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HomeMy WebLinkAboutNCD986187128_20000511_North Belmont PCE_FRBCERCLA LTRA_Treatability Study Evaluation Report for In Situ Bioremediation-OCRI I I I I I I I I I I I I I I I I I I RESPONSE ACTION CONTRACT FOR REMEDIAL, ENFORCEMENT OVERSIGHT, AND NON-TIME CRITICAL REMOVAL ACTIVITIES AT SITES OF RELEASE OR THREATENED RELEASE OF HAZARDOUS SUBSTANCES IN EPA REGION 4 U.S. EPA CONTRACT NO. 68-WS-0022 TREAT ABILITY STUDY EVALUATION REPORT FOR IN SITU BIOREMEDIATION AT THE NORTH BELMONT PCE SITE, NORTH BELMONT, GASTON COUNTY, NORTH CAROLINA ')" "''"' -~ tlt4;-,,,,,r-. IS'u,.. I <....'/' ,-,~ii;._ ,9 V Work Assignment No. 071-RDRD-04QD Document Control No. 3280-071-RT-OTHR-07776 May 11, 2000 Prepared for: U.S. Environmental Protection Agency Region IV Atlanta, Georgia Prepared by: COM Federal Programs Corporation 2030 Powers Ferry Road, Suite 490 Atlanta, Georgia 30339 "1l <ooo v~(Cc ~Ott, I I I I I I I I I I I I I I I I I I I TABLE OF CONTENTS Section LIST OFT ABLES ...................................................... iv LIST OF FIGURES ...................................................... V LIST OF ACRONYMS AND ABBREVIATIONS ............................. vi 1.0 INTRODUCTION ................................................. 1-1 2.0 PROJECT DESCRIPTION ........................................... 2-1 2.1 SITE LOCATION AND DESCRIPTION ........................... 2-1 2.2 SITE HISTORY .............................................. 2-1 2.3 ENVIRONMENT AL SETTING .................................. 2-4 2.3.1 SITE GEOLOGY ....................................... 2-5 2.3.2 SITE HYDROGEOLOGY ................................ 2-6 2.4 REMEDIAL INVESTIGATION SUMMARY ....................... 2-8 2.4.1 REMEDIAL INVESTIGATION ........................... 2-8 2.4.2 SUMMARY OF SUPPLEMENTAL INVESTIGATIONS ....... 2-8 2.5 RECORD OF DECISION SUMMARY ........................... 2-10 2.6 REMEDIAL ACTION STRATEGY .............................. 2-10 3.0 IN SITU BIOREMEDIA TION DESCRIPTION AND RES UL TS ............ 3-1 3. I BIOASSESSMENT FIELD STUDY RES UL TS ..................... 3-2 3.1.1 VOLATILE ORGANIC GROUNDWATER CONTAMINATION 3-2 3.1.2 GROUNDWATER GEOCHEMISTRY .................... 3-11 3.1.3 BIOCHEMISTRY ..................................... 3-18 3.2 MICROCOSM STUDY ....................................... 3-30 3.2.l GENERAL TECHNICAL APPROACH .................... 3-30 3.2.2 MATERIALS AND METHODS .......................... 3-31 3.2.3 DAT A ANALYSES .................................... 3-4 I 4.0 CONCLUSIONS .................................................. 4-1 4.1 ENHANCED ANAEROBIC BIOREMEDIA TION FEASIBILITY ....... 4-1 4.2 FULL SCALE EVALUATION ................................... 4-2 5.0 REFERENCES .................................................... 5-1 00-018/3280-071/05] 0 11 I I I I I I I I I I I I I I I I I I I LIST OFT ABLES Table Page 2-1 PERFORMANCE GOALS ........................................ 2-11 3-1 JANUARY1999FIELDVOCDATA ................................ 3-3 3-2 JANUARY 1999 FIELD BIOCHEMICAL AND GEOCHEMICAL DATA ........................................................ 3-19 3-3 JANUARY 1999 LABORATORY BIOCHEMICAL AND GEOCHEMICAL DATA ......................................... 3-20 , 3-4 SAMPLING REQUIREMENTS AND ANALYTICAL METHODS ........ 3-32 3-5 NUTRIENT STOCK SOLUTION COMPOSITION .................... 3-33 3-6 COMPONENTS OF RST TRACE METAL AND VITAMIN SOLUTIONS ................................................... 3-34 3-7 TREATMENTS USED IN MICROCOSM STUDY .................... 3-35 3-8 VOLATILE ORGANIC COMPOUND ANALYSIS FOR THE MICROCOSM STUDY .......................................... 3-37 3-9 MISCELLANEOUS COMPOUND ANALYSIS FOR THE MICROCOSM STUDY .......................................... 3-39 00-0 I 8/3280.071105 JO 111 I I I I I I I I I I I I I I I I I I I LIST OF FIGURES Figure 2-1 SITE LOCATION MAP ........................................... 2-2 2-2 NORTH BELMONT PCE AREA .................................... 2-3 3-1 PERCHLOROETHENE-TOP OF BEDROCK GROUNDWATER PLUME ........................................................ 3-4 3-2 TRICHLOROETHENE-TOP OF BEDROCK GROUNDWATER PLUME ........................................................ 3-5 3-3 TOT AL 1.2-DICHLOROETHENE-TOP OF BEDROCK GROUNDWATER PLUME ........................................ 3-6 3-4 PERCHLOROETHENE-BEDROCK GROUNDWATER PLUME ........ 3-7 3-5 TRICHLOROETHENE-BEDROCK GROUNDWATER PLUME ......... 3-8 3-6 TOT AL 1.2-DICHLOROETHENE-BEDROCK GROUNDWATER PLUME ........................................................ 3-9 3-7 ALKALINITY-TOP OF BEDROCK GROUNDWATER PLUME ....... 3-13 3-8 ALKALINITY-BEDROCK GROUNDWATER PLUME ............... 3-14 3-9 TOTAL ORGANIC CARBON-TOP OF BEDROCK GROUNDWATER PLUME ....................................... 3-15 3-10 TOTAL ORGANIC CARBON-BEDROCK GROUNDWATER PLUME ....................................................... 3-16 3-11 DISSOLVED OXYGEN-TOP OF BEDROCK GROUNDWATER PLUME ....................................................... 3-21 3-12 NITRATE-TOPOFBEDROCKGROUNDWATERPLUME ........... 3-22 3-13 FERROUS IRON-TOP OF BEDROCK GROUNDWATER PLUME ..... 3-23 3-14 SULFATE-TOP OF BEDROCK GROUNDWATER PLUME ........... 3-24 3-15 DISSOLVED OXYGEN-BEDROCK GROUNDWATER PLUME ....... 3-25 3-16 NITRATE-BEDROCK GROUNDWATER PLUME .................. 3-26 3-17 FERROUS IRON-BEDROCK GROUNDWATER PLUME ............ 3-27 3-18 SULFATE-BEDROCK GROUNDWATER PLUME .................. 3-28 00-018/3280-071/0510 IV I I I I I I I I I I I I I I I I I I I CAH CDM Federal DCE DO DOC EAB EPA Fe(II) HPLC µg/L mg/L PCE ppb RAMM RI ROD SU TCE TOC vc voe 00-0IR/3280-07110510 LIST OF ACRONYMS AND ABBREVIATIONS chlorinated aliphatic hydrocarbon CDM Federal Programs Corporation dichloroethene dissoh·ed oxygen dissolved organic carbon enhanced anaerobic biodegradation U.S. Environmental Protection Agency ferrous iron high-performance liquid chromatography micrograms per liter milligrams per liter perchloroethene parts per billion revised anaerobic minimal medium remedial investigation Record of Decision standard unit trichloroethene total organic carbon vinyl chloride volatile organic compound V I I I I I I I I I I I I I I I I I I I 1.0 INTRODUCTION The North Be/mom PC£ Site, Nor1h Be/1110111 Gaston Co11111v. North Carolina: Record of Decision (ROD) (EPA, 1997a) included in situ biorcmediation as a potential treatment technology for dissolved phase groundwater contamination at the site. As indicated in the Data Acquisitions Report for the North Belmont PC£ Site, North Be/mom. North Carolina (EPA, 1998a), limited data collected from several monitoring wells in December 1997 indicated a low availability of electron acceptors/metabolic products at the site. Evaluation of this and other data concluded that enhancement of intrinsic biodegradation processes may be a feasible technology at the site and should be further investigated. Enhanced anaerobic biodegradation (EAB) relies on the addition of sufficient organic compounds to contaminated groundwater to induce highly reducing methanogenic conditions necessary to~iev\ reductive dechlorination of chlorinated solvents. By inducing highly reducing methanogenic conditions, EAB may improve both the extent and rate of dechlorination reactions. Inherent in the technically and economically feasible implementation of EAB is that: (I) site groundwaters have only low levels of alternative electron acceptors, such that only a minimal addition of organic compound is necessary to achieve and sustain a highly reduced groundwater environment, (2) the existing microbial ecology is capable of dechlorinating perchloroethene (PCE) to innocuous end-products, (3) the addition of electron donor/nutrient mixtures will increase the rate (and extent) of apparent dechlorination reactions. and (4) EAB can be shown to be protective of human health and the environment while being cost-effective. As outlined in the Final Treatabili1y Study Work Plan for 1he North Be/mom PC£ Site, North Belmont, North Carolina (EPA, 1998b ), additional field data were collected in January 1999, and a laboratory microcosm treatability study was initiated in February 1999 to further investigate the potential of enhancing in situ bioremediation processes for remediation of groundwater contamination at the site. 00-01813280-07 liOS 10 1-1 I I I I I I I I I I I I I I I I I I I The following sections provide an evaluation of field data collected in January l 999 and a discussion of the laboratory microcosm treatability study results. The four criteria listed above for technical and economically feasible implementation of EAB were evaluated. It was determined the EAB is not a feasible technology for the treatment of contaminated groundwater at the site. oo.o 1813280-071, 05 10 1-2 I I I I I I I I I I I I I I I I I I I 2.0 PROJECT DESCRIPTION 2.1 SITE LOCATION AND DESCRIPTION The site consists of two closed dry cleaning operations located in North Belmont, Gaston County, North Carolina. These two areas are referred to as "Source Area A" and "Source Area B" (Figure 2-1). Source Area A, which was operated by the Untz family from 1960 to 1975 as a dry cleaning business, is located at Roper's Shopping Center in Land Lot 5, Parcel I 5-l 8A on Woodlawn Avenue. The shopping center includes Roper's Furniture Store, a Baptist church, and a cabinet manufacturing shop. The former dry cleaning facility is approximately 0. 75 acre in size and is bounded to the east and west by residential neighborhoods, to the north by a cemetery and an undeveloped wooded tract, and to the south by North Belmont Elementary School. Source Area B is located at the northeastern comer of Acme Road and Suggs Road in Land Lot 11, Parcel 15-18. This parcel has been converted to residential property. The majority of the area surrounding Source Area Bis residential with a few small businesses. A cabinet shop is located to the north. A previous refrigerator repair shop and a machine shop were also suspected to be potential sources of contamination. The refrigerator repair shop, now closed, is located at the intersection of Julia Street and Acme Road in land lot 15-18A, Parcel 32. This is a small commercial strip area with residential property surrounding the site, except for a cabinet shop and a well drilling company located to the east. The machine shop is located at the comer of Acme and Centerview Roads and is encompassed by residential neighborhoods. Figure 2-2 shows the approximate study area. 2.2 SITE HISTORY Source Area A was operated by the Untz family from 1960 to 1975 as a dry-cleaning establishment. A boiler located behind the building was used to "distill" the waste dry cleaning solvents. The spent solvent residue from the boiler distillation unit was reportedly disposed onto the ground surface behind the building, and spent solvents were disposed 00-018/3280-071/0510 2-1 I I I I I I I I I I I I I I I I I I I CDM FEDERAL RAC VIII SITE LOCATION MAP NORTH BELMONT PCE SUPERFUND SITE COIi FEDERAL PROGRAMS CORPORATION .