ML11214A190

Laboratory Testing of Zeolitic Materials Submitted by Department of Civil, Structural and Environmental Engineering of the University of Buffalo

ML11214A190
Person / Time
Site:	West Valley Demonstration Project, P00M-032
Issue date:	12/14/2009
From:	Rabideau A, Ross E, Seneca S, Bronner C University of Buffalo
To:	NRC/FSME, West Valley Environmental Services
References
WVDP-506, Rev. 0
Download: ML11214A190 (562)

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VERIFY HARD COPY AGAINST WEB SITE IMMEDIATELY PRIOR TO EACH USE West Val ley Doc. ID Number WVDP-506 Demonstration Project Revision Number REV. 0 Revision Date 1211412009 LABORATORY TESTING OF ZEOLITIC MATERIALS SUBMITTED BY DEPARTMENT OF CIVIL, STRUCTURAL AND ENVIRONMENTAL ENGINEERING UNIVERSITY OF BUFFALO ALAN J. RABIDEAU SHANNON SENECA COLLEEN E. BRONNER Cognizant Author: ERIN ROSS Cognizant Manager: LAURENE E. ROWELL WestValley DemonstrationProjen WVES LLC West Valley Environmental Services LLC 10282 Rock Springs Road West Valley, New York USA 14171-9799 WV-1816, Rev. 6

Final Report Laboratory Testing of Zeolitic Materials Submitted to West Valley Environmental Services, LLC Submitted by Alan J. Rabideau, Shannon Seneca, Colleen E. Bronner and Erin Ross Department of Civil, Structural, and Environmental Engineering State University of New York at Buffalo November 23, 2009

FINAL REPORT LABORATORY TESTING OF ZEOLITIC MATERIALS TABLE OF CONTENTS PAGE Introduction 1 Conceptual approach to performance assessment 2 Methods 4 Results 13 Summary and conclusions 25 LIST OF TABLES 1 Scope of column experiments 2 Groundwater cation concentrations 3 Selected results of mechanical tests (Geotechnics, Inc.)

4 Batch sorption test results 5 Preliminary CEC test results (TMP) 6 Preliminary CEC test results (BR 7 Sorbed cation concentrations at end of column experiments 8 Column simulation parameters 9 PTW simulation scenarios 10 PTW simulation parameters i

LIST OF FIGURES 1 Effluent concentrations for Column 1 (TMP zeolite) 2 Effluent concentrations for Column 2 (TMP zeolite) 3 Effluent concentrations for Column 3 (BR zeolite) 4 Effluent concentrations for Column 4 (BR zeolite) 5 Effluent concentrations for Column 5 (TMP zeolite with 20% WV soil) 6 Effluent concentrations for Column 6 (TMP zeolite with 20% WV soil) 7 Effluent concentrations for Column 7 (BR zeolite with 20% WV soil) 8 Effluent concentrations for Column 8 (BR zeolite with 20% WV soil) 9 Effluent concentrations for Column 9 (WV soil) 10 Effluent concentrations for Column 10 (BR zeolite with 20% WV soil and 10% iron) 11 Sorbed cations at end of experiment for Column C2 (100% TMP) 12 Sorbed cations at end of experiment for Column C4 (100% BR) 13 Calibrated effluent concentrations for Column C4 (100% BR) 14 Calibrated sorbed concentrations for Column C4 (100% BR) 15 Calibrated effluent concentrations for Column C8 (BR zeolite with 20% WV soil) 16 Conceptual model for PTW simulations 17 Hypothetical PTW simulations: flow variation 18 Hypothetical PTW simulations: zeolite variation LIST OF EXHIBITS 1 UB doctoral candidate Shannon Seneca with zeolite experimental columns 2 UB experimental columns C2 (left, 100% TMP) and C3 (right, 100%BR) ii

APPENDIX NUMBER OF PAGES TMP product information 1 BR product information 3 Mechanical test reports from Geotechnics Inc. 5 XRD/XRF results from The Mineral Lab 3 Summary of UB zeolite washing procedure 1 Overview of MOUSER software 6 CEC results from Hazen Research (1 = TMP, 2 = BR) 1 Lab reports for cation analyses (Columbia Analytical services) 478 iii

LABORATORY TESTING OF ZEOLITIC MATERIALS INTRODUCTION This report summarizes the results of laboratory experiments performed as part of the study entitled Laboratory testing of zeolitic materials, under West Valley Environmental Services (WVES) Purchase Order 19-001849-C-JK.

