United States Environmental Protection Agency

Office of Research and Development Washington DC 20460

EPA/600/R-99/095a September 1999

An In Situ Permeable Reactive Barrier for the Treatment of Hexavalent Chromium and Trichloroethylene in Ground Water:
Volume 1 Design and Installation

EPA/600/R-99/095a September 1999

An In Situ Permeable Reactive Barrier for the Treatment of Hexavalent Chromium and Trichloroethylene in Ground Water: Volume 1 Design and Installation
David W. Blowes1 Robert W. Gillham1 Carol J. Ptacek1 Robert W. Puls2 Timothy A. Bennett1 Stephanie F. O’Hannesin1 Christine J. Hanton-Fong1 Jeffrey G. Bain1
1

Department of Earth Sciences University of Waterloo Waterloo, Ontario, Canada

2

Subsurface Protection and Remediation Division National Risk Management Research Laboratory U.S. Environmental Protection Agency Ada, OK 74820

Cooperative Agreement No. CR-823017

Project Officer Robert W. Puls Subsurface Protection and Remediation Division National Risk Management Research Laboratory Ada, OK 74820 National Risk Management Research Laboratory Office of Research and Development U.S. Environmental Protection Agency Cincinnati, OH 45268

Notice

The U.S. Environmental Protection Agency through its Office of Research and Development partially funded and collaborated in the research described here under Cooperative Agreement No. CR 823017 to the University of Waterloo. It has been subjected to the Agency's peer and administrative review and has been approved for publication as an EPA document. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. All research projects making conclusions or recommendations based on environmentally related measurements and funded by the Environmental Protection Agency are required to participate in the Agency Quality Assurance Program. This project was conducted under an approved Quality Assurance Project Plan. The procedures specified in this plan were used without exception. Information on the plan and documentation of the quality assurance acitivities and results are available from the Principal Investigator.

ii

and prevention and control of indoor air pollution.Foreword The U. state and federal regulators. Clinton W. There currently is no other site which has used this innovative technology and reported on its performance to the extent detailed in this report. typically under natural gradient.” The goal of such installations is to eliminate the possibility that a contaminant plume can move toward and endanger sensitive receptors such as drinking water wells or discharge into surface waters. Under a mandate of national environmental laws. Environmental scientists are generally familiar with the concept of barriers for restricting the movement of contaminant plumes in ground water. or sheet pilings to form a subsurface “wall. cost-effective environmental technologies. air. The focus of the Laboratory’s research program is on methods for the prevention and control of pollution to air. understand how pollutants affect our health. It was also the first full-scale installation of this technology to use a trencher to install a continuous reactive wall to intercept a contaminant plume. and subsurface resources. Permeable reactive barrier walls reverse this concept of subsurface barriers. land. The information will be of use to stakeholders such as implementors. To meet these mandates. slurries. The National Risk Management Research Laboratory (NRMRL) is the Agency’s center for investigation of technological and management approaches for reducing risks from threats to human health and the environment. remediation of contaminated sites and ground water. Native American tribes. contractors. and provide technical support and information transfer to ensure effective implementation of environmental regulations and strategies. Rather than serving to constrain plume migration. Environmental Protection Agency is charged by Congress with protecting the Nation’s land. installation and performance monitoring data on a full-scale PRB application which successfully remediated a mixed waste (chromate and chlorinated organic compounds) ground-water plume. EPA’s research program is providing data and technical support for solving environmental problems today and building a science knowledge base necessary to manage our ecological resources wisely. and prevent or reduce environmental risks in the future. remedial technology. consultants. water. Such barriers are typically constructed of highly impermeable emplacements of materials such as grouts. Hall. Director Subsurface Protection and Remediation Division National Risk Management Research Laboratory . and all other interested parties. permeable reactive barriers (PRB’s) are designed as preferential conduits for the contaminated groundwater flow. The goal of this research effort is to catalyze development and implementation of innovative. the Agency strives to formulate and implement actions leading to a compatible balance between human activities and the ability of natural systems to support and nurture life. passive. The purpose of this document is to provide detailed design.S. and water resources. It is hoped that this will prove to be a very valuable technical resource for all parties with interest in the implementation of this innovative. develop scientific and engineering information needed by EPA to support regulatory and policy decisions. A permeable reactive subsurface barrier is an emplacement of reactive materials where a contaminant plume must move through it as it flows. and treated water exits on the other side. protection of water quality in public water systems.

and cost. North Carolina. rather than Cr(VI) reduction because Cr(VI) reaction rates are significantly faster. The reactive medium was selected from various mixtures on the basis of reaction rates with Cr(VI). 7. The wall was installed in approximately 6 hours using a continuous trenching technique.6 m wide continuous reactive wall.3 m deep. in addition to treating portions of a larger overlapping trichloroethylene (TCE) ground-water plume which has not yet been fully characterized.3 m deep and 0. in June 1996. Coast Guard anticipates that using this reactive barrier will result in a saving of $4 million U. The continuous wall configuration was chosen over a Funnel-and-Gate configuration. hydraulic conductivity. Simulations of contaminant transport within the granular iron wall indicate that 10. The reactive wall was designed to remediate hexavalent chromium [Cr(VI)] contaminated ground water at the site. based on three-dimensional computer simulations of ground-water flow and contaminant transport. initial cost comparisons suggested that a reactive wall would have a lower material and installation cost than a Funnel-andGate.S. iv . within 0. 70. including site assessment.3 m of travel through the wall under the maximum flow velocities expected at the site. soil treatment and follow-up. was approximately $985. which simultaneously removed aquifer sediments and installed the porous reactive medium. TCE and degradation products.S. 7.6 m wide permeable subsurface reactive wall was installed at the U. and 2 µg/L respectively. with an average grain size (d50) of 0.000 µg/L TCE. compared to a pump-and-treat system.4 mm. installation. For this site. Coast Guard (USCG) Support Center. The U. The simulations indicated that both configurations could be designed to achieve the same capture areas and residence times with the same volume of reactive material./ linear meter for a 46 m long. However.S. The minimum required width of the granular iron wall was determined from simulations of TCE decay within the barrier. the installation and material cost was approximately $7550 U. porosity. 900 µg/L cis-dichloroethylene (cDCE) and 101 µg/L vinyl chloride (VC) are reduced to less than maximum contaminant level (MCL) values of 5. near Elizabeth City.Abstract A 46 m long. and cost.S.S. in operation and maintenance costs over a 20 year period. reactive barrier design. and 0. The reactive medium was composed entirely of granular iron. The total project cost.000 U.

....................................................................Table of Contents Abstract ..................................................... 6 Analytical Procedures ............................... 5 Aquifer Materials ....... 3 Remediation Strategy .......................................................................................................................................... 13 Cations and Anions ................................................................ 7 Geochemical Modeling ................................................................... 5 Laboratory Batch Tests ........................................................................................................................... 5 Laboratory Column Tests ................................................................12 Inorganic Results ................................................ 2 Conceptual Model of Plume Development ........................................................................................................................................................................................ 5 Materials ............................................................................................. 2 Site History ............... 5 Ground Water ......................................................................................................................................................... 13 v ..... 8 Boundary Conditions ............................................................................................................................... 1 Background ........................................................... 7 Flow and Reactive-Transport Modeling ............................................................................10 Batch Results ................................................ viii List of Appendices ..................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................... x Introduction ................................................ 13 Chromium ................................................................................................. 10 Organic .....................10 Column Results ......................................................................................................................... 7 Model Description ...................................................................................................................................................... 8 Reactive Barrier Configurations .............................................................................................................................. 5 Methodology ............................................................................................................................................................................ 10 Inorganic ..................................................................................... 6 Inorganic Analysis .........................................................................................................................................................................................................................................................................................................................................10 Column and Batch Tests ....................... v List of Tables ..................... 8 Hydraulic Parameters ........................................................................................................................ 5 Introduction ................................................................................................................................................................ vii List of Figures .............................................................................................................................. 6 Organic Anlysis ..................................................................... 9 Results and Discussion ........................................................................................................................................... 8 Reactive-Transport Parameters ........................................................................................................................................... 12 Low Flow Velocity Tests ..... 11 High Flow Velocity Tests ...................................................................................................................................................................................................................................................................................................................................................... iv Table of Contents .................................................................................................................................................................................................................................................................................................................... 2 Geologic Setting ............................................................................................................................ 5 Zero Valent Iron ...............................................10 Geochemical Modeling – Inorganic Data .... 7 Model Limits and Grid ................ 11 Organic .......................................................................... 3 Design Methodology ...........................................................

..................................................................................................................................................................................................Eh............................................................................. 19 Conclusions ... 18 Configuration ............................... 20 References ...................................16 Final Selection of a Reactive Barrier .... 17 Barrier Installation ................................................................................................................................................................................................................. 13 Geochemical Modeling ........................................................................................ 18 Barrier Costs and Performance .................................................................................................................................................................................................. 17 Final Reactive Barrier Design .............................18 Site Preparation ........... 15 Reactive Barrier Designs ........................................................................................ 15 Determination of Reaction Parameters: Halogenated Hydrocarbons ...................................................................... 18 Post-Installation Work ................ pH and Alkalinity ..................................................................................................... 18 Installation ........................................................................................................................................................................................................................................................13 Determination of Reaction Parameters: Cr(VI) ............................................................................................ 21 vi .......

...................................... Table 8... Table 18........................................................... Three Reaction Vials and One Control Vial Were Sampled at Each Time...... 1996) ..)............... 26 Reactive Mixtures Used in Batch Experiments .................. Table 16.. .................30 Inorganic Concentrations of All Columns for Both Influent and Effluent Samples at Steady State Conditions.............. Horizontal Hydraulic Gradients and Water Levels Observed in Monitoring Wells Screened Between 3 and 4....27 Method Detection Limits (MDL) ... Source Concentrations............ Table 12. 29 Summary of Cr Removal in Batch Tests . Table 2...... Comm. Table 14..... Table 3........................................S.................. Table 7......... ............................................32 Ground-water Velocities and Residence Times within the Reactive Material Zones of the Funnel-and-Gate and the Continuous Wall......................... 32 Capture Areas for the Funnel-and-Gate Under Varying Aquifer Hydraulic Conductivity Conditions..... .... 31 First Order Rate Constants in Various Reactive Iron Mixtures (Rate Constants Not Normalized to Surface Area)................................................. Table 17............................ 31 Hydraulic Properties and First-order Rate Constants for Peerless and Master Builders Granular Iron.. Table 11.................. Predicted Breakthrough Volumes Calculated from These Data Are Shown............... Table 13.................. ...................................................... DCE Isomers........................ and VC (after Johnson et al.. Table 5..... Table 4.....................................34 vii .............................. 33 Reactive-transport Parameters. for Reaction and Control Vials.. 1995) ... .. 28 Changes in TCE Concentration in Batch Experiments Over Time......... 26 Reactive Mixtures Used in Column Experiments .... . Table 9....32 Capture Areas for the Continuous Wall Configuration Under Varying Aquifer Hydraulic Conductivity Conditions.. ........ Table 15......5 m Below Ground Surface ..................................... .................................................................31 Hydraulic Conductivity Values Used in Ground-water Flow Simulations to Compare Relative Capture Areas and Residence Times of Two Barrier Designs... 26 First-order Rate Constants for the Dehalogenation of TCE.................................. Table 19........................................................ Table 6............................. Table 10.......33 Hydraulic Parameters (Source of Values Indicated in Brackets) Used in Ground-water Flow Modeling to Determine Minimum Barrier Dimensions... 30 First Detection of Cr at the 2.. 33 Barrier Installation Project Costs in U...........5 cm Sample Port in Each Column......................... ...$ (Jim Vardy.............. Pers..................List of Tables Table 1...........................26 Column Flow Velocities and Hydraulic Properties of Reactive Mixtures Used (after O’Hannesin et al................ and Minimum Distance within Reactive Barrier before Contaminant Falls Below MCL... ........................................................................... ...................... ..... Only TCE Was Analyzed..............................

.............................. 48 Figure 21........................... river sampling....................... time in each of the four batch test mixtures .......................37 Figure 5.... ML21.....................................................List of Figures Figure 1.............. Model domain dimensions...................... 41 Figure 13.... and (b) cross-section A-A’ indicating total chromium concentrations (mg/L)........... and deep wells (after Parsons Engineering Science... 38 Figure 7........42 Figure 14...........) ...........39 Figure 9... 39 Figure 8............... and (B) permeable wall configurations used in flow simulations [all dimensions in meters] .......................41 Figure 12......... Plan view map showing approximate locations of temporary wells............ 47 Figure 20............... Schematic of the apparatus used in the column experiments . cone penetrometer tests......... and (b) cross-section A-A’ indicating TCE concentrations (µg/L)................l....................... 40 Figure 10....... 49 Figure 22............. Plan view map showing TCE concentrations (µg/L). (A) Funnel-and-Gate....... Elizabeth City. TCE concentration versus time in each of the four batch test mixtures ................ 46 Figure 19................ (a) Cross-section B-B’.............. Cr concentration profiles (mg/L) at multilevel samplers in the approximate locations of piezometer bundles ML11...........................S...................................................... 1994) .s...........a................................... 36 Figure 2............................ 1997) ................................. calculated with MINTEQA2 ......... with Funnel-and-Gate barrier shown (all dimensions in m) .....00 mg/L contours in June 1994 ....................... and (b) hydrogenolysis reaction steps in degradation of TCE (after Arnold and Roberts.. and inferred 5 and 100 µg/L contours ............... 51 viii ................... TCE concentration profiles (mg/L) at multilevel samplers in the approximate locations of piezometer bundles ML11. Geologic cross-section B-B’ extrapolated from cone penetrometer test data ....... Mineral saturation indices for batch tests.... Cr(VI) concentration vs......05 and 1 mg/L contours . versus time.............45 Figure 18..............40 Figure 11............... ML21......... TCE concentration versus distance along all six columns at the first flow velocity (FV1)........... and ML31..... Water levels in wells screened 3 to 4...........05 mg/L and 1....................................... 37 Figure 4........... Conceptual model diagram ..............5 m below ground surface (ft....... upgradient of proposed Reactive Barrier (April 1996) ................ 44 Figure 16.......... approximately 61 cm/day (2 ft/day)................45 Figure 17..... Geologic cross-section A-A’ extrapolated from cone penetrometer test data ................................. Location map showing U...... Cross-sections extrapolated from borehole log data .......................... North Carolina ........................ upgradient of proposed Reactive Barrier (April 1996) ................. ... Batch test inorganic geochemistry for all mixtures........ Coast Guard Support Center...................... and inferred 0.............................................................. with Funnel-and-Gate barrier shown ................................50 Figure 23................................................ and inferred 5 µg/L and 100 µg/L contours in June 1994 .............. and inferred 0............ Model boundary conditions........................ (a) Reductive β-elimination..................... (a) Cross-section B-B’................... 36 Figure 3.................. and ML31........ Plan view map showing total Cr concentrations (mg/L)........38 Figure 6.................... 43 Figure 15...............

................72 Figure 51...... 51 Figure 25.................... 67 Figure 44.... 71 Figure 50.......................................5 cm sample port........... ........ .... TCM concentration versus distance along three columns at the second flow velocity (FV2).... Inorganic results for column 100PL at FV1 and FV2.. 52 Figure 26.. approximately 61 cm/day (2 ft/day).. Vertical ground-water flow divergence around a Funnel-and-Gate .. ..... approximately 61 cm/day (2 ft/day).. 73 Figure 53................................................. approximately 30 cm/day (1 ft/day)............................ ... Mineral saturation indices for column 50PLSSAQ at FV1 and FV2..........................................65 Figure 42............................................ ................................. .................. cDCE. 76 ix ........................ Mineral saturation indices for column 100MB at FV1 and FV2. 57 Figure 34........................... Picture showing collapse of concrete ..................... cDCE concentration versus distance along three columns at the second flow velocity (FV2)................. Experimental and calculated VC concentration profiles in column ...... 60 Figure 37....... and (B) Capture area ........................ 66 Figure 43........... 68 Figure 45....Figure 24............. 54 Figure 30.... 75 Figure 56.. TCE concentration versus distance along three columns at the second flow velocity (FV2)......... ........................................ Ground-water flow divergence around a continuous wall ...................... Predicted TCE........... approximately 61 cm/day (2 ft/day)........ Picture showing erosion control measures during installation ................................................................... Mineral saturation indices for column 100PL at FV1 and FV2........... ................ Cr detection at the 2............ approximately 30 cm/day (1 ft/day)... 52 Figure 27..... and VC concentration profiles through the iron-filings wall ................. TCM concentration versus distance along all six columns at the first flow velocity (FV1).......... .......................... Experimental and calculated cDCE concentration profiles in column ............. Picture showing excavated aquifer sediments forming a soil slurry .......... 71 Figure 49.... Mineral saturation indices for column 48PL/52AQ at 78. VC concentration versus distance along all six columns at the first flow velocity (FV1).......................................... ...... 58 Figure 35.......... 74 Figure 54..... (a) Plan view. ......... 61 Figure 38.......72 Figure 52................... approximately 30 cm/day (1 ft/day).................... 75 Figure 57...................59 Figure 36. . ........................... ............ ....... Mineral saturation indices for column 50MBSS at FV1.... VC concentration versus distance along three columns at the second flow velocity (FV2).... (A) Ground-water flow divergence in vicinity of a Funnel-and-Gate............... approximately 30 cm/day (1 ft/day)......... 53 Figure 28. Horizontal ground-water flow divergence around a Funnel-and-Gate ....... Picture showing trenching machine ........ Experimental and calculated TCE concentration profiles in column ............... 62 Figure 39............................................... 74 Figure 55....... Inorganic results for column 50MBSS at FV1.............................................................. 63 Figure 40................. ..........4 PV and FV1.... 53 Figure 29............ 64 Figure 41.......................................... 54 Figure 31..... and (b) cross-sectional view of reactive barrier ............... 55 Figure 32............56 Figure 33............................................ Inorganic results for column 50MBSSAQ at FV1..................... 70 Figure 48.............. Picture showing storage of granular iron at the site ................ .............. Inorganic results for column 100MB at FV1 and FV2.. Inorganic results for column 48PL/52AQ at FV1...............69 Figure 47.... ................................................. ......................................................... cDCE concentration versus distance along all six columns at the first flow velocity (FV1)....... Mineral saturation indices for column 50MBSSAQ at FV1................... Inorganic results for column 50PLSSAQ at FV1 and FV2............................. 68 Figure 46........... ..

......................................... 84 Appendix E: Batch test mineral saturation indices ...................................................................................................................................................................................................................... 103 Appendix H: Reactive column mineral saturation indices ....List of Appendices Appendix A: Grain size distribution curves ............... 79 Appendix B: Elemental and TCLP analyses ............................................................................... 85 Appendix F: Reactive column organic data .................................................................................86 Appendix G: Reactive column inorganic data ................................. 82 Appendix D: Batch test inorganic data .............................................................................. 111 x ..................................................................... 80 Appendix C: Bromide tracer test data (lab columns) . 107 Appendix I: Analytical laboratory procedures ....................................................................................

S. hydraulic properties and cost of these mixtures were included in the selection criteria. 1994). 1992). 1992. similar to those observed at the site. 1989). Gillham and Burris. follow-up soil treatment. 1997). 1993. and discharge to the Pasquotank River which borders the northern extent of the USCG Support Center. Elizabeth City. Inherent in the pump-and-treat method are several disadvantages such as: long treatment times. 1993. Laboratory batch and column tests were conducted using materials from the USCG Elizabeth City site to determine the granular iron mixture which would be the best suited for simultaneously treating Cr(VI) and TCE contaminated ground water. Ground-water contaminant concentrations can be reduced to less than MCL values with this method. contains hexavalent chromium [Cr(VI)] and trichloroethylene (TCE) derived from historical electroplating and degreasing operations.. composed of granular iron.05 mg/L for Cr and 5 µg/L for TCE. large volumes of ground water to treat and discharge. Gillham and O’Hannesin.394 and 5. A patent held by the University of Waterloo covers the in situ removal of dissolved halogenated organic contaminants from water using zero valent iron installed in the pathway of the contaminated ground water (U. One alternative remediation technique that avoids the limitations of pump-and-treat is the use of passive in situ reactive barriers (McMurty and Elton. 1995. Previous laboratory and field studies indicated that reactive mixtures composed of granular iron can successfully remediate ground water contaminated with Cr(VI) (Blowes and Ptacek. These barriers are installed in the subsurface. (1995) describe a variety of contaminants which can be treated using subsurface permeable reactive walls. O’Hannesin. 1997) and TCE (O’Hannesin and Gillham. and loss of land-use. Peerless granular iron was selected for the reactive barrier. Patents held by the University of Waterloo cover the removal of dissolved metals from ground water through the in situ precipitation of harmless. and alternative remediation methods (Mackay et al. Parsons Engineering Science. The barriers do not require on-going maintenance or energy input.Introduction Ground water at the U. 1992. allowing continued use of the land. insoluble reduced metal phases in a permeable reactive mixture placed in the path of the contaminated ground water (U. 1985. Blowes and Ptacek. Patents 5. Coast Guard Support Center. but experience has shown that contaminant source zones can persist for very long time periods due to mass transfer limitations (Mackay and Cherry. In situ reactive barriers are composed of a permeable reactive material that passively removes contaminants from flowing ground water.514. The traditional method to remediate contaminated ground water is often a variant of a pump-and-treat system. 1996).S. These concentrations exceed the maximum contaminant level (MCL) values of 0. Blowes et al. The limitations and disadvantages of the pump-and-treat method have prompted questions regarding remediation goals. the reactive wall must be large enough that the entire groundwater plume passes through it.213). 1992. A passive in situ barrier. Patent 5. to less than MCL values.000 µg/L TCE. and above ground treatment and disposal of ground water is not required. 1993). using the selected reactive material and barrier configuration are described. Gillham and O’Hannesin. 1994. Blowes et al.. (Puls et al. Simulations of contaminant transport through the reactive barrier under the maximum flow conditions expected at the USCG site were conducted to determine the minimum barrier thickness required to remediate contaminant concentrations. Puls et al. Site investigations conducted since 1991 have shown maximum ground-water concentrations of greater than 10 mg/L Cr and 19. was proposed as an innovative ground-water remediation technology to treat both dissolved Cr(VI) and TCE in ground water at the USCG Support Center.. operation and maintenance costs. An alternative reactive barrier design is the Funnel-and-Gate (Starr and Cherry. 1 . 1997).. Focht et al.266. The Cr and TCE ground-water plumes overlap. trenching installation.. NC (Figure 1).279). 1994. The reaction rates. Three-dimensional ground-water flow simulations were conducted to assess the relative efficiency of a Funnel-and-Gate versus a continuous wall (Bennett. These systems pump both contaminated and uncontaminated ground water to an above-ground treatment facility where large volumes of ground water are treated and discharged. The site preparation. The Funnel-and-Gate barrier utilizes cutoff walls to focus or funnel ground-water flow through a smaller in situ reactive material zone.362.S. 1995. and overall project costs. 1992. In order to successfully remediate a plume.

1993) (Figure 9) indicate that the surficial aquifer is complex and heterogeneous. 1995). TCE was detected in ground-water samples collected during the Cr(VI) delineation program.500 mg/kg Cr. A subsequent site investigation indicated that a plume of ground water containing Cr(VI) in excess of the MCL value extended from the electroplating shop. 1994. 1993). the general ground-water flow field downgradient of the plating shop varied in direction from approximately N30° W to N10° E (Figure 12). Sampling results from a monitoring network of more than 40 wells indicated that the Cr(VI) plume was approximately 35 meters wide.5 m (Figure 5). Multilevel sampling wells installed in the vicinity of the proposed reactive barrier similarly indicate that the TCE is heterogeneously distributed with depth (Figure 8). TCE concentrations that exceed MCL were detected in temporary wells installed near the riverbank (T1. The full vertical extent of the TCE has yet to be determined. Ground-water velocities of 0.6 m below ground surface.18 m/day were measured in this test. Water levels measured in the monitoring wells fluctuate between approximately 1. Hydraulic conductivity values calculated from these tests vary from 0. defined by the MCL value of 0.3 m to more than 3 m (Figures 10 and 11).5 and 2. Multilevel sampling wells installed in the vicinity of the proposed reactive barrier similarly indicated that the Cr(VI) plume predominates between depths of 4. Elizabeth City. 1993). and is larger in lateral extent (Figure 6). R12. as the plume nears the Pasquotank River (Figure 4). and east of the apparent source area (Parsons Engineering Science. T4.400 µg/L observed in T1. R21. Dennis and Such. 1993. 2 . The TCE plume overlaps the Cr(VI) plume.05 mg/L. where fill sands have been added.13 m/day and 0. The aquifer is underlain at approximately 18 meters depth by dense clay of the Yorktown Confining Unit. screened between 12 m and 15 m below ground surface. Very low Cr(VI) concentrations were detected in two deep wells. In 1991.0011 and 0. R22) indicating that the TCE plume impacts the river. with the highest concentrations of 2. T6). and concentrations greater than MCL exist at 9.5 m long.5 and greater than 7.5 and 6. Sediments beneath the plating shop floor were found to contain up to 14. The bottom fringe of the plume. Geologic Setting The contaminated surficial aquifer at the USCG site consists of Atlantic coastal plain sediments. Coast Guard Support Center. and extended 65 meters from the hangar to the river. Cone penetrometer tests also indicate that the surficial aquifer is very heterogeneous with fine sands interfingered with silty clay lenses. but TCE concentrations of up to 580 µg/L have been observed in wells at 12 m depth below ground surface (Parsons Engineering Science.1 m/day to 4.38. Borehole log data (Parsons Engineering Science. The CPT ground-water samples indicate that the core of the Cr plume exists between approximately 4. Groundwater samples taken during cone penetrometer testing indicate that a TCE plume exists between 4. composed of varying amounts of fine sands and silty clays. The plating shop was in operation for 30 years.8 m/day (Parsons Engineering Science. The plume also extends to the west. TCE concentrations which exceed the MCL and approach 8 µg/L were also observed in river water samples (R2. The contaminated sediments were removed at that time. where higher concentrations.S.9 m depth below ground surface was conducted by Puls et al. the upper 2 m of the aquifer are sandy silty clays which pinch out toward the north. The maximum observed Cr(VI) concentration exceeds 10 mg/L (Puls et al. The thickness of these lenses varies from 0. T5. Fine sands. has been the focus of numerous studies since the discovery of a leak of acidic chromium solution beneath a former electroplating shop in 1988. The extent of the TCE in the ground water has not been completely delineated to the west. extends to a depth of approximately 7 m. Water level measurements indicate that the ground-water flows northwards toward the Pasquotank River (Figure 11). The source of the TCE is speculated to be an existing sewer manhole located adjacent to the electroplating shop (Parsons Engineering Science.Background Site History The U. with varying amounts of silt and clay. south. these velocities correspond to an average hydraulic conductivity of approximately 26 m/day. A series of water samples was taken from cone penetrometer test(CPT) locations (Figure 3). In five monitoring events over a three year period. NC. toward the Pasquotank River (Figure 2) (Parsons Engineering Science. In general. The TCE may be associated with the historical plating operations in Hangar 79. A multiple borehole tracer test in wells screened between 3. (1995). 1994).. 2. toward the Pasquotank River.0033 (Table 1). 1972).1 m depth (Figure 7).9 to 5. prior to its closure in 1984. MW21 and MW22.05 cm diameter screened intervals between 3 m and 6 m below ground surface. 1993).1 m below ground surface.1 m below ground surface. Slug tests were conducted on monitoring wells with 1.200 µg/L. and silty clay lenses form the lower portion of the shallow aquifer. Assuming an average gradient of 0. The calculated average horizontal hydraulic gradient varies between 0. The highest TCE concentration reported in sampling events since 1991 was 19.5 6. 1971.0023 and a porosity of 0. R11. T3. as TCE is commonly used to degrease parts prior to chrome plating (Greenwood. in Hangar 79. 1993). T2.

Conceptual Model of Plume Development
The chromium plume exists in the ground water as a result of leakage from a chromic acid tank located in an old plating shop in Hangar 79. The dissolved Cr(VI) water moves with the ground water. The general ground-water flow direction varies between N30°W and N10°E, and the aqueous chromium plume extends northward toward the Pasquotank River. The chromium plume is predominantly located in the silty-clayey fine sand unit, which underlies the surficial clay, because hydraulic conductivities and thus ground-water velocities are the highest within this sandy unit (Figure 13a). TCE exists in the ground water as a result of the release of pure-phase TCE into the subsurface. TCE is a dense nonaqueous phase liquid (DNAPL) that is relatively immiscible with water, and has a relatively low solubility of 1,100 mg/L (Pankow and Cherry, 1996). Once released into the subsurface, pure-phase TCE migrates downward as a result of its higher density than water. TCE will pond and spread laterally on lenses where small-scale variations in entry pressure exist, due to differences in grain size or clay content. The sensitivity of TCE migration to fine scale structure of sands has been previously documented (Poulsen and Kueper, 1992; Pankow and Cherry, 1996). Ponded TCE zones can form multiple sources, and can be extremely difficult to delineate due to the random migration pathways which result from its density and immiscibility. Aqueous TCE plumes which extend from residual source zones will flow with the ground water. Dissolved TCE concentrations within these plumes can be orders of magnitude greater than the MCL value of 5 µg/L. The larger lateral extent of the TCE plume probably arises from the spreading and ponding of TCE, or possibly from multiple release locations. The presence of TCE at depths of greater than 12 m most likely results from the downward migration of purephase TCE due to its higher density (Figure 13b).

Remediation Strategy
Hexavalent chromium [Cr(VI)] is the oxidized valence state of chromium, and is a strong oxidant. The reduction of Cr(VI) to the less soluble and therefore less mobile Cr(III) valence state by a variety of reductants is thermodynamically favorable and kinetically rapid (Schroeder and Lee, 1975; Hem, 1977; Eary and Rai, 1988; Palmer and Wittbrodt, 1991; Palmer and Puls, 1994; Wittbrodt and Palmer, 1997). Reductants that are commonly found in soils include ferrous ironbearing minerals and organic matter. Laboratory experiments indicate that the reduction of Cr(VI) by aqueous ferrous iron and ferrous salts under acidic conditions can be very rapid, reaching equilibrium within a matter of minutes (Eary and Rai, 1988; Buerge and Hug, 1997). However, the reduction of Cr(VI) by ferrous iron bearing minerals involves the dissolution of ferrous iron and can be significantly slower, taking tens of minutes to tens of hours depending on the pH and the ferrous mineral (Eary and Rai, 1989; Eary and Rai, 1991). Blowes and Ptacek (1992) suggested that iron bearing solids such as elemental iron (Fe0) and pyrite could be used in a porous subsurface reactive wall to reduce and remove Cr(VI) from ground water under intermediate pH conditions. Their laboratory experiments indicated that the rate of Cr(VI) removal by fine grained iron is greater than that for coarse grained iron and pyrite. Cr(VI) concentrations decreased from 25 mg/L to less than 0.05 mg/L within a matter of hours with high purity granular iron (0.5 - 1 mm diameter), as opposed to tens of hours for iron chips or pyrite. Their results suggested that the reaction was surface area and pH dependent. A similar surface area and pH dependence was found by Gould (1982), who determined a rate expression for the reduction of Cr(VI) by Fe0:

d Cr VI dT

= −k Cr VI

0.5

H+

0.5

A

(1)

where A is the surface area of zero-valent iron (cm2/L), and the rate constant k has a value of 5.45 x 10-5 L cm-2 min-1. The reduction of Cr(VI) by Fe0 produces ferric iron [Fe(III)] and Cr(III) and (eqn. 2). Chromium may be removed through the precipitation or co-precipitation of mixed Fe(III)-Cr(III) hydroxide solid solution (eqn. 3; Eary and Rai, 1988; Puls et al.; 1994; Powell et al., 1995; Blowes et al., 1997) or mixed Fe(III)-Cr(III) (oxy)hydroxide solid (eqn. 4; Schwertmann, 1989): Cr6+ + Fe0 (1-x)Fe
3+ 3+ 3+

⇔ Cr3+ + Fe3+
+ +

(2) (3) (4)

+ xCr + 3H2O ⇔ (CrxFe1-x)(OH)3(s) + 3H + xCr + 2H2O ⇔ Fe1-xCrxOOH(s) + 3H
3+

(1-x)Fe

Goethite (FeOOH) and Cr(III) substituted goethite containing up to 27 mass % Cr(OH)3 have been identified as the principal precipitates in this reaction (Blowes et al., 1997; Pratt et al., 1997). The substitution and incorporation of Cr(III) into ferric oxyhydroxides is similar to the findings of Eary and Rai (1988) who report a 3:1 stoichiometry for Fe/Cr in a mixed hydroxide precipitate. These hydroxides have a minimum solubility between pH 7 and 10 (Rai et al., 1987; Sass and Rai, 1987). In this pH range, Cr(III) concentrations in equilibrium with Cr(III) and mixed Cr(III)-Fe(III) hydroxides are

3

less than the MCL. Thus, the reduction of Cr(VI) by zero-valent iron provides a method of treating Cr(VI) contaminated ground water. Elemental iron has also been found to promote the relatively rapid degradation of a wide range of halogenated aliphatics, including TCE, dichloroethylene (DCE) and vinyl chloride (VC;) (Gillham and O’Hannesin, 1992; Gillham et al., 1993). One proposed reaction scheme (Figure 14) suggests that the degradation of TCE by Fe0 to non-toxic hydrocarbons occurs via concurrent reductive β-elimination and hydrogenolysis reactions (Roberts et al., 1996; Arnold and Roberts, 1997). The reductive β-elimination pathway involves the breakdown of TCE to chloroacetylene and acetylene intermediates. The alternative reductive-dechlorination pathway involves the breakdown of TCE to DCE isomers and VC intermediates. The cis-dichloroethylene (cDCE) and VC intermediates are also of concern as they are carcinogenic and have low MCL values of 70 and 2 µg/L, respectively. However, laboratory experiments indicate that cDCE and VC account for less than 10% of the TCE breakdown products (Orth and Gillham, 1996), and that these chlorinated products are themselves reductively-dechlorinated in the presence of Fe0. Laboratory experiments have indicated that the ultimate end-products of both reaction pathways are ethene and ethane, with lesser amounts of other C1 to C4 hydrocarbons (Sivavec and Horney, 1995; Orth and Gillham, 1996). Batch experiments indicate that the TCE, cDCE and VC degradation reactions are pseudo first-order and dependent on the surface area of iron (Gillham and O’Hannesin, 1994). The first-order rate constant appears to decrease with decreasing degree of chlorination, and each subsequent dechlorination from TCE to cDCE to VC occurs more slowly. A similar surface area and rate dependence was observed in the sequential dehalogenation of chlorinated methanes by Fe0 (Matheson and Tratnyek, 1994). Johnson et al. (1996) describe a pseudo first-order kinetic model for the dehalogenation of various hydrocarbons by Fe0:

dP = k saas ρ m P dt

(5)

where ksa is the specific reaction rate constant (L h-1 m-2), as is the surface area of Fe0 (m2 g-1), and ρm is the mass concentration of Fe0 (g L-1 of solution). The first-order rate constants for the dehalogenation of TCE, DCE isomers and VC by elemental iron, calculated from various batch and column experiments (Johnson et al., 1996), are given in Table 2. These rates are significantly greater than those reported for the abiotic hydrolysis of TCE under normal environmental conditions, where half-lives are on the order of years (Vogel et al., 1987). The use of Fe0 in subsurface reactive iron walls has also been previously shown to successfully degrade a variety of halogenated organics in ground water (O’Hannesin and Gillham, 1992; Focht et al., 1996).