-...,..,Caa,;p-•-""'· GASTON COUNTY, NORTH CAROLINA 2-2 NOTTO SCALE FIGURE NO. 2-1 - N ' \;.) -- -- 62 LOT NUMBERS e PRf.\10l.1S ORY Cl.EMILNC fACIUTIES a Pff£'¥10US REFRIGERATOR REPAIR fACUJTY ■ MACHINE SHOP o· soo· """ -w -- - 1000' ---- -- -- - COM FEDERAL RAC VIII NORTH BELMONT PCE AREA NORTH BELMONT PCE SUPERFUND SITE COIi FEDERAL PROGRAMS CORPORAnON GASTON COUNTY, NORTH CAROLINA .-..,.-~-·-- - --- N l FIGURE NO. 2-2 I I I I I I I I I I I I I I I I I I I through the on-site septic tank system. Source Area B was also operated by the Untz family prior to moving the dry cleaning establishment to Roper's Shopping Center. Source Area B was discovered during the site reconnaissance in October 1995 from an interview with a local resident. In February 1991, the Gaston County Health Department sampled the well that provided water to the North Belmont Elementary School and two single family dwellings. This sampling was associated with an effort by the County to evaluate community water supplies for volatile organic compounds (VOCs) contamination. The results of this sampling indicated significant VOC contamination in the well. U.S. Environmental Protection Agency (EPA) Region 4 Emergency Response was notified. EPA and the Gaston County Health Department sampled 25 drinking water wells. PCE, trichloroethene (TCE) and cis-1,2-dichloroethene (1,2-DCE) were detected in sixteen samples. PCE concentrations were found as high as 15,000 parts per billion (ppb ). The elementary school was immediately connected to the City of Belmont water system. Twenty- nine of the neighborhood drinking water wells were taken out of service and connected to the Belmont city water service. All but 12 of the residential wells were subsequently abandoned by grouting them to the surface; 12 wells remained intact and were proposed as monitoring wells. Seven residences in the neighborhood were informed of the contamination but chose to continue to use their wells and not connect to city water. 2.3 ENVIRONMENT AL SETTING This section provides a description of the geology and hydrogeoiogy in the site vicinity. Refer to the North Belmont PCE Site, North Belmont. Gaston County, North Carolina: Remedial Investigation Report (EPA, 1997b) for more information. 00-0 l 8/J280-071,05 10 2-4 I I I I I I I I I I I I I I I I I I I 2.3.l SITE GEOLOGY The site is located within the central portion of the Charlotte Belt of North Carolina. The rock types that underlie this terrain are dominated by granitic type rocks, metavolcanics, and gneisses and schists of varying types. The rock types are of varying metamorphic grade, and all rock units trend parallel with the strike of the Appalachian Mountains, which is typically northeast to southwest. These same units typically dip to the southeast along with the regional topographic trend. Structurally, the area is complex with rock units displaying one or two types of metamorphism or structural changes such as faulting or folding. A large, unnamed fault is located approximately six miles to the west of the site. According to the Geologic Map ofNorth Carolina, the site is underlain by foliated to massive metamorphosed quartz diorite and massive to weakly foliated, hornblende rich granitic type rock. These rock units have undergone periods of deformation that have produced folding and fracture planes in the rock, as well as brittle zones where the rock is actually crushed, sheared, or faulted in some manner. As these rock types become weathered, soil profiles develop that are characteristic of the original rock (also referred to as saprolite). During the field activities, the soil profile varied with each location; however, a common pattern was observed. From top to bottom, the materials consist of a saprolite layer, a partially weathered rock zone, and the underlying fractured crystalline bedrock. The saprolite is clay-rich, residual material derived from in-place weathering of bedrock. Typically, the saprolite is silty clay near the surface. With increasing depth, the amount of mica, silt, and fine~grained sand and gravel tend to increase. Remnant fracture planes with quartz infilling appear in this layer. The saprolite zone is thickest ( approximately 125 feet) along the ridgeline on the western edge of the site, thinning towards the lower elevations or stream valleys to approximately 30 feet in thickness. Underlying the saprolite is a partially weathered rock layer derived from the weathering of bedrock which ranges in thickness from 00-018/3280-071/0S 1 0 2-5 I I I I I I I I I I I I I I I I I I I approximately IO to 50 feet. This layer is composed of saprolite and fragments of weathered bedrock. Particle sizes range from silts and clays to large boulders ofunweathered bedrock. The weathering occurs in bedrock zones less resistant to physical and chemical degradation (i.e., fault zones. stress relief fractures, and mineralogic zones). The predominant rock types appear to be metamorphosed quartz diorite and metamorphosed granite or granitic gneiss. The bedrock is fractured and these fractures contain quartz deposits that remain unweathered in the saprolite and therefore are likely to act as confining layers. 2.3.2 SITE HYDROGEOLOGY Regionally, the water bearing units that underlie the site and surrounding areas represent an aquifer system consisting of metamorphosed and fractured quartz diorite and granitic type rocks in varying proportions and thicknesses. Geologic structures that produce high-yielding wells include contact zones of multi layered rock units, zones of fracture concentration, and stress-relief fracture zones. Previous studies have indicated that wells in Gaston County that are set within granite have an average depth of 165 feet and an average yield of 18 gallons per minute. Within this area, well depths range from 85 to over 1,000 feet and well yields range from 2½ to I I 6 gallons per minute. The aquifer system underlying the site generally consists of the saprolite/partially weathered rock aquifer and the underlying bedrock aquifer; however, interconnection between these units is likely, thereby influencing contaminant transport. Aquifer designations used during the remedial investigation (RI) for the site are the saprolite aquifer. the top of bedrock aquifer, and the bedrock aquifer. These same designations apply to this report. In the site area, the top of the water table is typically found in the saprolite aquifer and will generally mimic the overlying land surface. The depth to water across the area ranges from approximately 3 to 35 feet belmv ground surface. Based on groundwater elevations collected in November 1996 aquifers generally flow to the northeast to east across the site. Furthermore, Roper's Shopping Center appears to be positioned within the top ofa localized groundwater mound with potentiometric contours emanating in a semi-circular pattern from Q0.018/3280-07 IIOS I 0 2-6 I I I I I I I I I I I I I I I I I I I this point. Insufficient data of groundwater elevations along the western edge of the site prevent completion of the potentiometric contours. Based on depth-to-water measurements for monitoring wells MW-13 and MW-21, groundwater discharges from the saprolite and bedrock aquifers into the small stream along the northern edge of the site: however, fractures present in the partially weathered rock and bedrock will affect the direction of groundwater flow, and relict fractures present in the saprolite may also control groundwater flow directions. Most of the natural flow in the bedrock system is probably confined to the upper 30 feet of bedrock where fractures are concentrated, and the overlying transition zone which has the highest hydraulic conductivity. Data were collected during the 1996/1997 RI for estimating hydraulic gradient and hydraulic conductivity at the site. The hydraulic gradients for the saprolite and bedrock aquifers were calculated to be 0.0298 and 0.0275, respectively. Data from rising-head slug tests were used to calculate hydraulic conductivity in the saprolite and bedrock aquifers. The resultant values ranged from 0.24 to 1.99 feet/day in the saprolite aquifer and 0.016 to 3.41 feet/day in the bedrock aquifer. During the RI, five monitoring wells (MW-14, MW-15, MW-I 8, MW-20, and MW-21) were examined for identification of geophysical fractures and indications ofhydrologic activity. Hydrologically active fractures are those that appear to be contributing water to the water column under static well conditions, and these hydrologically active fractures may potentially act as contaminant transport pathways. Locations of fractures, strike and dip angles, and potential hydrologic activity at these locations are outlined in the RI Report (EPA, 1997b). However, the lateral and vertical extent of the hydrologically active, or potentially active, fractures were not determined. Furthermore, the interconnectivity of the fractures was not defined. 00·0 I 813280-071/05 10 2-7 I I I I I I I I I I I I I I I I I I I 2.4 REMEDIAL INVESTIGATION SUMMARY 2.4.1 REMEDIAL INVESTIGATION A RI was conducted by EPA to determine the nature and extent of contamination at the site (EPA. 1997b ). The following briefly summarizes conclusions from the RI Report: 1. The contaminant plume is spreading. Private wells in the vicinity of the site that were not contaminated in 1991 when EPA first investigated the site are now contaminated. 