection pumps, collect data from sensors, and to operate a sample collection system during anaerobic operations. Aerobic in situ bioremediation was subsequently applied using cometabolic methanotrophic metabolism in an in situ biofilter approach to treat the residual VC. The separate aerobic system was designed to amend groundwater from four extraction wells with methane and oxygen prior to injection in a central injection well. The aerobic system relied on two eductors and downstream mixing tanks to saturate the groundwater with the gaseous nutrients without any offgas. A process control system collected data and insured safe operation of the aerobic system. INTRODUCTION A site at the Naval Base Ventura County's Point Mugu facility had trichloroethene (TCE) releases to groundwater from an underground oil/water separator that was used as part of paint stripping operations. An evaluation of in situ bioremediation (ISB) of the TCE [Johnson et al., 1998] concluded that accelerated anaerobic ISB should be implemented. Thus a pilot-scale demonstration of anaerobic ISB was conducted, beginning in December 1998. Lactic acid was distributed throughout the portion of the contaminated aquifer with the highest concentration of TCE using a single cell (2-well) recirculation system to stimulate anaerobic biotransformation of the contaminants. It was thought (based on laboratory microcosm results and literature information) that dechlorination would occur mainly under methanogenic conditions; hence, the naturally high sulfate (~ 700 mg/L) would need to be removed from the system before methanogenic conditions would be established. The lactic acid was distributed in

periodic, high concentration pulses to stimulate sulfate reduction. To promote chloroethene biodegradation, a final large pulse of lactic acid was injected when sulfate in the flow field had been reduced to less than 20 mg/L. Recirculation was halted at day 64 and long-term monitoring began, continuing through April 2002. Upon removal of the sulfate, TCE and dichloroethene (DCE) were rapidly dechlorinated to vinyl chloride (VC), which slowly declined over the next 2 years while the dissolved ethene concentration increased (although not stoichiometrically) [Johnson et al., 1999; Leigh et al., 2000; Granade et al, 2003]. The rate of VC dechlorination in the field (as calculated from ethene production) was at least two orders of magnitude slower than the rate measured in lactate-fed laboratory microcosm tests with site sediments and groundwater The plume characterization in the summer of 2001 (some 31 months after initiation of nutrient injection for the anaerobic ISB pilot-scale test) indicated that essentially all of the TCE in the original plume was gone, as was the majority of the DCE. Given these facts (slow anaerobic VC degradation and no TCE present), it was proposed that the full-scale anaerobic treatment not be performed and instead that aerobic in situ treatment be applied. In situ cometabolic aerobic biodegradation had the potential to accelerate destruction of the residual VC and DCE. A pilot-scale demonstration of cometabolic aerobic ISB was performed beginning in April 2002. The aerobic ISB design was based on methanotrophic cometabolic destruction of VC (and DCE) implemented as an in situ biofilter [Truex et al., 2002]. The biofilter approach used a recirculation cell to move groundwater through a treatment zone that is established in situ in the area surrounding the injection well. Groundwater containing VC and DCE was extracted from the formation through multiple (4 or 5) extraction wells, amended with nutrients, and re-injected into an injection well. Operation of the in situ aerobic biofilter required injection of dissolved methane, oxygen, and nitrate to stimulate the methanotrophic bacteria that are used for destroying VC. After a period of injection with excess stoichiometric oxygen, recirculation was halted to allow the bacteria to consume the methane and subsequently for VC to be destroyed by available methane monooxygenase enzyme. The pilot-scale aerobic ISB test demonstrated successful destruction of VC and (to a lesser extent) DCE. This paper discusses the assembly of equipment required for operation, monitoring, and control of sequential anaerobic/aerobic ISB. Proper design and construction of the treatment system is important for minimizing the cost of the treatment and obtaining the demonstration objectives. Although the equipment discussed was designed and constructed as two systems (anaerobic and aerobic), they could be readily combined into a single mobile treatment system. ANAEROBIC IN SITU BIOREMEDIATION SYSTEM The anaerobic ISB system was designed to volumetrically deliver lactic acid to the region of highest TCE concentration. The two-well recirculation cell was set up as shown in Figure 1, with an extraction well (EW-1), an injection well (IW-1), and monitoring wells (MW-1 to MW-5). Three monitoring wells were in line between IW-1 and EW-1 and two monitoring wells were offset. The anaerobic ISB equipment had to satisfy the needs of the system design, providing operational flexibility, simplicity, and automation. There were three main subsystems: the recirculation equipment (both down-hole and aboveground), the nutrient injection equipment, and the groundwater sampling system. The process control system