4

Design Methodology
Introduction
A series of batch tests were conducted in the laboratory to assess the potential effectiveness of various commercial iron materials in simultaneous removal of both Cr(VI) and TCE from Elizabeth City site water. After identifying suitable iron sources, column tests were undertaken to determine if the organic compounds would degrade under flowing conditions through the various reactive materials. Parameters obtained from the column experiments would ultimately assist in the design of a field treatment system.

Materials

Ground Water
Ground water for the batch and column experiments was collected from monitoring well MW34 at the USCG Support Center. The site water was initially analyzed to determine the concentrations of TCE and Cr(VI) [750 µg/L and 8 mg/L, respectively]. For the batch and column tests, TCE and Cr(VI) concentrations were increased to approximately 2,000 µg/L TCE and 10 mg/L Cr(VI).

Zero Valent Iron
Three different sources of commercially available iron were tested: Ada (batch test only), Master Builders (MB) of Cleveland, Ohio, and Peerless (PL) Metals and Abrasives of Detroit, Michigan. The grain size of the iron ranged from 0.25 to 1.0 mm for both MB and PL. Ada iron was composed of 0.5 mm shavings of various lengths. The specific surface area measurements were 1.1 and 0.81 m2/g for MB and PL, respectively, determined by the BET method (Brunauer et al., 1938). Particle density measurements were 6.97 and 6.98 g/cm3 for MB and PL, respectively, as determined with an air compression pycnometer (Beckman model 930). Surface area and particle density measurements were not performed for Ada iron due to the large particle size.

Aquifer Materials
Depending on the construction method used (i.e., the width of the excavation) it is often more cost effective to mix sand with the granular iron. Natural sand from the site (AQ) and high purity silica sand (SS) were considered as potential bulking agents. Elizabeth City aquifer material was selected to evaluate the potential benefit and complications associated with using the native aquifer material in the reactive mixture. At the University of Waterloo, the materials were dried and screened through a 2 mm sieve. The washed silica sand that was used ranged between 0.15 to 0.5 mm in diameter. Grain size distribution curves are shown in Appendix A. Hydraulic conductivity measurements were performed on all column mixtures. The column mixtures and hydraulic conductivities are described in the Methodology section of this report. Elemental analysis and toxicity characteristic leaching procedures (TCLP) were conducted on both MB and PL iron sources (Appendix B).

Methodology

Laboratory Batch Tests
Four batch tests were conducted using the three different sources of commercially available iron; Ada, MB, PL and a combination of Elizabeth City aquifer material (AQ) and MB iron. Each laboratory batch treatability test consisted of 60 samples prepared in 60 mL glass vials. Two types of samples were prepared: blank vials, which contained only spiked site water, and reactive vials containing 6 g of an iron source, 6 g of silica sand (SS) or aquifer material (AQ) along with the spiked site water (Table 3). The mass of iron to volume of solution ratio in the reactive vials was 1 g: 9.4 mL. For each treatability test, the site water was gravity fed into a 4 L glass bottle with a spigot at the bottom, and was stirred on a magnetic stirrer for 30 minutes. The vials were filled by gravity flow, leaving no headspace, then sealed immediately with aluminum crimp caps with Teflon®-lined septa. The test vials were filled in sequence of one blank and three reactive vials. Sample bottles with no iron or sand were also filled at the beginning, middle and end of the pouring process, to determine initial values of TCE, Cr(VI), redox potential (Eh) and pH. The test vials were then placed on a rotating disc (three complete revolutions per minute), allowing for complete mixing without agitation. At predetermined time intervals (sampling more frequent at early times), the vials were removed from the rotating disc and samples were extracted for TCE analysis, Eh and pH measurements. Filtered samples (0.2 µm) were collected for alkalinity and inorganic constituent analyses, including Cr(VI). Four vials were sacrificed for each sampling time: one blank and triplicate reactive vials, allowing a maximum of fifteen sampling times. All tests were conducted at room temperature (≅ 25 o C).

5

12 and 16 in) from the inlet end (Figure 15).538 mm ID.0 µL aliquot of pentane with an internal standard was automatically injected directly onto a Hewlett Packard series II gas chromatograph. Samples were analyzed within two days of collection.29 to 0. cDCE and VC and the removal of Cr(VI) under flowing conditions.79 m/day (1. The second set of tests. All column experiments were conducted at room temperature. 6 .).Laboratory Column Tests Six column tests were conducted to determine the degradability of TCE. x 1. 8. 10. Using a Hewlett Packard 7673 autosampler. The lower velocity corresponds to the natural ground-water velocity at the site. was conducted with a lower flow velocity of approximately 0. The columns were constructed of Plexiglas™ with a length of 50 cm (1. When not in operation the ports were sealed by Luer-Lok™ plugs. This included two detailed sampling sessions of the column effluent and column ports as described above. corresponding to the velocity expected in a funnel and gate configuration. Cr and other ions.16 cm) tapped into the side of the column. only half of the column ports were sampled at a given sampling session. After removing stagnant water from a sampling needle. 1995. All measurements were determined gravimetrically and are shown in Table 5.64 ft) and an internal diameter of 3. An Ismatec™ IPN pump was used to feed the solution from a collapsible Teflon® bag to the bottom influent end of the column. Filtered (0. Analytical Procedures Organic Analysis All organic samples collected from the batch and column experiments were analyzed at the University of Waterloo. such that a glass sampling syringe could be attached to the port to collect a sample. Testing at FV2 was started on May 26. Each sampling port consisted of a nylon Swagelok® fitting (0. Samples were collected in glass syringes to prevent oxidation during collection.6 ft/day = FV1) (Table 5). The analyses were performed on two types of gas chromatographs. Detailed sampling was conducted of the effluent and all column sample ports for Eh. The carrier gas was helium and makeup gas was 5% methane and 95% argon. 2. The columns were initially flushed with carbon dioxide to avoid air entrapment during wetting. The samples were placed on a rotary shaker for 10 minutes to allow equilibration between the water and pentane phases. Sampling ports were positioned along the length of each column at distances of 2. with a temperature time program of 15°C/min reaching a final temperature of 150°C.43 to 0. Additional Cr(VI) profiles were obtained at five different intervals to monitor Cr(VI) movement through the column.30 m/day (1 ft/day = FV2). 4. The detector temperature was 300°C. The higher velocity is about ten times greater.43 to 0. In the first set of tests (0. 20. aliquots of the sand-iron mixtures were packed in lifts. all other tubing was Teflon® (0. 2.5.0 mL (Henderson et al.79 m/day). 30 and 40 cm (1.2 µm) samples were analyzed for major ions and trace metals at the University of Waterloo. Porosity values ranged from 0.8 cm (1.0 to 2. 2-dibromoethane. MB iron and PL iron.D. using mixtures containing a combination of Elizabeth City aquifer material (AQ). A detailed column profile was obtained three times during the experiment for each column and the effluent was sampled more often. which extended the period of operation of only three of the columns. Pore volume measurements were determined experimentally by weight and ranged from 166 to 254 mL. the five columns were sampled more than ten times for inorganic parameters. at a water to pentane ratio of 2.45. 15.5 mL samples were collected from the sampling ports. sampling was conducted at least 7 times for Cr(VI) concentration. The first set of column tests was started on March 31.52 cm O. The less volatile halogenated organics such as TCE were extracted from the aqueous phase using pentane with an internal standard of 1. 1976). taking care to avoid layering by roughening the surface of the preceding layer before adding the next layer. 6.33 cm I.4 to 2. At the lower flow velocity (FV2). The column mixtures used are listed in Table 4.0 or 1. with a flow rate of 30 mL/min. Samples for organic analyses were collected from each port. 1995. The columns were sampled periodically over time until steady-state organic concentration profiles were achieved.5 in). alkalinity. Eh and pH measurements were made in sealed containers. Glass wool was placed in the needle to prevent the entry of solid material.D. For columns containing the 50% iron and sand mixtures. and the hydraulic characteristics of these columns are described in Table 5.. Each column was carefully packed insuring that the mixture was homogeneously distributed. Each sampling port was fitted with a Luer-Lok™ fitting. Several pore volumes of distilled water were flushed through each column before the site water was introduced. pH. with a flow velocity range of 0. with a syringe needle (16G) secured by the fitting. a 1. Iron mass to volume ratios and surface area to volume ratios are shown in Table 5. The columns also allowed for collection of samples from the influent and effluent solutions. A minimum of 8 mL was needed for analysis. The gas chromatograph had an initial temperature of 50°C. film thickness 3 µm). The needles were positioned such that the water samples were obtained along the central axis of the column. Due to the reduced flow rate and the large volume of sample required for analysis. silica sand (SS). 5. The pump tubing was Viton®. The chromatograph was equipped with a 63Ni electron capture detector (ECD) and DB-624 Megabore capillary column (30 m x 0.

1992. These samples were analyzed at the Water Quality Laboratory (WQL) at the University of Waterloo. The Model 10S50 chromatograph was fitted with a TFE packed column with 5% SE-30 on Chromosorb G. Method detection limits (MDL) were determined for each compound as the minimum concentration of a substance that can be identified. Cation analysis for Cr(VI) was determined using a diphenylcarbazide colorimetric technique (Standard Methods. For analysis. Flow and Reactive-Transport Modeling Model Description FRAC3D. measured and reported with 99% confidence that the analyte concentration is greater than zero. Anions including Br. Detection limits for all compounds studied. 1991). Sr. Because of the low sample volumes available for analysis. The MDL for TCE and PCE was 1 µg/L. Due to the limited volume of sample available. K. 1946. Si. a three-dimensional finite element computer model designed to simulate saturated-unsaturated ground-water flow and chain-decay solute transport in porous or discretely-fractured porous formations (Therrien and Sudicky. duplicate measurements of alkalinity could not be conducted. The samples were acidified to a pH of 2 with nitric acid and stored at 4oC until analyzed. Zn and a suite of other cations. was used. This model has been used previously 7 . Standards for TCE and PCE were run at the beginning of each day and an additional set of standards was run later in the day or dispersed throughout the analysis run. Model 10S50 and/or Model 10S70. Na. gas chromatograph equipped with a photoionization detector (PID). Alkalinity was measured on filtered subsamples at the time of sample collection using a Hach® Digital Titrator. Standards for VC and DCE analysis were run twice per day.500 µg/L. AW-DMCS (100/120 mesh).4 mg/L.000 µg/L respectively. Similar to the VC and DCE analyses.5 mL aqueous sample. Millivolt readings were converted to Eh using the electrode reading and the standard potential of Ag/AgCl electrode (SHE) at a given temperature. Cr(total). with an isothermal oven temperature of 30oC and a flow rate of 3 mL/min. Nordstrom. Mg. Geochemical Modeling The geochemical speciation/mass transfer computer code MINTEQA2 (Allison et al. 3500-Cr D). The pH measurements were made using a combination of pH/reference electrode (Orion Models 9172BN and 915600). Detection limits for the inorganic parameters are included in Table 6. Fe. Inorganic Analysis Redox potential (Eh) was determined using a combination Ag/AgCl reference electrode with a platinum button (Orion 9678 BN). The highest VC and c-DCE standards run via headspace analysis were 700 µg/L and 1. Ca.. Each sample and standard were spiked with an internal 1. The samples were placed on a rotary shaker for 15 minutes to allow equilibration between the water phase and gas phase. a headspace was created in the samples with a ratio of 0. as given in Table 6. standardized H2SO4 titrant and bromocresol green-methyl red indicator. B.For the more volatile compounds. 1972. with oven temperature of 30oC and carrier gas of ultra-zero with a flow rate of 10 mL/min.5 mL headspace to 1. The MDL for VC and DCE was 1 µg/L. 1996). such as cDCE. 1977). The MDL for total Cr concentrations on the ICP is 0. Cd. tDCE and VC. a 50 µL gas sample was injected onto Photovac™. The method detection limit for Cr(VI) measured in the lab is between 0. The MDLs were determined from analysis of samples from a solution matrix containing the analytes of interest. The thermodynamic database of MINTEQA2 was adjusted to be consistent with that of WATEQ4F (Ball and Nordstrom. Light. standardized with the pH buffer 7 and 10 (NIST standard). were determined using an inductively coupled plasma Atomic Emission Spectrometer (ICP-AES) instrument (Thermo Jarrell Ash Iris Plasma Spectrometer). Other cation analyses.02 mg/L. Cl and SO4 were analyzed using a Dionex System 2000 Ion Chromatograph (IC) or a Waters IC with conductivity detectors. Linear calibration curves were comprised of eight different standards plus a blank. including Al. Ni. 1982). Mn.2-dibromoethane sample to ensure complete capture by the detector. Calibration curves were run with seven different standards plus a blank. The relative percent difference for each standard was determined and if the average of all the relative differences exceeded 10% then the analyses were repeated. Appendix I describes the analytical procedures used for cation analysis. the average of the relative percent differences was calculated to a cutoff limit of 10%. 1990) was used to aid in the interpretation of inorganic aqueous geochemical data. Approximately 30 samples were run during the day using a gas chromatograph equipped with a photoionization detector (PID). were determining using the EPA procedure for Method Detection Limits (USEPA. The model 10S70 was fitted with a capillary column CP Sil5. the detection limit for alkalinity measurements varied from 2 mg/L CaCO3 for the batch experiments to between 5 and 8 mg/L CaCO3 for the column experiments. Appendix I describes the analytical procedures used for anion analysis. The highest TCE standard run via this pentane extraction method was 2. The electrode was standardized with ZoBell and Light solutions (Zobell. FRAC3D has been verified and validated against analytical solutions.2 and 0.

The total volume of granular iron within this simulated barrier was 35 m3. 1995. Using the maximum anticipated hydraulic conductivity value will yield a conservative estimate of ground-water velocities and required residence times within the reactive barrier. a Funnel-and-Gate and a continuous wall. In this configuration. The continuous wall configuration simulated was composed entirely of granular iron. 1997). and 0. Reactive Barrier Configurations For the ground-water flow simulations. the reactive barrier was located with the center of its long axis coinciding with the east symmetry/no-flow boundary. and 9. For efficiency. and a downgradient pea gravel zone. For the reactive transport simulations. the reactive barriers.15 m to 1. which is a low hydraulic conductivity confining clay layer. and capture areas of. For the flow simulations.1 m deep. the funnels were oriented perpendicular to the ground-water flow direction (Starr and Cherry. This hydraulic gradient corresponds to the maximum observed hydraulic gradient.0033. The 0. A uniform hydraulic conductivity was assigned to the domain to facilitate comparison of the hydraulic characteristics of the different reactive barrier designs. This configuration results in a uniform flow field from south to north. and the north and south boundaries (Type 1) were assigned constant head values of 18 m and 18. differ only in how they are configured to intercept ground-water flow. Shikaze et al. with the finer grid spacing within the vicinity of the reactive barrier. For the reactive transport simulations. the model domain was 26 m x 18 m x 18 m (Figure 16). with the finer spacing located near the vertices of the reactive barrier. bottom. The west no-flow boundary is far enough from the reactive barrier. The east boundary represents a symmetry boundary. flow underneath the barriers is possible.5 m. which only approximates the heterogeneous nature of the aquifer. east and west boundaries were assigned as no-flow boundaries (Type 2). The Funnel-and-Gate has a gate zone that contains the reactive material. respectively. The top. 2 m wide and 9. in that they do not intercept an underlying low permeability unit. A simulation was also conducted with an assigned hydraulic conductivity of 46. which runs through the center of the reactive barrier. FRAC3D was chosen to model the Elizabeth City USCG site because of its versatility and applicability to chain-decay solute transport (Bennett. Hydraulic Parameters The entire domain was assigned a uniform hydraulic conductivity. The total volume of granular iron in this simulated barrier was also 35 m3. 7. This value was chosen as a realistic estimate of the maximum anticipated hydraulic conductivity.45 m wide pea gravel zones promote an even ground-water velocity distribution and minimize any heterogeneities in ground-water flow through the 1. the model domain was 30 m x 18 m x 18 m. The continuous permeable wall is composed entirely of reactive material and does not rely on funnels to direct ground-water flow. 8 . a central granular iron zone.5 m. Within the model domain.1 and 26 m/day. The finer grid spacing within the vicinity of the reactive barrier was chosen to satisfy the grid Peclet number criteria and minimize numerical dispersion. For the reactive-transport simulations. and relies on impermeable funnels to direct ground-water flow through this gate. two pilot-scale barriers composed of equal volumes of reactive material were modeled (Figure 18). Boundary Conditions The boundary conditions are shown in Figure 17. This corresponds to the average calculated hydraulic conductivity for the reactive mixtures. a 36 m by 7.for a number of Funnel-and-Gate ™ remediation scenario simulations (Shikaze and Austrins. the hydraulic conductivity was varied between 0.1 m deep.. The grid spacing was varied between 0. the domain was assigned a hydraulic conductivity of 17 m/day. justifying the no-flow assumption.0594 m. The gate zone consists of three zones: an upgradient pea gravel zone. The grid spacing was varied from 0. The simulated gate zone was 3.6 m by 0.1 m wide granular iron treatment zone. These two reactive barrier designs. with a constant horizontal hydraulic gradient of 0. 1994). It is 10 m long. These values correspond to the lowest and highest hydraulic conductivity values calculated from slug and tracer tests at the site.6 m long. This range in hydraulic conductivities was chosen to bracket the anticipated range in calculated ground-water velocities within. 1995).45 m continuous reactive wall was modeled.6 m deep.4 m/day.06 m long. The barriers are “hanging” in these simulations. The funnels of the simulated Funnel-and-Gate were 6.03 m and 1. Model Limits and Grid For the ground-water flow simulations. The bottom no-flow boundary represents the Yorktown confining unit.5 m wide.

This ignores the partitioning or adsorption of the organic contaminants onto the granular iron or aquifer material within the wall. time data (Appendix C) to the one-dimensional advection-dispersion equation using CXTFIT (Toride et al. Klotz et al. 9 . cDCE and VC diffusion coefficients at 200C were assigned values of 10. based on laboratory column experiments. Longitudinal dispersivities between 0. 1979. This assumption will yield conservative estimates of the minimum wall thickness in order to provide the required ground-water residence time within the wall. TCE.2 times the longitudinal dispersivity (Freeze and Cherry.85 are typical for sands. Tortuosity values between 0. The reduction-precipitation reaction of Cr(VI) was not modeled because previous lab experiments indicated it to be the most rapidly reduced contaminant in the granular iron. First-order reaction rates and molar transfer coefficients for the reductive-dechlorination of TCE.3 x 10-6 cm2/s. cDCE and VC concentrations along the centerline of the plume within the granular iron wall. However. assigning equivalent longitudinal and transverse dispersivity values may provide an inaccurate representation of transverse spreading at the fringes of the simulated plume. the longitudinal dispersivity value obtained from the 50 cm laboratory granular iron column may reasonably represent the field dispersivity within a 45 to 60 cm granular iron wall. The tortuosity was assigned a value of 0.. Previous studies have indicated that laboratory values of transverse dispersivity are usually 0. cDCE and VC concentrations to less than MCL values.Reactive-Transport Parameters The goal of the reactive transport simulations was to determine the minimum thickness of a granular iron wall necessary to degrade selected TCE. no attempt was made to accurately portray the TCE source zone.6 and 1. the small value of transverse dispersivity used is not expected to significantly influence declining TCE. Given the sparse TCE characterization at the site. 11. 1980). 1955).8 for both aquifer and granular iron media. and 13. Kd. and VC concentrations were assigned to a source zone upgradient of the wall.1 x 10-6 cm2/s. Thus. Although it is generally accepted that laboratory scale dispersivity measurements do not accurately reflect field scale problems. Two simulations were conducted in which the anticipated and maximum observed TCE.4 x 10-6 cm2/s.5 cm in the model. cDCE. The source zone was a 12 m by 5 m plane of nodes located at the southern upgradient boundary of the domain.. The reactive transport simulation was run for 100 days. The distribution coefficient. 1995).05 to 0.7 cm were calculated by fitting the effluent concentration vs. This simulation time allows more than 10 pore volumes (PV) to pass through the barrier and establish steady-state conditions.7 and 0. and results in no retardation of contaminant transport. or significantly bias the estimate of the minimum required thickness of the iron wall. respectively. was assigned a value of zero. These values were calculated using a semiempirical correlation equation developed for dilute organic solutes in water (Wilke and Chang. cDCE and VC were incorporated into the reactive-transport model. A bromide tracer solution was introduced into 50 cm long laboratory columns containing different granular iron reactive mixtures. Longitudinal and transverse dispersivities were assigned values of 1.

Geochemical Modeling – Inorganic Data MINTEQA2 was used to calculate the state of saturation of the water with respect to a variety of minerals versus time and batch composition. Cr remained below detectable levels (< 0. 6.000 mV for the experiments using MBSS and PLSS. Mn and Na concentrations increase slightly (~10%) from the input water composition during the batch experiments. the MBSS and AdaSS mixtures had mid-range values. Most other dissolved species are present at concentrations < 1 mg/L during the experiment. and generally decreased slowly afterwards. Si and SO4 (Appendix D). Cr. The percent standard deviation for the reaction vial TCE values are generally less than 5% (Table 7). goethite. Mg. The reactive vials containing the PLSS iron showed a more rapid decline in TCE concentration. Na. with a concentration of 17 µg/L being reached by the 192 hr sampling. the alkalinity increased rapidly from an initial value of 30 mg/L CaCO3. Cl. Dissolved Si concentrations decrease by ~70% from the input water composition of ~6 mg/L. MINTEQA2 calculations indicate that the batch input water is undersaturated with respect to Cr(III) bearing solids. rhodochrosite [MnCO3]. Chemical analyses indicate that the Cr in the input water occurs almost entirely as Cr(VI).000 µg/L over the 313 hr duration of the test (Table 7. dolomite [CaMg(CO3)2]. This water would only approach saturation with respect to crystalline and amorphous Cr(OH)3 if the Cr(III) concentration approached 50% of the total Cr concentration. Similar declines in Cr(VI) concentration were observed when natural Elizabeth City aquifer material (MBAQ) was substituted for silica sand in the reactive mixture. Dissolved Ca. These species are at concentrations > 1 mg/L at some time during the experiment. The reactive vials containing Ada iron and silica sand (AdaSS) showed a gradual decline in TCE concentration from an initial concentration of 2. Dominant ions in the batch water include Ca. Early time removal of Cr(VI) from the spiked ground water solution is shown in Figure 21. followed by MBSS (nd at 35 min) and Ada iron (AdaSS) (nd at 70 min). crystalline [Cr(OH)3].02 mg/L Cr(VI)) during the remainder of all experiments (200 hours). the similarity of total Cr and Cr(VI) concentrations in the spiked ground water suggest that Cr in this water is dominantly in the Cr(VI) valence for the duration of the experiments. Fe.9 to between pH 7 and 8 (Figure 20. with losses of about 95% of the initial TCE during the first 50 hours. The degradation rate for MBAQ appeared to be slightly greater than MBSS. Iron corrosion and the reduction of Cr(VI) by Fe0 (eqn.04).05 mg/L (input) to maximum values between 1 and 64 mg/L within 5 hours. calcite [CaCO3]. Although the method detection limit for Cr(VI) in the laboratory is fairly high. the pH increased from an initial value of 5. The concentration of TCE in blanks for all four experiments shows minor fluctuations. The alkalinity then decreased slowly until the end of the experiment. The reactive vial concentration values are averaged triplicate values. Dissolved Fe concentrations increased rapidly from < 0. The reaction was rapid for all four batch tests. Inorganic Trends in the dissolved aqueous geochemistry measured during the batch experiments are plotted in Figure 20 and are described in detail in Appendix D.Results and Discussion Column and Batch Tests Batch Results Organic The results of the batch tests are plotted as a concentration of TCE in µg/L versus time in hours (Figure 19). quartz and amorphous silica are plotted in Figure 22 and are listed in Appendix E. High pH and Eh conditions preclude reduction to Cr(III) in the absence of a reductant. The most rapid loss of TCE was obtained using Master Builders (MB) iron. amakinite [Fe(OH)2]. aragonite [CaCO3]. to near 150 mg/L CaCO3. MBAQ and MDSS gave similar results. In all four batch tests. Appendix D) within 5 hours. As each batch reacts. The final pH was lowest for the AdaSS mixture (pH 7. siderite [FeCO3]. with complete removal within the first 70 minutes (Table 8). 7) are probably responsible for the observed pH-increase and Eh-decrease in the batch flasks. Analytical charge balance errors of < 5% were regularly achieved. 2Fe0 + O2 + 2H2O ⇔ 2Fe2+ + 4OH 8H + CrO + 24 0 3+ 3+ - (6) (7) + Fe ⇔ Fe + Cr + 4H2O Over the first 3-6 hours. but was relatively constant over time. Trends for SO4 concentrations are not evident. amorphous [Cr(OH)3]. Figure 19). PLSS showed the fastest reaction (non-detect (nd) at 23 minutes). The results for ferrihydrite [Fe(OH)3]. 10 . The highest Fe concentrations were measured in the PLSS and the lowest in the MBAQ mixture. similar trends in the state of saturation of the water are observed. The Eh dropped by at least 500 mV during the experiments and by as much as 1.

respectively. Between 0 and 0. it is unlikely that amorphous or crystalline Cr(OH)3 are precipitating and limiting the concentration of dissolved Cr in the short time of the experiments. and is undersaturated with respect to amorphous silica at all times (SI = -0. Cr = 0. with silica sand and Elizabeth City aquifer as the mixing materials. respectively. Water in each of the batches is initially undersaturated with respect to calcite.e. dolomite and siderite (Figure 22). Noted decreases in dissolved Si concentrations may be attributed to the precipitation of amorphous silica or coprecipitation of silica with ferrihydrite or goethite. Fe = 0. As noted in Appendix F by reservoir number (RN). as Fe0 is oxidized to Fe3+ (eqn.600 µg/L and 10 mg/L.. and 40 µg/L. predictions about the solubility control for Fe(III) cannot be verified without mineralogical study. After the detection limit for Cr was reached. Fe concentrations rise sharply (Appendix D). The main organic compounds detected in the site ground water were TCE. equilibrium was also attained (SI = -0.02 to 0.35) with respect to quartz (SiO2). Organic Concentration profiles were measured along the columns at intervals of approximately 5-7 pore volumes. with concentrations of about 750.With the exception of the AdaSS mixture. the reacted water is supersaturated with respect to goethite.5 hours. obtained when steady state conditions were reached. 20. The Fe3+ released during the Cr removal reaction may then be reduced to Fe2+ by the oxidation of Fe0.5 hours. The site water was siphoned from 4 L amber bottles used for shipping into a collapsible 22 L Telfon® bag. 50. Trace levels of tetrachloroethylene (PCE) and trans-1.2-dichloroethylene (tDCE) were detected (2 µg/L each). Blowes et al. and Pratt et al. aragonite and siderite. are plotted as concentration 11 .5 hr). in order to have an adequate amount of time to accurately determine declines in concentrations.5 hours indicate moderate supersaturation with respect to Cr(OH)3. Using these assumptions. the calculated SI values for Cr(OH)3 after 0. Fe was not detected. Although an analysis of solids from the batch flasks was not conducted. Under this assumption. dissolved Cr was speciated with MINTEQA2 based on the measured Eh. 1997. respectively.0) with respect to Cr(OH)3 (c) (Figure 22). 1989.5 hours (Appendix D). Column Results Based on the results from the batch tests. 1988. In each of the batch experiments. cDCE. The accumulation of SiO2 in iron oxyhydroxide coatings (goethite) surrounding zero valent iron grains has been noted previously by Blowes et al. As the pH and alkalinity increase during the batch experiments. Noted increases in the concentrations of dissolved Ca and Mn may be attributable to ion exchange or the gradual dissolution of trace amounts of minerals in the batch mixtures. the column tests focused on Master Builders and Peerless iron.75 < SI < 1. The results are listed in Appendix F. Within 24 hours. 2Fe3+ + Fe0 → 3Fe2+ (8) Between 0 and ~0. dolomite and rhodochrosite in the MBAQ batch. FV1) and reservoirs c-e in the second set (low velocity.30) with respect to calcite. In particular.. this iron is dominantly in the ferrous state. the initial TCE and Cr(VI) concentrations were increased to approximately 1. with speciation based on the Eh. it is probable that this phase also controls Fe(III) concentrations.01 mg/L)..5 hours.0). Cr was assumed to be 50% of the MDL (i. trichloromethane (TCM. Powell et al. generally within one hour of the start of the experiments. The initial Cr(VI) concentration was 8 mg/L. The results. During this period the water in each batch experiment is supersaturated (SI ~ 2 to 3) with respect to Cr(OH)3 (a) and near equilibrium (-0. Schwertmann. the water gradually becomes less undersaturated with respect to amakinite. If a solid solution such as (CrxFe1-x)(OH)3 controls Cr(III) concentrations during this period. Because Fe(III) concentrations are small and not quantified. 1995. Reservoirs a-c were used in the first set of tests (high flow velocity. the water gradually approaches equilibrium with respect to the carbonate minerals calcite. As each batch ages (>0.. It is more likely that the Cr(III) is incorporated into a mixed Fe(III)-Cr(III) oxyhydroxide precipitate. FV2). all the site water could not be held in the collapsible bag and thus the reservoir had to be filled five times over the course of the tests.20 to + 0. This decrease in Fe concentration possibly results from the precipitation of siderite.600 µg/L and 10 mg/L. while Cr concentrations are measurable. 2). In increase both the initial TCE and Cr(VI) concentrations to approximately 1. goethite and other Fe-bearing minerals during this time is based on the assumption that the total Fe concentration is 10% of the MDL (i. the water is near equilibrium with respect to ferrihydrite (Appendix E). Because of kinetic limitations. 1997). similar to those observed in previous studies (Eary and Rai. The calculated saturation of the water with respect to ferrihydrite. After ~0.. chloroform) and VC. (1997).01 mg/L).e. Dissolved Fe(II) concentrations decrease gradually after 3 hours in all but the AdaSS batch mixture. however. Based on the measured Eh.5 to -1. the water attains and exceeds saturation with respect to siderite. total Cr concentrations generally reach the detection limit within approximately 0. the water is near equilibrium (SI = -0. The reduction of Cr(VI) to Cr(III) is accompanied by the release of dissolved iron.