2. Contamination detected in the shallow aquifer appears to be localized in Source Area A (Ropers Shopping Center). See Figure 2-1 for source area locations. 3. Contaminants have migrated from the shallow aquifer into the top of bedrock zone and into the bedrock aquifer. Maximum PCE concentrations detected in the saprolite aquifer. the top of bedrock aquifer, and the bedrock aquifer during the 1996 RI sampling were 2200 micrograms per liter (µg/L), 2500 µg/L, and 3500 µg/L, respectively. 4. The source of contamination in the southern edge of the plume may be either Source Area A or Source Area B. 5. Neither source area contains residual soil volatile organic contamination. It is believed that the contaminants migrated through the soil directly into the shallow aquifer. VOCs in surface soil evaporated. 6. Surface water and sediment in the area are not affected by the VOCs. 2.4.2 SUMMARY OF SUPPLEMENT AL INVESTIGATIONS As described below, two supplemental investigations were performed after the RI. The first supplemental investigation was conducted during July and August of 1998. The second supplemental investigation was conducted during January and February of 1999. 00-01813280-071,0510 2-8 I I I I I I I I I I I I I I I I I I 2.4.2.1 .July and August of 1998 As required in the ROD. supplemental field work was conducted in July and August of 1998 to further define the nature and extent of site contamination. Three monitoring wells were installed, groundwater samples were collected and analyzed, and a limited well survey was conducted. Details of this investigation are outlined in the Da!a Acquisitions Report for the North Belmont PC£ Site. North Belmont, North Carolina (EPA, 1998a). The following briefly summarizes the conclusions of this report: • Groundwater data indicate that the contaminants of concern identified in the RI (EPA, 1997b) have remained the same. The data support the existing site conceptual model presented in the RI (EPA, 1997b) with only a slight change in the distribution around the edges of the plumes. • The data suggest that biotransformation is occurring at the site. • A limited response was obtained from site residents during the well survey. Additional survey work will be required to determine which residents (of the ones not currently connected to city water) desire individual well head treatment units and which residents desire connection to city water. 2.4.2.2 January and February of 1999 A bioassessment field study was conducted in January of I 999 to further investigate the potential for enhancing intrinsic anaerobic biodegradation at the site and to develop a conceptual design for this technology. The study consisted of groundwater sampling and analysis. The data suggested that enhanced anaerobic biodegradation may be a suitable technology for the site. Details of this investigation are outlined in the Draft Conceptual Design Report for the North Belmont PC£ Site. North Belmont. North Carolina (EPA, i 999) and Section 3 of this report. 00-0 l 813280-071/0S I 0 2-9 I I I I I I I I I I I I I I I I I I I 2.5 RECORD OF DECISION SUMMARY The North Belmont PC£ Site. North Belmont Gaston County. North Carolina: Record of Decision (EPA, 1997a) recommended that the groundwater remedy consist of the following: l. Connection of all homes, churches, and businesses in the "North Belmont PCE Area" to the public water supply. 2. Optional installation of carbon filters on private wells, including one year of filter operation and maintenance, and filter replacement after one year. 3. Groundwater treatment via in-well vapor stripping and in situ bioremediation. The goal of this remedial action is to restore the groundwater to its beneficial use. Based on information obtained during the RI and the analysis of all remedial alternatives, EPA and the state of North Carolina believe that the selected remedy will be able to achieve this goal. The selected technologies are proven methods to reduce levels of site-specific contaminants in groundwater. However, COM Federal Programs Corporation (COM Federal) stresses that the fractured, heterogeneous. and anisotropic geological conditions at the site make it difficult to model the extent to which contaminant reductions will occur, especially considering that in situ bioremediation via EAB is not feasible. The performance goals for groundwater cleanup arc presented in Table 2-1. 2.6 REMEDIAL ACTION STRATEGY Previously the remedial action strategy was to clean groundwater contamination using in- well vapor stripping and EAB. In-well vapor stripping is proposed to address source area and high concentration portions of the groundwater plume generally within the upgradient regions of the site. The remaining downgradient portions of the plume were to be addressed using EAB. However, since EAB is not feasible at the site. a different strategy is , recommended. 00-01813280-071105 JO 2-10 I I I I I I I I I I I I I I I ·1 I I I TABLE 2-1 PERFORMANCE GOALS NORTH BELMONT PCE SITE NORTH BELMONT, NORTH CAROLINA Contaminant Methylene Chloride Cis-1,2-Dichloroethene Trichloroethene Perchloroethenc (Tetrachloroethene) Bis(2-ethylhexy I )phthalate Chloroform I, 1-Dichloroethcne Lead Remediation Level 5 µg/L 70 µg/L 2.8 µg/L I µg/L 3 µg/L I µg/L I µg/L 15 mg/L It is recommended that the phased approach described below should be used to address groundwater contamination at the site. • Phase I includes connection to city water, wellhead treatment, and in-well vapor stripping at the source area and high concentration portions of the groundwater contamination (not the entire plume). Phase I in-well vapor stripping activities will include the establishment ofa baseline for evaluation of the source area treatment (not an entire plume baseline), in-well vapor stripping system construction and operations, followed by an evaluation to determine the effectiveness. • Phase II operations will address the remainder of the contamination plume. The remedial actions for Phase II will be determined using the information obtained in Phase I operations and the EAB treatability study. Data gaps will be identified and other studies will be completed if required. All historical analytical data have been reviewed and the following conclusions have been made. 00-018/3280-071105 J 0 2-11 I I I I I I I I I I I I I I I I I I I • The source area (as represented in MW-6 and CW-6) has recently had comparable or higher VOC concentrations when compared to historical data. This suggests that the area around these wells is the main source area. Phase I in-well vapor stripping should be implemented in and around the main source area. Existing analytical data is sufiicient to implement Phase I activities. No additional sampling will be required. • VOC concentrations in most non-source area wells have not changed significantly from historical levels. The exceptions are MW-12 and CW-2, which show an increase in VOC concentrations. Although it is likely that the shape for the plume has and is changing, it is recommended that this area of the plume be addressed during Phase II remedial action activities. COM Federal acknowledges that although there is insufficient data to design a remedy for cleanup of the entire plume. Additional data should not be collected at this time because Phase I operations have not been completed and evaluated; therefore, it would not be cost- effective to completely characterize the entire plume at this time. It is recommended that the collection of baseline information be targeted to evaluate Phase I operations and should be completed just prior to implementing the Phase I in-well vapor stripping. The development and implementation of a groundwater monitoring plan for the entire site is not recommended at this time for the reasons stated above. 00.0 I 8/3280-071,0510 2-12 I I I I I I I I I I I I I I I I I I I 3.0 IN SITU BIOREMEDIATION DESCRIPTION AND RESULTS The ROD included in situ bioremediation as a potential treatment technology for dissolved phase groundwater contamination at the site. Limited data collected from several monitoring wells in December 1997 indicated a low availability of alternate electron acceptors that would compete with the implementation of EAB at the site (EPA, 1998a). Furthermore, the natural anaerobic dechlorination of chlorinated aliphatic hydrocarbon (CAH) compounds at the site is likely limited by the availability of electron donor compounds to drive dechlorination reactions. Evaluation of this and other data concluded that enhancement of intrinsic biodegradation processes may be a feasible technology at the site and should be further investigated. EAB relies on the addition of sufficient organic compounds to contaminated groundwater to induce highly reducing methanogenic conditions necessary to achieve reductive dechlorination of chlorinated solvents. By inducing highly reducing methanogenic conditions, EAB may improve both the extent and rate of dechlorination reactions. Inherent in the technically and economically feasible implementation of EAB is that: (I) site groundwaters have only low levels of alternative electron acceptors, such that only a minimal addition of organic compound is necessary to achieve and sustain a highly reduced groundwater environment, (2) the existing microbial ecology is capable of dechlorinating PCE to innocuous end-products, (3) the addition of electron donor/nutrient mixtures will increase the rate (and extent) of apparerit dechlorination reactions, and (4) EAB can be shown to be protective of human health and the environment while being cost-effective. As outlined in the Final Treatability Study Work Plan for the North Belmont PC£ Site, North Belmont. North Carolina (EPA, 1998b ), additional field data were collected in January 1999, and a laboratory microcosm treatability study was initiated in February 1999 to further investigate the potential of enhancing in situ bioremediation processes for remediation of groundwater contamination at the site. OQ.O 18/3280-07 l/OS I 0 3-1 I I I I I I I I I I I I I I I I I I I The following sections provide an evaluation of field data collected in January 1999 and a discussion of the laboratory microcosm treatability study results. 