tied together the data collection and automation of operations. Figure 2 depicts the major equipment for the recirculation and nutrient injection systems. A Process Control Trailer was designed and built for a demonstration of in situ bioremediation of carbon tetrachloride under denitrifying conditions at the U.S. Department of Energy's Hanford site in Washington state [Hooker et al., 1998]. The trailer is a 35 ft (10.6 m) long semi-truck van that is divided into two sections. The front section houses a process control system, a sample collection manifold, and laboratory
Process Control Trailer Direction of Recirculation Flow
IW-1 MW-1 MW-2 Flow Control Valve

Sediment Filter EW-1

10 ft Elevation (ft relative to Mean Sea Level, NGVD) 5 ft MSL

Nutrient Injection Line

MW-3

Potentiometric Surface

Sand & Gravel (fill)

Water Table

Clay -5 ft Sand -10 ft -15 ft -20 ft -25 ft

Direction of Groundwater Flow

FIGURE 1. Section view of the Point Mugu demonstration site showing the general approach for volumetric anaerobic ISB.
Signals to/from Process Control System

FT
Flow Sensor Solenoid Valve Gear Strainer Pump

Stock Solution Tank

Ball Valve Check Valve Union

Signal to Process Control System

FT

Direction of Aboveground Flow Injection Well (inflatable packer)

Shutoff Valve

Flow Control Valve

Flow Sensor (with bypass)

Sediment Filter
(with bypass)

Diversion Valve

Extraction Well (submersible pump)

FIGURE 2. Schematic drawing showing major equipment for the anaerobic ISB recirculation and nutrient injection systems. Down-hole equipment is noted in parentheses by the corresponding well.

bench space. The back section holds the nutrient injection system, comprised of four 250-gallon (946-liter) polypropylene tanks with stand mixers, 6 gear pumps (two per tank, with one spare tank not used for nutrient injection), plus associated plumbing, all of which is within an 8-inch (20 cm) deep stainless steel containment pan. The Process Control Trailer was designed to be a mobile system that could provide the process control and nutrient pumping flexibility to do everything from pilot-scale ISB demonstrations to full-scale ISB. The Process Control Trailer was used in just that manner at Point Mugu to plug into the recirculation system and sampling lines. Recirculation Equipment. Recirculation equipment consisted of a submersible centrifugal pump in the extraction well (Grundfos, Olathe, KS), aboveground piping, and injection well equipment. The aboveground piping was placed in a 0.5 m (1-2 ft) deep trench that was covered with steel plating to allow for third party vehicle access to the site while the equipment was operating. The aboveground recirculation plumbing included a 5-micron sediment filter (Pall Corp., Timonium, MD) to avoid injecting sediment into the injection well, a turbine flow sensor/transmitter (Omega Engineering, Stamford, CT), and inlets for the nutrient injection lines. An inflatable packer (Tam International, Houston, TX) was placed in the injection well to avoid excess stagnant water above the well screen and to allow the injection to continue even with pressure build-up. The groundwater recirculation flow rate was adjusted manually with a gate valve placed downstream of the flow sensor. Bypasses on the flow sensor and sediment filter provided a means for maintenance while the system continued to operate. Substrate Injection Equipment. Lactic acid was the nutrient selected to stimulate anaerobic microbial activity. The lactic acid was stored in a Process Control Trailer tank as an 88-wt% solution to inhibit microbial growth in the tank. Gear pumps (Micropump, Vancouver, WA) were used with variable speed magnetically coupled pump drives to deliver lactic acid (or bromide tracer solution) to the recirculating groundwater. A variety of gear pump capacities are available for mounting on the same drive, providing flexibility and easy maintenance. The process control computer was used to control lactic acid injection intervals, duration, and flow rate by manipulating in-line solenoid valves and the variable speed gear pump drive. The nutrient injection system had feedback inputs to the process control computer, including line pressure and flow rate. An in-line check valve at the connection of the nutrient injection lines to the groundwater recirculation line provided back-pressure against the static groundwater head and prevented the lactic acid from draining out of the injection line. The gear pump was selected to provide the positive pressure necessary to open this check valve. A pressure relief valve was placed downstream of the gear pump to vent excess pressure back to the bulk storage tank if normal operating pressures were exceeded. A level switch in the stock solution tank provided a low level alarm as an indication of either a leak into the containment pan or siphoning of the feed solution into the well. Sampling Equipment. Sampling equipment was designed to obtain representative samples of groundwater for analysis of chloroethenes and anions. Dedicated in-well Redi-Flo2 pumps (Grundfos, Olathe, KS) were used to pump groundwater to the sample manifold in the front section of the Process Control Trailer. Groundwater from well EW-1 was also sampled from a port in the groundwater recirculation piping (upstream