cDCE and VC.16 ft) distance into the columns. Though the compounds of greatest interest were TCE and the less chlorinated ethenes. these two mixtures were not tested at the second slower flow velocity. At this flow velocity. while the remaining columns peaked at concentrations of approximately 180 µg/L (Figure 25). Because slower treatment of cDCE and VC was observed for both the 50MBSS and 50MBSSAQ columns at the high flow velocity.64 ft) distances along the column. However.7 µg/L.5 m (1.33 . then at steady-state. fluctuations in VC concentrations were observed with effluent concentrations of approximately 20 µg/L (Figure 26). The cDCE concentration then gradually declined to effluent values of 120 and 70 µg/L for 50MBSS and 50MBSSAQ and < 8. If the reaction is indeed first-order. respectively.3 m/day (1 ft/day. The rate of cDCE removal (Figure 29) was slower due to its appearance as an intermediate product of the dechlorination of TCE.600. and nondetectable concentrations were observed beyond 0. a rapid decline in TCM concentration was observed with non-detectable concentrations occurring from 0. In this case. PCE was only detected up to 0.1 . Low Flow Velocity Tests Steady-state concentration profiles of organic concentrations for the three column tests conducted at the low flow velocity are shown in Figures 27-30.(µg/L) versus distance (cm) along the column. The 48PL/52AQ column test was conducted later.17 m (0. Though present at trace levels in the source water. along the columns.55 ft) along the column. Though TCM degraded rapidly. however. with the exception of the water used in the 48PL/52AQ column. FV2) another 35 to 75 pore volumes of site water passed through the columns. 75 and 12 µg/L were measured for TCE. further testing of the 48PL/52AQ column at the lower velocity was not conducted because the hydraulic properties could potentially be problematic. In these columns. 23. High Flow Velocity Tests Steady-state concentration profiles for the six column tests are shown in Figures 23-26. and due to the presence of trace levels of tDCE in the source water. At a flow velocity of approximately 0. DCM analyses were not performed. PCE concentrations were non-detectable for the remainder of the profiles for all columns (Appendix F). depending upon the porosity of the particular packing material (Table 5). from an initial concentration of 23 µg/L for TCM. at the low initial TCM concentrations. as shown in Figures 27 and 28. cDCE and VC.4 µg/L for all the other columns. with both the 50MBSS and 50MBSSAQ columns. 23.61 m/day (2 ft/day. As shown in Figure 24. 100PL and 50PLSSAQ). At steady-state. initial concentrations of 1. 12 . For the three columns (100MB. The tDCE concentrations in the columns fluctuated due to the dechlorination of TCE. one pore volume corresponds to a residence time ranging from 34 -50 hours (Table 5). FV1) a total of 40 to 50 pore volumes of spiked water had passed through the column at the time the profiles shown in Figures 23-27 were determined.0. TCM.28 hours.2 m distance in all of the columns (Appendix F).30 m distance.5 and 0. TCM.400. analyses for TCM were performed since it was detected in the water obtained from the site. an exponential decline in concentration along the column would be expected. The cDCE concentration increased due to the dechlorination of TCE. However. The VC concentration declined steadily in four of the six columns (Figure 26). TCE and TCM showed a steady decline in concentration (degradation) along the column length. In addition.4 and 0. at distances ranging from 0. a portion of the initial TCM would appear as dichloromethene (DCM). Previous experience indicated that DCM would not degrade in the presence of iron. reached when the rate at which the contaminants were degrading was equal to the rate at which they were entering the column. 50 and 40 µg/L were measured for TCE. any DCM that formed would be below the MCL for DCM. the profiles of most interest are the steady-state concentration profiles. respectively.66 ft) along the column for all six columns. Thus the initial cDCE concentration of about 75 µg/L increased to peak concentrations ranging from 80 to 150 µg/L. These VC concentration fluctuations were attributed to the dechlorination of TCE and cDCE. with an initial concentration of 12 µg/L VC. At steady-state.600 µg/L to non-detectable values between the 15 cm and 30 cm sampling ports for all six columns.20 m (0. with non-detectable concentrations measured between 0. one pore volume corresponds to a residence time ranging from 15 . However.2 and 0. At a flow velocity of approximately 0. once the concentration peaked. the highest tDCE concentration observed during the tests was 5. giving cumulative pore volumes ranging from 85 to 125. initial concentrations of 1.33 ft) distance for the 100PL. Figure 23 shows a rapid decline in TCE concentration from an initial value of 1. with all three columns having non-detectable concentrations at the 0. 50PLSSAQ and 48PL/52AQ columns.15 and 0.05 m (0.0.31 and 1. The cDCE concentration increased from 50 µg/L to peak concentrations ranging from 65 to 94 µg/L at the 10 cm (0. The VC concentration in the site water was about 40 µg/L. a steady decline in concentration was observed.

regardless of solid reactive mixture. Appendix G includes all inorganic analytical data. complete removal of Cr was observed within the first 2.5 cm sample port during the first stage of the experiment. Cr was not detected in the effluent at termination of the experiments.02 mg/L) before the 2. pH and Alkalinity In all cases. The appearance of Cr at the 2. Figure 37). In contrast. declines in concentrations were observed. along the length of each column. Appendix H). 100PL and 50PLSSAQ) were operated at a lower flow velocity of 0. Mg concentrations decrease significantly (> 25%) in all but the 50MBSS column. Refer to Table 5 for the calculated flow velocities in each column. The 48PL/52AQ column was operated for 78 pore volumes at FV1.11 µg/L. Dissolved H4SiO4 concentrations decrease sharply from ~31 mg/L to < 2 mg/L within a short distance in the columns. In all of the columns. All columns exhibited similar Cr properties at all of the times. There is little change in the Na.1 m of the column (Figures 31-36). and a total column length of 50 cm. These results suggest the removal of these dissolved cations through ion exchange or mineral precipitation may be occurring. K. and dissolved Si (as [H4SiO4]) decrease along the length of the columns. At FV1 (~ 61 cm/day). including profile data. although some Cr was detected at the 2. amorphous silica and mackinawite [FeS]).2020 pore volumes (Table 10). regardless of the solid reactive mixture. The Ca concentration decreases by ~ 8-12 mg/L.5 cm port. Appendix G). With initial concentrations ranging from 8 .5 to pH 9 within the first 0. respectively. This prediction is preliminary because many factors such as flow rate and input Cr concentration may affect the actual breakthrough of Cr(VI) at the effluent end of the column.9 mg/L to < 0. Trace amounts of PCE and tDCE were present in the influent solution. amorphous [Cr(OH)3]. high pore volume measurements).125 pore volumes. Mg. 13 . including both flow velocities. measurable Cr was observed only at the 2. The concentrations of Ca.1 m of each column (Figures 31-36. Eh. with non-detectable concentrations beyond a distance of 0. Final cumulative pore volumes for these columns are 98. three of the columns (100MB. The column experiments were terminated after the treatment of 85 . Eh and alkalinity properties at all sampling times. suggests that Cr(VI) could be effectively removed by any of the reactive mixtures in the columns for 1380 .5 cm port as early as 69 pore volumes (100MB. siderite. Cations and Anions Table 9 summarizes the inorganic analyses of samples from the influent and steady-state effluent for all six columns. After running all of the columns at FV1. the SI values calculated at several pore volumes are plotted together on each figure. For comparison. crystalline [Cr(OH)3]. to near 0 mV values within the first 0.36). Fe. goethite. the concentrations of Ca.5 cm port (Figures 36. Mn. Table 9 summarizes the results of the inorganic analyses of samples from the influent and steady-state effluent for all six columns. low pore volume measurements) and slow velocities (FV2.5 m) of the column. Detailed column chemistry is listed in Appendix G. The pH values then remained constant throughout the length of the column. After 78 PV. All columns exhibited similar pH. Geochemical Modeling MINTEQA2 was used to calculate the saturation indices of a variety of minerals (ferrihydrite.5 cm of each column for more than 40 pore volumes (Figure 31 . quartz. with minor fluctuations in concentrations (Figure 30). the pH rose from about pH 6. dolomite. amakinite. Mg and Mn in the batch experiments increased over the duration of the experiments. while the second (lower flow velocity) was indicated by FV2.1 m for all three columns (Appendix F). rhodochrosite. The figures show the results for measurements collected at both the fast (FV1. 37). The first (high flow velocity) is indicated by FV1 in the figure caption. Mn concentrations decrease from ~ 0. Inorganic Results Chromium Figures 31 to 36 summarize the detailed sampling results for dissolved Cr(VI) for all six columns. 115 and 135. along each of the columns (Figures 38-43. however. Cl and SO4 concentrations with passage of the water through the column materials (Appendix G and Table 9). in all columns except 50MBSSAQ. calcite.2 mg/L within a short travel distance in all columns.3 m/day (1 ft/day = FV2). the Eh values declined from influent values of 300 .400 mV (SHE). non-detectable concentrations were observed at the effluent end (0.The VC concentration declines steadily for all three columns. Figure 37) and as late as 101 pore volumes (50PLSSAQ. Dissolved Cr concentrations dropped from maximum values of 11 mg/L input to non-detectable levels (< 0. Pore water alkalinity was maintained near 50 mg/L CaCO3 with slightly higher values observed near the influent end of the column (Figure 31-36).

Schwertmann.7 PV (FV2). Calculated SI values for amorphous Cr(OH)3 range from 3. Fe(II) is the dominant dissolved Fe species. the pH increases significantly downgradient from the source.6 to 1. 1988..5 cm and 5 cm locations.01 mg/L (10% MDL) was assumed to be present. calculations of pore-water saturation with respect to siderite assume Fe(II) concentrations that are 10% of the analytical detection limit (i.5 cm) and second (5 cm) sampling ports (Appendix G). The input water for the columns is undersaturated with respect to calcite. SI values for Cr(OH)3 beyond the first port are overestimated. the water would be slightly undersaturated with respect to amakinite. 1989. MINTEQA2 saturation index calculations for iron minerals are considered reasonable only at locations where measurable iron concentrations were detected (0-5 cm). and the alkalinity decreases slightly. Dissolved Fe concentrations are otherwise at analytical detection limits in all columns at all times. Because the behavior of Fe is linked to the geochemical reactions that remove the dissolved Cr. significant measurable Cr concentrations (>1 mg/L) were detected at the 2. 1997. the precipitation of goethite (molar volume 20. 7). The water is undersaturated. These calculations suggest that calcite or other carbonate mineral precipitation could adversely affect the permeability or reactivity of the granular iron over longer treatment periods.. but approaches equilibrium with respect to rhodochrosite in each of the columns. Precipitation of aragonite or calcite is consistent with the decrease in alkalinity and dissolved Ca concentrations observed along the length of columns 50MBSS.4 PV (FV1). as has been observed previously (Eary and Rai.5 to +1). In a few cases.3 PV (FV2) and the 48PL/52AQ column at 78. and undersaturated with respect to crystalline Cr(OH)3. the water is supersaturated with respect to goethite (SI ~ 6). because Cr concentrations generally are depleted to approximately analytical detection limits beyond the first sampling port. Occasionally. As with the batch test results. Blowes et al. 1997). generally within the first 5 cm of the column (Figures 38-43). equilibrium is attained further along the column.2 to 3. The water samples that contain measurable concentrations of dissolved iron are supersaturated with respect to goethite. It is 14 . aragonite. the 100PL column at 100. The Ca concentration decreases by approximately 12 mg/L.01 mg/L).5 and 114.8 ml/mol) results in a 10% decrease in porosity over the length of the column in about 82 years. Assuming that this decrease is due to calcite precipitation (calcite molar volume 35 ml/mol).e. The dissolved Fe concentration is below the analytical detection limit in the input water. At FV2 (31 cm/day) and a maximum observed iron concentration of ~18 mg/L. Powell et al. Fe=0. This Fe probably results from corrosion of the iron filings by oxygen and by water. High pH and Eh conditions limit Cr(III) concentrations in the source input water to low levels. MINTEQA2 calculations indicate that at the 2. and during the reduction of Cr(VI) to Cr(III) (eqn. 100MB.MINTEQA2 calculations suggest that the source water is generally close to equilibrium or undersaturated with respect to amorphous Cr(OH)3. 100PL and 48PL/52AQ. 1995. Beyond the first sampling port. These include the 100MB column at 79 and 98 PV (at FV2). At these locations. and is undersaturated (SI ~ -2. the trends for siderite are unlike those of calcite and dolomite (Ca and Mg are not involved in the Cr removal reactions). suggesting the precipitation may be rate dependent. equilibrium is reached at the first port of the columns at the slower flow velocity. In locations where Fe concentrations are measurable. Pratt et al. the 50PLSSAQ column at 135.. Goethite precipitation may passivate the iron filing surfaces over longer periods of treatment. the water approaches equilibrium with respect to siderite. As in the case for Cr. In each of the columns. At the higher flow velocity.5 cm port (Appendix G). the water along each of the columns would be supersaturated with respect to goethite and would be near equilibrium with respect to ferrihydrite if an Fe concentration of 0. In parts of the column where the Fe concentrations are below the detection limit. With the same assumption. The water approaches equilibrium with respect to calcite and aragonite and becomes supersaturated with respect to dolomite between the first and third sampling ports (10 cm). dolomite and siderite.9.5 to –4) with respect to amakinite (Appendix H. Although the water is also slightly supersaturated with respect to calcite and dolomite in the 50MBSSAQ column. as confirmed by the similarity of total Cr and Cr(VI) values (Appendix D).4. The observed decrease in Mg concentrations may be due to the precipitation of a magnesium carbonate or hydroxycarbonate. higher dissolved Fe concentrations (> 1 mg/L) are detected at the first (2. Within each column. 6. a 10% decrease in the porosity of the first 10 cm of a column would occur in about 16 years at the slower velocity (31 cm/d) or in about 9 years at the higher velocity (53 cm/d). However. it is not likely that a pure Cr(OH)3 phase would precipitate within the short duration of the experiments.. is near equilibrium with respect to ferrihydrite (SI ~ -0. and for crystalline Cr(OH)3 range from 0. Trends in the SI values of crystalline and amorphous Cr(OH)3 are similar for each column composition and at all pore volumes. The water also approaches and attains equilibrium with respect to magnesite. The precipitation of siderite in this location may limit Fe mobility in the columns. It is more probable that the Cr is removed by co-precipitation within a mixed Fe(III)-Cr(III) hydroxide solid solution or mixed Fe(III)-Cr(III) (oxy)hydroxide solid. dissolved Ca concentrations along the length of these columns remain relatively unchanged. Figures 38-43). however.

9 to 11 (eqn. Concentration profiles along the column were obtained after 40-50 pore volumes had flowed through the column. k2. cDCE and VC with various reactive mixtures were calculated from column experiment data (O’Hannesin et al. It is likely. the water becomes more undersaturated with respect to amorphous SiO2 (SI = -1 to –2). With the decreasing H4SiO4 concentrations along the length of each column. 14 respectively): 15 . Kinetic limitations prevent the direct precipitation of quartz. The first order rate expressions for the decay of TCE. x % of the TCE decays to cDCE. this would correspond to chromium breakthrough in a 0. (1997). Chromium concentrations decrease from approximately 10 mg/L to less than 0.5 cm) for 69 to 101 PV. The reaction rates were calculated to determine the relative reactivity of different zero-valent iron mixtures. d TCE = −k 1 TCE dT (9) d cDCE = xk 1 TCE − k 2 cDCE dT d VC = yk 2 cDCE − k 3 VC dT (10) (11) where k1. Determination of Reaction Parameters: Halogenated Hydrocarbons Reaction rates for the reductive-dechlorination of TCE. 13. possibly as a result of changing reactivity of the Fe0 surface due to precipitation.400 to 2. The observed sharp decrease in Mn concentrations at the first port is consistent with this conclusion. The molar transfer coefficients represent the mole percentage of the parent compound that degrades to a daughter product. depending on the column reactive mixture (Table 10. The model assumes that of all the reaction products from TCE degradation. Cr(VI) concentrations in the column effluent are predicted to exceed the MCL value of 0. including the production or accumulation of cDCE and VC breakdown products and their first-order decay. 1995). The accumulation of SiO2 within iron oxyhydroxide coatings (goethite) surrounding zero valent iron grains has been noted previously by Blowes et al. the H4SiO4 concentration decreases sharply by the first or second sampling port. Cr(VI) concentrations at this port were above MCL. k3 represent first-order rate constants (d-1). Ground-water residence times within the column were calculated by dividing distances along the column by the groundwater velocity. therefore. These results suggest that the reaction with Cr(VI) is very rapid and that the Cr front is migrating slowly through some of the columns. to these profiles. with the remaining (1-y) % of the cDCE degrading to alternative breakdown products such as acetylene. with the other (1-x) % of the TCE degrading to alternative breakdown products such as chloroacetylene.05 mg/L (MCL) at the first sampling port (2.58) with respect to quartz and are undersaturated with respect to amorphous SiO2 (SI = -0. 12. only y % of the cDCE decays to VC. Rate constants and molar transfer coefficients were then calculated from non-linear least squares fit of concentration versus residence time data to analytical solutions for eqn. and x. the association of Si with mixed Fe(III)-Cr(III) hydroxide solid solution (eqn.05 mg/L Cr after 1. y represent mole transfer coefficients (mole %).4). as well as for use in conjunction with reactive-transport modeling. Figure 37). At later times. In the downgradient direction. Rate constants for the reductive-dechlorination of the chlorinated organics were obtained by fitting a consecutive first-order decay model. cDCE and VC are shown in eqn.000 pore volumes (Table 10). This model describes the first-order reductive-dechlorination of TCE. that H4SiO4 concentrations decrease as a result of the coprecipitation of amorphous silica with Cr and Fe bearing solids.possible that precipitation of rhodochrosite or a less crystalline precusor limits dissolved Mn concentrations. At an estimated flow velocity of 10 cm/day at the Elizabeth City site. Determination of Reaction Parameters: Cr(VI) Data from the column tests were used as a basis for the selection of reactive materials for the reactive barrier. The input waters are slightly supersaturated (SI = 0. Palmer (1999) confirmed the presence of silicacontaining goethite and/or amakinite on the surface of iron filings collected from the downgradient side of the Elizabeth City full-scale barrier. 9 through 11. adapted from Hill (1977). 3) or mixed Fe(III)-Cr(III) (oxy)hydroxide solid indicates that Si may contribute to the passivation of the granular iron surfaces over longer treatment times.. Although a discrete solid silica phase is not expected to form and thereby affect the reactivity of the iron filings.5 m granular iron barrier within 19 to 28 years. Similarly.

while the normalized rate for VC degradation was significantly greater for 100PL (Table 12). Orth and Gillham. the cost of Peerless iron (~ $375 US/ton. 1994. TCE concentrations decrease more rapidly than the concentrations of cDCE and VC within the columns. are shown in Figures 44 through 46. Previous laboratory experiments indicated that less than 10% of TCE degrades to chlorinated degradation products (Gillham and O’Hannesin. Consequently. and there was the further concern of segregation of the sand and iron during installation. The remaining two reactive materials. These higher values may be advantageous in offsetting potential long-term precipitate formation. These pathlines were traced from an upgradient grid of 0. the selection of the barrier width and reactive material will be based upon the reactivity of the reactive mixtures toward cDCE and VC. 16 .3 m spacing. Pathlines that enter the “gate” zone of a Funnel-and-Gate or the continuous wall were considered to be within the capture area of that barrier. 1995). Comparison of the molar transfer coefficients of various reactive mixtures indicates that between 4 and 17% of the TCE mass degrades to cDCE. capture areas and residence times. The certainty in the calculated values therefore decreases with increasing scatter in the data. The 100MB and 100PL columns also have similar hydraulic conductivity and porosity values. 1996). shown previously in Table 2. TCE.TCE cDCE t = TCE o e − k1t xk 1 TCE k 2 − k1 o (12) t = cDCE o e − k 2t + ce − k 1t − e − k 2t h (13) VC t = VC o e − k 3t + cDCE o y + TCE o xy FG k e H k 2 − k 2t − k 2e − k 3t 3 − k2 IJ K gb g b gb U | gV W (14) R Sbk | T k 1k 2e −k 1t k 1k 2e −k 2t k 1k 2e − k 3t − − k 3 − k 2 k 2 − k1 k 3 − k 2 k 3 − k1 3 − k 1 k 2 − k1 gb g b This model neglects the effects of dispersion and diffusion within the columns. First-order rate constants and molar transfer coefficients for TCE. Thus. (1996). Normally this is the case for compounds that degrade slowly or are present at low concentrations. The impermeable funnels of a Funnel-and-Gate increase the capture area of the Gate (reactive material) zone. In these simulations. and calculated concentration profiles using least-squares fit parameters. These normalized reaction rates are similar to those reported by Johnson et al. based on suitable reaction rates. desirable hydraulic properties and lower cost. It should be noted that reaction rates determined from the filtering procedures can be influenced significantly by one or two data points that fall off the trend.8 m wide. cDCE and VC are shown in Table 11. 9. the entire model domain was assigned a uniform hydraulic conductivity (Table 13). The capture area of a reactive barrier is the cross-sectional area of ground water intercepted by the reactive barrier (Figure 47) and which flows through the reactive material. the sand-iron mixtures were eliminated as potential candidates for the installation. hydraulic properties (Table 12) and cost. with the remaining mass degrading to other products. The surface area normalized reaction rates for TCE and cDCE were within 20% agreement for 100PL and 100MB. and between 1 and 100% of the cDCE degrades to VC. Capture areas were estimated from the ground-water flow pathlines. However. Based on this observation. The simulated capture areas of the 15. which may reduce the hydraulic conductivity and porosity of the barrier. A range in aquifer hydraulic conductivity values was simulated in order to bracket the anticipated range of ground-water velocities. The capture area results are presented as overall capture areas and as values relative to the total area of the front face of the Funnel-andGate or continuous wall. 1997). were compared on the basis of reaction rates. cDCE and VC steady-state concentration profiles within the 100MB and 100PL columns after 40-50 pore volumes. 100 % Peerless iron (100PL) was chosen as the reactive material. which were the highest measured for all reactive materials. There appeared to be no substantial advantage in mixing sand with the iron materials. 1995) was less than that of Master Builders iron (~ $700 US/ton. and 2 m thick Funnel-and-Gate barrier are shown in Table 14.1 m deep. 100PL and 100MB. Reactive Barrier Designs Five three-dimensional numerical flow simulations were performed to assess the relative efficiency of a Funnel-and-Gate versus a continuous wall configuration (Bennett.

Based on the observed aquifer hydraulic conductivities. Very little ground-water flow divergence is observed in the vicinity of the barrier (Figure 50). This similarity arises because the ground water velocity within the reactive material is proportional to the volumetric ground water flux through it.5 m deep. Without funnels to intercept ground-water flow and increase the capture area of the reactive material. As a result.45 m thick continuous wall configuration are shown in Table 15. The funnels increase the capture area of the reactive material zone 2 to 2. relative to the velocity in the aquifer. the simulations indicate that 10.6 m was used to give a slight safety factor for residence time. is similar to the increase in capture area of the reactive material zone.000 µg/L TCE. based upon cost and flow modeling results.3 m depth of the barrier were felt to be sufficient to intercept the Cr(VI) plume. Flow modeling indicated that. simulated ground water velocities within the Funnel-and-Gate are approximately 2 to 2. there are no hydraulic advantages of a Funnel-and-Gate over a permeable wall in terms of both increased capture area and increased residence time. and the flux is directly related to the capture area of the reactive material zone. Final Selection of a Reactive Barrier Final Reactive Barrier Design The continuous wall was the reactive barrier design chosen for the site. 7. Similar residence times are calculated for the two barriers. indicating that ground water will begin to preferentially flow around it. cDCE and VC concentrations similar to those at the site to less than MCL values. The increased velocity within the reactive material. Two simulations were conducted with different hydraulic parameters assigned to the granular iron which comprise the barrier (Table 17). or longest residence time.33 m of travel in the iron (Table 18). and under the maximum anticipated flow conditions.4 m long x 7. The similar capture areas indicate that the same volumes of ground water are flowing through both barriers. 900 µg/L cDCE. the capture area is expected to be between 67 and 85 m2 for the Funnel-and-Gate configuration simulated. hydraulic properties and cost. If the hydraulic conductivity of the reactive media comprising the wall falls below that of the aquifer.6 m.3 m x 0. Both barrier designs can be configured to achieve similar residence times and capture areas using the same volume of reactive material. Residence times (Table 16) within the reactive material were calculated by averaging the component of the elemental velocity vectors parallel to the shortest path through the barrier. The calculated ground water velocities within the continuous wall are approximately equal to the velocities within the aquifer. These results indicate that for the Elizabeth City site. which is approximately 35 m wide and 6. The capture areas of a wall at the site are expected to be between 105% and 114%. Under these flow conditions. Reactive transport simulations were conducted to determine whether a 36. The simulated capture areas of the 10. 49).However. The capture area of the wall increases by only 14% when the hydraulic conductivity of the reactive material is two orders of magnitude greater than that of the aquifer. limiting the increase in capture area (Figures 48.45 m thick continuous wall composed entirely of granular iron (100PL) would provide a sufficient residence time to remediate TCE. A width of 0. This corresponds to a capture area of 82 m2 to 89 m2 for the simulated pilot-scale configuration. The hydraulic conductivity of the aquifer also has an impact on the capture area of the Funnel-andGate.0033. for the Elizabeth City site. 17 . These similar velocities arise because there is only slight preferential ground water flow through the higher hydraulic conductivity reactive material. there is only slight preferential ground-water flow through the barrier when the hydraulic conductivity of the wall is much larger than the aquifer. The similar residence times arise because both barriers have similar capture areas. there was no hydraulic advantage of a Funnel-and-Gate over a wall. A reactive medium composed entirely of Peerless granular iron was chosen for the barrier based on reactivity. which have the same volume of reactive material. The final dimensions chosen for the reactive barrier were 46 m x 7. and 101 µg/L VC will be reduced to MCL values within approximately 0. A significant volume of ground-water flows around and underneath the “hanging” Funnel-and-Gate.6-fold. for the hydraulic conductivity range observed within the aquifer.6-fold greater than in the aquifer. The 46 m length and 7. The capture area of the barrier is larger when the hydraulic conductivity of the aquifer is less than that of the gate.3 m wide. These capture areas are very similar to those obtained with the Funnel-and-Gate. The maximum anticipated flow conditions arise when the horizontal hydraulic gradient is 0. only a third to a half of the ground-water flow approaching the funnels is directed through the gate. VC requires the longest travel distance within the wall. This is because VC has the lowest MCL value and is the last degradation product produced of the decay of TCE and cDCE. however initial cost estimates suggested that the wall configuration could be more cost-effective for this site. the capture area of the wall is equal to or slightly larger than the face of the wall. before it falls below its MCL value.6 m deep x 0. the capture area of the wall will be less than 100%. The residence time is expected to be between approximately 2 and 500 days. and hydraulic conductivity is 17 m/day. This parameter indicates the minimum period of contact between the contaminant and the reactive material.6 m deep and 0. A concentration profile through the center of the reactive wall is shown in Figure 51. Thus.

additional samples were taken and analyzed. which was subsequently paved with asphalt. Approximately one month later. Alternatively. residence times would be only approximately 60% of the design value. The aquifer material that was excavated by the trenching machine liquefied. and therefore required additional management before disposal. The excavated soils were taken to a Corrective Action Management Unit (CAMU). The plastic sheets and berms were used to prevent excavated soil from washing into the river. the overall surface-area dependent reaction rates may be as low as 60% of the laboratory measured values. The bottom of the barrier was the maximum depth of installation with the trenching machine employed. A high capacity pump and large tanker were also kept onsite in the event that excavated materials exceeded the capacity of the bermed area. In addition.69 g/cm3. approximately perpendicular to the ground water flow direction. and this concrete was disposed of in the local landfill (Parsons Engineering Science. The granular iron was installed within a 0.62 and decrease in ground water velocity within the granular iron. The trench was backfilled with the natural excavated soils. which is approximately 60% of the laboratory measured bulk density. A total of 280 tons of granular iron was placed into the trench. is calculated assuming that the granular iron fills the entire trench. this volume corresponded to approximately 450 tons of granular iron. (HTI) using a continuous trenching machine.6 m wide rectangular box. TCE concentrations in the soil exceeded MCL values. 1997).72 g/cm3. Lower reaction rates at this lower emplacement density. The lower mass of granular iron within the wall is expected to have an impact on the surface area dependent reductivedechlorination rates. Excavated aquifer material was brought to the surface by an excavating belt and then conveyed to one side of the machine. 1996.6 m wide trench located between approximately 2 m and 7. Approximately 150 m3 of granular iron were required for the barrier. The soils were worked with earth moving equipment and then covered by plastic. kept the trench open while granular iron was poured in. 55) used to install the subsurface barrier simultaneously removed aquifer material and deposited the granular iron. Post-Installation Work The concrete removed from the initial 80 m by 1 m trench cut was tested for VOCs and chromium. Using the laboratory measured bulk density of 2. An emplaced granular iron density of 1. TCE concentrations were found to be below the laboratory quantitative limits. Excavated soils from the trench were stockpiled on the site. At this density. and that the granular iron may not occupy the entire volume of the trench. the granular iron thickness within the trench may be as low as 37 cm at an emplaced density of 2. Studies using borehole radar. A 0.3 m depth (Figure 52). This simultaneously loaded and undermined the concrete pavement and led to the collapse of approximately 3 m of pavement on either side of the trench (Figure 57). However. followed by a coarse aggregate. aquifer soils within the trench slumped in as the excavation proceeded. Four samples and one duplicate were collected the day after installation and analyzed for VOCs and Cr. electromagnetics. Site Preparation An 80 m long and 1 m wide cut was made in the concrete parking lot to facilitate the trenching installation. forming a soil slurry on either side of the trench (Figure 56). due to the compaction and slumping of aquifer material into the trench.72 g/cm3. It was installed on June 22. and other geophysical techniques are planned to confirm the extent of the granular iron zone. Prior to installation. The trenching machine (Figures 54. beneath the parking lot downgradient of the electroplating shop in Hangar 79. the granular iron was shipped to the Elizabeth City site and stored beneath plastic sheets on the parking lot. 18 . A decontamination area was set up with plastic liners and hay-bails for the steam cleaning of all equipment. may be offset by an increase in porosity to as high as 0. The top of the granular iron barrier was planned to coincide with the approximate depth of the water table. however. The actual volume and shape occupied by the granular iron is irregular. The lower mass of granular iron within the trench suggests that emplaced density may be less than the laboratory density. The parking lot installation area was completely fenced off. Under this extreme case. Installation The installation was performed by Horizontal Technologies Inc. The mass of granular iron used was significantly less than the 450 ton mass calculated using the laboratory bulk density for granular iron. located behind the excavating belt.Barrier Installation Configuration The subsurface granular iron wall was oriented in an east-west direction. None was detected. This formed the subbase. Plastic sheets with covered hay-bail berms were laid out on either side of the cut (Figure 53). Total Cr concentrations were found to be at background levels. The CAMU consisted of a plastic liner surrounded by concrete barriers. The USCG was then permitted to use the soil as a clean backfill at the Support Center.