3.1 BIOASSESSMENT FIELD STUDY RESULTS A bioassessment field study ,,·as conducted in January 1999 to further investigate the potential for enhancing intrinsic anaerobic biodegradation at the site and to develop a conceptual design for this technology. The study consisted of groundwater sampling and analysis. This section presents the results of groundwater sampling conducted at nine locations in the top of bedrock aquifer and ten locations in the bedrock aquifer, as outlined in the Final Treatability Study Work Plan.fir the North Belmont PCE Site, North Belmont, North Carolina (EPA, 1998b). The following provides an analysis of the collected VOC and biochemical data. A background discussion of biological systems is provided in the Final Treatability Study Work Plan for the North Belmont PCE Site, North Belmont, North Carolina (EPA, 1998b). 3.1.1 VOLATILE ORGANIC GROUNDWATER CONTAMINATION Analytical results from sampling conducted in January 1999 confirmed the presence of contaminants of concern identified in the North Belmont PCE Site. North Belmont. Gaston County, North Carolina: Remedial Investigation Report (EPA, 1997b) and in the Data Acquisitions Report for the North Belmont PCE Site, North Belmont, North Carolina (EPA, 1998a). The main chlorinated solvents detected (PCE, TCE, and 1,2-DCE) and their biotransformation products [vinyl chloride (VC), ethene, and ethane] are presented in Table 3-1. The complete set of analytical results is presented in Appendix D of the Drafi Conceptual Design Report for the North Belmont PCE Site, North Belmont. North Carolina (EPA, 1999). PCE, TCE, and 1,2-DCE plots for both the top of bedrock and bedrock aquifers are presented in Figures 3-1 through 3-6. Data presented in Table 3-1 indicate a good correlation with data collected during July and August of I 998 and are discussed separately below for the top of bedrock and bedrock aquifers. 00-01813280-071/05 10 3-2 I I I I I I I I I I I I I I I I I I I TABLE 3-1 ,JANUARY 1999 FIELD voe DATA NORTH BELMONT PCE SITE NORTH BELMONT, NORTH CAROLINA Date PCE TCE 1,2-DCE VC Location ID Sampled (ue/L) /ue/L) (ue/L) (uo/L) Top of Bedrock Aquifer TW-OIGW 28-Jan-99 250 I 9J 100 20UJ NB-MW04DP 25-Jan-99 IOU IOU IOU IOUJ NB-MW06DP 29-Jan-99 2800 3l0U 770 3l0UJ NB-MW07DP 22-Jan-99 IOU IOU IOU IOU NB-MW09DP 2 I-Jan-99 13 IOU IOU IOU NB-MWIODP 23-Jan-99 IOU IOU IOU IOUJ NB-MWl2DP 28-Jan-99 170 IOU IOU IOUJ NB-MWl3SH 20-Jan-99 IOU IOU IOU IOU NB-CW08DP 24-Jan-99 IOU IOU IOU IOUJ Bedrock Aquifer NB-MW03DP 25-Jan-99 59 3J 24 IOUJ NB-MWl4DP 24-Jan-99 100 IOU 2J IOUJ NB-MWISDP 22-Jan-99 IOU IOU IOU IOU NB-MW17DP 20-Jan-99 IOU IOU IOU IOU NB-MW18DP 24-Jan-99 IOU IOU IOU IOUJ NB-MW2IDP 19-Jan-99 IOU IOU IOU IOU NB-MW22DP 2 I-Jan-99 IOU IOU IOU IOU NB-CW06DP 30-Jan-99 5400 350] 1900 IOOOUJ NB-CW07DP 29-Jan-99 97 4J 7J IOUJ NB-PW408DP 30-Jan-99 IOU IOU IOU IOUJ NOTES: PCE = pcrchlorocthcne TCE = trichloroethcnc 1.2-DCE 1,2-dichlorocthcne (total) VC vinyl chloride J estimated value U material was analyzed for but not detected 00-01813280.071,0!i 10 Ethane Ethene (ue/L) (ue/L) 0.19] 0.20J 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U 2.5U 2.6U ------------------- • Monitoring Well <10 1999 Treotability Study Doto (<1) 1996 RI Data 1" = 500' r-..•c- 250 0 500 MW21• MW13• <10 (<1) CDM FEDERAL RAC VIII PERCHLOROETHENE(PCE) TOP OF BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA N FIGURE NO. 3-1 ------------------- t,.) ' V, LEGEND • Monitoring Well <10 1999 Treatability Study Data (<1) 1996 RI Data 1" = 500' ,.._.._. 250 0 500 MW13• <10(<1) CDM FEDERAL RAC VIII TRICHLOROETHENE (TCE) TOP OF BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA N FIGURE NO. 3-2 ------------------- LEGEND • Monitoring Well <10 1999 Treatability Study Data (<1) 1996 RI Data 1" = 500' r---? 250 0 500 --·-----.... _.., ____ , __ _ CDM FEDERAL RAC VIII TOTAL 1,2-DICHLOROETHENE (DCE) TOP OF BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA ,. ; J J: N FIGURE NO. 3-3 ------------------- LEGEND • Monitoring Well <10 1999 Treatability Study Data ( <1) 1996 RI Data 1" = 500' r--•a- 250 0 500 coNCRETE-. SUPPlY --- CDM FEDERAL RAC VIII PERCHLOROETHENE (PCE) BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA N FIGURE NO. 3-4 ------------------- w ' 00 • Monitoring Well <10 1999 Trecitability Study Data (<1) 1996 RI Data 1" = 500' r---c-250 0 500 CONCRETE __ _ SUPPlY ---- MW17 _! <10 (~1) COM FEDERAL RAC VIII TRICHLOROETHENE (TCE) BEDROCK GROUNDWATER PLUME ) I NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA N FIGURE NO. 3-5 ------------------- LEGEND • Monitoring Well <10 1999 Treatability Study Data (<1) 1996 RI Data 1" ; 500' ,._.? 250 0 500 ration MW21• <10 (<1) CDM FEDERAL RAC VIII MW17 • <10 (~1) . _ TOTAL 1,2-DICHLOROETHENE (1,2-DCE) BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA • • I Ji N FIGURE NO. 3-6 I I I I I I I I I I I I I I I I I I I Top of Bedrock Aquifer Figures 3-1 through 3-3 present top of bedrock aquifer field data (PCE, TCE, and 1,2-DCE) for January 1999. The 1996 top of bedrock field data produced during the RI are also presented in the figures for comparison purposes. The extent of chlorinated solvent contamination in the top of bedrock aquifer is similar to that presented in the RI and the Data Acquisition Report. The highest concentration of PCE was recorded at MW-6 (2,800 µg/L) and corresponds with elevated biodegradation daughter product concentrations (1,2-DCE = 770 µg/L). Chlorinated contaminants were also detected at TW-0 I (PCE = 250 µg/L, TCE = 19 µg/L, 1,2-DCE = 100 µg/L): MW-9 (PCE = 13 µg/L); and MW-12 (PCE = 170 µg/L). The presence of PCE and its biodegradation daughter products at MW-6 and TW-0 I provide evidence ofactive reductive dechlorination reactions in the top of bedrock aquifer. Although analytical results from the July and August 1998 sampling event at MW-6 indicate concentrations of PCE (910 µg/L) and 1,2-DCE (310 µg/L) that are substantially less than those collected in January I 999 [PCE (2800 µg/L) and 1,2-DCE (770 µg/L)], the general distribution of contaminants is similar. Furthermore, PCE concentrations recorded at MW-9 (13 µg/L) and MW-12 (170 µg/L) in January 1999 are similar to those recorded in July and August of 1993 (MW-9 = 16 µg/L: MW-12 = 160 µg/L), indicating a good correlation between the two data sets. The downgradicnt extent of contamination is defined by CW-8 which had non-detect levels of chlorinated contaminants. Monitoring wells downgradient of CW-8 (MW-7, MW-I 0, and MW-13) also had non-detect levels of chlorinated contaminants, indicating that the chlorinated solvent plume is confined to the upgradient regions of the aquifer. Bedrock Aquifor Figures 3-4 through 3-6 present bedrock aquifer field data (PCE, TCE, and 1,2-DCE) for January 1999. The 1996 bedrock aquifer field data produced during the RI are also presented in the figures for comparison purposes. The extent of chlorinated solvent contamination in 00-018/]280-071/0510 3-10 I I I I I I I I I I I I I I I I I I I the bedrock aquifer is similar to that presented in the RI (EPA, 1997b) and the Data Acquisition Report (EPA. 1998a). In general, contaminant (PCE, TCE, 1,2-DCE) concentrations recorded at CW-6 during 1999 were 20% to 50% higher than those recorded in 1996. The highest concentration of PCE was recorded at CW-6 (5,400 µg/L) and corresponds with elevated bi ode gradation daughter product concentrations (TCE = 350 µg/L, I ,2-DCE = 1,900 µg/L). Chlorinated contaminants were also detected at MW-03 (PCE = 59 µg/L. TCE = 3 µg/L, 1,2-DCE = 24 µg/L); MW-14 (PCE = 100 µg/L, 1,2-DCE = 2 µg/L); and CW-07 (PCE = 97 µg/L, TCE = 4 µg/L, 1.2-DCE = 7 µg/L). The presence of PCE and its biodegradation daughter products at several groundwater wells provides evidence of active reductive dechlorination reactions in the bedrock aquifer. 3.1.2 GROUNDWATER GEOCHEMISTRY General groundwater chemistry parameters were measured to better define environmental conditions that can affect the presence and activity of microbial populations across the site. These general groundwater chemistry parameters are similar for both the top of bedrock and bedrock aquifers and are therefore discussed together below. Groundwater pH Groundwater pH has an effect on the density and activity of microbial populations in groundwater. Generally, microbes prefer pH values varying from 6 to 8 standard units (SU), although lower activity levels of some microbes can extend substantially beyond this range. Non-optimal pH conditions tend to slow reaction rates but do not necessarily inhibit biological activity unless the specific process (enzyme) is very sensitive to pH. Groundwater pH values range from 5.5 to 8. 7 SU, with only wells falling slightly outside the optimal pH 6 to 8 range (MW-10, MW-13, MW-03. MW-14, and PW-4.08). This range in pH values is expected to support biological activity throughout the site. 00-01813280.071,0510 3-11 I I I I I I I I I I I I I I I I I I I Groundwater Temperature Groundwater temperature directly affects the rate of microbial metabolic activity. Biodegradation rates roughly double for every I 0-degree Celsius ( 0 C) increase in temperature. between the temperature range of 5 °C and 25 °C. At temperatures below 5 °C, metabolic rates are generally too low to be significant, while temperatures above 35 °Care generally inhibitory to groundwater microbial populations. Groundwater temperatures ranged from 1·1.3°C (PW-4.08) to 19.2°C (MW-04), and are expected to support moderate biological activity. Groundwater Alkalinity The total alkalinity of a groundwater system is indicative of the capacity of the water to neutralize acid. Alkalinity results from the presence of hydroxides, carbonates, and bicarbonates of elements/compounds such as calcium, magnesium, sodium, potassium, or ammonia. The1;e species result from the dissolution of rock, transfer of carbon dioxide from the atmosphere, and respiration of microorganisms. Total alkalinity values throughout the site range from 30 to 195 milligrams per liter (mg/L) as CaCO3• with background alkalinity values in the top of bedrock aquifer (55 mg/L as CaCO3) and bedrock aquifer (30 mg/L as CaCOi) among the lowest at the site (Figures 3-7 and 3-8). Alkalinity values elevated above background levels are likely due to influences from biological activity within contaminated regions. Furthermore, regions of elevated total alkalinity indicate a moderate ability of groundwater to buffer against pH changes. Groundwater TOC Total organic carbon (TOC) groundwater concentrations throughout the site are generally low, ranging from 3 to 13 mg/L (Figures 3-9 and 3-10). TOC is an indicator of the total electron acceptor demand within an aquifer and a measure of the energy substrate available 00-018/3280-071,05 I 0 3-12 ------------------- w ' -w LEGEND • Monitoring Well 1" = 500' ,._._. 