from the nutrient injection inlets). All sample lines were connected to an automated sampler for computer-controlled collection of anion samples for specific tests during the demonstration. Manually collected groundwater samples (i.e., for VOCs) were also obtained from the sampling manifold, with the process control computer being used to select which well to pump and to time the well purging. Process Control and Data Acquisition. Operation of the anaerobic in situ bioremediation system required process control for unmanned nutrient injection and sample collection, as well as data acquisition of process measurements. The process control system consisted of an IBM-compatible personal computer running the AIMAX software (TA Engineering, Moraga, CA) and several I/O Plexers (duTec, Jackson, MI) to interface with process equipment. The process control system was used to turn on and off the nutrient injection gear pumps and to adjust the nutrient injection flow rate as needed. The injection line pressure and injection flow rate were monitored (and recorded) to determine that (1) the proper amount of nutrient was being delivered to the well, (2) there was no plugging of the feed lines, and (3) there were no leaks in the feed lines. The process control software was used to control the autosampler system during the intensive sample collection required by in situ tracer tests. The process control system was used to collect data on groundwater levels and process flowrates. Pressure transducers were placed in each well to monitor the hydraulic head. Of particular interest was the injection well pressure, a rise in which could signal well plugging (although such an increase was not seen during the test). The groundwater recirculation flow rate was recorded, as were the times and flow rates for the nutrient injections. AEROBIC IN SITU BIOREMEDIATION SYSTEM The aerobic ISB system operated in much the same manner as the anaerobic system, but with the key differences that the primary nutrients injected were dissolved gases and that the nutrient injection and groundwater recirculation systems were integrated into skid-mounted units. The objective was to stimulate methanotrophic bacteria, which require dissolved methane and oxygen as well as a nitrogen source [Truex et al., 2002] for growth and energy. The in situ bioactive zone also differed in the aerobic treatment, being a biofilter instead of volumetric treatment. Figure 3 shows a conceptual diagram of a single aerobic recirculation cell. The aerobic ISB system was assembled on two 4 ft 8 ft (1.2 m 2.4 m) diamond-tread steel skids with forklift slots for easy transportation and placement. Equipment on the first skid (#1) consisted of an extraction well mixing manifold, the power distribution panel, and the process control panel. The second skid (#2) held the substrate amendment systems, two 240-gallon (908-liter) steel pressure tanks, one 100gallon (378-liter) polypropylene tank, a booster pump, a metering pump, and a sediment filter. Two skids were used because (1) the skid dimensions allow the use of a standard full-size truck for transportation and (2) skid #1, containing the power distribution panel and most of the high power electrical work, could be separated from the oxygen and methane gas sources used on skid #2. Equipment on skid #2 was either low voltage/low amps or explosion proof because of the use of gaseous methane and oxygen. Separating the two skids made the system cheaper to construct, easier to move, and safer. Figure 4 shows a schematic representation of the aerobic injection system.