Barrier Costs and Performance
The total cost of the barrier installation, including the initial design work, soil treatment and follow-up work, was approximately $985,000 U.S. (Table 19). The actual installation and granular iron costs are estimated to be approximately $350,000 U.S. This corresponds to an installation and materials cost of approximately $7550 U.S./linear meter for the 5.3 m thick and 0.6 m wide continuous reactive wall. An internal USCG report indicates that this reactive wall will lead to a cost savings of $4,000,000 U.S. over a 20 year span compared to a traditional pump-and-treat system (USCG, Pers. Comm.). The report states that the installation costs for the reactive barrier and a pump-and-treat system were comparable, however a cost savings results from the lower monitoring and maintenance costs associated with the continuous reactive wall barrier. Annual costs are estimated to be approximately $32,000 U.S. for the reactive wall compared to $200,000 U.S. for a comparable pump-and-treat system. A similar cost analysis conducted by Manz and Quinn (1997) indicates that permeable treatment walls can result in significant cost savings over a comparable ground-water extraction and treatment system. In their study of two sites, they indicate that while capital costs vary, the annual estimated operation and maintenance costs for a treatment wall were $20,000 and $27,120 U.S., as opposed to between $55,000 and $100,000 U.S. for a pump-and-treat system. The long-term cost savings associated with a reactive barrier result from its lower operation and maintenance costs, compared to a pump-and-treat system. However, the actual savings also depend on the initial capital costs for the barrier installation and the estimated longevity of the reactive barrier. Previous studies with granular iron indicate that carbonate and hydroxide minerals precipitate on the iron surfaces from anaerobic high alkalinity ground waters (Reardon, 1995; Schuhmacher et al., 1997; Mackenzie et al., 1997). These precipitates can influence the long-term performance of the barrier by potentially altering both the reactivity towards contaminants, and the hydraulic conductivity and porosity of the barrier. Granular iron column experiments indicated minimal loss in reactivity toward Cr(VI) or TCE, even after more than 100 pore volumes passed through the columns (Blowes et al., 1992; O’Hannesin et al., 1995; Blowes et al., 1997; Cippolone et al., 1997). Based on laboratory column data in this report, the extrapolated breakthrough of Cr(VI) is not expected to occur for 19-28 years at ground water velocities of 10 cm/day. Other laboratory studies to assess the impact of precipitate formation on ground water flow hydraulics within granular iron media indicated porosity losses that levelled off at 5-15% (Mackenzie et al., 1997). These porosity losses were attributed mainly to H2 gas formation, and mineral precipitation was suggested to have a more significant impact on porosity at later times. In future studies, cores will be collected from the granular iron zone to assess the extent of precipitate formation.

19

Conclusions
Ground-water flow simulations indicate that a Funnel-and-Gate and a continuous wall can be configured to achieve the same capture area and residence time, with the same volume of reactive material. Therefore, there is no hydraulic advantage in using a Funnel-and-Gate over a continuous wall. The choice of barrier design then depends on the logistics and cost of the site-specific situation. For the Elizabeth City site, the wall configuration was selected. The selection of the granular iron mixture that the reactive barrier would be composed of was based on reactivity, hydraulic properties and cost. Fast reaction rates were desirable to minimize the amount of granular iron required and high hydraulic conductivity and porosity are desirable to ensure that ground water preferentially flows through the barrier. Of the reactive mixtures tested in laboratory batch and column experiments, the ones containing 100% granular iron had the most rapid reaction rates for Cr(VI), TCE, cDCE and VC removal and the highest hydraulic conductivity and porosity values. In the column tests, input concentrations of 11-12 mg/L Cr were depleted to < 0.02 mg/L over less than 10 cm travel distance in the columns. Input TCE concentrations of 1,500-2,000 µg/L were reduced to non-detectable concentrations (<1.7 µg/L) before reaching the half-way point (30 cm) in the columns. The PL and MB granular iron materials tested had similar surface-area normalized reaction rates and hydraulic properties. A reactive material composed entirely of Peerless brand granular iron was chosen for the reactive barrier, with the final choice of granular iron source based on reactivity, hydraulic properties and cost. Contaminant reactive transport simulations indicate that 10,000 µg/L TCE, 900 µg/L cDCE, and 101 µg/L VC would be reduced to less than MCL values in 0.33 m of travel within a reactive wall composed of this granular iron at a density of 2.72 g/cm3 and under the maximum anticipated ground-water velocity conditions. The final barrier width of 60 cm was chosen to provide a safety factor for the treatment of TCE, cDCE, and VC contaminated ground water that is intercepted by the barrier. The length and depth of the barrier were chosen to intercept the entire Cr(VI) plume. The full-scale granular iron reactive wall was installed quickly and relatively inexpensively using a trenching technique, although the maximum width and depth were dictated by the trenching machine configuration. The installation was completed in 6 hours, with the only complication arising from the failure of the concrete pavement alongside the trench. The speed and relatively low cost of the installation is attributed to the effectiveness of the trenching machine, which simultaneously removed aquifer sediments and emplaced granular iron. The emplaced mass of the granular iron was approximately 60% of that calculated, suggesting a lower emplacement density and smaller volume of granular iron within the 60 cm trench. This lower iron density may result in slower reaction rates, due to decreased available mass and surface area of granular iron. Alternatively, greater porosity in the wall may lower ground water velocities within the wall, increasing the available reaction time. The extent or distribution of granular iron within the trench and the impact of the lower mass of granular iron on reaction rates will be assessed in future studies.

20

References
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24 .

Tables 25 .

47 .4) x 10-4 (4.0033 0.37 0.06 1.0.10 1.5) x 10-5 (1. DCE Isomers. First-order Rate Constants for the Dehalogenation of TCE..2. 1996) Halocarbon TCE 1.0.61 .0029 0.1.0025 Table 2. and VC (after Johnson et al.1 DCE Trans 1.18 .59 .31 .4 ± 5.21 0.0.53 .2.57 .0.15 .18 .7) x 10-5 (5 ± 1.6) x 10-4 (6.23 .9 ± 3.2.Table 1.03 1.2-DCE cis 1.0011 0.46 0.25 0.04 1.2-DCE VC KSA (L m-2 h-1) (3.2 ± 0.91 0. Horizontal Hydraulic Gradients and Water Levels Observed in Monitoring Wells Screened Between 3 and 4.1 ± 1. Reactive Mixtures Used in Column Experiments Column name 100PL 100MB 48PL/52AQ 50MBSSAQ 50PLSSAQ 50MBSS Peerless Iron 100 % 48 % Master Builders Iron 100 % 50 % Silica Sand Elizabeth City Aquifer Material 50 % 50 % 25 % 25 % 50 % 52 % 25 % 25 % 26 .0.5) x 10 -5 Table 3.5 m Below Ground Surface Water level measurement date Range in observed water levels (meters below top of well casing) Range in observed water levels (meters above sea level) Approximate horizontal hydraulic gradient (m/m) October 1994 October 1993 March 1993 April 1992 September 1991 1.0012 0.31 0. Reactive MixturesUsed in Batch Experiments Batch name AdaSS MBSS PLSS MBAQ Iron 6 g Ada 6 g MB 6 g PL 6 g MB Silica Sand 6g 6g 6g 0 Aquifer Material 0g 0g 0g 6g Table 4.2.

9E-03 2.6E-02 3.7 : 1 2.33 3.20 3.63 : 1 2. June 28 .18 : 1 1.8 24 0.2 68 17.5 245 0.Table 5.8 53 22.43 9. 1995 .3 : 1 3.9 : 1 7.35 2. 1995 FV1* = First flow velocity.2 36 34 1.41 6.3 71 17 189 0.May 17.33 8.2 : 1 2.8 55 21.6E-02 2.7E-02 2.. May 26 .6E-02 2.59 : 1 2. Mar 31 .78 : 1 3. Column Flow Velocities and Hydraulic Properties of Reactive Mixtures Used (after O’Hannesin et al. 1995) Column Name Mixture 50MBSS 50% MB Iron 50% Silica FV1 50MBSSAQ 50% MB Iron 25% Silica 25% ECAQ FV1 48PL/52AQ 48% PL Iron 52% ECAQ FV1 50PLSSAQ 50% PL Iron 25% Silica 25% ECAQ FV1 FV2 100MB 100% MB Iron 100PL 100% PL Iron FV1 FV2 FV1 FV2 Flow Velocity (FV) (ft/day) (cm/day) Residence Time (hours) Pore Volume (mL) Porosity 27 1.8E-02 2.09 6.06 : 1 1. 1995 FV2 = Second flow velocity.3 166 0.4 : 1 5.Aug 12.Aug 12.0 31 39 Hydraulic Conductivity (cm/sec) Bulk Density (g/cm3 ) Iron to Volume of Solution Ratio (g:mL) Surface Area to Volume of Solution Ratio (m2:mL) FV1 = First flow velocity.17 2.8 1.45 8.6 79 15.6 233 0.97 : 1 2.72 6.7 254 0.7 201 0.21 3.29 3.4 43 27.6 : 1 0.

1-DCE) Vinyl Chloride (VC) Inorganic Compounds Chromium VI [Cr(VI)]* Chromium (total) Iron (Fe) Sodium (Na) Magnesium (Mg) Calcium (Ca) Potassium (K) Manganese (Mn) Chloride (Cl) Sulphate (SO4) Alkalinity (as CaCO3)* MDL (µg/L) 1.0 0.00 0.Table 6.02 0.20-0.10 1.00 0.05 0.2 1. Method Detection Llimits (MDL) Organic Compounds Trichloroethene (TCE) Chloroform (TCM) Tetrachloroethene (PCE) cis 1.7 2.02 1.8 MDL (mg/L) 0.2-Dichloroethene (tDCE) 1.5 1.2 1.05 2-10 *MDL varied due to small sample volumes available for analysis 28 .7 2.05 0.1-Dichloroethene (1.02 0.40 0.2-Dichloroethene (cDCE) trans 1.

8 23.8 313.9 7 14.9 48.0 6.6 43 95.77 1.50 0.2 10 0.1 16 1. Three Reaction Vials and One Control Vial Were Sampled at Each Time.5 24.20 0.0 5.0 120.2 Control TCE (µg/L) 1517 1505 1824 1812 1839.Table 7.8 2 7.2 50 2.8 23.9 192.1 MBAQ Time (h) 0 0.8 120 7. Changes in TCE Concentration in Batch Experiments Over Time.75 1.3 Control TCE (µg/L) 1614 1658 1704 1812 1821 1786 1813 1665 1696 1519 1609 1467 Average TCE (µg/L) 1800 1546 1565 1724 1744 1758 1775 1763 1646 1520 1307 655 45 Reaction Vial Standard % Standard Deviation Deviation (µg/L) 83 4.1 61 5.23 0.2 35 2.5 8 1.9 120.50 0.4 8 1.0 17 5.3 59 4.1 71 4.4 Control TCE (µg/L) 1839 1970 1962 1900 1670 1786 1849 1798 1678 1670 1463 1652 1543 Average TCE (µg/L) 1948 1489 1114 1113 954 845 705 597 474 268 96 24 9.6 17 1.9 239 17.1 35 2.8 20 1.6 13 8.2 1 14.2 18 2.0 1.4 12 0.5 40 3.2 34 7.1 1726 1796 1740 1778 1575 1815 1678 1588 Average TCE (µg/L) 1393 1588 1514 1393 1483 1415 1403 1213 1160 1040 782 528 298 131 Reaction Vial Standard % Standard Deviation Deviation (µg/L) 415 29.58 0.9 0 0.0 1.10 0.9 1 40.7 91 7.6 29 .6 71 4.8 18 1.0 96. for Reaction and Control Vials.8 24.9 Control TCE (µg/L) 1618 1602 1572 1635 1606 1589 1538 1648 1552 1573 1561 1624 1540 1417 Average TCE (µg/L) 1561 1416 1250 1084 1003 913 879 636 482 299 149 48 11 3.9 192.4 PLSS Time (h) 0 0.0 3.2 97.4 15 11.3 22 3.0 33 3.50 0.25 0.8 2 1.1 48.8 29 1.0 48.2 72.42 0.1 23 3.0 10.10 0.3 313.0 6.7 10.8 18 1.4 2 16.0 6.0 37 2.1 14 0.5 3.8 22 1.1 3.6 21 2.2 3 0.0 11.6 23 2.5 3.8 40 4.9 16 1.5 18 2.4 19 6.0 43 6.5 82 7.0 AdaSS Time (h) 0 0.0 11.1 2 Reaction Vial Standard % Standard Deviation Deviation (µg/L) 134 6.2 Reaction Vial Standard % Standard Deviation Deviation (µg/L) 114 7.27 0.36 0.3 13 4.6 20 4. Only TCE Was Analyzed MBSS Time (h) 0 0.75 1.2 167.75 1.

4 NA 0.8 11 9 4.8 0.7 NA bd bd bd bd 101 104 11 6.1 <0.2 4.51 NA bd NA bd NA 106 NA 12 NA 19 NA 4.4 7.1 NA 0.37 bd NA bd NA 88 NA 0.06 0.89 0.8 NA 7.09 0.39 0.9 20 15 4.1 0.02 0.7 0.8 0.1 11.8 4.09 0.10 NA 0.88 9. Summary of Cr Removal in Batch Tests Batch ID Cr(VI) Co (mg/L) 11.12 0.6 <0.4 bd NA bd NA 107 NA 15 NA 12 NA 4.4 4.Table 8. 50MBSS 50MBSSAQ 50PLSSAQ 48PL52AQ 100MB 100PL Cations Chromium Cr(total) Iron (Fe) Sodium (Na) Magnesium (Mg) Calcium (Ca) Potassium (K) Manganese (Mn) Silica (Si) Anions Chloride (Cl) Sulphate (SO 4) Alkalinity (as HCO3) FV1 FV2 FV1 FV2 FV1 FV2 121 113 99 89 55 59 117 NA 95 NA 31 NA 123 NA 102 NA 57 NA FV1 FV2 FV1 FV2 FV1 FV2 FV1 FV2 FV1 FV2 FV1 FV2 FV1 FV2 FV1 FV2 8.57 NA mg/L bd bd bd bd 100 102 12.4 NA 0.0 AdaSS PLSS MBSS MBAQ Co = Initial Concentration Time to Nondetect (min) 70 23 35 43 Table 9.0 9.4 12.32 0. Inorganic Concentrations of All Columns for Both Influent and Effluent Samples at Steady-state Conditions FV Influent Conc.4 12.6 8.23 bd bd bd bd 104 104 12 6.1 104 104 15 15 24 22 5.7 NA 4.06 NA 0.25 0.8 4.9 16 9.1 NA 0.4 3.12 118 106 100 95 58 55 110 NA 81 NA 56 NA 119 118 97 92 39 33 116 110 99 90 52 31 30 .06 0.

1 3.09 0.62 13.72 9.02 MOLAR TRANSFER COEFF.81 15.06 Table 12.27 1.31 1.76 x 10-5 8. k1SA cDCE degradation rate. k2SA VC degradation rate.09 16. Predicted Breakthrough Volumes Calculated from these Data Are Shown Column First detection of Cr at 2.83 6.83 0.7 0.3 0.53 0.98 x 10-5 3.63 x 10-5 100MB 74.5 cm port (Pore Volumes) 69 82 101 78 Cr(VI) or Cr(tot) (mg/L) 0.Table 10.77 Predicted Breakthrough at Column Effluent (Pore Volumes) 1380 1640 2020 1560 100MB 100PL 50PLSSAQ 48PL/52AQ Table 11.17 7% 4% 3. k2 VC degradation rate.99 12.71 MOLAR TRANSFER COEFF.43 0.08 9.27 5.27 9. First Detection of Cr at the 2.61 7.31 8.5 cm Sample Port in Each Column.40 4. (TCE⇒CDCE) 17% 8% 9% CDCE RATE CONSTANT [1/D] (T1/2 HRS) 5.93 6.22 x 10-5 3.40 10. Hydraulic Properties and First-order Rate Constants for Peerless and Master Builders Granular Iron Hydraulic Conductivity Porosity Surface Area bulk density TCE degradation rate. k3SA UNITS m/day m2/g g/cm3 d-1 d-1 d-1 L hr-1 m-2 L hr-1 m-2 L hr-1 m-2 100PL 84.61 10. k3 TCE degradation rate.23 100% 100% 10.11 3.81 2.92 9% 2.15 1. k1 cDCE degradation rate.45 1. First Order Rate Constants in Various Reactive Iron Mixtures (Rate Constants Not Normalized to Surface Area) REACTIVE MIXTURE 100% Master Builders iron 50% Master Builders iron 50% Silica sand 50% Master Builders 25% Silica sand 25% Aquifer sed.62 3. 100% Peerless iron 50% Peerless iron 25% Silica sand 25% Aquifer sed.82 x 10-5 2.48 x 10-5 kxSA: Surface area normalized reaction rate constants 31 . AVERAGE TCE RATE CONSTANT 1/D (T1/2 HRS) 16. (CDCE ⇒ VC) 27% 100% 1% VC RATE CONSTANT [1/D] (T1/2 HRS) 6.

1 x 1.45 m thick) WALL: 78 m2 32 .6 m wide by 9.09 4.35.6 m deep by 0.6 x 2.1 m wide by 9.17 14.7 26.5 22. hydraulic conductivity 864 m/day Granular iron: porosity 0.4 Pea gravel: porosity 0.4 m/day Table 14.8 16.0 x Total FUNNEL-AND-GATE area: 143 m2 Area of each (6.38.6 40. Hydraulic Conductivity Values Used in Ground-water Flow Simulations to Compare Relative Capture Areas and Residence Times of Two Barrier Designs SIMULATION 1 2 3 4 5 VAQUIFER cm/day 0.1 x 2.3 KAQUIFER m/day 0.Table 13.1 x 1.76 m2 Table 15.1 m deep) FUNNEL: 55.0 46.1 4.5 x 2.1 m deep by 2m thick) GATE: 32.1 x 1.1 x 1.0 x Total area of (10. Capture Areas for the Continuous Wall Configuration Under Varying Aquifer Hydraulic Conductivity Conditions Simulation 1 2 3 4 5 Kiron Kaquifer 464 10 3 2 1 Capture Area (m2) 89 87 84 82 78 Capture Area (% of total WALL area) 114% 111% 108% 105% 100% Capture Area (relative to WALL area) 1. Capture Areas for the Funnel-and-Gate Under Varying Aquifer Hydraulic Conductivity Conditions Simulation Kiron Kaquifer Capture Area (m2) 85 83 79 70 67 1 2 3 4 5 464 10 3 2 1 Capture Area (% of total FUNNEL-ANDGATE area) 59% 58% 55% 49% 47% Area of Groundwater directed to GATE (% of FUNNEL area) 45% 44% 41% 35% 34% Capture Area (relative to GATE area) 2.3 m wide by 7.2 m2 Area of (3. hydraulic conductivity 46.4 x 2.

7 m/day 0.41 Velocity (m/day) 9.57 x 10-1 2.0011 to 0.40 100% 900 21 cm 20 cm VC 13.5 10.7 m/day 0.3 x 10 -6 10.38 43. Reactive-transport Parameters.0033 SIMULATION 1 17 m/day 0.29 to 0.0033 SIMULATION 2 17 m/day 0.38 x 10-1 4.18 x 10-4 4.0 Residence Time (days) 495 9.7 to 84. Source Concentrations. Hydraulic Parameters (Source of Values Indicated in Brackets) Used in Ground-water Flow Modelling to Determine Minimum Barrier Dimensions PARAMETER Aquifer hydraulic conductivity (Field estimates) Aquifer porosity (Estimated) Granular iron hydraulic Conductivity (Lab estimates) Granular iron porosity (Lab estimates) Horizontal hydraulic gradient (Field estimates) RANGE OBSERVED 0.0 m/day 0.23 -1 7. Ground-water Velocities and Residence Times within the Reactive Material Zones of the Funnel-and-Gate and the continuous Wall SIMULATION 1 2 3 4 5 Funnel-and-Gate Residence Velocity Velocity Time (m/day) relative to (days) aquifer 2.74 x 10-2 1.0033 Table 18.1 1.90 1. k (day -1 ) Transfer coefficient (%) Source Concentration (µg/L) MINIMUM DISTANCE WITHIN BARRIER Simulation 1 Simulation 2 10.02 x 10-3 2.45 0.13 Table 17.43 0.4 x 10 -6 3.1 2.91 1.03 x 10 2.Table 16.38 84.1 1. and Minimum Distance Within Reactive Barrier Before Contaminant Falls Below MCL TCE MODEL PARAMETERS Diffusion coefficient.9 1.1 to 26 m/day 7.27 4.76 x 10-1 2.000 24 cm 23 cm COMPOUND cDCE 11.62 7% 10.24 x 10-1 2.29 3.59 2.1 1.2 1.6 525 -1 1.2 3. D o (cm 2/s) Rate Constant.61 N/A 101 33 cm 32 cm 33 .52 x 10 1.03 x 10-1 Wall Velocity relative to aquifer 1.1 x 10 -6 9.40 0.

000 $200.000 34 .000 $50.000 $75. Barrier Installation Project Costs in U.000 $40.) Preliminary work Barrier Design Barrier Construction Post Installation work Reports DESCRIPTION Site Assessment RFI Workplan RFI Implementation Model Bench Test Pilot Study Design Granular iron Trenching Installation Setup/cleanup CAMU RFI Report CMS/Interim Report Baseline Report TOTAL COST $60.000 $150. Comm.000 $40.Table 19.000 $60.000 $35.000 $150. Dollars (USCG.000 $985.000 $40.000 $ 50. Pers.000 $10.000 $25.S.

FIGURES 35 .

Elizabeth City.s. and inferred 0.0 5m g/ L 1 mg/L 0.01 2 .01 MW13 5. 36 . Coast Guard Support Center.Elizabeth City REACTIVE BARRIER STUDY SITE Nixonton Weeksville Approximate Scale (km) Figure 1.01 MW37 <0.s. Monitoring Well screened 15-20 ft b. Monitoring Well screened 20-25 ft b.0 1 Cr (mg/L) June 1994 M W 20 MW27 0.01 N 0.2 MW39 <0. Plan view map showing total Cr concentrations (mg/L).6 ? M W 35D MW33 M W 19 < 0 .g.01 20 Monitoring Well screened 10-15 ft b.01 0 Figure 2.s.S.8 0 MW8 <0.01 D MW15 MW21 0. 0 MW38 <0.22 MW31 3. 0 5m g/L ? MW16D 0.8 D MW28 1 mg/L MW22 MW17 <0.08 MW2 HANGAR 79 10 meters D Plating Shop MW3 <0.s. BUILDING 78 MW36 <0.05 and 1 mg/L contours. Location map showing U.g.g.6 MW14 MW18 <0. North Carolina. Not all wells are shown.01 2 4 ? ? ? M W 35 1 .g. Monitoring Well screened 40-50 ft b.011 M W 34 8 .

591 0.28 3. (a) 0 5 10 15 20 25 30 35 Depth below groundsurface (ft) B CPT27 CPT22 West East CPT16 CPT30 B' BQL ? 1. cone penetrometer tests.0923 ? 0.0 0 ? ? 0.025 0.18 0. Scale (ft) Plating Shop HANGAR 79 Figure 3.13 1.521 0. and inferred 0.815 1. (a) Cross-section B-B’.795 1.00 0.26 0.0086 1 .26 0.55 0.124 0.0682 0.05 <0 2.93 0.0289 ? 0 .43 0. Plan view map showing approximate locations of temporary wells. and deep wells (after Parsons Engineering Science.62 0.622 3.65 4.0289 ? ? ? ? 40 BQL 0.) A 0 40 D Approx.13 1.05 0.099 3.0047 2.g.R31 R32 R3 T8 R21 R22 R2 T4 CPT22 R11 R12 R1 T2 Pasquotank River T3 CPT30 B CPT27 A' T1 CPT16 CPT15 CPT14 CPT13 CPT17 B' BUILDING 78 N River sample D CPT12 MW22 CPT11 MW21 D Temporary well Cone penetrometer location Deep well (40-50 ft b.09 0. river sampling.22 3.0 5 ? ? 0 25 Groundwater flow direction Approximate Scale (ft) Figure 4.0309 0. and (b) cross-section A-A’ indicating total chromium concentrations (mg/L).038 <0 2. 37 .0408 0.011 0 Approximate Scale (ft) (b) 0 5 10 15 20 25 30 35 Depth below ground surface (ft) A North CPT11 CPT12 CPT17 CPT13 CPT14 CPT15 CPT16 A' ? 0.s.05 mg/L and 1.00 mg/L contours in June 1994.269 0. 1994).124 0.574 1.97 0.

ML21. Monitoring Well screened 15-20 ft b.s.g.0 MW16D 4300.5 Figure 5.0 D 0 10 g/L 5µ / µg L ? MW36 0.0 MW33 M W 3 5D 0.0 MW34 620 .8 0 MW8 0.0 MW38 0.s.s.4 5 µg/L MW22 MW17 580 MW13 73. Plan view map showing TCE concentrations (µg/L). Monitoring Well screened 40-50 ft b.0 20 Monitoring Well screened 10-15 ft b.g. upgradient of proposed Reactive Barrier (April 1996).3 D MW15 MW14 MW21 53 MW2 HANGAR 79 0 10 meters D Plating Shop MW3 2 .0 MW18 1. Monitoring Well screened 20-25 ft b. Not all wells are shown.0 MW39 440.s. 38 .g.0 TCE (µg/L) June 1994 BUILDING 78 ? MW20 MW27 13. Cr concentration profiles (mg/L) at multilevel samplers in the approximate locations of piezometer bundles ML11.0 N µg/L 100 MW28 MW31 500. ? ? ? ? ? ? MW35 175 .0 MW37 1. and ML31. Figure 6. and inferred 5 and 100 µg/L contours.ML11 0 Depth (m) 2 4 6 8 0 5 0 2 4 6 8 0 ML21 5 0 2 4 6 8 0 ML31 0.0 MW19 0.g.

8 113 BQL ? 173 202 27. TCE concentration profiles (µg/L) at multilevel samplers in the approximate locations of piezometer bundles ML11.57 3. upgradient of proposed Reactive Barrier (April 1996).1 98.91 15.(a) 0 5 10 15 20 25 30 35 Depth below groundsurface (ft) B CPT27 CPT22 West East CPT16 CPT30 B' ? ? ? 5 100 3.06 9 18 74.37 4.91 15. and ML31.7 377 284 8.5 13.9 8.9 ? ? ? ? 0 40 BQL Approximate Scale (ft) 1500 BQL ? ? 5 ? 7.3 93. and (b) cross-section A-A’ indicating TCE concentrations (µg/L).5 5.6 47.94 264 362 4.61 5 10 0 ? ? 149 415 217 16. ML21.2 7. ML11 0 Depth (m) 2 4 6 8 0 100 0 2 4 6 8 0 ML21 10000 0 2 4 6 8 0 ML31 1500 Figure 8.94 264 362 4.9 ? ? 5 ? ? 0 25 ? Groundwater flow direction Approximate Scale (ft) Figure 7. 39 .7 100 68.1 ? ? (b) 0 5 10 15 20 25 30 35 Depth below groundsurface (ft) A North CPT11 CPT12 CPT17 CPT13 CPT14 CPT15 CPT16 A' ? 4. and inferred 5 µg/L and 100 µg/L contours in June 1994.04 ? 57. (a) Cross-section B-B’.

N Depth (m. A 0 5 10 15 20 25 30 35 CPT11 CPT12 CPT17 Depth below groundsurface (ft) North CPT13 CPT14 Silty fine sand CPT15 A' CPT16 ? ? Clayey fine sand to Clay ? Fine Sand with varying amounts of silt and clay ? ? Clayey fine sand ? ? ? ? 0 Organic Matter Fine Sand Silty fine sand Silty to clayey fine sand Cemented sand to HardPan Clayey fine sand Sandy clay Silty clay Clay 25 Approximate Scale (ft) Groundwater flow direction Figure 10. 40 .g. Cross-sections extrapolated from borehole log data.) 0 A B' A' B 21 0 5 5m LITHO LOG Y F in e S a n d y S ilty C la y F in e S a n d S ilty C la y e y F in e S a n d Figure 9. Geologic cross-section A-A’ extrapolated from cone penetrometer test data.b.s.

70 MW 19 0.20 MW 20 MW 19 MW38 MW39 MW27 MW34 MW31 MW28 MW16D N MW17 MW21 M W 13 M W 15 M W 12 MW 8 MW 4 M W 13 M W 15 M W 12 0 .).7 6 Groundwater flow direction 0.10 April 1992 MW 20 MW 19 Site map Pasquotank River MW33 MW35 M W 3 5D MW 19 Water levels MW 16 1. 78 0 MW 16 0.5 m below ground surface (ft. 80 0.s.30 MW 17 MW 18 MW 16 MW 17 MW 18 0. Geologic cross-section B-B’ extrapolated from cone penetrometer test data.B 0 5 10 15 20 25 30 35 CPT27 Clay Depth below groundsurface (ft) CPT22 West East CPT16 CPT30 B' ? Clayey fine sand ? ? Fine Sand with varying amounts of silt and clay ? ? Fine Sand Silty fine sand Silty to clayey fine sand Clayey fine sand Sandy clay Silty clay Clay Cemented sand to HardPan ? ? 0 40 Approximate Scale (ft) Figure 11. September 1991 MW 20 1. 6 6 Figure 12.l.7 0 BUILDING 78 1. 41 .a.61 MW 17 MW 18 MW 16 MW 17 MW 18 0.8 Extrapolated Water level contour Water level contour MW 13 MW 2 MW 8 MW 3 MW 13 MW 8 MW 3 MW 4 MW 15 MW 12 MW4 MW 15 M W 12 MW 2 Plating Shop MW6 Plating Shop 0 MW 6 10 20 meters N 0. 74 0.90 MW 8 MW 4 MW36 MW37 MW 2 MW 3 MW22 MW13 D MW18 MW 2 MW 3 Plating Shop MW 6 Plating Shop MW15 MW14 D MW2 MW3 MW8 MW4 MW 6 HANGAR 79 Plating Shop 2. Water levels in wells screened 3 to 4.56 October 1994 M W 20 0.80 MW6 October 1993 MW 20 MW 19 0.

42 . Diagram of conceptual model Cr(VI) and TCE plume development.Building 79 0 5 10 15 20 25 30 35 Clayey fine sand to clay Fine sand with varying amounts of silt and clay Groundwater flow direction Pasquotank River Depth below groundsurface (ft) Chromium Plume Building 79 0 5 10 15 20 25 30 35 Clayey fine sand to clay Fine sand with varying amounts of silt and clay Groundwater flow direction Pasquotank River Depth below groundsurface (ft) TCE Source zones Aqueous TCE plumes Figure 13.

1997).1 DCE C H H Chloroacetylene (b) H Cl trans 1.2-DCE (b) Cl C H VC (b) H C H Ethene (b) H H C H H C H H Ethane C H H C H (b) (b) H H C C H Acetylene Figure 14.Cl C Cl (a) (b) Cl C C H H C C H Cl Cl C C (b) TCE C Cl H (b) Cl H Cl C Cl 1. and (b) hydrogenolysis reaction steps in degradation of TCE (after Arnold and Roberts. (a) Reductive β-elimination.2-DCE (a) (a) (b) cis 1. 43 .

Schematic of the apparatus used in the column experiments.Figure 15. 44 .

0594 m Figure 17. with Funnel-and-Gate barrier shown. Model domain dimensions. Model boundary conditions. 3D PERSPECTIVE VIEW 18 Z 18 Y X 26 PLAN VIEW Constant Head h y=60 = 18 m FRONT VIEW No flow Boundary qn = 0 No flow Boundary qn = 0 Y Symmetry Boundary qn = 0 X No flow Boundary qn = 0 Z Symmetry Boundary qn = 0 X Constant Head hy=0 = 18. with Funnel-and-Gate barrier shown (all dimensions in m). Y-axis parallels the groundwater flow direction.Z Y X Sheet piling 18 NORTH Pea Gravel Iron filings Pea Gravel 18 Model domain bisects the reactive barrier. No flow Boundary qn = 0 45 . 26 Figure 16.

(A) Funnel-and-Gate. 46 .45 m thick Pea gravel zones.A 2 Impermeable Funnels 3. and (B) permeable wall configurations used in flow simulations [all dimensions in meters].1 Gate 2 m thick Gate zone: 1.45 7.6 Total Volume of iron3 filings: 35 m 10.1 m thick iron-filings zone.3 Figure 18.6 Iron 9. Total Volume of iron3 filings: 35 m 6 B 0. surrounded by two 2 0.

AdaSS PLSS MBAQ TCE concentration versus time in each of the four batch test mixtures.batch tests 100 150 200 250 300 350 Reactive 1500 TCE (µg/L) 1000 500 0 0 50 100 150 200 250 300 350 Time (h) MBSS Figure 19. 47 .2500 Input 2000 TCE (µg/L) 1500 1000 500 0 0 2000 50 TCE Removal .

versus time.8 800 600 Eh (mV) 0 5 10 15 20 25 7 400 200 0 -200 pH 6 5 -400 0 5 10 15 20 25 Alkalinity (mg/L CaCO 3) 160 120 80 40 0 0 5 10 15 20 25 120 100 SO4 (mg/L) 80 60 40 20 0 0 5 10 15 20 25 12 10 8 6 4 2 0 0 5 10 15 20 25 80 60 40 20 0 0 5 10 15 20 25 Time (h) Fe (mg/L) Cr (mg/L) Time (h) MBSS Figure 20. AdaSS PLSS MBAQ Batch test inorganic geochemistry for all mixtures. 48 .