250 0 500 --- MW13• 50 ---- COM FEDERAL RAC VIII ALKALINITY J I TOP OF BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA N FIGURE NO. 3-7 ------------------- • Monitoring Well 1" = 500' ~2" 250 0 500 CONCRETE--. SUPPLY ---- MW21 70 • CDM FEDERAL RAC VIII ALKALINITY MW17 • 115 . -.. - BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA , I }' N FIGURE NO. 3-8 ------------------- w ' -Vo LEGEND • Monitoring Well , .. = 500' ri-----250 0 500 COM Federal Pro ---------- CDM FEDERAL RAC VIII TOTAL ORGANIC CARBON (TOC) TOP OF BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA N FIGURE NO. 3-9 ------------------- <.;J ' -°' LEGEND • Monitoring Well 1" = 500' Pi----250 0 500 CONCRCTE - SUPPLY COM FEDERAL RAC VIII MW17 • 3 ----- TOTAL ORGANIC CARBON (TOC) BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA .. ' /: J N FIGURE NO. 3-10 I I I I I I I I I I I I I I I I I I I to drive biodegradation of the CAH compounds. These low TOC levels indicate only limited electron donors available to: (I) reduce groundwater redox conditions. and (2) drive reductive dechlorination reactions. Thus. the anaerobic biological dechlorination of CAI-I compounds at the site is likely to be limited by the availability of sufficient electron donors (TOC) and suggests enhancement should include the addition of a carbon source. Macronutrient Availability Ammonia and ortho-phosphate are essential macronutrients for biodegradation processes. Ammonia concentrations are generally very low throughout the site (i.e., less than 0.05 mg/L). with the exception of MW-03 (1.76 mg/L). Similarly, ortho-phosphate concentrations are low throughout the site, with values all falling below 0.5 mg/L. Although the observed ammonia and ortho-phosphate concentrations are not expected to limit intrinsic biodegradation processes, amendment of such nutrients would likely be necessary during the implementation of EAB technologies. Additional Groundwater Parameters In addition to the above-mentioned parameters, groundwater samples were analyzed for chloride, specific conductivity, and turbidity. Chloride and. specific conductivity measurements were used to distinguish between potentially different hydrologic zones. Although chloride and specific conductivity values varied throughout the site, values for each generally fall within one order of magnitude and support the assumption that groundwater within the top of bedrock and bedrock aquifers is hydraulically connected. Turbidity measurements were used to determine when groundwater purge water reached "stable" conditions, thereby verifying that purge water was representative of the local aquifer formation. 00-01813280-071/0510 3-l 7 '· \ l I I I I I I I I I I I I I I I I I I I 3.1.3 BIOCHEMISTRY Field and analytical laboratory results for; biochemical and geochemical data are provided in Tables 3-2 and 3-3 and discussed below. Electron acceptor/metabolic by-product concentrations are presented in Figures 3-1 I through 3-18. Electron acceptor/metabolic by-product concentrations were compared at locations within and outside of contaminated areas to assess intrinsic biodegradation processes occurring at the site. The comparison required identification of background conditions (i.e .• reference points) that were representatiw of groundwater upgradient of contaminated regions and therefore outside the influence of contaminant stimulated microbial activity. Background conditions for the top of bedrock aquifer are defined by monitoring well MW-04, while background conditions for the bedrock aquifer are defined by PW-4.08. Top of Bedrock Aquifer Electron acceptor and metabolic byproduct data suggest that much of the site is oxidized and under aerobic conditions (i.e., dissolved oxygen concentrations > 1.0 mg/L). Dissolved oxygen (DO) concentrations are highest at the background well (MW-04 = 7.1 mg/L) and only slightly depleted at downgradient locations. The lowest levels of DO are recorded at TW-01 (3.2 mg/L) and CW-08 (2.0 mg/L) and correspond with the highest levels of TOC in the top of bedrock aquifer (TW-01 = 12 mg/L; CW-08 = 11 mg/L). These findings suggest that TOC concentrations may be depleting DO concentrations within the top of bedrock aquifer; however, sufficient TOC is not available to drive DO concentrations low enough to be conducive to the reductive dechlorination of chlorinated solvents. Alternate electron acceptor concentrations within the top of bedrock aquifer that have the potential to compete with chlorinated solvent biodcgradation (i.e., nitrate, ferric iron, and sulfate) are low. Nitrate concentrations at the background location (MW-04 = 0.9 mg/L) and the highest nitrate concentration within the contaminant plume (TW-0 I = 8.6 mg/L) suggest oo.o 1813:!80-07110510 3-18 ----- -- -- --- --- -- --- TABLE 3-2 JANUARY 1999 FIELD BIOCHEMICAL AND GEOCHEMICAL DATA NORTH BELMONT PCE SITE NORTH BELMONT, NORTH CAROLINA pH Temperature Conductivity Turbidity Alkalinity Chloride Ammonia Phosphate TOC Location ID Date Sampled (SU) (C) (mS/cm) (NTU) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) Top of Bedrock Aquifer TW-0IGW 28-Jan-99 6.62 17.6 0.26 72 120 6.4 0.01 0.05 12 NB-MW04DP 25-Jan-99 6.93 19.2 0.085 0 55 I. 7 0.01 0.28 3.9 NB-MW06DP 29-Jan-99 7.07 17.2 0.077 0 50 1.9 0.01 0.31 3.2 Nll-MW07DP 22-Jan-99 6.41 17.6 0.244 7.72 85 10.8 0 0.25 4.4,\ Nl3-MW09DP 2 I-Jan-99 6.36 17.4 0.178 29 75 4.3 0.01 0.23 5.2* NB-MW!0DP 23-Jan-99 5.49 18 0. 198 19.2 70 7.7 0 0.22 10 NB-MWl2DP 28-Jan-99 NA NA NA NA 80 2.2 0.1)1 0.15 8.1 Nll-MWl3SII 20-Jan-99 5.7 16.6 0.18 1.5 50 6 0 0.15 .t.X* '-'' ' NB-CW081JI' 24-Jan-99 6.52 15.4 0.286 0 105 11.7 !l.ll I 0.21 II '-0 Bedrock Aquifer Nll-MW03DI' 25-Jan-99 8.48 18.8 0.348 0 195 7.2 1.76 0.21 8,1 Nll-MWl4IJ1' 24-Jan-99 8.66 17.3 0.134 0 80 2.1 0.01 0.21 4.8 Nll-MWl5DP 22-Jan-99 6.32 17.2 0.236 43 125 23.6 0.04 0.1 13 Nll-MWl7DP 20-Jan-99 7.55 15.7 0. 192 605 115 5.2 0 0.19 3' NB-MW18DP 24-Jan-99 7.12 16.3 0.223 0 85 10.9 0.02 0. 12 6.8 Nll-MW21DP I 9-Jan-99 6.04 16.4 0.191 4.8 70 5.5 0.01 0.1 2.3A* NB-~'1\V22DP 2 I-Jan-99 6.48 16.8 0.198 14.2 80 9.3 0 0.17 5.2* Nll-Cll'06DP 30-Jan-99 7.07 16.2 0.143 0 85 2.4 0 0.31 6.5 N13-CW07DP 29-Jan-99 6.88 17.2 0.223 0 100 4.9 0.0 I 0.19 8.4 NB-PW408DP 30-Jan-99 5.92 14.3 0.095 0 30 4.6 0.01 0.02 7.3 NOTES: Alkalinily = Alkillinity as cakium carbonate TOC = Total Organic Carbon. dissolvi.xl A = Avcragc value * Includes dissolved and suspended --- - ------------ --- TABLE 3-3 JANUARY 1999 LABORATORY BIOCHEMICAL AND GEOCHEMICAL DATA NORTH BELMONT PCE SITE NORTH BELMONT, NORTH CAROLINA DO Nitrate Ferrous Iron Sulfate HS Methane Carbon Dioxide Red ox Location ID Date Sampled (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (µg/L) (mg/I,) (mV) Top of BedrtKk Aquifer TW-OIGW 28-Jan-99 3.23 8.6J 0.04 2 0 I.SJ 30 46.5 NB-MW04DP 25-Jan-99 7.14 0.9J 0 0 0 l.3U IO 188.5 Nll-Mll'06DP 29-Jan-99 7.14 0.05UJ 0.06 4 0 0.54J 15 196 Nll-Mll'07DP 22-Jan-99 6.01 6.2J 0.01 0 0 l.3U 35 136 Nll-MW09Dl' 21-Jan-99 4.75 1.5 0.01 I (I 23A 35 126 Nll-MWIODP 23-Jan-99 6.39 l.6J 0.02 0 0 l.3U 75 238 Nll-Mll'l2DP 28-Jan-99 NA l.3J 0.03 0 I. IJ 35 NA Nll-MWl3S1-1 20-Jan-99 NA 2.3 0.04 16 0 l.3U 35 205 <.,; Nll-CW08D1' 24-Jan-99 1.98 7.8J (1.01 21 0 l.3IJ 30 197.3 ' Iv Be,lrot·k Aquifer 0 Nll-MW031ll' 25-Jan-99 1.36 4.6J 0 0 0 3400 10 48 NB-MWl4DP 24-Jan-99 5.21 l.4J 0 0 II 0.25J 15 166.J Nil-MW I 51ll' 22-Jan-99 3.5.l 20J 0.63 0 0 l.3J 60 77 NB-MWl71ll' 20-Jan-99 0.65 2.8 0 II 20 0.38AJ 0 -5,1 NB-MW 181ll' 24-Jan-99 2.65 4.6J 0.12 0 0 l.6AJ 15 30.3 Nll-MW21DP I 9-Jan-99 NA 1.7 0.08 18 0 l.3U 20 126 NB-rv1W22DP 21-Jan-99 3.25 7A 0.07 0 0 16 30 84 NB-CW06DP 30-Jan-99 5.15 l.2J 0 0 0 0.42AJ 15 278 NB-CW07DP 29-Jan-99 4.09 -7.2J 0.1 0 l.2J 15 61.7 NB-PW408DP 30-Jan-99 5. 19 3J 0 0 0 l.3U 30 274 NOTES: DO Dissolved oxygen 11S Hydrogen sulfide A A veragc value J Estimated value lJ t\faterial was an.:ilyzi:J for but not detected ------------------- • Monitoring Well 1" = 500' l"'r--250 0 500 -CONc:RET£--._ SUPPLY MW12• --- CDM FEDERAL RAC VIII DISSOLVED OXYGEN TOP OF BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA N FIGURE NO. 3-11 - ---- - - - - - -----·-- - - w ' N N • Monitoring Well , .. = 500' ,-.-.. -250 0 500 -CONCRITE--- SUPP>.Y MW12•. 1.3 --- COM FEDERAL RAC VIII NITRATE ! TOP OF BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA • l )' N FIGURE NO. 3-12 ------------------- w ' N w • Monitoring Well , .. = 500' Pi---c- 250 0 500 CDM FEDERAL RAC VIII FERROUS IRON TOP OF BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA N FIGURE NO. 3-13 ------ - - ----- - - --- - - - LEGEND • Monitoring Well 1" = 500' r---.-250 0 500 COM FEDERAL RAC VIII SULFATE TOP OF BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA N FIGURE NO. 3-14 --------~---------- w ' N V, • Monitoring Well 1" = 500' ,-..-? 