N u trie n t A m e n d m e n ts R e c irc u la te d g ro u n d w a te r R e c irc u la te d g ro u n d w a te r

EW

EW

IW

EW

Vadose Zone or C o n fin in g L a y e r

EW

Packer

A q u ife r B io filte r B io filte r

P la n v ie w w ith s u b s u rfa c e g ro u n d w a te r flo w lin e s

Pump

G ro u n d w a te r F lo w

G ro u n d w a te r F lo w

E x tra c tio n W e ll (E W )

In je c tio n W e ll (IW )

E x tra c tio n W e ll (E W )

FIGURE 3. Conceptual cross section and plan view of a single recirculation cell for implementation of an in situ aerobic biofilter. Groundwater is recirculated through an annular treatment region around the injection well (i.e., the biofilter).
Nitrate Stock Tank
Signals to Process Control System

FT
Piston Pump Flow Sensor Mixing Tank

Oxygen Gas Supply

Solenoid Valve Flow Sensor Rotameter

Signals to/from Process Control System From other Extraction Wells

Mixing Tank

Pump

FT FT

Methane Eductor

FT
Flow Sensor

Flow Control Valve Injection Well (inflatable packer)

Sediment Filter
(with bypass)

In-Line Static Mixer Methane Gas Supply

Solenoid Valve

Booster Pump

Oxygen Flow Eductor Sensor

Flow Control Valve

Rota- FT Flow Sensor meter

Signal to Process Control System

Direction of Aboveground Flow

Ball Valve Check Valve Union

Typical Extraction Well (submersible pump)

FIGURE 4. Schematic drawing showing the major aerobic ISB system equipment. Down-hole equipment is noted in parentheses next to the wells. Groundwater sampling was not integrated into the aerobic equipment. Samples were manually collected using a peristaltic pump (or a sample port in the combined recirculation stream). Recirculation and Nutrient Amendment Equipment. Submersible pumps (Grundfos, Olathe, KS) extracted groundwater from (typically) four wells oriented in a 5-spot pattern (the center well was the injection well). Groundwater was combined at skid #1 where manual gate valves were used to set the flow rate of each extraction leg to an equal value. Readings from pressure gauges and flow sensors were recorded for the extraction legs and the combined stream. The combined stream was sent to skid #2, where nutrients were added to the groundwater. Two separate eductor systems (Mazzei Injector Corporation, Bakersfiled, CA) were used in series to transfer the oxygen gas (first eductor) and methane gas into the groundwater. A 240-gallon (908-liter) mixing tank downstream of each eductor provided residence time for the entrained gas to dissolve.

The whole system was operated under a pressure of nominally 40 psi (276 kPa) to increase the gas solubility. A booster pump was used downstream of the first mixing tank to insure the pressure in the second mixing tank was high enough and to provide sufficient fluid velocity for proper operation of the eductor. Downstream of the two eductors, an aqueous solution of nitrate (stored in the 378-liter polypropylene tank) was amended to the groundwater using a manually set piston-drive metering pump (Liquid Metronics Incorporated (LMI, Milton Roy), Acton, MA) connected to the recirculation line via a check valve. An in-line static mixer downstream of the nitrate injection insured complete mixing. A bag filter was used downstream of the in-line mixer to remove any sediment or precipitates that might have formed (i.e., iron oxides) so that material would not be injected into the injection well. A gate valve at the injection well head was used to control the injection flow rate. Oxygen and methane gases were introduced into the recirculated groundwater through an eductor (venturi tube with an inlet at the flow restriction). Five standard oxygen cylinders (1,685 SCF, 47.7 standard m) were combined through a manifold to supply sufficient oxygen to the system over a 2-week period. The oxygen line passed through a normally closed solenoid valve, a rotameter, and a mass flow meter. The methane assembly was similar except that only one gas cylinder could be used at a time. The normally closed solenoid valve acted as a safety feature. In the event that the system lost power or shut down, the valve automatically closed to insure that the system failed safe. The rotameter was used to control the gas flow rate and the mass flow meter was used to record the gas flow rate. Process Control and Data Acquisition. To improve the productivity and safety of process operations, the aerobic equipment used a process control and data acquisition (SCACA) unit (phonetics, Aston, PA). The SCADA unit had programmable logic control that allowed it to start automatically with the push of a single button or from a remote computer. The startup routine of the SCADA unit insured the proper order of equipment operation and would not allow operations if water levels in mixing tanks, flow rates, or pressures were out of the specified operational limits. To improve reliability of data collection and productivity of site personnel, the SCADA unit recorded groundwater flow rates (each extraction leg and the combined stream), pressure in the mixing tanks, and mass flow rates of oxygen and methane gas amendment, of the system every 10 minutes while groundwater was recirculating. A common alarm was programmed to trip if certain events occurred, whereupon the SCADA unit would automatically shut down the groundwater pumps and call project personnel via fax, pager, or phone. Several conditions could cause the common alarm to trip. Five analog (4-20 mA) flow sensors corresponding to the extraction well legs and the combined stream of the recirculation system were monitored. An extraction flow rate less than the set point of 1.5 gpm (5.7 lpm) was programmed to cause system shutdown and notification of project personnel. This alarm condition was designed to detect a break in an extraction well line or failure of a groundwater pump. The system was also equipped with four digital pressure switches with a high and low settings and one analog pressure switch that would shut the system down in the event that the pressure went beyond the set point. A low-pressure alarm would indicate a break in the line and a high pressure would indicate a blockage or closed valve. If the system turned off due to an