0 0. Cr(VI) concentration vs.0 Time (h) 1.0 MBSS AdaSS PLSS MBAQ Figure 21.12 8 Cr(VI) (mg/L) 4 0 0.5 1.5 2. 49 . time in each of the four batch test mixtures.

I.I. Cr(OH)3 (c) 2 0 -2 -4 0 12 5 10 15 20 25 S.I.I. 50 . Cr(OH)3 (a) 2 0 -2 -4 0 12 5 10 15 20 25 S. Ferrihydrite 4 0 -4 -8 -12 0 5 10 15 20 25 S.I. Siderite (d) 0 -2 -4 -6 -8 -10 0 4 5 10 15 20 25 S. Goethite 8 8 4 0 -4 -8 -12 0 5 10 15 20 25 Time (h) MBSS Figure 22.I. Calcite 0 5 10 15 20 25 7 -2 -4 -6 -8 pH 6 5 -10 0 2 5 10 15 20 25 2 S. Dolomite 0 -2 -4 -6 -8 -10 0 4 5 10 15 20 25 S.8 2 0 S.I. calculated with MINTEQA2. Time (h) AdaSS PLSS MBAQ Mineral saturation indices for batch tests.

Trichloroethene (TCE) 2000 1800 1600 Concentration ( µg/L ) 1400 1200 1000 800 600 400 200 0 0 10 20 30 40 50 Distance Along Column ( cm ) 50MBSS Figure 23. TCM concentration versus distance along all six columns at the first flow velocity (FV1). Chloroform (TCM) 25 FV = 61 cm/day (2 ft/day) 20 Concentration ( µg/L ) 15 10 5 0 0 10 20 30 40 50 Distance Along Column ( cm ) 50MBSS 50MBSSAQ 50PLSSAQ 100MB 100PL 48PL/52AQ Figure 24. approximately 61 cm/day (2 ft/day). 51 . FV = 61 cm/day (2 ft/day) 50MBSSAQ 50PLSSAQ 100MB 100PL 48PL/52AQ TCE concentration versus distance along all six columns at the first flow velocity (FV1). approximately 61 cm/day (2 ft/day).

approximately 61 cm/day (2 ft/day).2-Dichloroethene (cDCE) 250 FV = 61 cm/day (2 ft/day) 200 Concentration ( µg/L ) 150 100 50 0 0 10 20 30 40 50 Distance Along Column ( cm ) 50MBSS Figure 25. 52 . 50MBSSAQ 50PLSSAQ 100MB 100PL 48PL/52AQ VC concentration versus distance along all six columns at the first flow velocity (FV1). 50MBSSAQ 50PLSSAQ 100MB 100PL 48PL/52AQ cDCE concentration versus distance along all six columns at the first flow velocity (FV1). approximately 61 cm/day (2 ft/day). Vinyl Chloride (VC) 50 Concentration ( µg/L ) FV = 61 cm/day (2 ft/day) 40 30 20 10 0 0 10 20 30 40 50 Distance Along Column ( cm ) 50MBSS Figure 26.cis 1.

100PL 50PLSSAQ TCM concentration versus distance along three columns at the second flow velocity (FV2). Chloroform (TCM) 25 FV = 30. approximately 30 cm/day (1 ft/day).5 cm/day (1 ft/day) 100PL 50PLSSAQ TCE concentration versus distance along three columns at the second flow velocity (FV2). approximately 30 cm/day (1 ft/day). 53 .Trichloroethene (TCE) 2000 1800 1600 Concentration ( µg/L ) 1400 1200 1000 800 600 400 200 0 0 10 20 30 40 50 Distance Along Column ( cm ) 100MB Figure 27.5 cm/day (1 ft/day) 20 Concentration ( µg/L ) 15 10 5 0 0 10 20 30 40 50 Distance Along Column ( cm ) 100MB Figure 28. FV = 30.

Cis 1.5 cm/day (1 ft/day) 100 Concentration ( µg/L ) 80 60 40 20 0 0 10 20 30 40 50 Distance Along Column ( cm ) 100MB Figure 29. 54 . 100PL 50PLSSAQ VC concentration versus distance along three columns at the second flow velocity (FV2). approximately 30 cm/day (1 ft/day).5 cm/day (1 ft/day) 10 Concentration ( µg/L ) 8 6 4 2 0 0 10 20 30 40 50 Distance Along Column ( cm ) 100MB Figure 30. approximately 30 cm/day (1 ft/day). 100PL 50PLSSAQ cDCE concentration versus distance along three columns at the second flow velocity (FV2).2-Dichloroethene (cDCE) 120 FV = 30. Vinyl Chloride ( VC ) 12 FV = 30.

48 PV 9 PV 55 . Inorganic results for column 50MBSSAQ at FV1.50% MB Fe + 25% EC aquifer material + 25% sand 12 8 4 0 0 10 9 8 7 6 0 600 300 28 0 -300 -600 0 150 10 20 30 40 50 9 PV 48 10 20 30 40 50 10 20 30 40 50 100 50 0 0 10 20 30 40 50 Distance (cm) 0 50 100 28 PV Figure 31.

50% MB Fe + 50% sand 12 8 4 0 0 10 9 8 7 6 0 600 300 0 -300 -600 0 150 10 20 30 40 50 10 20 30 40 50 10 20 30 40 50 100 50 0 0 10 20 30 40 50 Distance (cm) 28 PV Figure 32. 34 PV 54 PV 56 . Inorganic results for column 50MBSS at FV1.

57 . FV1 29 PV FV2 98 PV FV2 47 PV Inorganic results for column 100MB at FV1 and FV2.100% MB Fe 12 8 4 0 0 10 9 8 7 6 0 600 300 0 -300 -600 0 150 10 20 30 40 50 10 20 30 40 50 10 20 30 40 50 100 50 0 0 10 20 30 40 50 Distance (cm) FV1 24 PV FV2 79 PV Figure 33.

100% Peerless Fe 12 8 4 0 0 10 9 8 7 6 0 600 300 0 -300 -600 0 150 10 20 30 40 50 10 20 30 40 50 10 20 30 40 50 100 50 0 0 10 20 30 40 50 Distance (cm) FV1 26 PV FV2 100 PV Figure 34. Inorganic results for column 100PL at FV1 and FV2. FV1 35 PV FV2 115 PV FV2 58 PV 58 .

59 .50% Peerless Fe + 25% EC aquifer material + 25% sand 12 8 4 0 0 10 9 8 7 6 0 600 300 0 -300 -600 0 150 10 20 30 40 50 10 20 30 40 50 10 20 30 40 50 100 50 0 0 10 20 30 40 50 Distance (cm) FV1 30 PV FV2 117 PV Figure 35. FV2 66 PV FV2 135 PV FV1 5 PV Inorganic results for column 50PLSSAQ at FV1 and FV2.

Inorganic results for column 48PL/52AQ at FV1.48% Peerless Fe + 52% EC aquifer material 12 8 4 0 0 11 10 9 8 7 6 0 600 300 0 -300 -600 0 150 10 20 30 40 50 78 PV 10 20 30 40 50 10 20 30 40 50 100 50 0 0 10 20 30 40 50 Distance (cm) 55 PV Figure 36. 60 .

5 cm sample port. 61 .8 100MB 100PL 50PLSSAQ 48PL/52AQ 6 C(VI) or Crtot (mg/L) 4 2 0 0 20 40 60 80 100 120 140 Pore Volumes Figure 37. Cr detection at the 2.

I.7 PV 48. Cr(OH)3 (c) 2 0 -2 -4 0 10 10 20 30 40 50 S. Goethite 5 0 -5 -10 0 10 20 30 40 50 Distance (cm) 8.10 2 8 7 6 0 2 0 -2 -4 -6 0 4 10 20 30 40 50 10 20 30 40 50 S.1 PV Mineral saturation indices for column 50MBSSAQ at FV1.I. Siderite (d) S.I.I. Calcite 9 0 -2 -4 -6 0 2 10 20 30 40 50 pH S. Distance (cm) 27.I.I.6 PV Figure 38. Dolomite 0 -2 -4 -6 0 4 10 20 30 40 50 S. Cr(OH)3 (a) 2 0 -2 -4 0 10 10 20 30 40 50 S. Ferrihydrite 5 0 -5 -10 0 10 20 30 40 50 S. 62 .I.

Cr(OH)3 (a) 2 0 -2 -4 0 8 10 20 30 40 50 S.10 2 0 S.I. Cr(OH)3 (c) 2 0 -2 -4 0 8 10 20 30 40 50 S. Calcite 0 10 20 30 40 50 9 -2 -4 -6 -8 -10 0 2 10 20 30 40 50 pH 8 7 6 2 S. Distance (cm) 34. Mineral saturation indices for column 50MBSS at FV1.I.5 PV 63 .9 PV Figure 39.I. Dolomite 0 -2 -4 -6 -8 -10 0 4 10 20 30 40 50 S. Goethite 6 6 4 2 0 -2 0 10 20 30 40 50 Distance (cm) 27.I.4 PV 53.I.I. Siderite (d) 0 -2 -4 -6 -8 -10 0 4 10 20 30 40 50 S.I. Ferrihydrite 4 2 0 -2 0 10 20 30 40 50 S.

Cr(OH)3 (c) 2 0 -2 -4 -6 0 8 10 20 30 40 50 S.I.I.I. Dolomite 0 -2 -4 -6 -8 -10 0 4 10 20 30 40 50 S.2 PV Mineral saturation indices for column 100MB at FV1 and FV2.I.I. Siderite (d) 0 -2 -4 -6 -8 -10 0 4 10 20 30 40 50 S.I. Distance (cm) 46.I.2 PV 98 PV 29.10 2 0 S. 64 .6 PV 79. Calcite 0 10 20 30 40 50 9 -2 -4 -6 -8 -10 0 2 10 20 30 40 50 pH 8 7 6 2 S. Cr(OH)3 (a) 2 0 -2 -4 -6 0 8 10 20 30 40 50 S. Ferrihydrite 4 0 -4 -8 0 10 20 30 40 50 S. Goethite 4 0 -4 -8 0 10 20 30 40 50 Distance (cm) 24 PV Figure 40.

I. Calcite 0 10 20 30 40 50 9 -2 -4 -6 -8 -10 0 2 10 20 30 40 50 pH 8 7 6 2 S. Goethite 5 0 -5 -10 0 10 20 30 40 50 Distance (cm) 26 PV 35 PV 58 PV Distance (cm) 100.I.I. Ferrihydrite 5 0 -5 -10 0 10 20 30 40 50 S. Cr(OH)3 (c) 2 0 -2 -4 0 10 10 20 30 40 50 S. Mineral saturation indices for column 100PL at FV1 and FV2.I. 65 . Siderite (d) 0 -2 -4 -6 -8 -10 0 4 10 20 30 40 50 S.I.I.I.5 PV 114.7 PV Figure 41.10 2 0 S. Cr(OH)3 (a) 2 0 -2 -4 0 10 10 20 30 40 50 S. Dolomite 0 -2 -4 -6 -8 -10 0 4 10 20 30 40 50 S.

I.I.I. Siderite (d) 3 0 -3 -6 -9 0 4 10 20 30 40 50 S. Distance (cm) 66.3 PV Mineral saturation indices for column 50PLSSAQ at FV1 and FV2. Goethite 6 6 3 0 -3 -6 -9 0 10 20 30 40 50 Distance (cm) 5.2 PV Figure 42. Dolomite 3 0 -3 -6 -9 0 4 10 20 30 40 50 S.I. Calcite 0 10 20 30 40 50 9 3 0 -3 -6 -9 0 6 10 20 30 40 50 pH 8 7 6 6 S.8 PV 135.3 PV 30.2 PV 116.10 6 S.I. Cr(OH)3 (a) 2 0 -2 -4 -6 0 9 10 20 30 40 50 S. Cr(OH)3 (c) 2 0 -2 -4 -6 0 9 10 20 30 40 50 S.I. 66 . Ferrihydrite 3 0 -3 -6 -9 0 10 20 30 40 50 S.I.

Mineral saturation indices for column 48PL/52AQ at 78. 67 .4 PV and FV1.I. Cr(OH)3 (a) 2 0 -2 -4 0 8 S.I.I. Dolomite 0 -2 -4 -6 -8 -10 0 4 S.I. Ferrihydrite 6 4 2 0 0 S.10 2 0 S. Siderite (d) column (cm) vs pH 0 -2 -4 -6 -8 -10 0 4 column (cm) vs Calcite Calcite 10 20 30 40 50 10 20 30 40 50 S.I.I. Cr(OH)3 (c) column (cm) vs Dolomite Dolomite 2 0 -2 -4 column (cm) vs Siderite (d) Siderite(d) 10 20 30 40 50 8 0 10 20 30 40 50 S. Calcite 0 10 20 30 40 50 9 -2 -4 -6 -8 pH 8 7 -10 0 2 10 20 30 40 50 2 S.I. Goethite column (cm) vs Cr(OH)3 (a) Cr(OH)3a 6 4 2 0 column (cm) vs Cr(OH)3 (s) Cr(OH)3s 10 20 30 40 50 0 10 20 30 40 50 Distance (cm) Distance (cm) Figure 43.

Experimental and calculated cDCE concentration profiles in column. 200 180 100% Peerless 100% Master Builders 100% Peerless (calculated) 100% Master Builders (calculated) Concentration ( µ g/L) 160 140 120 100 80 60 40 20 0 0 10 20 30 40 50 60 Distance (cm) Figure 45.2000 1800 100% Peerless Concentration ( µ g/L) 1600 1400 1200 1000 800 600 400 200 0 0 10 20 30 40 50 60 100% Master Builders 100% Peerless (calculated) 100% MasterBuilders (calculated) Distance (cm) Figure 44. Experimental and calculated TCE concentration profiles in column. 68 .

45 Concentration ( µ g/L) 40 35 30 25 20 15 10 5 0 0 10 20 30 40 50 60 100% Peerless 100% Master Builders 100% Peerless (calculated) 100% Master Builders (calculated) Distance (cm) Figure 46. 69 . Experimental and calculated VC concentration profiles in column.

Funnel Gate A 60 50 40 30 20 10 0 Groundwater Flow Pathline Groundwater flow is diverted both through and around the Gate by the Impermeable Funnels. 70 . and (B) Capture area. Figure 47. B 60 50 40 30 20 10 0 Capture Area Groundwater within the Capture Area flows through the Gate zone. (A) Groundwater flow divergence in vicinity of a Funnel-and-Gate.

Funnel Gate FLOW DIRECTION Groundwater Flow Pathlines Figure 49. Vertical groundwater flow divergence around a Funnel-and-Gate. Horizontal groundwater flow divergence around a Funnel-and-Gate.Funnels Groundwater Flow Pathlines FLOW DIRECTION Figure 48. 71 .

Predicted TCE. and VC concentration profiles through the iron-filings wall. Groundwater flow divergence around a continuous wall.Groundwater Flow Pathlines FLOW DIRECTION Figure 50. 72 cDCE and VC Concentrations (µg/L) TCE Concentration (µg/L) . 10000 9000 1000 900 800 700 600 8000 7000 6000 5000 4000 3000 2000 1000 0 0 5 10 15 20 25 30 35 40 45 50 TCE cDCE 500 400 300 200 VC 100 0 Distance within iron-filings wall (cm) Figure 51. cDCE.

73 .3 m 5.6 m Depth = 2-7.6 m BUILDING 78 A IRON FILINGS BARRIER Length = 46 m Width = 0.5 m Iron Filings CROSS-SECTION A-A' (Not-to-Scale) 0.2 m Asphalt pavement 0. (a) Plan view.6 m Coarse aggregate 0.1.(A) A' 46 m 0.2 m Excavated natural soils 7.3 m GROUNDWATER FLOW DIRECTION Cr(VI) SOURCE ZONE PLAN VIEW HANGAR 79 (B) A A' 0.6 . and (b) cross-sectional view of reactive barrier.6 m Figure 52.

Plastic sheets laid down around trench for erosion control. 74 .Figure 53. Peerless iron filings stored on site. Figure 54.

3 m deep.Figure 55. Figure 56. Trenching machine used to install the 7. 75 . Excavated aquifer sediments on either side of the trench. 0.6 m wide granular iron barrier.

Figure 57. 76 . Picture showing collapse of concrete pavement on either side of the trench.

LIST OF APPENDICES Appendix A: Grain size distribution curves Appendix B: Elemental and TCLP analyses Appendix C: Bromide tracer test data (lab columns) Appendix D: Batch test inorganic data Appendix E: Batch test mineral saturation indices Appendix F: Reactive column organic data Appendix G: Reactive column inorganic data Appendix H: Reactive column mineral saturation indices Appendix I: Analytical laboratory procedures 77 .

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Appendix A: Grain size distribution curves Grain Size Distribution Curves 100 Silica Sand (SS) 90 EC Aquifer (AQ) 80 MB Iron Percent Passing 70 PL Iron 60 50 40 30 20 10 0 0.1 1 Grain Diameter (mm) 10 79 .01 0.

3400 MDL wt% 0.7400 Peerless (PL) wt% 0.00045 0.01000 Total % < = less than MDL %Wt = ((mg/Kg)/1000000) *100 95.0000 0.0577 0.00025 0.0019 0.00005 0.1970 0.0156 < 0.01000 0.2500 82.0036 0.00010 0.00100 0.1700 < 0.1100 3.0044 0.2850 88.00005 0.00010 0.00010 0.01000 0.0022 0.0000 0.0001 0.2000 0.0030 0.0737 0.Appendix B: Elemental and TCLP analyses Master (MB) GX-27 Element Al B Ba Be Cd Ca Cr Co Cu Fe Pb Mg Mn V Zn Ni P Ag Sr Na Mo Ti Zr S C Si wt% 0.0159 0.1400 2.0384 89.0152 0.0004 0.00160 0.0058 0.00020 0.0001 0.1420 0.00010 0.0750 < < < 0.00010 0.00005 0.7000 < 0.00100 0.00025 0.00005 0.5570 < 0.00005 0.0043 0.4717 1.00010 0.0013 0.00025 0.7052 80 .0700 0.0064 0.5060 0.0073 0.2910 0.0149 0.0002 < < < 0.0000 1.0210 0.2440 2.00030 0.00005 0.00005 0.00050 0.

0005 <0.04 <0.04 <0.008 0.04 Hexachlorobenzene <0.0002 0.4.008 0.04 <0.01 <0.04 0.05 <0.200 0.20 0.025 Thallium <0.05 <0.04 <0.0 0.2 0.04 <0.20 <0.025 Lead <0.10 <0.4-Dichlorobenzene <0.05 <0.05 .10 <0.04 <0.05 VinylChloride <0.5 3.005 Methoxychlor <0.04 <0.0 400 0.7 ***Volatiles*** (mg/L) Benzene <0.100 <0.025 <0.05 1.0002 Nickel <0.0 0.04 <0.025 <0.100 0.084 <0.13 100 200 5.6-Trichlorophenol <0.05 <0.5 2.05 <0.01 <0.025 0.05 Chloroform <0.100 <0.04 2.05 Carbon Tetrachloride <0.05 <0.04 Hexachloroethane <0.001 <0.05 Methyl Ethyl Ketone <0.08 2.0005 <0.04 Nitrobenzene <0.10 0.025 <0.04 <0.05 <0.100 Zinc 0.05 <0.04 <0.153 81 Leach Blank <0.12 <0.025 NA 0.0 200 0.07 Beryllium <0.10 <0.0002 <0.0 0.025 0.063 7.08 <0.Appendix B: Elemental and TCLP analyses Toxicity Characteristic Leaching Procedure (TCLP) Client ID MasterBuilder Peerless <0.038 <0.04 <0.0002 <0.20 <0.4-Dinitrotoluene <0.005 <0.025 ***Metals***(mg/L) Antimony <0.05 Leach Blank Regulatory 0.025 <0.0005 <0.025 <0.05 Chlorobenzene <0.001 Heptachlor <0.04 <0.05 <0.025 0.05 Trichloroethylene <0.10 Tetrachloroethylene <0.0005 Heptachlor Epoxide <0.005 <0.200 Barium 1.13 0.1-Dichlorethylene <0.025 <0.20 Total Cresols <0.05 <0.5 0.05 <0.04 <0.200 0.025 <0.02 0.08 <0.05 ***Semi-Volatiles*** (mg/L) 1.5 0.001 <0.0005 Lindane <0.12 Pyridine <0.200 Silver <0.04 <0.04 ***Pesticides*** (mg/L) Chlordane <0.100 <0.100 0.025 Cadmium <0.200 <0.10 <0.10 0.4.040 Selenium <0.10 1.100 Copper <0.20 0.05 1.0005 <0.7 0.04 2.100 Arsenic <0.005 <0.12 <0.0 2.040 <0.03 0.05 <0.04 <0.281 <0.025 <0.4 10.01 Endrin <0.10 0.100 <0.005 Toxaphene <0.04 Pentachlorophenol <0.04 <0.040 <0.100 Mercury <0.025 Chromium <0.05 <0.04 Hexachlorbutadiene <0.005 <0.2-Dichloroethane <0.100 <0.0 100 6.5-Trichlorophenol <0.05 <0.200 <0.025 0.431 <0.5 POL 0.05 <0.10 0.20 0.

F.9 41. indicates High Flow rate Column 101: Low flow in S.N.N.63 30.48 0.1 92.6 L.5 78.7 L.4 0. (2) 11/17/95.4 H.16 100% PL 110 93.8 92 91.5 92.3 87. 100 0.4 80.2 46.41 2 3 2 3 1 0. 67 Date Analyzed: (1) 10/26/95.12) COLUMN 102 Date analyzed 4 S.53 0.N. COLUMN 101 Date analyzed S.67 7. 10 20 30 40 44 46 48 50 55 60 66 68 70 73 75 76 77 80 90 93 97 98 103 110 120 130 140 1 0 0. (0. 1 0.2 63. PL: Peerless. 100 Average flow rate mL/min 0.8 103 110 91.F.6 56.6 0.7 106 110 10 20 25 30 33 35 37 40 42 44 46 48 50 60 82. (4) 1/17/96 82 .24) L.F.N.28 12 25.4 0.2 98.19 Composition 100% MB (MB: Master Builders.1 72.(0.17 52% PL/48% AQ µg/L Stock solution concentration 104.3 104 104 98.35 0. AQ: Aquifer sediments) COMMENTS S.8 0.8 100 102 New Pump New Pump New Pump New Pump 119 101 102 Column 101 102 104.37 0. New pumping rate slightly lower Column 102: No Flow in Samples 65.5 99.3 57.1 97 96. Bromide concentrations (mg/L) during tracer tests.58 2 3 8.7 88.9 99 98. Pump stops and is replaced.Appendix C: Bromide tracer test data (lab columns) TABLE H-1. 10 20 30 40 45 50 53 55 57 60 64 68 69 70 72 75 78 79 80 82 85 90 100 110 115 120 130 139 140 150 160 COLUMN 110 Date analyzed 4 S.N.5 1.6 94.7 79.38 0 1.4 90 100 91.F. (3) 12/8/95.(0.13) 75.45 33.5 75.2 70 80 82. indicates Sample Number (samples were taken every 30 minutes) L.7 93.8 98.36 11.2 107 112 111 102 99.7 55.F.1 110 83.1 89. indicates Low Flow rate H.7 83.15) 75 85.F. 98. 66.2 104 89.4 75.(0.8 91.

98 102 1.4 Measured 0.2 0 0 20 TIME (hrs) 40 60 CXTFIT Concentration (ppm) Final Results (April 1996) COLUMN 102 Tracer experiment 120 100 80 60 40 CXTFIT 20 0 0 10 20 30 Time (hrs) 40 50 60 Measured COLUMN 110 Tracer experiment data 100 90 Concentration (ppm) 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 * Measured CXTFIT COLUMN 101 102 110 MATERIAL* 100% Master Builders (100 MB) 100% Peerless (100 PL) 48% Peerless/ (48 PL52AQ) 52% Aquifer material Master Builders and Peerless are Iron Time (hrs) RESULTS CASE 1 CASE 2 Calculated (see (1) below) Measured results V column [cm/hr] 101 1.51 0. CASE 2 : Finding unknowns (dispersivity. R) using lab.66 0.43 0.51 0.73 from effluent flux 0.09 1.97 2. 83 . [mL] 254 245 189 2.33 fixed R (R=1) using lab velocity calc. D) assuming a known retardation of R=1.2 1 0.11 1.37 [mL] 288 264 211 V [cm/hr] porosity [lab] Pore vol. measured velocities (1): Calculated porosity.51 D [cm] 1.47 0. D.20 1.81 110 2. and retardation.41 D [cm] 1.8 C/Co 0.58 R 1. [calc] 0. from CXTFIT Velocity CASE 1 : Finding unknowns (velocity. measured effluent flux.6 0.13 porosity Pore vol. V. and pore volume from CASE 1 velocity and lab.45 0.Appendix C: Bromide tracer test data (lab columns) Bromide tracer results COLUMN 101 Tracer Data 1.03 1. and dispersivity.15 1.

11 0.94 0.7 88.01 0.08 Ca 27.66 1.76 4. Water Quality Lab Time (h) pH Eh (mV) CaCO3 Composition: MB+SS 0 5.05 <0.01 2.7 0.45 0.5 <0.02 0.13 0.02 0.08 0.04 103.1 42.14 0.02 Co Cr Cr(VI) 11.07 0.71 0.02 <0.48 0.9 29.07 0.2 <0.9 28.1 0.02 0.49 0.0 28.1 3.56 11.1 6.01 0.48 23 24 7.49 0.03 <0.9 29.13 0.8 36.14 5.07 26.25 0.7 18.01 0.01 <0.17 0.2 Mg 17.06 <0.04 101.02 0.50 0.01 0.02 0.19 0.08 0.11 <0.46 184 3 6.9 0 0 0 0.08 11.04 0.3 18.5 0.7 62.5 <0.03 630 0.33 5.7 33.48 0.7 <0.87 -47 Al 0.0 49.02 <0.76 0.01 100.03 0.008 11.11 34 138.00 <0.01 2.3 0.6 Mn 0.4 36.05 <0.48 0.01 0.5 Ba 0.02 <0.5 .01 0.02 0.5 <0.01 Mo Na Ni Pb Si 5.00 <0.26 0.08 0.1 32.02 <0.2 <0.7 27.01 0.92 11.45 -161 Composition: MB+AQ 0 6 611 0 6.2 0.0 16.5 6.02 112.5 <0.03 2.9 18.7 18.4 18.17 <0.21 1.02 <0.1 <0.27 0.5 0.9 107.01 1.47 0.13 0.01 0.0 79.9 98.01 0.00 94.6 30.3 7.61 5.5 <0.3 <0.47 0.1 97.00 0.66 <0.03 101.08 0.02 <0.02 0.00 130 129 128 130 131 88.25 6.01 0.00 Cl 123 126 107 107 106 107 112 110 SO4 89.10 0.05 15.2 106.5 <0.02 <0.1 4.13 <0.5 <0.06 0.08 0.W.06 0.5 <0.25 0.01 97.05 6.00 <0.5 <0.5 7.01 <0.1 0.2 <0.6 17.02 <0.15 0.03 0.01 0.4 87.09 0.31 0.96 0.06 0.01 0.22 0.05 <0.1 93.1 0.09 0.47 0.1 11.88 <0.59 0.5 6 7.991 10.3 Cd <0.6 30.01 0.Concentrations in mg/L analysed at U.6 84.04 0.27 6.02 <0.01 <0.93 1.00 0.02 <0.02 <0.84 <0.92 552 0.22 2.02 0.96 1.5 <0.01 113.26 608 0.05 0.5 76.45 0.75 6.05 <0.02 <0.06 0.16 0.5 <0.01 98.05 0.07 0.81 0.7 28.02 0.06 0.38 <0.3 84 88.5 <0.47 0.6 18.03 0.3 67.98 6.2 123.2 94.98 16.34 0.92 551 43.4 3 7.0 125.7 0 5.01 100.00 0.8 <0.88 2.5 <0.02 <0.09 0.03 0.7 7.35 0.04 0.04 0.32 0.1 87.3 0.02 <0.0 17.88 0.01 <0.5 12.49 0.0 <0.8 <0.08 0.7 18.12 4.75 6.01 <0.2 Composition: Ada+SS 0 5.5 <0.2 3.06 0.3 38.92 7.14 0.08 As <0.47 4.3 36.1 91.00 0.07 0.02 <0.44 0.07 0.00 126 124 125 125 119 120 122 122 125 121 121 90.74 10.05 <0.67 3.01 96.7 30.92 1.04 1.5 <0.48 0.76 1.5 121.9 18.13 0.09 0.6 98.02 <0.72 6.4 7.01 0.42 6.05 0.01 0.47 0.10 0.11 0.11 0.09 116 0.96 368 23.5 <0.64 5.44 159 3 7.01 <0.10 5.56 -0.5 95.28 4.90 20.00 <0.48 0.4 <0.14 0.13 6.01 0.92 5.84 5.0 30.6 104.79 5.6 11.3 89.02 <0.98 2.5 0.3 35.5 6.17 1.7 91.01 1.39 15.71 2.44 0.01 <0.5 0.91 1.20 0.47 188 92.5 <0.11 <0.48 0.20 1.6 0 0 0 0.25 0.7 17.08 0.29 -266 23.00 0.3 17.1 85.96 352 0.95 458 0.01 0.2 <0.1 7.1 <0.5 <0.3 0.49 0.00 0.7 0.06 0.00 105.7 32.33 2.5 -92 140.21 6.28 <10 11.11 1.3 0.0 101.01 0.1 0.2 <0.9 17.6 1.01 0.1 80.02 <0.2 41.6 <0.02 <0.2 34.51 1.0 29.5 29.08 0.08 0.44 0.12 315 1.5 <0.01 Appendix D: Batch test inorganic data 51.45 0.9 0.02 0.06 0.2 90.4 16.05 0.10 0.1 0.2 18.49 0.88 <0.00 11.49 3.10 0.69 0.14 563 0.01 0.2 <0.16 0.1 0.7 93.5 30.01 0.2 134.13 0.07 0.05 0.33 204 5.04 28.09 15.75 6.5 0.3 18.2 15.027 11.06 0.48 0.00 12.5 6.01 0.01 <0.04 34 Composition: PL+SS 0 5.00 Sr 0.14 <0.03 0.01 1.5 <0.12 0.01 0.39 3.01 0.2 <0.07 0.00 0.45 0.69 5.5 <0.00 <0.24 93.0 47.01 0.71 55 23.3 418 0.1 6.01 <0.4 97.4 <0.00 0.2 17.11 0.01 <0.05 <0.12 7.4 0.02 0.05 100.09 0.79 <0.2 95.0 29.02 <0.2 17.06 0.3 17.01 0.05 0.45 7.0 18.02 0.96 0.2 63.49 Zn 0.01 <0.46 <0.02 <0.3 18.01 0.00 0.03 0.6 <0.25 5.51 0.01 <0.16 0.13 0.7 <0.98 0.4 92.00 0.39 42.02 0.46 0.2 <0.82 <0.3 84 45.05 <0.05 <0.47 3.7 16.21 <0.5 17.37 0.2 20.6 29.52 0.49 0.02 <0.2 0.02 <0.6 0 0 0 0 0 Cu 0.9 25.00 0.3 121.05 0.87 -47 24 7.7 155.4 2.01 <0.01 <0.01 <0.03 0.00 122 125 106 118 101 115 130 90.00 0.80 4.8 124.15 <0.02 0.4 106.01 101.96 12.47 0.31 35.6 <0.9 95.09 0.52 29 137.15 459 51.86 5.6 38.9 39.02 0.1 11.02 1.02 <0.4 99.52 42.10 0.12 0.5 <0.3 <0.49 0.02 <0.1 7.00 0.5 <0.05 0.5 <0.01 0.12 0.01 0.08 0.02 Fe <0.66 1.5 <0.95 4.3 93.01 0.17 0.14 563 0.5 89.05 0.17 0.2 96.01 <0.0 53.77 5.20 8.01 0.8 33.01 0.5 <0.4 0.02 0.5 18.01 2.5 <0.6 11.12 11.47 0.01 <0.12 0.14 0.4 38.51 2.01 1.00 97.6 96.02 <0.1 0.5 <0.02 0.5 <0.02 <0.6 42.70 42.05 0.99 554 0.01 5.5 97.00 0.9 <0.6 91.06 0.01 0.5 117.10 0.1 5.01 0.55 6.2 3.5 <0.3 <0.7 49.01 2.97 17.02 <0.02 0.16 0.5 76.02 115.05 <0.51 5.58 0.00 0.07 0.43 42.01 99.01 <0.02 0.09 0.4 0 0 0 0 0 0.05 114.01 <0.14 5.07 0.40 3.08 28.05 <0.2 31.18 0.08 0.92 0.83 62 6 7.03 11.85 7.43 <0.4 17.4 18.39 K <0.99 4.02 <0.9 17.55 <0.4 -378 100.5 <0.01 <0.04 10.09 0.7 16.6 90.8 24.4 <0.4 94.08 0.16 0.1 0.03 112.21 1.01 1.76 2.6 <0.02 6.48 0.01 112.00 0.