250 0 500 ---- ---------------- COM FEDERAL RAC VIII DISSOLVED OXYGEN BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA , l J.' N FIGURE NO. 3-15 ------------------- l,.) ' N °' • Monitoring Well , .. = 500' ,.._..a- 250 0 500 -- MW17 •2.8 --------------·--- COM FEDERAL RAC VIII NITRATE / BEDROCK GROUNDWATER PLUME / NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA N FIGURE NO. 3-16 --- - - --· ----·-- --- - - - w ' N --.J • Monitoring Well 1" = 500' ~--250 0 500 COHCROE ·- SUPPlY --- COM Federal Pro ams Co raUon CDM FEDERAL RAC VIII FERROUS IRON BEDROCK GROUNDWATER PLUME / NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA N FIGURE NO. 3-17 ------------------- l;.) ' N 00 • Monitoring Well 1" = 500' ~-250 0 500 CONCRat ~-- SUPf'LY ~(lil_ -- CDM FEDERAL RAC VIII SULFATE BEDROCK GROUNDWATER PLUME NORTH BELMONT PCE SUPERFUND SITE NORTH BELMONT, NORTH CAROLINA N FIGURE NO. 3-18 I I I I I I I I I I I I I I I I I I I that nitrate is not a significant electron acceptor for this aquifer. The background concentration of ferrous iron [Fe(II)], the metabolic by-product of ferric iron reduction, is non-detect and low throughout the site (less than 0.1 mg/L). Finally, sulfate concentrations at the background location arc non-detect (MW-04) and generally below 5 mg/L, with exceptions at MW-13 (l 6 mg/L) and CW-08 (21 mg/L). Elevated levels of sulfate at MW-13 and CW-08 may be the result of low-level localized sulfate sources, and do not indicate that sulfate is a significant electron acceptor for the top of bedrock aquifer. Methane concentrations are generally below detection limits throughout the site ( ~ 1.5 µg/L ), with the highest methane concentration at MW-09 (23 µg/L ). Low methane concentrations suggest that groundwater is not highly reduced and that methanogenic conditions, which are conducive to the rapid and complete biodegradation of PCE, have not been achieved. Electron acceptor and metabolic by-product concentrations suggest that the groundwater within the top of bedrock aquifer is fairly oxidized. However, the minimal presence of alternate electron acceptors supports the economic and technical feasibility of EAB technologies for this aquifer since only minimal addition of organic compounds (i.e., electron donors) should be necessary to achieve and sustain highly reduced groundwater conditions. Bedrock Aquifer Electron acceptor and metabolic byproduct data suggest that much of the site is oxidized and under aerobic conditions. DO concentrations are highest at the background well (PW-4.08 = 5.2 mg/L) and slightly depleted at downgradient locations. The lowest DO concentration was recorded at MW-17 (0.65 mg/L) and indicates the presence of anaerobic groundwater conditions. All other downgradient monitoring wells have DO concentrations greater than l mg/L, thereby indicating aerobic groundwater conditions. Alternate electron acceptor concentrations within the bedrock aquifer that have the potential to compete with chlorinated solvent biodegradation (i.e., nitrate, ferric iron, and sulfate) are low. Nitrate concentrations at the background location (PW-4.08 = 3 mg/L) and the highest 00-018/3280•071/0510 3-29 I I I I I I I I I I I I I I I I I I I nitrate concentration within the contaminant plume (MW-15 = 20 mg/L) suggest that nitrate is not a significant electron acceptor for this aquifer. The background concentration ofFe(ll) is non-detect and low throughout the site (less than I mg/L). Finally, sulfate concentrations at the background location are non-detect (PW-4.08) and generally below I mg/L, with MW- 21 as an exception (18 mg/L). Elevated levels of sulfate at MW-21 may be the result ofa low-level localized sulfate source and do not indicate that sulfate is a significant electron acceptor for the top of bedrock aquifer. Methane concentrations are generally low throughout the site ( ~ 1.5 µg/L). with the primary exception at MW-03 (3,400 µg/L). The elevated methane concentration at MW-03 indicates highly reduced groundwater conditions at this location (i.e., methanogenic) which are conducive to the rapid and complete biodegradation of PCE, provided a fully dechlorinating microbial culture exists. Similar to the top of bedrock aquifer, electron acceptor and metabolic by-product concentrations suggest that the groundwater within the bedrock aquifer is fairly oxidized. However, the minimal presence of alternate electron acceptors supports the economic and technical feasibility of EAB technologies for this aquifer since only minimal addition of organic compounds (i.e., electron donors) should be necessary to achieve and sustain highly reduced groundwater conditions. 3.2 MICROCOSM STUDY 3.2.1 GENERAL TECHNICAL APPROACH During the January 1999 bioassessment field study, soil and groundwater samples were collected from a PCE-contaminated region of the top of bedrock aquifer and shipped on ice to the laboratory. Upon arrival, site soils and groundwater were used to prepare microcosm test studies, and in some instances, amended with various electron donors (i.e., organic substrates) and nutrients to determine the dechlorination ability of organisms found at the site. The following provides a more detailed description of the microcosm setup, operation, and data interpretation. 00-0 I 8/3280-071/05 JO I .I I I I I I I I I I I I I I I I I I 3.2.2 MATERIALS AND METHODS 3.2.2.1 Microcosm Preparation Microcosms were prepared in an anaerobic glove box containing an atmosphere of 1 to 5% hydrogen in nitrogen. Fifty (50) grams of homogenized soil were weighed out and dispensed into 160 mL serum bottles with Tef1on"'-lined, butyl-rubber septa and aluminum crimp caps (Wheaton 224100-175, autoclaved prior to use for sterilization and to drive off organics that could potentially interfere with the assay). Site groundwater was used during preparation of the microcosms. Groundwater was sparged with nitrogen gas to remove any pre-existing PCE and daughter products-TCE, DCE. and VC. Sparged groundwater was sampled and analyzed for VOCs, dissolved organic carbon (DOC), alkalinity, pH, and DO by methods presented in Table 3-4. Supplemental nutrients were added to the sparged groundwater to achieve final nutrient concentrations equivalent to those presented in Tables 3-5 and 3-6. Tables 3-5 and 3-6 list nutrient solutions and trace metal solutions used in the anaerobic biodegradation studies. Groundwater pH was adjusted to between 6.5 and 7.5 using a phosphate buffer, as necessary. Resazurin, a redox-sensitive color indicator, was added to the groundwater mixture at 0.5 mg/L. Each serum bottle was filled with the prepared groundwater mixture to zero-headspace conditions to prevent partitioning of volatile contaminants into the vapor phase. Microcosms were prepared as described in Table 3-7. Three separate electron donors (lactate. benzoate, and molasses) were tested. These electron donors were selected due to their proven effectiveness in similar anaerobic treatability studies, and their availability in bulk quantities as commodity products (i.e .. cost-effectiveness). Additional electron donors were added as required to reach a final equimolar carbon concentration (2.0 mole carbon/L) for the three various substrates. Sodium lactate (74.7 g/L), sodium benzoate ( 41.2 g/L), and molasses ( 42 mL/L) were added to the prepared groundwater mixture using concentrated aqueous stock solution. 00-0 I S/3280-071,0510 3-31 I I I I I I I I I I I I I I I I I I I I TABLE 3-4 SAMPLING REQUIREMENTS AND ANALYTICAL METHODS NORTH BELMONT PCE SITE NORTH BELMONT, NORTH CAROLINA Analvte I Method/Reference Electron Acceptors/Metabolic Byproducts Dissolved oxygen Dissolved oxygen meter Nitrate/nitrite EPA 353.1 Iron (II) HACH 8146 Sulfate HACH 8051 Methane/ethane/ethene RSKSOP-175 or SW38 IO modified Electron Donors Lactate Benzoate Fennel et al. (1997) Acetate Additional Geochemical Parameters pH pH meter Alkalinity HACH 8221 Dissolved organic carbon EPA 9060 Volatile organic comoounds EPA 8021 or 8260 modified* * See Section 3.2.2 for details on the modified methods. 00-018/3280-07 [105] 0 3-32 I I I I I I I I I I I I I I I I I I I I I KH,PO, KH,PO, NH,CI CaCl,2H,O MgCl,2H,O FeCl,4H,O TABLE 3-5 NUTRIENT STOCK SOLUTION COMPOSITION NORTH BELMONT PCE SITE NORTH BELMONT, NORTH CAROLINA Comeonent I Concentration (g/L) RAMM Solution I (use IO mUL of medium? 27.20 34.80 RAMM Solution 2 (use I(} mUL of medium? 53.50 7.35 10. 15 2.00 Trace Metal Solution (use I mL/L of medium)' Vitamin Solution (use I mL/L of medium)' 1 RAMM = Revised anaerobic minimal medium as per Shelton and Tiedje (I 984). 2 See Table 3-6 00-01 S/3280-071/0510 3-33 I I I I I I I I I I I I I I I I I I I I I TABLE3-6 COMPONENTS OF RST TRACE METAL AND VITAMIN SOLUTIONS NORTH BELMONT PCE SITE NORTH BELMONT, NORTH CAROLINA Comeonent I Concentration RST Trace Metal Solution Nitrilotriacetic acid (adjusted to pH 6.0 with KOH) 2.0 g/L MnSO,H,O 2.0 g/L F e(NH, ),(SO,),6H,O 2.0 g/L CoCI,6H,O 2.0 g/L ZnS0,7H,O 2.0 g/L CuCl,2H,O 2.0 g/L NiCl,6H,0 2.0 g/L Na,Mo0,2H,0 2.0 g/L Na,SeO, 2.0 g/L Na,WO, 2.0 g/L Vitamin Solution Biotin 5.0 mg/L Folic acid 5.0 mg/L Pyridine-HCI 5.0 mg/L Riboflavin 5.0 mg/L Thiamine 5.0 mg/L Nicotinamide 5.0 mg/L Pantothenic acid 5.0 mg/L Cyanocobalamin 5.0 mg/L p-Aminobenzoate 5.0 mg/L Lipoic acid (thiotic acid) 5.0 mg/L 00.0 l 8/J280-071/05 IO 3-34 I I I I I I I I I I I I m 0 I , I I I I I Treatment No. 1-3 4-6 7-9 10-12 13-15 16-18 TABLE 3-7 TREATMENTS USED IN MICROCOSM STUDY NORTH BELMONT PCE SITE NORTH BELMONT, NORTH CAROLINA I Descrietion Unamended Control-Site soil and groundwater only Killed Control-Site soil and groundwater only, autoclaved with mercuric chloride added Positive Control-Lactate, nutrients, site soil and groundwater inoculated with yeast extract or organisms from Moody Air Force Base (if available) Lactate, nutrients. site soil and groundwater Benzoate. nutrients. site soil and groundwater De-sulfured molasses. nutrients. site soil and groundwater I Microcosm controls consisted of site soil and groundwater without the addition of electron donors or nutrients, and were used to determine the extent and rate of dechlorination expected without added organic substrates. Killed microcosm controls consisted of site soil and groundwater, autoclaved twice over a two-day interval, with mercuric chloride added at 500 ppb to inhibit microbial growth. The killed controls are used to determine loss of contaminants due to abiotic processes. The positive microcosm controls consisted of site soil and groundwater, inoculated with yeast extract (200 mg/L final concentration) known to mediate complete PCE dechlorination to ethene and ethane. The positive control can be used to indicate the extent of dechlorination expected if all required microorganisms are present in the soils used in the inoculum. As a final preparation step, all microcosms were spiked with neat, analytical grade PCE using autoclaved. gas-tight micro-syringes (glass) to an approximate concentration of I mg/Land immediately sealed. All microcosms were prepared in triplicate, mixed and allowed to equilibrate. 