The goal of the project was to evaluate two candidate zeolite materials for potential use in a permeable treatment wall (PTW) designed to remove strontium-90 (Sr-90) from groundwater at the West Valley Demonstration Project (WVDP). The evaluation includes batch testing to assess the removal of strontium by cation exchange, mechanical testing to evaluate the grain size and hydraulic conductivity of the candidate materials, and column testing to further assess potential long-term efficacy of the ion-exchange process by the candidate zeolites and provide the basis for predictive modeling to support the PTW design phase.

All zeolite geochemical characterization, batch tests, column experiments and numerical modeling were performed at the University at Buffalo (UB) Jarvis Hall Laboratory, under the direction of Dr. Alan J. Rabideau. Outside laboratories were utilized as noted to perform mechanical testing, mineralogical characterization, and all chemical analyses of water samples.

The objectives and procedures described in this report are referenced to the approved Quality Assurance Project Plan (QAPP) of February 11, 2009. A DOE-WVDP surveillance reviewed adherence to the QAPP requirements and WVES oversight of the testing program. WVES responded to all surveillance findings and comments as documented by Biedermann (2009).

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Laboratory Testing of Zeolitic Materials: November 23, 2009 CONCEPTUAL APPROACH TO PERFORMANCE ASSESSMENT The removal of Sr-90 from groundwater by natural zeolites has been an ongoing subject of evaluation since the mid-1990s (Aloysis, 1995; Fuhrmann et al., 1995; Cantrell, 1996; Lee et al., 1998; Rabideau et al., 2001; Rabideau et al., 2005). A pilot zeolite PTW was installed at the WVDP in 1999 (Moore et al., 2000); subsequent monitoring confirmed the effectiveness of the cation exchange removal mechanism (e.g., WVNSCO, 2007) and provided important insights relevant to full-scale design (Geomatrix, 2001a, 2001b). The laboratory studies described in this report build on previous work and are designed to support a more focused performance assessment of natural zeolites for full-scale PTW deployment, including a comparison of two candidate materials.

Because of the anticipated large sorption capacity and relatively slow groundwater flow rates applicable to a field scale PTW, it is not practical to operate an experimental system to directly determine the complete lifetime of the zeolitic system (i.e., zeolite emplacement time-to-replacement) under field conditions, particularly when the design objective is considered long by typical remediation standards (e.g., approximately 20 years). As discussed by Rabideau et al.

(2001), efforts to accelerate column aging by using unrealistically high flow rates introduce experimental artifacts (e.g., nonequilibrium sorption) that violate key interpretative assumptions.

Instead, mathematical modeling is used to extrapolate the shorter-term observations from laboratory columns for use with predicting longer-term field PTW conditions. Therefore, a primary objective of the laboratory testing was to provide data to support robust parameterization of a geochemical transport model to aid in PTW design; a key component of experimental design was the inclusion of post-flushing sorbed phase measurements, leading to greater confidence in the quality of model calibrations. Another key objective was to use the laboratory observations to demonstrate whether a substantial reduction in strontium concentrations across an experimental column is possible, and to vary the column conditions in such a way as to work toward an optimal design of the zeolitic treatment media (type of zeolite and percent of zeolite in the system) as part of an effective in situ treatment process that meets the functional requirements of the project as defined by WVES.

The UB experimental program was developed to characterize key zeolite sorbent properties that serve as sensitive inputs to a numerical contaminant transport model used in conjunction with the PTW design. Important assumptions underlying this approach include:

The removal (sorption) of strontium by zeolite occurs primarily by a competitive cation exchange process.

Nonradioactive Sr-882+ (henceforth Sr2+) will exhibit identical cation exchange behavior to the target contaminant Sr-902+ (henceforth Sr-90), and is therefore used as a suitable experimental surrogate.

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Laboratory Testing of Zeolitic Materials: November 23, 2009 Cation competition in the WVDP groundwater will be dominated by naturally occurring calcium (Ca2+), magnesium (Mg2+), sodium (Na+), potassium (K+) and nonradioactive strontium (Sr2+), leading to the development of a 5-solute (lab columns, nonradioactive Sr2+ only) or 6-solute (field PTW, with Sr-90 included) model.

The cation exchange reaction occurs rapidly relative to groundwater flow for the approximately sand-size zeolite particle size range under consideration (i.e., equilibrium conditions are assumed).

Cation exchange equilibrium relationships can be described using the standard convention developed by Gaines and Thomas (1953).