alarm, all pumps would be shut down immediately, and the solenoid valves on oxygen and methane gas lines would fail closed. After the system shut down, the unit would call and report the cause of the alarm. CONCLUSIONS The constructed anaerobic and aerobic equipment systems had sufficient robustness and flexibility to allow the ISB demonstrations to achieve their goals. As a result of successful deployment, the mobile skids containing the aerobic ISB equipment will be used on projects currently being planned by Shaw E & I at Hunters Point Naval shipyard, CA and Treasure Island, CA for the United States Navy. Similarly the Process Control Trailer will be used on future ISB projects. These new projects will also use sequential anaerobic/aerobic in situ bioremediation, as site conditions require. REFERENCES Granade, S., D.P. Leigh, and C.D. Johnson. 2003. "Chlorinated Solvent Bioremediation: 3 Case Studies." In: Proceedings of the Seventh In situ and On-Site Bioremediation Symposium (Orlando, Florida; June 2-5, 2003). Battelle Press, Columbus, OH. In press. Hooker, B.S., R.S. Skeen, M.J. Truex, C.D. Johnson, B.M. Peyton, and D.B. Anderson. 1998. "In situ Bioremediation of Carbon Tetrachloride: Field Test Results." Bioremediation Journal, 1(3):181-193. Johnson, C.D., R.S. Skeen, D.P. Leigh, T. P. Clement, and Y. Sun. 1998. "Modeling Natural Attenuation of Chlorinated Ethenes Using the RT3D Code." In: Proceedings of the Water Environment Federation 71st Annual Conference and Exposition, WEFTEC '98, Volume 3. Water Environment Federation, Alexandria, Virginia. pp. 225-247. Johnson, C.D., R.S. Skeen, M.G. Butcher, D.P. Leigh, L.A. Bienkowski, S. Granade, B. Harre, and T. Margrave. 1999. "Accelerated In situ Bioremediation of Chlorinated Ethenes in Groundwater with High Sulfate Concentrations." In: Engineered Approches for In situ Bioremediation of Chlorinated Solvent Contamination, A. Leeson and B.C. Alleman (eds.). Battelle Press, Columbus, Ohio. pp. 165-170. Leigh, D.P., C.D. Johnson, R.S. Skeen, M.G. Butcher, L.A. Bienkowski, and S. Granade. 2000. "Enhanced Anaerobic In situ Bioremediation of Chloroethenes at NAS Point Mugu." In: Bioremediation and Phytoremediation of Chlorinated and Recalcitrant Compounds, G.B. Wickramanayake, A.R. Gavaskar, B.C.Alleman, and V.S. Magar (eds.). Battelle Press, Columbus, OH. pp. 229-235. Truex, M.J., C.D. Johnson, D.P. Leigh, and S. Granade. 2002. "Pulsed Injection Flow Strategy for Aerobic Co-Metabolism of Vinyl Chloride." In: Remediation of Chlorinated and Recalcitrant Compounds2002, A.R. Gavaskar and A.S.C. Chen (eds.). Battelle Press, Columbus, OH. Paper number 2B-33.