714 -0.363 -2.934 Composition: MB+AQ 0 0. or freshly precipitated .979 24 -0.558 -0.626 -4.84 -3.214 -0.693 -0.422 -0.783 2.636 -0.915 -10.073 -2.613 Rhodochrosite -2.633 -2.778 -10.210 -0.396 -6.968 5.176 6 0.073 -2.070 -4.561 -2.371 -1.244 0.616 Amakinite -8.760 0.06 5.556 3.154 23.260 0.521 2.916 -4.979 -3.816 -0.367 -0. Notes: (c) = crystalline (a) = amorphous (d) = disordered.395 0.675 -1.143 -1.607 -0.610 -8.587 -11.665 -2.758 -1.082 -4.951 -6.880 -1.712 -1.732 -0.660 5.374 0.219 0.608 2.999 5.458 -3.099 1.607 -0.308 1.359 0.509 -0.13 -2.011 0.920 0.975 -6.366 -2.665 -0.383 0.882 -2.85 0.444 -3.619 -1.480 -1.201 5.511 -2.670 6.5 1.021 Quartz 0.060 -3.468 -0.053 -0.169 -1.323 -1.5 3 6 24.75 -2.863 0.379 -1.604 -1.197 -0.603 -0.007 -2.048 -6.797 6.169 -1.625 -0.205 -2.306 0.157 -1.122 -1.868 -0.867 2.759 -3.847 -1.957 Siderite (d) -4.352 -7.861 -4.283 -10.357 0.924 -2.Elizabeth City batch experiments Saturation indices calculated by MINTEQA2 Based on UW Water Quality Lab data Composition: MB+SS Time (h) Ferrihydrite 0 0 0.471 -3.52 -4.397 0.225 -0.271 -1.142 -0.598 -0.35 3 -0.680 -0.564 -7.637 -5.75 -0.265 4.278 -3.526 -0.289 0.622 -2.453 -2.821 -4.053 -0.527 1.763 -1.170 -1.1 0.27 0.614 -0.015 -8.653 -0.844 -2.52 -0.610 Goethite 4.9 -1.525 -0.135 0.644 Cr(OH)3 (c) -3.509 -0.600 5.085 0.534 6.345 0.537 -8.435 -3.164 0 0.866 5.307 -0.680 -0.087 0.303 -0.376 Appendix E: Batch test mineral saturation indices Composition: Ada+SS 0 -1.25 0.674 -0.344 23.289 0.586 -0.167 1.219 1.874 5.421 -1.844 0.006 0.310 -2.166 -2.172 -0.268 -0.545 -2.333 0.937 -3.396 0.521 -0.089 -1.199 -0.461 -0.751 -2.24 -0.607 -2.407 -0.245 -1.1 1.234 -0.593 -0.724 -2.051 -2.622 -0.78 2.100 5.046 -2.143 -1.384 -10.018 -0.578 2.015 -2.75 0.771 -1.302 0.426 -1.7 -0.566 0.999 6.332 -4.105 6.246 -11.608 -0.839 -1.984 -2.404 -4.311 -2.690 -2.090 -1.586 -0.169 -0.25 0.932 -2.087 -7.361 0.459 Dolomite -5.757 -1.634 -0.794 0.191 -2.468 -2.368 0.396 0.42 1.110 0.856 -4.486 1.789 0.944 0.657 -0.187 5.117 -0.197 24 -0.597 -2.687 0.374 0.087 0.837 -1.298 0.276 -4.103 -4.108 0.143 -3.663 -3.759 6.722 -0.495 -0.288 0.689 5.532 -3.677 1.099 -7.119 -0.049 0.262 -2.027 -0.893 -0.675 -2.326 -3.391 0.650 -7.615 -0.524 -2.263 -4.01 mg/L) is one half the analytical detection limit.268 0.991 -1.366 5.002 85 Composition: PL+SS 0 0.021 -0.535 -3.328 0.377 -10.358 0.370 0.968 0.125 -0.409 -1.334 -2.379 0.214 -0.195 -1.004 -2.122 -2.239 0.249 0.191 0.316 0.513 5.650 -6.848 6.479 -2.069 -0.586 -0.745 -4.946 -0.884 -2.401 -2.347 0.396 0.689 -4.370 5.171 0.611 -0.520 -2.1 -0.477 -0.246 -2.341 0.195 These calculations assume that the t=0 Cr composition is dominantly Cr(VI) and that the Cr(III) concentration (0.504 6.249 0.591 0.069 -0.1 0.779 -1.431 6.933 -1.571 -7.580 -1.210 -0.509 3 -4.554 -8.015 -3.581 -0.934 -1.467 -0.896 Calcite -2.304 0.778 -11.566 -1.590 -0.776 -0.723 0.759 -1.03 1.960 0.75 0.301 0.527 0.417 -0.479 1.155 -2.750 -2.973 -1.133 0.280 -4.252 -3.279 1.247 -2.428 2.370 -2.812 -1.05 -0.160 -2.106 1.517 -2.786 Aragonite -2.183 7.061 0.899 Cr(OH)3 (a) -0.37 0.782 -1.153 0.901 5.614 -1.5 -4.648 -0.398 1.763 -0.780 -2.289 0.417 -0.975 -0.025 -1.395 SiO2 -0.644 -4.742 0.138 0.620 -0.5 0.797 6.

3 4.3 8.5 47.9 nd 3.8 2.9 25.2 nd nd 2.6 nd nd nd 2.0 4.7 50 90 nd nd nd nd 41 70 nd = not detected RN = reservoir number 86 .3 4.2 18.7 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd 0.8 12.2 45.2 45.2 64 103 124 nd nd nd 4.4 2.0 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd cDCE FV1 8.66 Organic Concentration ( µg/L) 1.8 1.3 30.9 1.3 30.2 38.0 4.4 nd 1.9 39.4 11 8.2 0.8 12.4 3.64 Effluent 6.2 45.35 2.9 2.1 4.00 1.3 2.4 nd nd TCM FV1 6.2 2.00 PV TCE FV1 RN Influent 0.3 a a b b b c 1.1 6.2 38.1 16.3 a a b b b c 1553 1464 1588 1795 1393 1580 888 992 1104 1160 1048 1090 136 256 383 673 446 460 14 14 10 46 35 11 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd PCE FV1 6.6 nd 2.33 0.4 2.7 3.4 20.8 2.08 0.MasterBuilder 25 % Elizabeth City Aquifer Material 25 % Silica Sand 201 mL 0.Appendix F: Reactive column organic data REACTIVE COLUMN 99 50MBSSAQ Column Composition: Pore Volume (PV): Porosity: Flow Velocity 1 (FV1): Residence Time (FV1): 50 % Granular Iron .1 3.6 1.8 12.0 0.3 30.50 0.1 6.2 ft/day (68 cm/day) 17.7 a b b b c c 61 58 69 55 50 70 167 113 122 68 79 80 221 208 136 101 103 112 204 198 222 155 145 137 14 104 173 134 132 162 nd 83 99 155 112 189 nd nd 8.7 0.4 20.2 2.4 20.16 Distance Along Column ( ft ) 0.7 hr 0.5 6.9 nd nd 2.6 nd nd nd 0.31 1.3 a a b b b c 25 21 22 26 18 18 13 15 16 17 14 11 4.4 4.2 38.

0 9.3 9.2 1.2 18.1 1.50 0.4 9.0 9.33 0.66 Organic Concentration ( µg/L) 1.6 37.0 8.7 a b b b c c 17 41 39 38 28 43 pH Along Column 15 36 34 32 24 32 15 34 31 26 25 43 13 40 31 29 22 50 13 27 31 24 24 39 12 29 28 26 19 34 3.16 Distance Along Column ( ft ) 0.5 9.7 a b b b c c 1.0 9.5 nd 1.4 9.2 0.8 a a b b c 386 350 369 275 354 -47 -168 -144 218 -203 -139 -191 -16 317 -217 -157 -231 -132 -26 -256 -168 -218 -149 -44 -217 -205 -229 -126 -63 -140 -278 -260 -216 -67 -275 -269 -281 -150 61 -242 -38 274 -157 294 -42 nd = not detected RN = reservoir number 87 .1 9.8 17.3 Redox Potential Along Column ( mV ) Eh FV1 1.1 9.3 9.8 1.2 2.1 16.Appendix F: Reactive column organic data REACTIVE COLUMN 99 50MBSSAQ Column Composition: Pore Volume (PV): Porosity: Flow Velocity 1 (FV1): Residence Time (FV1): 50 % Granular Iron .00 PV RN Influent 0.0 9.5 7.2 9.7 1.64 Effluent tDCE FV1 8.08 0.2 9.2 9.2 9.4 9.9 9.31 1.1 39.2 18.3 8.1 9.3 11 10 17 7.8 9.2 16 pH FV1 1.3 8.4 19 nd 4.3 9.9 39.00 1.8 a a b b c 6.8 6.9 7.2 9.6 7.0 6.MasterBuilder 25 % Elizabeth City Aquifer Material 25 % Silica Sand 201 mL 0.0 8.0 19 22 20 12 25 0.2 10.5 7.9 39.8 17.8 nd 1.3 9.6 37.1 16.9 25.2 10.3 9.9 7.3 8.35 2.1 0.5 47.9 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd VC FV1 8.2 ft/day (68 cm/day) 17.2 9.2 9.0 9.7 hr 0.3 nd 9.9 nd 1.1 39.2 9.9 25.5 47.7 0.4 8.2 9.3 8.2 9.4 9.3 9.

4 nd nd nd nd a a a b b b 1584 1671 1538 1830 1621 1825 835 899 1185 846 1246 1250 328 538 798 634 943 835 13 85 172 197 260 204 0.9 7.3 3.08 0.4 33.6 hr Distance Along Column ( ft ) 0.7 1.5 2.7 18.9 2.8 nd nd nd nd nd nd nd nd nd nd nd nd nd nd 0.4 nd = not detected RN = reservoir number a a a b b 62 60 61 46 51 96 80 37 69 51 209 108 154 96 95 251 173 170 136 140 167 205 204 146 152 134 163 187 156 152 8.4 8.7 18.2 10.2 10.3 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd 0.41 1.0 11 13 6.50 0.7 18.64 Effluent Organic Concentration ( µg/L) cDCE FV1 7.0 1.7 4.5 nd nd 0.9 nd RN Influent 0.4 33.2 31 30 16 nd 1.0 8.8 2.9 0.2 1.4 27.0 nd nd 2.9 42.0 6.Appendix F: Reactive column organic data REACTIVE COLUMN 100 50MBSS Column Composition: Pore Volume (PV): Porosity: Flow Velocity I (FV1): Residence Time (FV1): 50 % Granular Iron .8 2.2 12.2 10.8 ft/day (55 cm/day) 21.5 4.6 1.9 5.4 nd nd nd nd nd a a a b b b 2.6 5.6 0.9 nd 1.7 5.3 26.MasterBuilder 50 % Silica Sand 233 mL 0.00 PV TCE FV1 4.9 42.2 1.0 4.9 TCM FV1 4.5 0.6 1.16 0.31 1.9 PCE FV1 4.5 1.3 26.8 nd 0.1 0.6 11.6 nd 1.8 1.8 19.2 119 204 127 183 nd 69 168 98 132 nd 12 137 62 122 88 .6 1.5 38.5 7.0 2.33 0.9 3.8 3.9 42.0 15 16 8.3 nd 35 14 18 15 13 nd nd nd nd nd nd nd 7.00 1.3 11.4 1.9 a a a b b b 20 20 23 23 22 19 11 12 15 8.3 26.4 33.66 1.

6 hr Distance Along Column ( ft ) 0.3 9.3 9.00 1.0 a a a b b 6.2 12.4 27.4 9.0 2.3 8.2 9.4 27.9 1.8 ft/day (55 cm/day) 21.5 6.4 0.66 1.9 9.3 9.5 38.8 19.8 19.4 9.0 9.64 Effluent nd nd nd 0.0 0.2 8.3 9.2 7.5 8.1 13.3 6.3 9.2 9.1 9.6 7.2 9.1 1.8 44.7 nd 0.8 29.0 9.0 1.9 1.8 7.33 0.0 7.MasterBuilder 50 % Silica Sand 233 mL 0.41 1.4 49.0 9.8 a a a b b c 32 37 15 37 40 35 pH Along Column pH FV1 5.5 7.1 13.4 0.9 9.3 22 20 20 27 26 28 29 32 17 28 28 14 30 28 17 27 27 28 25 29 19 31 28 29 24 24 18 32 24 30 20 23 16 28 24 21 16 22 17 27 21 20 12 26 16 20 21 20 Redox Potential Along Column ( mV ) Eh FV1 5.4 9.5 9.8 RN a a a b b c Influent 2.8 21.4 9.0 0.8 8.2 nd nd VC FV1 7.0 1.1 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd tDCE FV1 Organic Concentration ( µg/L) nd 0.7 nd 1.9 1.8 9.4 nd nd nd 0.16 0.4 0.08 0.7 9.2 9.0 a a a b b 344 371 354 360 360 -77 -120 9 31 159 -218 -121 65 -9 85 -204 -175 -187 -207 129 -221 -152 -265 -200 -7 -223 -206 -250 -239 -103 -197 -228 -201 -309 -201 -171 -310 -244 -279 -175 82 28 229 -181 156 nd = not detected RN = reservoir number 89 .6 9.3 1.5 nd 1.1 1.4 8.2 8.4 8.00 PV 7.8 29.4 9.7 9.4 nd 0.50 0.1 9.5 38.2 12.8 21.5 9.Appendix F: Reactive column organic data REACTIVE COLUMN 100 50MBSS Column Composition: Pore Volume (PV): Porosity: Flow Velocity I (FV1): Residence Time (FV1): 50 % Granular Iron .4 49.31 1.0 7.8 44.3 9.2 9.

4 ft/day (43 cm/day) 27.3 1.4 nd nd nd 1.2 177 378 649 602 857 713 848 386 975 1018 1016 791 1184 1203 1116 nd 2.2 46 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd FV2 PCE FV1 4.0 nd 2.7 hr 0.7 57.1 51.9 nd 1.2 1.0 nd 0.7 1.4 1.6 2.2 2.9 68.00 1.2 1.9 5.3 1.4 1.5 3.16 1.1 31.0 1.2 1.4 1.7 nd 1.66 Organic Concentration ( µg/L) 100 % Granular Iron Master Builders 254 mL 0.6 22.6 1.7 nd nd 2.5 a a a b b b c d d d d d d e e e 1.4 64.3 0.4 64.9 29.2 16.1 35.3 84.2 1.4 0.4 74.7 57.7 77.2 1.7 5.31 1.4 80.0 1.50 0.00 PV TCE FV1 RN Influent 0.9 29.5 51.8 2.8 ft/day (24 cm/day) 50 hr 0.3 10.1 1.6 22.08 0.4 1.3 10.64 Effluent 4.1 nd 0.9 61.2 71.3 1.33 0.4 1.2 71.3 1.9 68.7 77.5 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd FV2 nd = not detected RN = reservoir number 90 .4 74.4 nd nd nd nd nd 0.0 nd 0.5 7.6 1.2 16.5 nd nd 1.Appendix F: Reactive column organic data REACTIVE COLUMN 101 100MB Column Composition: Pore Volume (PV): Porosity: Flow Velocity 1 (FV1): Residence Time (FV1): Flow Velocity 2 (FV2): Residence Time (FV2): Distance Along Column (ft) 0.7 1.4 1.8 16 78 95 212 265 465 691 746 674 890 1019 904 nd 8.0 0.5 a a a b b b c d d d d d d e e e 1697 1634 1541 1691 1596 1825 1288 1462 1295 1214 1227 1069 861 1734 1436 1309 1.6 1.4 1.1 2.5 11.7 nd 0.0 1.6 48 6.9 2.5 1.45 1.9 61.3 84.8 6.4 80.1 nd 0.8 2.

3 65.6 22.64 Effluent nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd FV2 cDCE FV1 7.7 32.7 a a a b b c c c d d d d d d e 62 68 68 59 51 51 58 56 67 48 61 39 46 76 65 243 216 204 127 112 118 53 62 73 57 56 81 43 61 63 209 242 256 156 228 182 130 118 118 145 129 47 56 74 59 nd 2.1 12.1 5.8 6.00 PV TCM FV1 4.8 1.66 Organic Concentration ( µg/L) 1.1 51.3 10.3 1.7 hr 0.9 1.7 55.5 RN a a a b b b c d d d d d d e e e Influent 20 23 22 22 20 19 20 23 24 19 22 22 19 28 23 23 0.9 3.4 9.4 111 107 183 139 130 101 84 140 142 73 83 144 101 nd nd nd 37 81 100 88 73 78 67 57 49 53 81 59 nd nd nd nd 22 60 53 45 53 43 51 34 30 53 35 nd nd nd nd nd nd 3 nd 3.2 nd 0.7 78.8 2.5 5.7 7.9 12 12 nd nd nd nd nd nd nd nd nd nd nd nd 1.9 29.0 72.9 68.9 61.4 80.0 1.3 9.0 7.2 16.4 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd FV2 91 .6 7.00 1.31 1.2 11 12 6.4 84.4 6.2 71.6 4.1 35.3 4.7 15 18 20 16 17 19 19 0.8 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd 100 % Granular Iron Master Builders 254 mL 0.45 1.08 0.8 7.4 64.0 11.7 57.4 ft/day (43 cm/day) 27.33 0.4 11 5.1 17.0 75.1 58.0 8.7 77.Appendix F: Reactive column organic data REACTIVE COLUMN 101 100MB Column Composition: Pore Volume (PV): Porosity: Flow Velocity 1 (FV1): Residence Time (FV1): Flow Velocity 2 (FV2): Residence Time (FV2): Distance Along Column (ft) 0.0 53.4 23.4 39.8 62.8 ft/day (24 cm/day) 50 hr 0.4 9.4 74.50 0.7 69.4 5.16 1.3 3.

1 0.1 20 22 20 10 8.3 65.0 72.7 0.45 1.66 Organic Concentration ( µg/L) nd 0.7 13.7 69.5 RN a a a b b c c c d d d d d d e e e Influent 2.6 0.3 12 25 13 25 32 24 15 14 18 16 15 5.7 1.9 nd 0.1 5.7 78.3 7.1 7.3 nd 0.4 0.8 7.6 5.4 23.9 nd 1.3 2.5 0.2 1.0 0.6 nd 0.16 1.7 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd 0.9 12 9 11 29 26 12 30 26 22 12 13 22 11 21 10 8.3 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd 100 % Granular Iron Master Builders 254 mL 0.7 81.7 55.7 0.5 6.4 0.7 hr 0.4 0.0 2.3 10 26 29 12 26 28 27 12 12 22 19 26 3.3 5.0 1.Appendix F: Reactive column organic data REACTIVE COLUMN 101 100MB Column Composition: Pore Volume (PV): Porosity: Flow Velocity 1 (FV1): Residence Time (FV1): Flow Velocity 2 (FV2): Residence Time (FV2): Distance Along Column (ft) 0.9 3.1 2.33 0.5 0.0 78.8 ft/day (24 cm/day) 50 hr 0.4 ft/day (43 cm/day) 27.1 0.7 69.2 12 14 14 3.4 39.8 1.1 10 5.3 1.9 4.5 1.8 62.3 nd 0.8 5.5 1.9 nd nd nd nd nd nd nd nd nd nd nd FV2 92 .8 0.4 0.8 5.9 2.7 3.3 65.1 17.0 53.0 2.1 17.9 1.8 85.7 32.1 0.1 12.8 1.8 8.7 55.3 3.0 0.1 58.8 nd nd nd nd nd nd nd nd 0.5 a a a b b c c c d d d d d e e e 34 37 15 38 40 38 17 15 33 28 26 10 6.8 5.7 81.4 39.7 nd nd nd nd nd nd nd nd nd nd nd nd nd nd 2.6 0.7 0.9 0.3 7.1 1.5 2.0 75.6 3.5 0.8 6.0 1.8 1.2 1.2 0.4 5.4 23.7 32.1 58.6 1.3 0.31 1.2 6.4 0.1 4.6 2.4 7.3 nd 1.50 0.9 8.0 72.5 1.7 2.1 nd nd 0.8 0.00 1.8 62.2 12 7.8 85.08 0.1 12.64 Effluent nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd FV2 VC FV1 7.1 3.00 PV tDCE FV1 7.0 1.0 53.4 3.5 15 9.6 1.

0 9.7 7.7 9.4 9.3 9.4 9.5 9.6 9.Appendix F: Reactive column organic data REACTIVE COLUMN 101 100MB Column Composition: Pore Volume (PV): Porosity: Flow Velocity 1 (FV1): Residence Time (FV1): Flow Velocity 2 (FV2): Residence Time (FV2): Distance Along Column (ft) 0.2 12.7 9.3 77.2 60.4 9.1 54.5 9.1 a a a b b c d d d d d e e e 351 386 332 336 366 278 315 309 286 284 272 291 289 245 -213 -206 -159 -327 198 309 202 186 174 194 184 129 260 1 -289 -196 -268 -287 137 296 135 133 147 -97 164 -27 170 72 -256 -205 -329 -345 -168 -31 -7 -208 -137 -302 -195 -72 -100 -153 -297 -269 -437 -221 -347 -92 -14 -272 -174 -204 -108 -215 -145 -229 -274 -293 -380 -272 -265 -123 -129 -181 -257 -241 -145 -306 -232 -315 -222 -296 -432 -307 -349 -31 -37 -311 -347 -204 -282 -312 -199 -328 -197 -290 -447 -375 -254 -94 -107 -367 -290 -270 -196 -349 -209 -311 127 112 -443 -11 126 293 256 263 205 265 241 240 73 258 FV2 nd = not detected RN = reservoir number 93 .3 9.6 9.8 85.6 9.5 9.6 9.9 19.08 0.8 ft/day (24 cm/day) 50 hr 0.7 9.8 80.6 9.8 85.7 9.1 9.3 9.1 a a a b b c d d d d d d e e e 9.66 Organic Concentration ( µg/L) 100 % Granular Iron Master Builders 254 mL 0.0 9.3 9.3 9.6 9.5 9.6 9.2 7.0 8.2 6.4 36.5 9.3 6.5 9.7 6.4 9.5 8.2 9.8 9.1 8.4 9.4 9.5 9.6 7.1 9.2 9.6 71.50 0.16 1.7 7.6 8.6 9.3 9.8 8.6 9.3 9.9 5.7 hr 0.5 9.6 9.5 25.0 74.00 1.4 9.3 8.9 64.4 36.3 9.2 9.4 9.6 9.2 9.3 6.2 12.5 25.7 8.5 9.0 9.5 9.5 9.9 19.6 8.2 60.5 9.4 ft/day (43 cm/day) 27.3 9.6 9.8 9.6 9.5 9.4 9.2 57.5 9.6 9.5 9.0 9.4 9.7 9.4 9.5 9.7 9.5 9.8 6.7 9.2 57.1 8.2 9.5 9.4 9.6 71.4 9.4 9.8 6.6 9.1 54.3 9.1 8.2 7.9 9.5 9.3 9.6 FV2 Redox Potential Along Column ( mV ) Eh FV1 5.2 9.5 9.64 Effluent Influent pH Along Column 7.6 9.3 9.7 9.45 1.4 68.2 9.8 80.7 9.6 9.31 1.0 74.5 9.5 8.8 8.6 9.5 9.8 9.6 9.00 PV pH FV1 RN 0.9 68.1 9.2 9.3 9.33 0.4 7.4 9.9 9.5 9.1 7.3 77.2 9.2 9.1 9.1 8.2 9.3 6.5 9.6 9.0 9.

3 16.1 1.7 3.2 d 1.0 10.0 a a a b b b 1.7 1.9 85.0 1.7 1.1 RN a a a b b b c d d d d d d e e e Influent 1697 1750 1533 1830 1691 1825 1288 1462 1442 1214 1227 1069 815 1734 1436 1385 0.8 d 1.9 1.3 16.1 1.7 1.8 81.1 13 5.7 e 1.6 nd 1.2 98.5 32.8 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd FV2 65.5 hr 1.9 24.8 2.0 nd 1.3 7.1 nd = not detected RN = reservoir number 94 .0 0.6 41.7 102.50 0.1 0.7 1.2 22 56 76 97 95 147 nd 12 3.64 Effluent nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd FV2 PCE FV1 4.0 65.3 85.2 d 2.3 81.9 18 6.0 10.6 1.8 91.0 98.6 9.66 Organic Concentration ( µg/L) 245 471 1159 1256 1263 1031 652 623 223 1010 1038 1035 639 837 1000 941 53 190 473 931 1020 897 894 861 971 1041 975 1016 821 1026 1002 1025 nd 24 15 123 153 306 303 287 270 559 745 718 730 836 739 781 nd 15 5.2 95.4 100 % Granular Iron Peerless (-8 to 50 mesh) 245 mL 0.6 0.2 77.5 107.7 1.2 1.5 nd nd 0.5 e 1.7 1.00 PV TCE FV1 4.3 1.2 nd 2.2 1.8 72.2 107.9 1.6 1.7 nd 1.2 c 2.0 0.9 0.4 91.7 2.2 72.33 0.8 nd 1.1 e 1.3 nd nd nd nd 1.8 2.9 1.2 1.5 1.6 41.2 nd 1.7 6.8 ft/day ( 53 cm/day ) 22.6 0.2 77.4 1.0 ft/day ( 31 cm/day ) 39 hr 0.3 95.6 3.08 0.31 1.Appendix F: Reactive column organic data REACTIVE COLUMN 102 100PL Column Composition: Pore Volume (PV): Porosity: Flow Velocity 1 (FV1): Residence Time (FV1): Flow Velocity 2 (FV2): Residence Time (FV2): Distance Along Column (ft) 0.0 0.00 1.43 1.2 d 1.4 2.9 d 1.2 nd nd 1.0 1.4 1.5 4.8 d 1.16 1.5 1.6 1.2 2.6 6.9 1.7 2.6 1.5 102.5 32.9 24.

7 nd nd nd nd nd nd nd nd nd nd FV2 95 .8 7.1 5.9 24.2 77.3 3.5 100.0 12 12 8.8 8.9 14 12 15 12 8.5 nd nd nd 3.8 88.6 6.6 0.8 1.1 6.3 92.4 0.0 ft/day ( 31 cm/day ) 39 hr 0.8 2.2 72.9 25.7 3.5 5.9 85.1 2.4 nd nd 0.5 32.0 6.1 73.9 5.5 2.2 a a a b b c c c d d d d d d e e 67 56 66 62 51 51 53 56 73 52 57 39 49 59 65 89 167 108 93 60 54 58 46 62 55 52 57 45 43 81 59 56 181 130 148 78 96 84 48 53 67 67 78 20 46 68 59 70 94 108 136 98 107 94 59 78 84 109 93 51 53 97 71 100 38 71 96 76 75 73 35 34 56 52 67 54 62 101 65 92 8.3 104.8 91.4 38 58 38 52 47 18 17 30 25 24 21 25 57 42 45 nd 6.9 8.8 6.50 0.5 69.3 0.64 Effluent nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd FV2 cDCE FV1 7.6 0.4 5.8 5.7 2.43 1.16 1.7 36.1 12.9 0.00 PV TCM FV1 4.8 2.3 7.3 79.1 nd 5.6 0.2 17.3 0.0 65.8 10 13 nd 0.2 98.66 Organic Concentration ( µg/L) 2.1 11 14 0.1 RN a a a b b b c d d d d d d e e e Influent 20 25 21 23 23 18 20 23 22 21 22 25 18 28 23 22 0.5 100 % Granular Iron Peerless (-8 to 50 mesh) 245 mL 0.7 2.0 1.8 ft/day ( 53 cm/day ) 22.6 4.7 102.0 10.9 2.00 1.2 1.33 0.6 41.7 12 nd nd nd nd nd nd nd nd nd nd nd nd nd 1.2 95.2 2.7 5.1 nd nd nd nd nd nd nd nd nd nd nd nd 0.3 16.0 4.5 6.9 67.1 2.4 0.6 8.6 8.Appendix F: Reactive column organic data REACTIVE COLUMN 102 100PL Column Composition: Pore Volume (PV): Porosity: Flow Velocity 1 (FV1): Residence Time (FV1): Flow Velocity 2 (FV2): Residence Time (FV2): Distance Along Column (ft) 0.4 2.3 96.2 2.6 47.0 82.2 2.2 2.0 5.6 0.9 14 15 22 22 5.6 6.7 nd 7.0 0.31 1.7 5.08 0.8 81.6 13 17 19 12 6.5 hr 1.5 107.6 4.

3 1.16 1.8 5.1 1.0 51.7 1.9 nd 1.0 2.1 2.4 99.4 0.2 nd 3.0 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd 19 21 14 11 nd nd nd nd nd nd nd nd nd nd nd nd FV2 76.4 d 104.4 0.5 nd 4.8 16 20 27 34 50 % Granular Iron .5 21.6 94.5 2.0 nd nd nd nd nd 2.8 2.2 0.5 1.5 21.8 42.8 nd nd FV2 PCE FV1 3.6 nd nd nd nd nd 1.5 nd nd 1.5 RN a b b b b c c d d d d d d e e e Influent 1553 1560 1724 1795 1524 1580 1288 1462 1246 1214 1227 1069 905 1734 1436 1282 0.3 7.1 2.0 6.00 PV TCE FV1 3.2 nd nd 1.00 1.6 1.9 1.1 nd nd nd 0.2 6.4 4.0 e 124.6 ft/day ( 79 cm/day ) 15.3 d 89.2 2.3 1.7 2.3 0.0 c 84.4 nd 1.3 7.5 e nd = not detected RN = reservoir number 96 .4 12 2.4 1.29 2.5 1.5 d 113.2 1.8 nd nd nd 0.3 1.9 1.8 nd nd nd nd nd 0.0 51.08 0.9 nd nd nd nd nd 1.9 5.7 2.3 nd nd nd nd 1.3 d 109.2 ft/day ( 36 cm/day ) 34 hr 0.1 1.3 89.6 d 94.6 1.2 1.1 nd nd nd nd nd 3.50 0.Appendix F: Reactive column organic data REACTIVE COLUMN 105 50PLSSAQ Column Composition: Pore Volume (PV): Porosity: Flow Velocity 1 (FV1): Residence Time (FV1): Flow Velocity 2 (FV2): Residence Time (FV2): Distance Along Column (ft) 0.4 12 12 13 14 22 nd 4.9 33.6 2.3 109.6 4.5 6.9 4.2 7.6 nd nd 1.3 hr 1.0 84.4 d 99.0 3.8 nd nd nd nd nd 0.2 1.5 1.4 76.3 2.0 124.2 nd 9.4 a b b b b c 1.8 e 119.2 1.9 nd nd nd nd nd 1.0 2.6 1.33 0.6 1.31 1.8 nd nd nd 0.1 3.64 Effluent 2.5 9.9 1.3 3.8 119.4 1.8 42.0 3.0 nd 1.5 113.7 2.4 4.6 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd 1.1 2.2 1.4 104.5 9.2 0.9 33.1 1.2 1.5 1.1 1.3 1.4 1.Peerless 25 % Elizabeth City Aquifer Material 25 % Silica Sand 166 mL 0.66 Organic Concentration ( µg/L) 1141 1205 1200 1216 1220 1123 838 1134 683 1242 1022 1056 912 1231 1177 1245 676 716 812 680 981 696 403 936 648 1020 916 1056 896 1112 1134 1144 167 225 289 241 473 278 45 168 133 328 435 525 591 706 608 688 19 39 51 44 136 93 21 24 14 26 63 145 211 256 272 270 5.