00-01813180-071. OS 10 3-35 I I I I I I I I I I I D I I I I I I I Microcosms were incubated at ambient temperatures (20 to 25°e) under quiescent conditions. Although such temperatures are likely higher than subsurface field conditions, higher temperatures should accelerate the completion of the microcosm studies. without seriously altering the relative results and overall outcome of the electron donor comparisons. 3.2.2.2 Sampling and Analyses Sampling and analysis were performed as described below. Results are presented in Tables 3-8 and 3-9. Microcosms were sampled regularly (on the same day) to evaluate the effectiveness of each treatment. Microcosms were sampled (February 22, 1999) after a 2-day incubation period (time point "O" zero) to allow for sorption and other processes to reach equilibrium. Additional samples for voes were collected on the days indicated on Table 3-8. Sampling volume was minimized to the extent possible to prevent loss of reactive volume during the long-term testing. Aqueous samples were retrieved by removing the cap and rapidly sampling the liquid. In addition, sample volume removed was replace by adding solvent- cleaned, autoclaved (sterile) glass beads. The beads will normalize volume and minimize headspace in the microcosms which will prevent partitioning of the test contaminant into the vapor phase. voe analyses were performed using a modified version of EPA Method 8260 (as shown in Table 3-4). Modifications to this method were required so that sample extraction volumes could be minimized. Analyses for methane, ethene, and ethane were conducted on a limited basis as determined by visual inspection (i.e., color changes indicated by the presence of Resazurin) and analytical observations (e.g., gas production, and eAH depletion). Methane, ethane, and ethene analyses were performed as indicated on Table 3-9. Analyses for methane, ethene, and ethane were performed using modified versions of SW38 IO to limit sample volume. OO-0\S/3280•07110510 3-36 --------- --- - --- <.,J ' <.,J ___, TABLE 3-8 VOLATILE ORGANIC COMPOUND ANALYSIS FOR THE MICROCOSM STUDY NORTH BELMONT PCE SITE PCE Samr,lc No. (nnb) I 982 2 1028 3 I 102 Unamended Contrnl Avera2c 1037 4 1239 5 1233 6 1347 Killed Control Averae.e 1273 7 1183 8 1373 9 I 190 Positive Control A veraee 1249 10 1261 11 1214 12 1271 Lactic Acid Substrate Averae.e 1249 13 872 14 929 15 1073 Benzoate Substrate Averae.e 958 16 659 17 857 18 8119 Molasses Substrate Averae.e 775 Incubation Days 2 Time Point 0 NOTES: Microcosms prepared on 22-Feb-99. 13: Result not significantly greater than blank ND = Not detected 22-Fcb-99 TCE c-DCE (nnb) (nnb) ND ND ND ND Nil ND Nil Nil ND Nil Nil Nil Nil Nil Nil Nil Nil ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND Nil Nil Nil Nil Nil Nil Nil Nil ND " Significant pressure buildup noted in several of the bottles. NORTH BELMONT NORTH CAROLINA . 9-:-..•tar-99" 22-Mar-99~ VC l'CE TCE c-DCE vc PCE TCE c-DCE (nnb) (nnb) (nnb) (nnb) (nnb) (nnb) (nnb) (nnb) ND I 151 2.32 ND ND 1368 0.835 ND ND 1162 1.37 ND ND 1235 0.795 Nil ND 1120 2.12 ND Nil I 2 I 0 0.733 Nil Nil 1144 1.94 Nil Nil 1271 0. 788 Nil ND 1477 0.673 Nil Nil 1748 0.916 Nil Nil 1096 0.955 Nil Nil 1368 0.770 Nil ND 1259 0.899 Nil Nil 1611 0. 729 Nil ND 1277 0.842 ND ND 1576 0.805 ND ND 1247 0.531 Nil Nil 1867 1.084 Nil ND 1242 0.816 ND ND 1763 0.842 ND ND 1312 0.626 ND ND 1472 0.653 ND ND 1267 0.658 ND ND 1701 0.860 ND ND 1140 0.563 ND ND 1575 0.856 ND ND 1327 0.527 ND ND 1552 0.426 ND ND 1257 0.588 ND ND 1794 0.609 Nil ND 1241 0.559 ND ND 1640 0.630 ND ND 1086 0.478 ND 0.455 1250 0.693 ND ND 1031 0.525 ND 0.496 1092 0.664 ND ND 1221 0.563 ND ND 1156 0.481 ND ND 1113 0.522 ND ND 1166 0.613 ND Nil 1031 2.25 ND 0.870 1356 0. 726 Nil ND 1175 4.18 ND Nil 19118 0. 718 Nil Nil 1144 2.74 Nil ND . 888 · 0.640 I ND ND 1117 3.06 ND ND 1632 0.722 Nil 15 28 13 26 h Sample # I 8 bottle cap popped off on 3/17/99. resulting in the loss of some liquid and an unknown mass of VOCs. Data not used for averaging. vc (nnb) ND ND Nil Nil Nil Nil Nil ND Nil ND ND ND ND ND ND ND 0.263 0.123 0.228 0.193 Nil Nil Nil Nil PCE (nnb) 1259 1055 I 198 1170 1865 1409 1445 1573 1359 1304 1227 1297 1221 1730 1756 1569 1368 967 1371 1235 664 789 503 652 42 40 --- 5-Anr-99'. TCE c-DCE VC (nnb) (nnb) (nnb) 0.9885 ND ND 0 879 ND Nil Nil Nil Nil o.,,23 Nil ND 0.6805 Nil Nil 0.6545 · Nil Nil 0.706 Nil Nil 0.6803 ND Nil 1.586 ND ND 0.871 ND ND ND Nil Nil 0.819 ND ND ND ND ND 0.7055 Nil Nil 0.541 ND Nil 0.416 ND ND 0.383 ND ND ND ND ND 0.5255 ND ND 0.303 Nil Nil Nil Nil Nil Nil Nil Nil Nil Nil Nil Nil ND Nil ' All samples taken from bottles #7 through #18 were depressurized prior to GC injection. Bottles #7, 8, and 9 were later shaken for I hour and reanalyzed with the following results: Sampk No. 7- PCE = 1308, TCE = ND: Sample No. 8-PCE = 1572, TCE = ND; and Sample No. 9-PCE = 1830.5, TCE = ND . .1 All samples depressmized ' Standards tested. I mg/L tested as 0.89 mg/L. I I.Itch Method #8146. 1 Standards tested-JO mg/L, 20 mg/L, 30 mg/L. Test rcsults-14 mg/L, 22 mg/L, 29 mg/L. I latch Method #8051. Jl Standards tested. 0.1 mg/L tested as 0. IO I mg/L. Hatch Method #8507. '' Standards tested. 0.1 mg/L tested as 0.12 mg/L. Hatch Method #8192. - ---- -- -- - ----- L,; ' w 00 TABLE 3-8 (CONTINUED) VOLATILE ORGANIC COMPOUND ANALYSIS FOR THE MICROCOSM STUDY NORTH BELMONT PCE SITE !'CE Sample No. (nnb) I 576 2 517 3 580 Unamended Control Anrae:e 558 4 1064 5 677 6 851 Killed Control AveraPe 864 7 1087 8 675 9 962 Positin Control A vera2e 908 JO 723 I I 803 12 830 Lactic Acid Substrate A veraPe 785 13 893 14 520 15 673 Benzoate Substrate Averaee 695 16 332 17 435 18 262 Molasses Substrate AveraPe 343 Incubation Days 56 Time Point 54 NOTES: Microcosms prcpan:d on 22-Fl:h-99. B= Result nol significantly greater than hlank ND = Not detected 19-Aor-99J TCE c-DCE (nnb) (nnb) 1.49 ND 0.87 ND 0.68 ND I.OJ ND 0.89 ND 0.79 ND 0. 76 ND 0.82 NJJ 1.07 Nil 0.92 Nil 1.80 NIJ 1.26 Nil ND NIJ NIJ NIJ 1.88 NIJ 0.63 ND 0.90 ND 0.72 ND ND ND 0.54 ND ND ND ND ND 2.06 ND 0.69 ND " Significant pressure buildup noted in several of the bottles. NORTH BELMONT NORTH CAROLINA . 19-Mav-99 3-Jun-99 VC PCE TCE c-DCE VC PCE TCE c-DCE (nnh) (nnb) (nnh) (nob) (nob) (nob) (nob) (oob) ND 941 4.04 ND ND 1298 3.25 ND ND 843 0.31 ND ND 1191 ND ND ND 860 0.57 ND ND 1935.8 ND ND ND 881 1.64 ND ND 1475 1.08 ND ND 848 0.90 ND ND 1118 ND ND ND 699 ND ND ND 1001 ND ND ND 836 1.20 ND ND 1112 ND ND ND 794 0.70 NJJ NJJ 1077 NJJ NJJ NIJ I 135 0.'13 ND ND 1538 Nil ND ND 859 2.00 ND Nil 13711 Nil ND ND 1018 0.38 NIJ NIJ 1430 NIJ NIJ Nil 1004 1.10 Nil Nil 1446 Nil ND ND )003 2.68 NIJ NIJ 1292 ND NIJ ND 1220 0.34 NIJ ND 1121 NIJ NIJ NJJ 1202 ND NIJ NIJ 1090 ND NIJ ND 1142 I.OJ ND ND 1168 ND ND ND 908 ND ND ND 705 ND ND ND 1561 ND ND ND 661 ND ND ND 900 ND ND ND 785 ND ND ND 1123 ND Nil Nil 717 ND Nil ND 516 ND ND ND 495 ND NIJ ND 665 ND ND ND 959 ND ND ND 332 ND ND ND 436 ND ND ND 504 ND ND ND 630 ND ND 86 JOI 84 99 h Sample # 18 bottle cap p(ipped off on 3/17/99, resulting in the loss of some liquid and an unknown mass of VOCs. Data not used for averaging. VC (nob) ND ND ND ND ND ND ND NJJ ND ND NIJ ND NIJ ND NJJ ND ND ND ND Nil NIJ ND ND ND --- 12-Anr-00 PCE TCE c-DCE VC (nnh) (nnb) (nnh) (nnb) 68 58 ND ND 364 ND ND ND 827 ND ND ND 420 19 ND ND 115 ND ND ND 102 ND ND ND 281 ND ND Nil 166 NJJ NJJ Nil 315 Nil Nil Nil 208 ND Nil Nil 310 Nil Nil Nil 278 ND Nil Nil 284 ND ND ND 372 ND ND ND 375 NIJ ND ND 344 ND ND Nil 359 34 ND ND 278 ND ND ND 23 ND ND ND 220 11 ND ND 175 . ND ND ND 263 NIJ NIJ ND 151 ND NIJ ND 196 Nil ND ND 413 415 ' All samples taken from bottles #7 through# 18 were deprcssurizcd prior lo GC injection. Bottles #7, 8, and 9 were later shaken for I hour and reanalyzed with the following results: Sample No. 7- PCE = 1308, TCE = ND; Sample No. 8-PCE = 1572, TCE = ND; and Sample No. 9-PCE = 1830.5, TCE == ND . ., All samples deprcssurized ~ Standards tested. I mg/L tested as 0.89 mg/L. Hatch Method #8146. 1 Standards tested-IO mg/L, 20 mg/L, 30 mg/L. Test results-I 4 mg/L. 22 mg/L, 29 mg/L. Hatch Method #8051. 11 Standards tested. 0.1 mg/L tested as 0.101 mg/L. Hatch Method #8507. h Standards tested. 0.1 mg/L tested as 0.12 mg/L. Hatch Method #8192. - ---- ---- -------- - TABLE 3-9 MISCELLANEOUS COMPOUND ANALYSIS FOR THE MICROCOSM STUDY NORTH BELMONT PCE SITE NORTH BELMONT NORTH CAROLINA I 3-Anr-99 7-Jun-99 20-Mav-99 4-Jun-99 8-Jun-99 14-Anr-00 Acetate Benzoate Acetate Bcnzoate Samolc No. (nnm) (nnm) (n•m) (nnm) I 2 3 Unamended Control AveraPe 4 5 6 Killed Control Averai?e 7 8 9 Positive Control Avernee 10 11 12 Lactic Acid Substrate Averave 13 14 15 Benzoate Substrate AveraPe 16 17 18 Molasses Substrate Averaee NOTES: Incubation Days Time Point 150 259 443 284 50 48 Microcosms prep~n:~ on 22-Feb-99. B= Result not s1gmficantl} greater lhan blank ND = Not detected 7802 7461 6011 7091 " Significant pressure 1:mildup noted in several of the hollies. 190 2IO 512 304 l05 l03 I 1596 12404 14244 12748 l\-1cthanc (nnmv) ND ND ND ND 0.49 ND ND o.i6 39.85 ND ND 13.28 4.61 0.80 5.20 3.54 Nil ND ND ND 9.28 0.62 2.97 4.29 87 85 Methane ("0 /L) ND ND ND ND I. I 6E-02 ND ND 3.86E-03 9.43E-0l ND ND 3.14E-01 1.09E-0I J.89E-02 l.23E-0 I 8.37E-02 2.20E-01 J.47E-02 7.03E-02 I.0IE-01 Background = 3.831 ppmv Methane (nnmv) ND ND 7.30 2.43 ND 9.91 ND 3.30 32.87 2.4 I 3.96 13.08 7.99 3.62 7.31 6.31 Nil ND 1.35 0.45 12.05 ND 3.21 5.09 102 l00 Methane (ue/L) ND ND 1.73E-0l 5.76E-02 ND 2.34E-0l ND 7.82E-02 7.78E-0l 5.70E-02 9.37E-02 3.09E-0I l.89E-0l 8.5r,E-02 I. 731'-0 I 1.491:-0 I Nil Nil 3.19E-02 l.06E-02 2.85E-0l ND 7.59E-02 l.20E-01 Background = 3.22 ppmv Fl..'.2+'-' SO/ (me/L) (mP/1.) ND 40 I 10 I 10 0.7 I I ND 0.7 4 5 6 5 5 4 5 4.7 Nil ND ND ND 1900 400 640 980 l06 104 20 10 ND ND 3.3 40 50 50 47 60 40 30 43.3 10 ND 10 6.7 50 140 JOO 96.7 l06 l04 ~ Sample # 18 bottle cap popped off on 3/17/99, resulting in the loss of some liquid and an unknown mass of VOCs. Data no1 used for averaging. Fc2+'· (m<•/1.) ND ND ND ND ND ND ND ND 121 106 116 115 121 81 66 89 JO ND ND 3.4 3606 1051 1379 2012 417 415 SO/ (me/I.) ND ND ND ND ND ND ND ND ND ND ND ND Nil ND ND ND Nil ND ND ND ND ND ND ND 417 415 N-NO{ (me/L) 0.2 1.6 2.2 1.3 0.3 0.4 0.3 0.3 0.6 0.4 0.3 0.4 0.3 0.5 0.4 0.4 0.5 0.8 0.4 0.6 0.8 0.4 0.4 0.5 107 l05 - 14-Acr-00 N-NO,' (me/I.) (1.08 ().()5 0.10 0.IO (1.05 0.20 0.08 0.IO 0.15 0.18 0. 