6 0.7 7.0 84.8 42.2 10 4.7 1.4 nd nd nd nd nd nd nd nd nd nd FV2 97 .6 54.5 43.6 1.4 7.16 1.5 9.6 16.29 2.5 5.33 0.6 4.00 PV TCM FV1 3.3 80.7 13 13 18 16 15 13 16 4.1 6.64 Effluent nd nd nd nd nd nd nd nd nd nd nd nd nd 0.5 RN a b b b b c c d d d d d d e e e Influent 20 23 23 26 22 18 20 23 18 19 22 20 21 28 23 22 0.5 21.08 0.9 33.1 1.7 6.Peerless 25 % Elizabeth City Aquifer Material 25 % Silica Sand 166 mL 0.1 0.8 105.7 2.4 0.5 nd 6.8 95.9 4.5 100.7 1.6 ft/day ( 79 cm/day ) 15.6 3.3 2.0 124.3 8.8 0.2 0.7 nd nd nd 1.7 a b b b c c c c d d d d d d e e 61 58 54 49 50 65 51 56 67 49 51 39 37 66 65 74 86 54 67 47 46 50 55 47 56 57 52 32 34 77 59 62 138 72 99 59 58 65 44 67 51 52 45 34 37 64 56 60 137 93 99 86 58 80 42 67 62 40 57 47 59 90 71 69 110 94 81 51 54 60 47 51 46 31 57 51 71 88 50 83 104 60 38 34 36 50 34 22 31 12 32 28 59 105 43 68 39 29 30 22 17 22 4.2 ft/day ( 36 cm/day ) 34 hr 0.3 3.7 4.3 20.3 1.1 8.3 4.5 113.9 nd 0.5 1.66 Organic Concentration ( µg/L) 10 12 9.3 9.8 0.3 nd nd nd nd nd nd nd nd 3.0 51.2 1.6 0.9 2.4 2.3 89.8 0.Appendix F: Reactive column organic data REACTIVE COLUMN 105 50PLSSAQ Column Composition: Pore Volume (PV): Porosity: Flow Velocity 1 (FV1): Residence Time (FV1): Flow Velocity 2 (FV2): Residence Time (FV2): Distance Along Column (ft) 0.7 1.3 0.7 8.8 119.2 6.4 104.5 nd 0.7 110.8 7.2 1.6 0.8 0.31 1.9 4.4 1.2 28.4 76.7 18 4.0 nd nd nd nd nd nd nd nd 0.4 3.4 1.2 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd FV2 cDCE FV1 4.50 0.4 nd 0.4 99.3 1.6 3.3 5.7 90.3 109.5 1.9 116.3 hr 1.6 94.1 85.5 1.7 14 27 21 20 16 16 17 19 8.00 1.3 50 % Granular Iron .3 3.8 0.0 120.6 9.4 78.6 0.3 10 10 5.3 0.

2 2.4 1.5 100.9 116.3 6.7 90.2 1.8 14 21 18 17 12 23 9.5 100.0 17 2.4 2.2 nd nd 0.4 7.8 4.5 4.1 0.8 105.5 0.2 1.9 2.00 1.7 8.6 12 8.7 1.3 19 28 28 24 16 30 12 14 17 14 21 6.6 ft/day ( 79 cm/day ) 15.2 3.1 0.6 1.6 nd nd nd nd 0.7 116.7 a b b b c c c c d d d d d e e 16 41 39 36 27 43 17 15 33 28 26 10 6.4 78.7 a b b b c c c c d d d d d d e e 1.6 2.9 0.3 nd 0.2 nd 0.Appendix F: Reactive column organic data REACTIVE COLUMN 105 50PLSSAQ Column Composition: Pore Volume (PV): Porosity: Flow Velocity 1 (FV1): Residence Time (FV1): Flow Velocity 2 (FV2): Residence Time (FV2): Distance Along Column (ft) 0.8 105.1 1.29 2.6 54.1 1.1 2.8 1.50 0.3 nd nd nd nd nd nd nd nd nd nd 0.9 1.6 16.2 nd nd 0.5 0.5 4.0 6.7 0.2 1.4 3.6 5.7 1.6 1.2 4.8 1.0 1.9 4.66 Organic Concentration ( µg/L) 50 % Granular Iron .7 1.5 43.4 4.9 3.3 2.2 3.7 6.4 0.3 nd 1.6 nd nd nd nd nd nd 0.0 120.7 3.1 1.0 1.7 1.1 1.3 1.9 13 6.1 2.5 7.4 78.3 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd FV2 VC FV1 4.3 0.7 13 17 6.9 2.6 54.5 0.31 1.8 12 15 8.1 85.8 5.1 1.1 8.3 3.9 7.3 13 12 15 5.9 10 1.4 0.1 1.8 8.1 19 27 28 24 20 25 16 14 22 19 26 7.8 nd nd nd nd nd nd nd nd nd FV2 98 .7 90.00 PV tDCE FV1 RN Influent 0.2 2.6 0.1 nd nd nd nd nd nd nd nd nd nd nd 0.3 80.1 85.3 nd 0.5 1.4 6.8 95.5 0.7 12 5.0 5.7 0.0 1.3 80.4 4.9 5.8 1.2 28.7 12 10 6.8 6.9 15 26 24 22 21 27 4.3 hr 1.8 95.33 0.4 3.1 0.3 1.6 5.6 0.16 1.2 ft/day ( 36 cm/day ) 34 hr 0.0 120.5 6.5 43.6 16.8 2.0 1.2 0.Peerless 25 % Elizabeth City Aquifer Material 25 % Silica Sand 166 mL 0.7 nd 1.4 1.3 20.64 Effluent 4.2 nd nd 0.2 28.7 1.9 5.5 0.3 20.0 2.08 0.2 0.0 6.7 110.

00 1.3 8.4 9.6 6.5 9.4 9.6 9.2 6.2 9.0 8.0 8.4 9.3 hr 1.2 9.5 8.6 44.4 7.2 9.5 9.1 8.1 8.4 9.3 9.4 9.5 7.2 9.1 40.2 ft/day ( 36 cm/day ) 34 hr 0.5 9.0 79.7 119.4 125.4 9.3 9.5 9.2 9.3 18.5 8.6 9.2 9.Appendix F: Reactive column organic data REACTIVE COLUMN 105 50PLSSAQ Column Composition: Pore Volume (PV): Porosity: Flow Velocity 1 (FV1): Residence Time (FV1): Flow Velocity 2 (FV2): Residence Time (FV2): Distance Along Column (ft) 0.4 9.3 9.0 9.5 8.2 9.9 114.0 79.3 7.7 9.0 6.7 100.7 9.08 0.4 a a b b c c d d d d d d e e e 6.4 88.3 9.5 7.3 9.1 40.3 9.1 9.31 1.1 9.6 44.66 Organic Concentration ( µg/L) 50 % Granular Iron .7 9.7 108.00 PV pH FV1 RN Influent 0.5 9.4 9.4 125.7 119.3 9.1 9.4 8.6 ft/day ( 79 cm/day ) 15.50 0.5 9.1 9.6 9.8 9.4 8.9 114.4 8.8 9.1 103.1 9.33 0.3 18.1 7.Peerless 25 % Elizabeth City Aquifer Material 25 % Silica Sand 166 mL 0.3 9.2 9.3 7.3 9.2 9.4 FV2 Redox Potential Along Column ( mV ) Eh FV1 1.3 8.5 9.1 9.3 9.2 9.7 108.3 9.1 9.8 7.2 9.6 9.3 83.9 9.1 9.4 9.2 9.3 7.1 9.2 9.3 9.0 9.2 9.0 9.2 8.4 9.3 9.9 93.6 7.9 9.1 9.9 7.5 9.4 9.7 100.9 9.64 Effluent pH Along Column 1.1 7.6 9.6 8.0 7.0 9.4 9.16 1.4 88.9 93.1 9.4 a a b b c c d d d d d d e e e 386 340 312 275 345 257 334 266 317 293 329 281 233 293 257 -264 -129 -191 19 -195 229 182 230 211 192 222 175 133 188 246 -102 -226 -247 51 129 239 171 227 79 191 207 147 35 253 259 -244 -224 -311 -116 -209 260 80 254 3 72 -152 -142 -186 -84 52 -281 -273 -349 -279 -192 -78 -44 -125 27 -187 -156 -265 -301 8 -290 -325 -265 -136 -204 -272 73 18 84 76 -117 -206 -224 -287 -158 -248 -271 -296 -143 -250 -275 -167 -84 -409 -8 250 -233 -225 -282 -247 -282 -295 -304 -218 -214 -232 -86 23 -362 -2 -212 -279 -202 -242 -346 -347 -59 188 -211 104 25 306 123 217 79 -83 256 245 156 77 138 FV2 nd = not detected RN = reservoir number 99 .9 6.2 9.2 9.3 9.4 9.3 9.5 9.4 9.2 6.1 6.0 9.1 103.0 8.1 9.3 8.7 9.2 7.2 9.2 9.3 9.6 9.3 9.4 9.0 6.1 6.2 9.5 8.3 9.4 8.7 6.9 8.6 9.29 2.3 83.0 9.

8 5.8 0.2 1.1 5.2 nd nd nd 0.7 11 9.0 0.7 46.33 2.0 36.2 2.0 d d d d d e e e 1.00 1.2 1.1 1.7 1.0 0.2 18.7 58.2 9.2 9.4 1.0 nd 2.2 2.3 ft/day ( 71 cm/day ) 17 hr 0.8 28.5 3.00 PV TCE FV1 RN Influent 0.8 2.2 28 24 22 10 12 18 18 4.7 33.7 58.64 Effluent 3.4 0.0 3.7 5.5 6.2 2.8 28.31 1.8 1.5 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd PCE FV1 3.Peerless 52 % Elizabeth City Aquifer Material 189 mL 0.4 1.4 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd = not detected RN = reservoir number 100 .5 3.3 1.3 3.6 nd nd 2.33 0.7 58.Appendix F: Reactive column organic data REACTIVE COLUMN 110 48PL/52AQ Column Composition: Pore Volume (PV): Porosity: Flow Velocity I (FV1): Residence Time (FV1): 48 % Granular Iron .4 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd TCM FV1 3.8 28.2 18.2 9.4 0.1 1.3 1.7 46.9 nd nd 0.4 2.0 36.3 5.7 33.0 d d d d d e e e 1219 1227 1166 916 538 1734 1436 1309 803 864 1005 892 323 1231 1090 1105 424 568 803 723 227 1039 848 955 29 103 357 383 179 492 342 480 nd nd 50 82 25 32 13 33 nd nd 2.08 0.7 33.7 46.0 36.1 1.2 4.5 0.6 16 16 15 3.0 d d d d d e e e 21 22 26 22 8.2 18.1 nd nd 1.16 Distance Along Column (ft) 0.0 nd nd 0.66 Organic Concentration ( µg/L) 1.50 0.

9 1.4 0.7 1.7 31.8 1.08 0.1 2.4 4.4 nd = not detected RN = reservoir number 101 .7 0.6 21.3 1.7 1.8 5.1 nd nd 1.5 3.Appendix F: Reactive column organic data REACTIVE COLUMN 110 48PL/52AQ Column Composition: Pore Volume (PV): Porosity: Flow Velocity I (FV1): Residence Time (FV1): 48 % Granular Iron .6 21.5 1.2 nd nd nd nd 0.9 0.5 13 11 6.3 0.3 38.0 17.6 nd 2.33 0.5 1.0 5.0 12.9 4.9 1.3 ft/day ( 71 cm/day ) 17 hr 0.6 1.0 17.7 38.7 1.0 4.2 1.3 6.4 41.2 0.4 41.64 Effluent 12.00 1.3 38.2 1.0 8.9 3.7 31.33 2.16 Distance Along Column (ft) 0.5 6.4 2.4 4.31 1.6 nd nd nd 5.9 5.9 0.5 nd nd 0.8 6.0 9.3 2.8 8.1 4.0 5.4 41.5 9.1 1.0 6.7 8.8 1.5 2.9 2.7 nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd VC FV1 12.00 PV cDCE FV1 RN Influent 0.3 0.2 3.6 12.1 1.0 9.0 17.6 21.0 4.1 d d d d e e 41 41 37 36 57 65 51 41 37 76 73 58 41 55 37 80 52 59 26 65 34 77 94 65 11 38 24 73 72 59 0.1 tDCE FV1 12.7 11.1 d d d d e e 3.0 6.2 23 21 64 51 32 nd 2.66 Organic Concentration ( µg/L) 1.0 nd 0.4 3.2 nd 0.7 3.1 nd nd nd 6.2 0.6 nd 1.2 2.3 4.3 3.9 nd 1.1 d d d e e 10.8 0.50 0.9 5.Peerless 52 % Elizabeth City Aquifer Material 189 mL 0.

1 9.4 27.0 9.9 10.64 Effluent Influent pH Along Column 6.1 23.9 42.5 6.5 39.9 8.33 2.4 6.0 8.0 9.2 9.3 9.08 0.1 9.4 9.0 6.7 19.6 9.3 9.7 1.3 9.4 9.9 8.1 9.1 9.Appendix F: Reactive column organic data REACTIVE COLUMN 110 48PL/52AQ Column Composition: Pore Volume (PV): Porosity: Flow Velocity I (FV1): Residence Time (FV1): 48 % Granular Iron .1 9.1 9.7 8.0 9.5 8.3 7.66 Organic Concentration ( µg/L) 1.1 9.2 7.Peerless 52 % Elizabeth City Aquifer Material 189 mL 0.2 9.8 9.1 7.9 9.1 8.2 d d d d d e e e 344 298 264 256 298 322 294 313 68 149 136 194 134 74 123 140 -15 93 121 175 51 150 115 103 -29 -115 74 155 -51 -295 -213 -132 22 -155 -49 86 -293 -404 -211 -176 192 -35 -205 -10 -139 -310 -361 -208 166 -159 -146 -24 -172 -455 -395 -170 127 -225 -153 -86 -219 -418 -399 -146 273 226 275 252 266 229 32 41 nd = not detected RN = reservoir number 102 .9 9.4 6.50 0.5 9.0 9.5 39.3 ft/day ( 71 cm/day ) 17 hr 0.4 9.2 8.2 7.2 7.4 27.0 7.3 9.5 48.2 9.1 9.2 9.4 8.4 8.1 9.1 9.4 9.4 9.9 42.2 9.3 Redox Potential Along Column ( mV ) Eh FV1 1.3 9.1 23.2 d d d d d e e e 7.9 7.7 7.3 9.2 9.2 9.7 19.4 9.1 9.1 9.5 8.33 0.1 8.1 9.4 8.31 1.3 9.00 PV pH FV1 RN 0.3 9.00 1.1 9.9 10.5 48.0 7.0 9.16 Distance Along Column (ft) 0.

18 0.1 <0.0 104.06 0.0 27.20 0.1 <0.9 44.9 42.7 14.59 7.12 0.1 8.5 44.40 0.38 2.06 105 104 103 119 104 103 101 99.8 21.40 0.1 10.1 <0.44 0.26 0.07 0.2 0 <0.8 21.05 <0.18 9.05 <0.19 0.370 0.500 0.014 0.83 5.1 0.23 5.1 <0.1 <0.45 0.017 0.124 <0.1 0.2 <0.92 1.05 <0.05 <0.1 0.6 13.33 8.15 1.8 101 31.4 27.2 <0.2 <0.3 23 22.0 112.1 <0.0 44.94 16.1 <0.0 <0.1 15.0 <0.38 0.42 6.1 12.5 23.010 0.001 <0.008 0.2 97.06 0.46 1.04 0.03 0.2 0.55 4.08 0.51 14.032 0.97 1.1 15.1 <0.4 23.1 <0.1 <0.1 102.40 0.026 0.03 23.3 32.6 14.89 2.33 0.2 99 53.41 8.6 33.0 17.6 20.2 15.2 <0.10 103 115 111 102 107 105 104 104 107 <0.34 0.81 2.70 2.1 <0.93 1.149 <0.5 PV 0 2.42 28.1 <0.08 0.2 101 38.59 8.2 <0.3 14.63 8.7 4.0 <0.31 9.14 0.1 <0.0 106.8 34.05 128 120 121 117 118 118 133 136 122 7.073 <0.1 18.14 9.6 18. determined at UW Water Quality Lab Distance along column (cm) 50MBSSAQ at 8.1 4.39 0.28 6.1 <0.2 0.04 0.04 0.42 3.31 8.1 <0.2 <0.05 <0.3 40.79 0.1 4.2 0.1 0.05 <0.5 32.05 <0.0 108 31.1 0.85 0.5 14.2 19.45 0.05 <0.5 10 15 20 30 40 50MBSSAQ at 27.5 7 7.1 <0.04 1.2 14.94 15.255 <0.05 <0.3 39.2 22.9 16.1 <0.1 0.12 100 100 97.7 43.2 <0.17 297 107 23 283 2 -14 -88 -53 61 34.23 9.3 22.2 24.05 <0.53 7.1 <0.21 15.1 <0.07 0.32 1.08 4.1 <0.4 6.1 <0.06 24 22.155 <0.02 0.1 <0.1 41.5 12.016 <0.35 0.1 <0.46 15 14.4 15.2 <0.1 <0.1 <0.86 0.41 0.94 0.1 9.18 2.1 <0.71 0.1 PV 0 2.8 99 <0.2 22.18 32.05 <0.4 3.26 1.05 <0.80 2.9 25.93 8.24 0.38 0.94 9 9.0 104.92 8.1 <0.07 0.66 1.16 2.05 <0.10 0.06 0.4 23.27 8.1 <0.05 119 116 121 122 127 119 144 6.88 8.05 0.05 <0.6 22.5 5 10 15 20 30 40 50 50MBSSAQ at 48.0 93.08 0.1 <0.3 8.053 0.05 <0.24 0.61 0.8 0.09 9.1 <0.28 0.9 7.179 <0.41 0.1 3.1 <0.025 0.7 15 15 14.26 0.1 <0.1 <0.3 15.76 0.2 0.88 8.05 <0.9 10.2 <0.25 0.007 0.307 <0.1 29.6 14.05 0.2 <0.1 14.05 <0.2 <0.61 23.28 1.81 4.43 5.8 22.05 <0.32 0.2 0.1 <0.88 4.03 24 22.09 0.61 4.3 114.1 <0.1 5.4 15 15.46 8.29 8.43 0.1 <0.1 <0.46 1.1 <0.0 103.5 5 10 15 20 30 pH Eh (mV) CO3 SO4 Al Ba Ca Cr Fe K Mg Mn Na Ni Sr H4SiO4 Zn Cl 6.048 <0.40 0.49 0.38 6.32 7.5 3.03 0.05 0.7 44.05 <0.2 <0.5 16.05 148 128 123 126 122 122 120 129 117 103 .9 100.1 <0.06 0.023 0.6 102 103 103 103 <0.66 5.1 5.3 100 97 93 94 101 100 102 100 100 0.05 <0.05 <0.4 104 30.56 1.1 <0.05 <0.7 98.001 0.1 <0.2 <0.05 <0.13 0.1 <0.4 101.66 3.05 120 118 123 119 120 121 124 50MBSS at 27.3 13.38 0.3 36.1 0.800 0.05 <0.41 0.26 <0.034 0.35 6.4 101.7 26.71 <0.41 4.82 0.1 96.9 99 45.013 0.05 <0.52 2.3 15.5 29.012 0.1 <0.207 <0.1 <0.3 8.05 <0.07 0.1 <0.8 94.06 0.2 95.019 <0.1 <0.04 0.06 9.016 0.7 13.2 0.006 0.05 <0.56 3.943 0.83 4.04 0.3 45.21 0.9 14.2 <0.40 0.Appendix G: Reactive column inorganic data Elizabeth City reactive columns Concentrations in mg/L.05 119 119 120 122 126 132 125 123 125 6.10 103 102 97.12 9.04 0.1 0.42 0.05 <0.1 <0.92 9.36 10.1 5.5 34.15 9.5 22.05 121 125 122 122 121 120 122 117 118 6.40 0.018 0.82 15.012 <0.2 <0.1 <0.07 9.47 0.7 24.47 0.1 0.41 0.84 4.40 0.1 <0.202 0.50 0.2 101 45.9 22.7 99.2 16.9 PV 0 2.10 0.43 178 -10 -132 -145 -140 -169 -143 FV1 = 68 cm/d 29.06 0.06 0.36 15.06 0.05 <0.08 0.18 32.05 0.3 49.6 PV 0 2.95 9.3 24 22.5 0.022 0.0 105.38 0.8 101 98.5 108 101 106 102 100 <0.39 32.28 0.0 26.300 0.1 22.4 <0.28 0.40 0.31 0.02 3 3.86 1.51 2.17 0.04 0.1 <0.00 3.43 0.60 0.33 0.024 0.5 22.9 10 0.14 4.05 <0.03 0.61 6.1 7.9 15.83 4.1 9.84 0.265 <0.2 <0.31 5.2 0.2 <0.638 0.051 0.5 95.5 5 10 15 20 30 40 50 50MBSS at 53.04 96.25 0.18 31.44 2.39 307 56 54 196 324 91 149 321 330 FV1 = 55 cm/d 27.71 3.9 13.06 0.9 10.07 0.9 20.0 90.40 0.46 0.20 0.92 9.47 0.7 PV 0 2.11 0.3 19.02 0.1 <0.6 96.001 0.19 8.60 1.02 23.5 40.4 7.28 20.04 0.02 0.82 8.1 <0.013 0.6 0.5 15.38 0.8 94.95 <0.27 9.44 3.014 0.001 0.6 97.38 4.5 10.06 0.016 0.1 <0.9 49.03 0.9 <0.1 <0.6 15.4 PV 0 2.0 102.17 0.73 1.31 1.032 0.013 0.2 <0.2 <0.2 <0.062 <0.020 0.108 <0.1 60.7 97.20 0.1 <0.2 <0.08 0.41 0.97 25.39 0.011 0.1 <0.2 <0.71 7.166 0.03 0.8 15 14.9 38.4 101 94.12 0.0 85 99 98 102 100 98 97 101 95 <0.028 0.56 7.84 0.05 <0.6 22.103 <0.62 4.1 <0.7 14.03 24.68 1.29 0.2 <0.0 102.45 1.01 7 6.4 14.25 4.85 1.05 <0.38 0.94 5.1 <0.9 <0.28 367 60 62 -14 -35 -8 -57 -94 -506 24.1 <0.2 <0.019 0.6 15.15 9.49 16 15.800 0.2 <0.2 <0.5 <0.37 1.14 241 35 134 -39 -89 -76 -137 38.2 <0.040 0.1 <0.08 3.9 15 14.06 3.1 <0.7 19.3 15.029 0.9 15.83 5.16 1.13 0.1 <0.31 0.59 1.11 0.0 39.9 15.72 4.08 0.041 0.2 <0.3 19.9 42.19 0.2 94.05 <0.42 0.1 <0.2 11 7.2 23.0 21.39 0.02 0.1 <0.42 0.18 9.10 99 100 104 98.04 0.33 451 113 431 237 90 -25 -105 -88 -77 28.12 9.48 0.02 0.05 <0.0 27.07 0.2 13 12.2 0.04 0.2 <0.24 9.5 5 10 15 20 30 40 50 50MBSS at 34.4 10.040 <0.0 104.1 <0.09 7.64 0.01 5.057 0.2 14.013 0.7 14.010 0.001 0.1 28.1 <0.1 <0.0 104.16 0.41 6.45 1.6 28.08 0.38 0.014 0.34 0.05 <0.05 <0.1 <0.23 4.05 <0.2 <0.30 1.04 25 23.8 15.53 1.45 0.87 0.08 0.5 5 10 15 20 30 40 50 6.44 4.43 0.95 9.0 104.83 3.3 15.17 24.617 0.3 17 14.4 98.5 24.0 105.8 105 61.05 <0.2 0.48 7.7 50.95 1.05 <0.3 9.

Appendix G: Reactive column inorganic data

Distance along column (cm) 100MB at 24 PV 0 2.5 10 15 20 30 40 50 100MB at 29.2 PV 0 2.5 5 10 15 20 30 40 50 100MB at 46.6 PV 0 2.5 2.5 10 15 20 30 40

pH 6.26 7.6 9.1 9.46 9.36 9.12 9.56 9.2

Eh (mV) 338 -86 -165 33 -145 -160 201 -24

Alkalinity CO3

SO4

Al <0.2 0.209 <0.2 <0.2 0.26 0.238 <0.2 <0.2

Ba 0.08 0.07 0.03 0.02 0.03 0.03 0.02 0.03

Ca 24.7 24 13.2 11.2 10.2 9.31 <9 9.88

Cr(OH)2+ 10.600 0.030 0.001 0.032 0.003 0.001 0.005 0.007

Fe <0.1 1.01 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

K 4.69 5.85 5.3 4.09 5.62 6.41 4.57 4.12

Mg 15.8 15.3 15 14.7 14.1 13 12 9.85

Mn 0.85 0.39 0.26 0.25 0.15 0.14 0.17 0.16

Na 101 97.5 97.9 101 98.1 97.6 102 103

Ni <0.1 0.101 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

Sr 0.46 0.44 0.19 0.14 0.13 0.10 0.11 0.13

H4SiO4 32.54 9.30 1.10 0.73 0.84 0.65 0.75 0.65

Zn 0.113 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05

Cl 125 129 125 122 132 123 120 118

FV1 = 43 cm/d 29.6 106 58.2 106 32.1 104 24.6 98 25.4 108 25.9 103 23.1 103 20.0 100

6.39 9.22 9.24 9.4 9.46 9.54 9.54 9.56

561 -94 -139 -90 -45 -99 -149 -165

25.1 45.6 28.6 31.0 24.8 16.0 16.5 13.6

103 99 97 99 98 98 104 98

0.32 0.707 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2

0.08 0.18 0.04 0.02 0.03 0.02 0.02 0.02 0.03

25.9 25.9 20.2 14.4 13 12.9 12.6 12.3 11.4

10.800 0.019 0.056 0.016 0.013 0.020 0.023 0.022 0.006

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

3.68 6.14 5.73 4.81 6.05 3.94 4.3 4.98 4.35

16 14.6 14.6 13.9 13.8 13.7 12.7 11.7 10.5

0.84 0.06 0.06 0.20 0.23 0.15 0.14 0.14 0.11

99.9 94.7 97.2 98.3 97.2 101 101 101 101

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

0.44 0.37 0.26 0.16 0.14 0.13 0.12 0.12 0.11

32.52 9.41 1.28 0.70 0.70 0.93 0.67 0.95 0.39

0.092 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05

123 121 117 119 122 123 126 124

6.6 8.84 8.84 9.22 9.34 9.42 9.48 9.44

276 195 195 71 -29 -53 -67 -115

38.4 40.5 40.5 35.5 24.4 26.7 28.0 23.1

102 100 100 100 103 100 107 104

<0.2 0.369 0.662 <0.2 <0.2 <0.2 <0.2 <0.2

0.08 0.06 0.13 0.02 0.02 0.02 0.02 0.02

25.1 21.6 21.8 12.5 11.4 11.1 10.4 9.78

9.270 0.009 0.033 0.001 0.007 0.010 0.017 0.001

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

5.6 6.21 8.61 5.38 4.9 5.04 4.87 5.05

16.2 13.7 13.8 12.8 12.6 12.5 11.8 10.9

0.86 0.08 0.09 0.08 0.15 0.12 0.12 0.13

108 102 107 103 101 103 102 99.6

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

0.44 0.37 0.36 0.17 0.15 0.14 0.13 0.12

32.32 15.82 17.20 0.98 0.78 0.53 0.92 0.87

0.097 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05

121 119 119 116 121 116 127 123

100MB at 79.2 PV 0 2.5 10 20 50 100MB at 98 PV 0 2.5 5 10 20 30 50 100PL at 26 PV 0 5 10 15 20 30 40 50 100PL at 35 PV 0 10 15 20 30 40 50

6.33 8.41 9.26 9.46 9.57

369 312 12 -49 -521

FV2 = 24 cm/d 32 98.1 77.0 93.8 47.0 91.4 39.5 94.2 16.3 98.1

<0.20 <0.20 <0.20 <0.20 <0.20

0.07 0.14 0.01 0.01 0.02

21.3 32.0 6.0 5.8 10.6

6.844 2.077 0.001 0.001 0.001

<0.10 <0.10 <0.10 <0.10 <0.10

5.0 5.8 5.1 5.3 5.2

14.1 15.6 16.3 15.1 4.4

0.78 1.41 <0.01 <0.01 <0.01

110 111 108 107 105

<0.20 <0.20 <0.20 <0.20 <0.20

0.388 0.602 0.060 0.062 0.143

30.7 30.4 1.4 1.1 1.4

0.010 0.010 0.010 0.010 0.010

115 115 111 115 115

7.37 8.98 9.69 9.48 9.35 9.55

266 250 12 81 -171 318

35.4 26.7 31.1 12.7 23.1 19.5

95.5 85.7 85.2 90.0 89.6 91.6

<0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20

0.07 0.04 0.03 <0.20 <0.20 <0.20 0.03

20.6 17.1 12.5 9.0 9.1 9.1 9.0

7.270 5.800 0.030 0.001 0.030 0.022 0.001

<0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10

5.4 5.5 5.6 5.2 4.2 4.0 3.8

14.1 14.5 10.0 9.8 8.9 8.2 6.8

0.86 0.13 <0.01 <0.01 0.06 0.06 0.06

99.3 102 102 100 106 105 104

<0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20

0.38 0.30 0.23 0.11 0.12 0.12 0.12

31.4 28.6 15.4 3.1 0.4 0.8 0.8

0.138 0.088 0.017 0.049 0.137 0.081 0.013

116 113 113 120 113 118

6.29 8.26 9.17 9.19 9.39 9.46 9.29 9.12

317 57 -87 -165 -145 -194 -171 -42

FV1 = 53 cm/d 23.0 98 51.4 104 50.8 102 34.5 99 45.2 102 40.2 96 33.3 97 29.8 99

<0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2

0.08 0.05 0.04 0.04 0.03 0.04 0.05 0.06

25.1 24.3 20 18 16.9 15.8 15.1 14.6

10.600 0.032 0.034 0.012 0.015 0.026 0.004 0.010

<0.1 0.629 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

5.07 5.05 5.02 4.96 4.82 4.84 5.37 4.83

16.1 15.7 15.7 15.7 15.4 14.6 13.4 12.1

0.87 0.38 0.28 0.23 0.12 0.10 0.12 0.11

102 101 99.8 102 100 99.8 101 100

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

0.47 0.44 0.33 0.29 0.26 0.25 0.23 0.23

32.63 5.69 1.21 1.01 0.90 1.56 0.71 0.81

0.121 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05

110 123 122 118 122 110 114 111

6.6 8.98 9.18 9.33 9.45 9.46 9.63

561 -124 -170 -97 -107 -160 -63

24.9 39.8 25.8 41.5 30.7 26.8 23.1

92 100 100 102 99 102 101

<0.2 0.219 <0.2 <0.2 <0.2 <0.2 <0.2

0.08 0.03 0.03 0.03 0.04 0.04 0.05

25 18.7 17.1 16.3 16 16.2 16.1

10.700 0.001 0.028 0.008 0.001 0.033 0.001

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

4.83 4.41 4.73 4.52 4.66 4.7 4.75

15.8 14.8 14.7 14.3 14.1 13.3 12

0.87 0.13 0.21 0.15 0.11 0.11 0.10

99.3 101 102 101 104 105 104

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

0.43 0.28 0.25 0.23 0.23 0.24 0.24

32.92 1.24 1.01 1.23 1.01 0.85 1.00

0.086 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05

124 121 121 124 124 124 123

104

Appendix G: Reactive column inorganic data

Distance along column (cm) 100PL at 58 PV 0 5 10 15 20 30 40

pH 6.58 8.47 9.19 9.23 9.25 9.39 9.46

Eh (mV) 266 351 70 -49 -102 -133 -36

Alkalinity CO3 27.0 41.7 33.2 40.4 34.5 41.7 31.5

SO4 101 96 96 98 97 101 100

Al <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2

Ba 0.08 0.04 0.02 0.02 0.03 0.03 0.03

Ca 24.5 22.9 16.3 14.8 14.6 13.9 13.2

Cr(OH)2+ 10.500 0.023 0.001 0.001 0.001 0.022 0.029

Fe <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

K 5.13 5.8 5.24 5.17 4.4 4.75 4.11

Mg 15.7 14.5 14.3 14 13.8 13.2 12

Mn 0.86 0.16 0.05 0.07 0.08 0.10 0.08

Na 101 107 107 107 107 104 104

Ni <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

Sr 0.43 0.41 0.26 0.22 0.21 0.20 0.19

H4SiO4 32.47 8.82 1.99 1.36 1.29 1.24 1.24

Zn 0.133 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05

Cl 118 116 115 116 119 119 122

100PL at 100.5 PV 0 2.5 10 20 50 100PL at 114.7 PV 0 2.5 5 10 20 30 50 50PLSSAQ at 5.2 PV 0 2.5 5 10 15 20 30 40 50 50PLSSAQ at 30.3 PV 0 10 15 20 30 40 50 50PLSSAQ at 66.2 PV 0 2.5 5 10 15 20 30 40 50