13 0.20 0.18 11.15 0.211 0.20 11.13 0.15 0.13 0.10 0.13 0.05 0.08 0.10 417 415 ' All samples taken from bottles #7 through # 18 were depressurizcd prior to GC injection. Bolllcs #7, 8, and 9 were later shaken tlir I hour and reanalyzed with the following re:;ulh: Sample No. 7- PCE = 1308. TCE = NJ); Sample No. 8-PCE = 1572. TCE = ND; and Sample No. 9-!'CE= 1830.5,-TCE = ND. " All samples depressurized e Standards tested. I mg/L tested as 0.89 mg/L. I latch Method #8146. 1 Standards tested-IO mg/I., 20 mg/L, 30 mg/L. Test rcsults-14 mg/I,, 22 mg/I., 29 mg/L. I latch Method #8051. ~ Standards tested. 0.1 mg/L tested as 0.10 I mg/L. Hatch Method #8507. 1, Standards tested. 0.1 mg/L tested as 0.12 mg/L. !latch Method #8192. - --- -- - -- - ---- TABLE 3-9 (CONTINUED) MISCELLANEOUS COMPOUND ANALYSIS FOR THE MICROCOSM STUDY NORTH BELMONT PCE SITE J 1-Jun-99 N-NO/ Samrlt.: No. (mg/L) I 1.8 2 4.4 3 9.8 Unamended Control Avera!?e 5.3 4 9.7 5 3.7 6 13.6 Killed Control Averae:e J0.7 7 6.7 8 5.4 9 4.6 Positive Control Averai:,e 5.6 JO 8.7 11 8.5 12 9.6 Lactic Acid Substrate Averai;ioe 8.9 13 11.5 14 14.2 15 13.6 Benzoatc Substrate Avera!?e 13.1 16 2.2 17 3.6 18 6.6 Molasses Substrate Ave.-a!?e 4.1 Incubation Days J09 Time Point 107 NOTES: Microcosms prepared on 22-Fch-99. B::: Result not significanlly greater than blank ND "" Not cklcctcd " Significant pn:ssure buildup noted in sever.ii of the bottles. NORTH BELMONT NORTH CAROLINA 14-Aor-00 6-Aor-99 7-Jun-99 2 I-Acr-00 18-Anr-00 N-NO,/' Lactate Lactate ()xygcn Methane (mg/L) (g/L) (e/L) (%) (ncm) 5.2 --6.7 ND 5.5 --11.8 NJ> 6.2 --I 7.5 NIJ 5.6 --12.0 Nil 6.2 --19.5 ND 7.3 --18.5 Nil 7.3 --I 8.3 ND 6.9 18.7 ND 1.0 28.7 25.6 ND 9.8E-0.J 2.1 61.7 16.9 8.6 3.4E-04 1.0 28.3 25.9 ND 7.2E-0.J 1.4 39.6 22.8 2.9 6.8E-04 4.9 26.3 14.5 I I.I 7.6E-05 4.9 30.4 9.6 ND 5.4E-04 3.9 72.4 17.4 ND 6.9E-04 4.6 43.0 13.8 3.7 4.3E-04 ND --2.9 4.1 E-05 NJ> --15.9 8.8E-06 11.5 --18.2 NIJ 0.2 --12.3 J.7E-05 JO --ND I.I E-03 68 --0.2 I. I E-114 36 --23.5 1.9E-04 38 --7.9 4.6E-04 417 43 105 424 421 415 41 J03 422 419 ~ Sample # 18 bottle cap popped off on 3/17/99, resulting in the loss of some liquid and an unknown mass of VOCs. Data not used for averaging. -- - I 8-Anr-00 18-Acr-00 Ethane Ethc111.: (""m) (nrm) ND 2.0E-114 NJ> NJ> NJ> NJ> Nil Nil ND Nil ND ND Nil Nil ND ND Nil 2.7E-0.J Nil 2.3 E-0.J Nil ND NO l.7E-04 ND l.8E-11.J Nil ND ND NJ> ND ND I .5E-114 .1.5E-114 Nil NI> Nil NI> 5.0E-05 l.2E-114 ND 3.SE-114 NIJ 6.6E-11.1 Nil 7.8E-03 Nil 4.9E-03 421 421 419 419 ,. All samples taken from bottles #7 through# 18 were de pressurized prior to GC injection. Bottles #7, 8, and 9 were later shaken for I hour and reanalyzed with the following results: Sam pk No. 7- PCE = 1308, TCE = ND: Sample No. 8-PCE = 1572, TCE = ND; and Sample No. 9-PCE = 1830.5, TCE = ND. " All samples depressurized ·· St:mdards tested. I mg/L ksted as 0.89 mg/L. Hatch Method #8146. 1 Standards tested-IO mg/L, 20 mg/L, 30 mg/L. Test results-14 mg/L. 22 mg/L, 29 mg/L. Hatch Method #8051. 1 Standards tested. 0.1 mg/L tested as 0.101 mg/L. llatch Method #8507. 1' Stand:irds tested. 0.1 mg/I, tcslcd as 0.12 mg/L. I latch Method #8192. - I I I I I I I I I I I I I I I I I I I Intermittent analysis for electron donors was performed using high-performance liquid chromatography (HPLC) methods. These analyses were. required for the three sets of electron donor amended microcosms (lactate. benzoate, and molasses) since depletion rates of the electron donors are unknown and microcosms may become electron donor-limited during the duration of the studies. The frequency of electron donor sampling was based on visual inspection (i.e .. color changes indicated by the presence ofResazurin) and analytical observations (e.g., gas production and CAH depletion). Analyses for lactate and benzoate were measured using HPLC equipped with an ultraviolet detector. Lactate and benzoate analyses were conducted twice for Treatments 7 through 15 (Table 3-7) as indicated on Table 3-9. Analyses for acetate (an indicator of molasses persistence) were conducted by aqueous injection to a gas chromatograph equipped with a flame-ionization detector. Acetate analyses were conducted twice for Treatments 16 and 18 (Table 3-7) as indicated on Table 3-9. Analyses for electron acceptors [ nitrate/nitrite, iron (II), and sulfate] were performed on the days indicated on Table 3-9 using the methods listed on Table 3-4. 3.2.3 DAT A ANALYSES The following text is an analysis of the data presented in Tables 3-8 and 3-9. The results from the 421-day microcosm study suggest little enhancement of PCE reductive dechlorination. In general, average PCE concentrations for each set of microcosm treatments remained stable through day IO I of incubation. ·Although extended incubation of the microcosm studies through day 415 indicated an overall loss in average PCE concentrations, the presence of PCE reductive dechlorination products (e.g., TCE, cis-1,2-DCE, VC, and ethene) was insignificant, suggesting that PCE losses were due to abiotic mechanisms (e.g., sorption and/or volatilization). The relative absence of PCE reductive dechlorination products suggests that EAB technologies are not a viable option for enhancing the total mass reduction of target VOCs in situ. oo.o 18/3280-071/0510 3-41 I I I I I I I I I I I I I I I I I I I Periodic monitoring of amended electron donor compounds (e.g., lactate, benzoate, and molasses) and their intermediate by-products suggests that sufficient electron donor was present to drive reductive dechlorination reactions through day 105, and presumably through the remainder of the study. However. the presence of alternate electron acceptors that compete with CAI-I reductive dechlorination were elevated throughout the study period, in particular ferrous iron (Fe''), and suggest a barrier to complete reductive dechlorination of PCE using EAB technologies. Ferrous iron production results from the biological reduction of ferric iron in the presence of excess electron donor. Ferrous iron concentrations were elevated as high as 3.600 parts per million in treatment vessel #16 (Molasses amendment) and suggest an extremely high concentration ofbioavailable iron that must be overcome prior to achieving complete anaerobic reductive dechlorination of PCE. The ability to overcome such a barrier suggests that EAB technologies are likely not cost-effective for treatment of PCE at the site. It should be noted that high concentrations of bioavailable iron were not evident from previous field investigations, presumably due to low natural electron donor availability as indicated by total organic carbon concentrations ( < IO mg/L) recorded during the January 1999 groundwater sampling event. Consideration of future remedial technologies at the site should take into account this availability ofbioavailable iron in their feasibility analyses. 00--018/3280-071105 I0 3-42 I I I I I I I I I I I I I I I I I I I 4.0 CONCLUSIONS 4.1 ENHANCED ANAEROBIC BIOREMEDIATION FEASIBILITY Based on evaluations of field and laboratory data collected to date and discussed above, enhancement of intrinsic biodegradation processes is not a feasible technology for remediation of chlorinated solvent contaminated groundwater at the site. The presence of PCE and its anaerobic biodegradation daughter products (TCE and 1,2-DCE) at numerous wells \\'ithin both the top of bedrock and bedrock aquifers provided evidence of active reductive dechlorination reactions. However. a complete anaerobic reductive dechlorination pathway of PCE to TCE, 1,2-DCE, VC and ultimately innocuous ethene was not evident from the microcosm study, as the latter two constituents were not detected. Several potential . reasons for the lack ofVC and ethene detection have been presented in Section 3.2.3. Groundwater redox conditions, as defined by the distribution of electron acceptors and metabolic by-products, suggest that the top of bedrock and bedrock aquifers are aerobic and fairly oxidized. Such conditions are not conducive to the ~eductive dechlorination of PCE to TCE and 1,2-DCE. The presence of TCE and 1,2-DCE, which are both anaerobic reductive dechlorination products of PCE, suggests that discrete zones within both aquifers may exist in which groundwater conditions are highly reduced. These discrete zones may be present on a micro-scale (e.g., soil grains) or on a macro-scale (e.g., lithologic zones within a well screen or open borehole). In the latter case, severe concentration well averaging, resulting from monitoring wells with large screened intervals or. open boreholes, may be mixing groundwaters from various redox zones, thereby masking the presence of highly reduced groundwater zones necessary to achieve PCE dechlorination. Evidence supporting well averaging of various redox zones is apparent at wells in which ferrous iron or methane were detected with DO concentrations greater than 1 mg/L ( e.g., MW-03, MW-5) since ferrous iron is rapidly oxidized to an iron oxide under aerobic conditions while methane is a rapidly consumed substrate. 00-01 s,nso-o; 1,os 10 4-1 I I I I I I I I I I I I I I I I I I I In summary, current data suggest that EAB is not a feasible technology for treatment of contaminated groundwater at the site. The results of the laboratory microcosm study suppons this conclusion. 4.2 FULL SCALE EVALUATION As discussed in Section 4.1, this technology is not recommended for the site. Therefore, a full-scale evaluation of the technology and a sensitivity analysis identifying the key parameters affecting full-scale operations was not performed. 00-0 t 813280-071105 !O 4-2 I I I I I I I I I I I I I I I I I I I 5.0 REFERENCES North Belmont PCE Site. North Belmont Gaston County, North Carolina: Record of Decision (ROD) (EPA. 1997a). North Belmont PCE Site. North Belmont. Gaston County. North Carolina: Remedial Investigation Report (EPA, 1997b ). Data Acquisitions Report/or the North Belmont PCE Site. North Belmont. North Carolina (EPA, 1998a). Final Treatahility Study Work Plan/or the North Belmont PCE Site. North Belmont. North Carolina (EPA, 1998b ). Draji Conceptual Design Report for the North Belmont PCE Site. North Belmont. North Carolina (EPA, 1999). 00-01813280-071/05 ]0 5-1