6.26 8.36 9.32 9.41 9.22

370 296 278 -512 156

FV2 = 31 cm/d 34.5 99.6 58.6 95.1 47.0 92.4 36.6 95.9 12.3 109.0

<0.20 <0.20 <0.20 <0.20 <0.20

0.08 0.10 0.03 0.02 0.03

22.9 27.4 9.1 6.5 14.1

7.255 1.203 0.001 0.001 0.004

<0.10 <0.10 <0.10 <0.10 <0.10

6.0 5.1 5.5 5.0 4.4

14.9 14.9 15.8 15.1 6.0

0.84 1.05 <0.01 <0.01 <0.01

113 107 111 109 107

<0.20 <0.20 <0.20 <0.20 <0.20

0.401 0.494 0.141 0.085 0.227

31.8 21.6 7.5 1.2 1.4

0.010 0.010 0.010 0.010 0.010

117 113 109 114 115

7.33 9.19 9.60 9.33 9.56 9.43

319 260 248 21 86 99

35.9 35.2 24.2 23.1 16.0 18.6

93.9 87.3 84.6 90.9 89.6 88.9

<0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20

0.07 0.04 <0.20 <0.20 <0.20 0.02 0.03

22.7 18.8 6.6 11.5 9.7 9.5 9.4

7.790 6.190 0.136 0.001 0.021 0.001 0.001

<0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10

4.1 4.3 2.1 4.8 4.3 4.5 4.1

14.9 15.0 5.7 9.2 7.4 7.4 6.9

0.89 0.09 0.01 <0.01 0.02 0.02 0.06

107 105 54.4 106 105 104 104

<0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20

0.40 0.31 0.11 0.18 0.13 0.13 0.14

32.5 29.6 11.4 8.3 2.9 2.1 0.4

0.279 0.081 0.189 0.016 0.022 0.034 0.083

117 113 109 118 107 110

6.84 8.68 9.04 9.2 9.26 9.22 9.15 9.31 9.16

213 -88 -85 -135 -155 -11 -149 -104 36

FV1 = 79 cm/d 31.4 95 34.0 100 35.4 116 31.4 105 46.5 101 36.0 101 23.8 100 14.9 96 25.0 101

<0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2

0.08 0.04 0.13 0.03 0.05 0.02 0.04 0.03 0.02

25.2 23.1 23.9 23.2 22.1 22.2 21.8 21.3 22.5

10.700 0.028 0.001 0.026 0.020 0.012 0.004 0.018 0.015

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

4.57 5.43 4.35 4.89 3.56 4.7 3.5 5.07 5.4

15.8 14.6 15.1 14.4 12.6 11.8 9.41 7.64 5.85

0.86 0.31 0.35 0.14 0.10 0.09 0.08 0.13 0.09

98.3 97.1 101 99.7 96.9 98 97.3 93.9 98.9

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

0.46 0.41 0.41 0.41 0.38 0.39 0.35 0.28 0.21

31.93 3.18 2.24 1.89 2.06 2.10 2.59 1.40 1.34

0.166 v <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05

110 113 118 114 113 115 116 116 121

6.46 8.8 8.9 9.02 9.08 9.14 9.16

355 -33 -44 -57 -124 -348 -68

21.7 37.8 45.2 42.5 39.9 37.2 37.2

100 99 96 93 98 99 97

<0.2 0.232 <0.2 <0.2 <0.2 <0.2 <0.2

0.08 0.06 0.06 0.04 0.03 0.02 0.03

25.3 22.9 22.9 22.6 22.4 21.9 20.9

10.800 0.066 0.036 0.026 0.022 0.025 0.046

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

4.49 4.62 5.15 4.13 4.35 4.88 4.91

16.2 14.8 14.5 14.1 13.3 12.6 11.8

0.85 0.33 0.52 0.41 0.14 0.14 0.09

100 98.2 97.3 96.4 95.2 94.7 95.5

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

0.44 0.41 0.38 0.37 0.38 0.39 0.39

32.54 1.42 1.70 1.81 1.84 1.67 1.88

0.261 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05

118 120 113 115 118 121 120

6.58 8.18 8.94 9.06 8.95 8.96 9.08 9.22 9.17

259 109 133 -50 -38 -93 -105 -78 22

29.7 51.9 49.6 45.9 57.6 47.3 40.6 34.9 43.8

104 106 104 105 99 105 102 100 100

<0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2

0.08 0.04 0.03 0.04 0.05 0.06 0.03 0.03 0.03

24.2 23 22.3 22.2 21.9 21.8 21.6 21.2 19.9

10.400 0.009 0.043 0.023 0.045 0.016 0.032 0.009 0.009

<0.1 0.286 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

5.12 5.7 4.48 5.03 5.22 5.18 5.33 4.82 4.77

15.4 14.7 14.1 14 13.6 13.4 13.4 13 12.6

0.86 0.39 0.05 0.07 0.18 0.30 0.17 0.12 0.09

100 99.9 100 100 99.8 101 102 101 99.7

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

0.43 0.40 0.38 0.38 0.37 0.37 0.38 0.38 0.38

32.06 13.27 1.85 1.44 1.63 1.23 1.08 2.02 1.28

0.103 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05

114 119 117 116 115 120 118 118 118

50PLSSAQ at 116.8 PV 0 2.5 10 20 50

6.27 7.41 9.17 9.37 9.26

364 99 197 -436 -121

FV2 = 36 cm/d 26.3 99.0 58.6 95.6 50.7 92.3 44.8 82.5 41.9 87.7

<0.20 <0.20 <0.20 <0.20 <0.20

0.08 0.12 0.03 0.03 0.03

22.1 23.8 16.6 14.5 14.9

7.128 0.001 0.001 0.001 0.001

0.01 0.62 0.01 0.01 0.01

5.4 5.6 5.2 5.4 6.2

14.6 15.5 17.5 18.1 11.1

0.82 2.93 <0.01 0.03 <0.01

108 105 106 105 105

<0.02 <0.02 <0.02 <0.02 <0.02

0.383 0.428 0.319 0.280 0.302

30.6 25.7 1.8 1.7 1.7

0.010 0.010 0.010 0.010 0.010

117 114 115 114 111

105

Appendix G: Reactive column inorganic data

Distance along column (cm)

pH 7.35 8.58 9.36 9.30 9.38 9.35

Eh (mV) 320 298 271 -286 178 321

Alkalinity CO3 34.4 45.0 30.0 39.8 32.8 26.5

SO4 86.3 90.3 92.3 99.6 96.7 94.8

Al <0.20 <0.20 <0.20 <0.20 <0.20 <0.20

Ba 0.08 0.03 <0.20 0.04 0.04 0.04 0.03

Ca 22.8 20.5 8.54 16.8 15.4 15.5 14.6

Cr(OH)2+ 7.810 1.610 0.001 0.001 0.001 0.023 0.001

Fe <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10

K 4.7 4.3 1.9 4.2 4.9 4.6 4.8

Mg 15.1 14.3 6.0 12.1 10.2 9.6 8.9

Mn 0.88 0.21 0.17 <0.01 0.04 0.02 0.02

Na 106 103 48.8 102 102 102 102

Ni <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20

Sr 0.40 0.32 0.14 0.29 0.28 0.29 0.31

H4SiO4 32.4 25.3 10.9 2.4 2.5 3.3 1.3

Zn 0.126 0.048 0.037 0.042 0.056 0.010 0.065

Cl 106 112 110 115 111 106

50PLSSAQ at 135.3 PV 0 2.5 5 10 20 30 50

48PL/52AQ at 78.4 PV 0 2.5 5 10 15 20 30 40 50

7.34 8.69 8.7 9.08 9.42 9.36 9.63 9.81 9.87

315 298 256 258 16 207 -130 -38 271

FV1 = 71 cm/d 31.3 97.8 30.5 93.4 31.6 85.7 39.8 90.5 25.4 91.8 41.9 98.9 37.5 77.2 25.2 60.9 33.8 49.4

<0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2

0.07 0.03 <0.02 0.05 0.02 <0.02 <0.02 <0.02 <0.02

23.2 22.6 21.2 19.6 18.5 17.9 16.4 10.5 7.66

7.710 3.770 0.032 0.041 0.001 0.022 0.001 0.024 0.027

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

4.78 4.55 4.34 4.43 4.26 4.64 4.79 4.3 4.06

14.8 14.8 12.7 11.8 9.44 7.76 4.77 2.03 0.775

0.88 0.06 0.05 0.03 0.03 0.01 0.02 0.01 0.01

106 104 102 103 103 102 103 103 87.7

<0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02

0.40 0.37 0.34 0.33 0.34 0.33 0.31 0.27 0.21

31.7 28.0 15.1 1.4 0.9 1.4 2.1 1.6 2.3

0.134 0.048 0.172 0.021 0.083 0.057 0.074 <0.010 0.083

107 105 106 107 107 108 108 111 110

106

550 1.710 0.577 1.225 -1.099 1.728 0.516 -3.291 0.412 -2.505 1.065 -1.431 -0.196 5 2.516 0.415 0.195 -0. or freshly precipitated 107 .708 -35.543 6.117 15 -0.30 9.95 9.482 -0.204 -0.92 9.878 0.493 6.523 -0.299 -2.703 -26.696 -0.097 SIO2 (a) pH Eh (mV) 4.646 -1.414 1.460 1.615 -1.500 6.324 -26.1 PV 0 -0.444 1.833 15 0.774 0.622 0.106 -30.23 9.09 9.041 20 0.474 -1.499 50 -9.15 9.654 1.413 -1.827 5.133 -1.335 1.107 -41.Appendix H: Reactive column mineral saturation indices Elizabeth City reactive columns Saturation indices calculated by MINTEQA2 Based on UW Water Quality Lab data Distance along column (cm) Ferrihydrite Goethite Cr(OH)3 (a) Cr(OH)3 (c) Calcite Dolomite Siderite (d) Mackinawite Magnesite Rhodochro Aragonite Amakinite 50MBSSAQ at 8.268 1.795 -1.089 -2.996 -0.209 -3.609 -1.124 -0.712 0.108 -2.202 -1.709 -6.509 0.179 -0.117 30 -0.666 -1.5 -0.686 -1.283 0.5 -0.456 0.894 -29.347 1. and that the Cr(III) concentration is one half the analytical detection limit (0.765 2.534 -39.723 0.845 -1.411 -1.140 -57.558 0.639 -0.108 -1.757 50MBSSAQ at 27.272 -1.128 -1.71 7.07 9.934 -1.397 40 0.339 5.923 1.287 1.92 8.854 30 0.674 -51.316 -1.744 1.296 -2.564 6.759 0.115 0.275 -1.556 -0.677 -0.314 -1.201 0.275 -1.253 -0.745 1.586 5.863 -2.683 -25.595 0.381 1.367 -2.864 -50.725 0.750 40 0.534 1.492 -33.613 0.703 -1.433 -0.024 -3.054 -0.741 -1.184 10 -0.09 7.43 178 -10 -132 -145 -140 -169 -143 6.169 -1.570 0.635 1.990 -0.982 0.7 PV 10 0.713 -1.746 -3.663 0.687 -1.693 -2.27 9.794 -1.475 1.386 -4.273 -1.583 -1.060 -1.211 0.264 1.727 0.423 30 -0.88 8.314 1.893 1.531 -32.511 -0.583 -34.229 1.668 -26.450 -0.792 -22.133 5.393 5.945 5.028 1.057 50MBSSAQ at 48.517 -0.745 6.834 -1.371 20 0.467 -2.294 -0.065 -2.700 1.669 6.317 2.594 5.272 -1.272 -0.944 -0.066 0.549 5.63 8.613 -1.750 0.790 20 0.491 -1.15 9.894 5.295 FV1 = 68 cm/d 0.227 -1.727 -1.460 6.01 mg/L) (a) = amorphous (c) = crystalline (d)= disordered.514 7.733 -1.054 -2.175 0.6 PV 0 -1.618 -3.902 -1.124 10 -0.637 -1.811 -1.412 1.161 15 -0.399 -24.204 -0.873 1.686 -1.31 9.877 -44.14 9.18 9.338 1.838 8.313 6.670 0.14 241 35 134 -39 -89 -76 -137 Notes: Calculations assume that the t=0 Cr composition is dominantly Cr(VI).964 -38.656 1.28 -14 -35 -8 -57 -94 -506 4.691 -1.

312 1.133 1.767 -1.522 -3.121 1.613 0.366 0.244 -0.308 -1.376 -89.049 2.263 0.431 -1.249 0.398 15 1.127 0.334 -2.035 0.856 -1.158 10 1.883 -1.339 -0.822 -29.489 0.385 -0.272 -0.755 50MBSS at 34.424 -0.181 1.036 6.559 -0.06 9.205 -1.838 6.584 -3.252 -0.542 -1.624 6.330 -0.114 5 0.686 50MBSS at 53.951 7.316 -30.504 -2.759 50 0.115 -0.853 -0.135 0.438 0.964 0.076 5.584 -2.477 -1.998 -0.541 -2.389 -1.816 5 -0.82 8.562 0.121 1.090 -0.306 -6.077 0.666 -0.547 -3.418 -1.164 0.255 0.24 9.5 -0.283 0.003 -0.110 -55.050 0.5 1.221 -39.246 1.204 0.139 -0.33 8.211 -1.458 0.728 1.246 -0.187 -1.833 -1.520 -57.95 9.4 PV 0 1.712 6.085 -1.919 1.38 6.383 -1.266 0.129 0.814 6.553 1.311 -4.5 PV 0 -0.474 -3.563 SIO2 (a) -0.288 1.018 10 1.437 -4.392 0.914 50 0.798 -1.324 0.730 6.002 30 0.128 15 0.597 0.848 -1.355 0.235 -43.634 2.459 7.034 0.010 -5.104 20 1.46 8.32 7.410 0.289 -2.080 1.384 1.00 9.863 20 0.022 0.30 8.416 -0.794 -28.047 0.573 6.009 0.707 1.12 9.396 0.210 -1.851 -5.624 6.857 -7.776 -33.353 -2.778 -0.90 7.933 -2.283 -1.004 -1.554 -41.526 5.803 -64.94 9.345 -6.368 0.252 -0.293 0.588 1.403 0.868 6.50 7.486 -2.156 1.891 -1.849 1.835 30 0.715 -0.670 -1.253 0.686 -3.832 -1.257 0.707 6.596 6.428 -1.099 0.099 0.111 0.546 -1.022 1.305 -1.453 2.080 0.258 -68.999 -0.323 -1.705 -1.621 -1.239 -3.504 -0.395 -0.007 1.084 1.578 -0.504 -1.013 -1.545 6.890 pH 6.359 -1.166 -0.297 -5.93 8.041 -99.489 -2.813 -2.010 0.744 -6.487 -0.383 -57.284 -1.329 -102.619 -1.620 -1.532 -0.872 -33.257 6.17 297 107 23 283 2 -14 -88 -53 61 108 .502 0.016 -0.39 Eh (mV) 307 56 54 196 324 91 149 321 330 6.496 -1.465 FV1 = 55 cm/d -0.364 -1.126 -1.845 -0.609 -0.216 -3.370 10 1.214 0.00 7.454 -1.727 -1.817 -95.191 -3.966 0.733 -42.431 -1.244 -3.788 -63.634 -0.076 1.351 -0.479 5.721 -1.12 9.Appendix H: Reactive column mineral saturation indices Elizabeth City reactive columns Saturation indices calculated by MINTEQA2 Based on UW Water Quality Lab data Distance along column (cm) Ferrihydrite Goethite Cr(OH)3 (a) Cr(OH)3 (c) Calcite Dolomite Siderite (d) Mackinawite Magnesite Rhodochro Aragonite Amakinite 50MBSS at 27.982 -81.546 50 0.581 -36.951 -1.914 40 0.850 -1.099 0.341 40 0.752 -3.469 6.493 0.051 6.157 -6.438 0.9 PV 0 -0.463 -1.723 -3.245 0.238 0.261 -0.247 0.692 6.639 1.31 8.328 -1.189 -0.734 0.020 15 0.291 -0.551 -1.068 -0.144 0.18 9.249 0.176 0.293 -1.963 -2.544 -1.210 -0.88 8.997 20 0.364 -1.548 -31.996 1.763 -0.395 -1.852 -0.5 0.429 -7.565 0.624 -1.276 -1.033 -1.227 0.607 -0.823 -3.19 8.124 -2.887 5.92 9.332 -0.478 0.174 -79.400 -0.489 -95.167 -66.741 -1.41 8.979 -9.966 1.692 6.769 30 -0.067 -1.157 -0.429 -1.404 -0.749 5 2.818 -38.852 -0.080 7.098 0.156 -0.023 1.617 -1.740 -1.59 8.401 0.33 451 113 431 237 90 -25 -105 -88 -77 5.374 1.345 0.510 0.852 -1.594 -2.027 -8.915 -8.689 0.290 0.048 0.018 40 0.999 -38.120 0.759 7.812 0.339 0.256 6.022 0.595 -1.540 -8.108 6.182 0.

044 -0.381 0.543 -2.336 -1.839 -72.454 -0.938 1.55 266 250 12 81 -171 318 109 .901 -3.747 -1.263 -2.283 -4.035 -2.379 -4.173 0.451 6.118 0.590 -3.624 0.691 6.405 5.239 -0.014 0.10 9.197 -1.810 1.600 0.354 0.236 0.388 0.637 -1.621 -1.548 FV1 = 43 cm/d -0.604 -1.146 -0.551 -1.44 276 195 195 71 -29 -53 -67 -115 100MB at 79.918 -2.37 8.941 -1.418 -72.034 0.346 -1.394 -2.902 0.206 -0.330 -0.60 9.538 5.379 0.845 6.227 0.127 1.174 0.667 0.339 0.281 0.819 -2.993 0.744 6.074 0.475 6.512 1.471 0.466 -2.505 -0.39 9.257 FV2 = 24 cm/d -0.162 0.699 -2.894 -3.293 0.399 -2.482 0.998 -41.728 3.263 -0.142 -0.414 -2.899 1.985 4.603 0.406 -4.024 0.102 -0.098 -2.814 -0.617 -0.111 -2.168 0.399 -2.194 -2.990 0.673 0.829 0.482 6.618 0.134 1.454 -0.241 -1.707 0.009 -7.520 0.5 10 15 20 30 40 50 100MB at 29.239 -2.583 -1.249 -1.396 -1.56 561 -94 -139 -90 -45 -99 -149 -165 -0.475 -54.798 0.230 0.005 1.422 6.246 6.372 0.850 -7.604 -43.155 -2.220 3.881 -3.667 -0.113 -2.615 -72.218 0.54 9.067 -1.649 -2.396 -0.642 -0.281 -34.168 -0.42 9.485 0.324 -1.942 -42.706 -48.366 -1.092 -2.121 -1.405 -1.377 6.636 0.504 0.54 9.194 0.874 -5.138 0.584 0.502 -2.717 -0.5 2.287 -1.739 0.5 10 15 20 30 40 50 100MB at 46.2 PV 0 2.966 0.470 0.248 1.648 -2.46 9.292 -1.22 9.801 0.554 -4.22 9.2 PV 0 2.085 -0.904 -4.548 -40.689 -7.164 5.524 0.345 -0.533 -26.653 -85.113 -21.777 -99.214 -4.160 -0.338 -1.46 9.627 -42.038 -62.5 10 20 30 50 0.007 -0.060 -2.806 -1.130 -1.027 -1.042 1.396 1.989 -1.800 -2.588 6.537 0.322 0.975 -1.252 -7.405 6.497 0.209 -1.346 6.331 1.096 5.532 -32.859 0.050 0.175 0.046 1.233 -7.536 0.493 0.586 -0.333 -4. 98 PV 0 2.421 -0.292 -1.6 PV 0 2.12 9.225 0.980 0.35 9.306 -31.638 -3.497 1.725 -0.008 0.212 0.225 0.086 -0.60 8.159 pH 6.33 8.84 8.268 -5.967 5.909 6.84 9.556 -102.98 9.162 0.120 1.272 -7.230 -9.907 -0.636 0.462 0.380 0.788 6.463 -0.46 9.161 -2.457 -22.246 -1.695 -0.280 -67.100 -0.419 1.301 -82.277 -0.624 -5.597 1.856 5.Appendix H: Reactive column mineral saturation indices Elizabeth City reactive columns Saturation indices calculated by MINTEQA2 Based on UW Water Quality Lab data Distance along column (cm) Ferrihydrite Goethite Cr(OH)3 (a) Cr(OH)3 (c) Calcite Dolomite Siderite (d) Mackinawite Magnesite Rhodochro Aragonite Amakinite 100MB at 24 PV 0 2.344 1.034 1.149 -2.074 -5.772 0.695 0.214 SIO2 (a) -0.915 -2.280 6.748 -2.769 1.816 -3.260 -6.644 0.436 -1.091 -3.202 -22.082 0.371 -3.387 0.989 -2.831 -6.539 -0.890 -2.720 -2.625 -2.198 6.859 -0.264 -7.654 -1.674 0.079 0.565 -54.529 -0.656 -0.029 -1.076 6.491 -1.046 1.491 -1.417 5.050 -2.158 -1.430 0.421 -3.004 1.539 6.135 0.472 1.234 0.305 -0.013 1.286 -0.905 -3.235 0.69 9.473 0.322 -1.307 1.060 3.570 6.886 6.439 -1.033 0.618 -1.759 1.868 -2.24 9.212 -2.734 -3.412 -0.194 -3.41 9.841 0.650 -2.297 -81.393 0.676 6.624 -2.625 -1.389 -0.26 7.509 0.34 9.57 369 312 12 -49 -521 0.366 0.272 -0.712 0.744 6.56 9.249 1.074 -2.420 -57.413 -67.639 -2.48 9.307 0.062 1.20 Eh (mV) 338 -86 -165 33 -145 -160 201 -24 0.017 0.496 -35.36 9.296 1.129 -0.248 0.460 -0.146 -4.48 9.756 -0.590 -2.932 -2.40 9.222 -0.469 -2.885 1.942 -1.631 -61.116 1.591 -1.835 -1.382 0.015 -0.682 -1.308 0.535 -0.078 1.915 -1.215 1.637 -18.526 0.596 -0.357 1.107 -0.168 -2.079 0.132 -0.793 0.352 -1.367 -2.386 0.838 5.205 0.792 -39.125 -27.382 1.437 -2.687 6.227 0.581 0.989 1.314 6.499 0.613 -2.810 -0.5 10 20 50 100MB.592 -25.078 1.607 -0.5 10 15 20 30 40 -0.026 -0.327 0.997 -2.346 6.603 -0.421 -2.628 -0.354 0.535 -26.239 1.634 0.023 0.350 -1.196 -6.329 0.137 7.036 0.335 -4.873 1.142 1.914 -9.109 0.26 9.133 -2.091 -1.214 6.644 6.042 0.449 0.

388 6.971 -0.696 -1.033 30 0.886 0.204 0.684 0.348 5. 135.071 1.545 -1.051 1.728 -2.075 -31.677 5.536 -0.238 -0.598 -1.128 0.243 0.623 50 0.080 5 1.927 0.503 0.403 -42.530 0.589 0.782 -1.082 -6.878 -2.438 0.377 10 -0.463 -86.620 -2.514 0.586 -3.119 1.15 9.69 8.232 5.196 0.216 -0.220 -2.477 0.286 15 -0.363 40 0.985 -1.704 1.527 2.100 -1.Appendix H: Reactive column mineral saturation indices Elizabeth City reactive columns Saturation indices calculated by MINTEQA2 Based on UW Water Quality Lab data Distance along column (cm) Ferrihydrite Goethite Cr(OH)3 (a) Cr(OH)3 (c) Calcite Dolomite Siderite (d) Mackinawite Magnesite Rhodochro Aragonite Amakinite 50PLSSAQ at 5.315 -1.386 6.280 -7.835 -0.439 50 0.740 -35.149 6.709 0.161 -1.294 -29.41 9.35 8.594 0.396 -1.197 1.209 50PLSSAQ.037 2.614 0.175 -0.472 6.653 -1.523 -1.379 30 0.716 0.125 -0.074 -0.465 -0.085 -2.785 7.433 -0.237 0.706 0.878 50PLSSAQ at 116.764 -59.96 9.276 0.374 6.20 9.420 1.106 10 0.933 -1.482 -0.872 8.998 -97.386 -1.991 -0.509 0.530 -3.998 0.750 6.050 0.838 30 -0.666 -3.049 -2.706 6.923 6.502 -0.231 -4.852 -8.249 -1.374 -0.179 0.860 0.720 1.635 1.22 9.129 -0.189 -3.025 -6.086 50 0.447 -1.694 -1.5 1.433 -2.842 2.728 -1.475 -2.141 0.87 315 298 256 258 16 207 -130 -38 271 110 .081 -0.36 9.391 -7.943 -0.809 -2.513 -1.974 -7.306 0.17 9.235 -31.922 -51.631 0.377 -1.192 0.754 6.599 FV1 = 79 cm/d 0.638 20 -0.096 6.062 -7.744 0.460 -0.17 259 109 133 -50 -38 -93 -105 -78 22 5.075 -2.093 -2.838 -4.782 48PL/52AQ at 78.658 -0.291 -1.875 0.460 15 0.341 -0.405 -1.604 -75.508 -1.447 1.969 FV1 = 71 cm/d 0.322 -1.747 6.483 -1.034 -30.969 1.522 -0.632 -2.762 50 0.758 -4.645 6.644 50PLSSAQ at 66.518 0.096 1.557 1.858 -96.190 -71.983 -9.279 -2.146 -8.370 -0.889 -0.769 -1.46 8.378 -0.487 -1.343 1.141 0.360 0.711 -1.492 0.611 -4.515 0.26 364 99 197 -436 -121 6.164 -1.479 2.095 6.788 6.499 -1.8 PV 0 -0.603 6.486 -0.80 8.405 1.485 6.4 PV 0 1.466 -80.199 -0.243 -76.265 -1.477 -1.292 -0.18 8.473 0.053 -4.263 -0.94 9.551 -0.273 0.390 4.354 0.038 -2.734 20 0.765 1.208 40 -6.150 -1.121 0.716 3.535 -7.520 0.243 0.840 pH 6.30 9.108 0.961 -24.785 -2.483 0.08 9.460 -0.395 -0.079 1.95 8.843 -1.22 9.157 -6.037 -1.002 0.925 -1.721 0.090 -2.199 -0.70 9.833 -49.561 0.678 -35.532 0.04 9.697 -3.475 1.560 1.800 -2.257 -0.287 1.775 30 0.327 -38.271 -1.472 -1.300 -1.433 1.287 5.179 -0.515 -2.037 -0.35 320 298 271 -286 178 321 6.664 0.012 -7.330 1.516 -2.739 -2.721 0.972 0.500 -63.5 0.402 -2.558 50 0.077 1.499 -1.566 -6.333 6.268 -1.660 -80.666 0.404 -6.408 -0.710 0.956 -27.06 8.964 1.354 1.435 -1.347 6.085 0.5 -0.689 0.180 -0.553 -1.106 -1.796 -2.225 0.2 PV 0 -0.636 -1.093 1.36 9.741 -3.365 1.603 -1.503 1.079 1.311 20 0.526 1.755 0.889 -3.785 -37.487 0.169 0.252 -1.399 6.790 6.030 0.014 0.774 -0.689 -3.951 -2.34 8.26 9.763 -1.600 0.522 0.658 -1.107 2.203 -0.146 -1.882 7.811 1.887 20 -6.521 -1.107 -0.705 -2.961 -37.221 -1.994 1.593 -31.342 -1.546 -75.348 -0.3 PV 0 0.999 0.833 -3.08 9.153 SIO2 (a) -0.777 1.092 -0.3 PV 0 1.191 0.222 -1.174 -0.27 7.710 -0.774 -1.422 -1.460 0.437 -90.473 40 0.002 -1.772 0.511 0.16 355 -33 -44 -57 -124 -348 -68 4.241 6.175 -3.308 -44.718 -0.38 9.125 -0.213 10 0.444 -1.424 5.438 5.722 -6.693 6.677 0.693 -0.668 1.775 20 -2.169 0.889 50PLSSAQ at 30.768 1.170 6.399 -0.5 2.044 2.301 1.516 0.988 -1.618 -1.090 -2.387 -29.676 15 0.668 -2.026 1.095 FV2 = 36 cm/d -0.5 1.535 0.183 2.119 -0.964 0.108 0.389 1.034 -6.795 0.862 -1.212 -55.468 -2.667 -1.424 1.943 50 0.059 -0.138 0.919 -2.432 -3.591 1.427 0.216 -0.492 -1.552 -1.555 -0.051 0.444 6.457 -2.186 0.531 20 0.16 Eh (mV) 213 -88 -85 -135 -155 -11 -149 -104 36 5.820 0.312 -0.577 30 -0.102 -28.742 -1.593 0.460 -0.016 0.852 -1.561 0.08 9.937 -9.893 -1.035 0.677 -4.256 0.640 0.355 -0.817 6.927 0.824 1.440 -0.827 -2.169 -1.220 -0.603 -6.124 1.263 0.790 6.816 -0.736 -1.242 0.462 1.078 10 0.42 9.435 1.84 8.424 -4.548 5.180 -4.665 1.366 0.678 10 0.682 2.340 1.926 -1.808 -0.719 -2.588 0.996 10 0.218 0.170 0.151 -1.745 -1.612 -0.547 -47.007 -0.31 9.602 -3.323 -1.455 -0.085 0.894 -1.085 -2.713 -1.647 1.868 5.576 -0.261 1.306 -50.192 0.551 1.615 5 0.651 0.283 0.087 5.670 0.590 -1.928 -4.240 0.197 -0.14 9.63 9.430 0.224 -7.625 -2.336 -36.500 -2.422 -0.293 -0.381 -1.436 -5.881 -9.616 -0.935 15 0.452 -1.824 0.290 -0.532 1.586 6.441 -2.191 -2.183 6.673 -1.988 -7.245 -1.68 9.02 9.509 1.756 1.2 PV 0 -0.795 1.502 -71.874 -51.523 -7.524 -0.080 40 0.750 -1.90 9.438 -1.588 -0.158 0.088 0.650 1.625 0.604 -3.700 -24.402 -1.206 0.061 0.81 9.715 0.695 -6.720 3.547 -5.268 6.205 0.657 0.37 9.58 8.839 2.235 -74.485 3.625 0.392 -85.362 0.317 -2.739 0.537 1.602 -3.670 0.153 0.386 5 0.426 -1.025 -6.58 9.754 -0.400 -1.497 0.672 0.315 -84.638 0.559 -2.721 -1.331 6.982 -1.275 0.658 -34.060 -0.566 0.215 -1.962 -26.555 0.706 -3.

The instrument conditions were set according to the manufacturer’s instructions. Cl and SO4 were analyzed using a Dionex System 2000 Ion Chromatograph (IC) or a Waters IC with a conductivity detector. 2 mg/L SO4. A commercial mixed standard was used to verify the prepared standards on a regular basis. 1 mg/L NO3. A prepared mixed standard containing 2 mg/L Cl. were run after every five to ten samples. The IC instrument was evaluated daily for calibration linearity. 111 . Cations were determined using an Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES) instrument (Thermo Jarrell Ash IRIS Plasma Spectrometer). Three sets of standards were run at regular intervals: 1. 1 mg/L Br. The setpoint standard was run at least twice per day as were blanks. with element concentrations of 10 mg/L. an additional prepared mixed standard containing 0. Analytical charge balance errors of < 5% were regularly achieved. Samples were run a minimum of two times and at different dilution ratios to verify sample reproducibility and linearity of the calibration. 10 mg/L SO4. Anions Anions including Br. a commercial setpoint mixed standard at ion concentrations similar to standard #1 The two in-house standards were run after every eleven samples.4 mg/L Cl. Samples were run in duplicate and were usually diluted due to the small sample volume available from the batch and column tests. 5 mg/L NO3 and 10 mg/L PO4 2. 5 mg/L Br. Sample analyses were repeated if the relative difference on the setpoint standard exceeded 5%. The Dionex IC was capable of running 55 samples per day plus standards and the Waters IC could run 33 samples per day plus standards. Sample analyses were repeated if the relative difference on the prepared standards exceeded 5%.Appendix I: Analytical laboratory procedures Cations Ion analyses of the lab treatability samples were performed at the Water Quality Lab (WQL). University of Waterloo. and 2 mg/L PO4 3. Prepared mixed standards.

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