Decay of Sr-90 (when present) occurs in both the aqueous and sorbed phases.

For the purpose of PTW design, mixtures of natural zeolite and WVDP soil are modeled by assuming that the soil does not participate in the cation exchange reactions.

Most of the key parameters required for the numerical simulation model can be independently measured, estimated, or specified, as discussed in the subsequent report sections.

The majority of the project effort was devoted to the estimation of four Gaines-Thomas selectivity coefficients that represent the cation exchange process in the model. These cation exchange parameters, along with the initial concentration of cations in the sorbed phase, are considered to be properties of the zeolite system that are unaffected by the geometry or flow regime. Thus, performance of the field PTW can be extrapolated from laboratory columns by appropriate modifications to physical parameters (e.g., domain length, porosity, density, velocity).

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Laboratory Testing of Zeolitic Materials: November 23, 2009 METHODS Materials Test materials were obtained directly from the suppliers: (1) Teague Mineral Products (TMP) of Adrian OR, and (2) Bear River Zeolite (BR) of Preston ID. Because these natural materials are not pure minerals, they are commonly referred to as zeolite-rich rock. However, for the purpose of this report, the simpler terms zeolite or natural zeolite are used.

For both TMP and BR materials, the requested particle size was 14x40, which corresponds to standard sieve openings of 1.4 and 0.425 mm, respectively. The 14x40 is a standard product for BR, but is a custom specification for TMP. However, both suppliers have indicated significant flexibility in milling capability. Previous UB studies (Rabideau et al., 2005) emphasized the chemical behavior of a finer 20x50 TMP product (0.85-0.30 mm), while the installed pilot PTW (Moore et al., 2000) utilized a slightly coarser 14x50 TMP material (1.4 -

0.30 mm).

Product information from TMP and BR is included in the Appendix. Also, independent analyses by x-ray fluorescence (XRF) and x-ray diffraction (XRD) were performed on duplicate samples of the specific materials used in the UB laboratory tests by The Mineral Lab Inc.

(Golden CO); these results are also included in the Appendix. In the supplier information, the percent by weight of clinoptilolite was given as 70-80 percent for TMP and 85 percent for BR.

The independent XRD testing indicated clinoptilolite fractions of 66 and 71 for the TMP material, and 85 and 88 for the BR material. Also, the XRD analysis indicated values of 10 and 12 percent smectite in the TMP samples, with none identified in the BR material.

Initial sieve analysis of the TMP material revealed that a significant portion of the supplied material fell outside of the specified size range. Communication with TMP personnel suggested that the most likely explanation was substandard quality control in the preparation of the 14x40 test materials, which were assembled by hand as a dedicated batch for the UB testing.

Subsequently, a second batch of TMP material was provided that had been prepared in a large quantity in a more rigorous fashion. The second batch was subjected to sieve analysis, but not used in the batch or column chemical testing, which was limited to the original supplied TMP material.

Six of the ten column experiments (Table 1) were conducted with mixtures of material that included WVDP soil collected from a radiologically non-contaminated area during field characterization performed in fall 2008. Visual inspection indicated that the soil was comprised generally of silty-clay with a soft brown color and silky texture. The soil was first air-dried 4

Laboratory Testing of Zeolitic Materials: November 23, 2009 overnight, and then sieved to remove particles larger than 1.18 mm. Because the soil was available in limited quantity, further characterization was not performed.

One of the column tests included a zeolite:soil mixture amended by adding approximately 10 percent by weight zero-valent iron. A sample of granular iron was provided by EnviroMetal Technology Inc. (Waterloo CA), who indicated that the material was standard iron used in the construction of iron-based PTWs. The iron was used as received without further processing or testing.

Mechanical Testing Sieve analyses were conducted on the original TMP and BR materials by Geotechnics Inc. (Pittsburgh PA) on February 26, 2009 using ASTM method D-422-63 (equivalent to AASHTO T88-00). Permeability testing on the original materials was completed by Geotechnics on March 5, 2009 using a modified method ASTM D-2434-68. Both procedures are described in the Geotechnics quality assurance manual, which was included with the QAPP.

Follow-up sieve analysis and permeability testing was performed on August 4, 2009 on the second batch of TMP material. Correspondence with Geotechnics indicated that the TMP and BR materials were unsuitable for the LA Abrasion and Slake Durability tests that were originally planned due to the small particle size.

Analysis of water samples The batch sorption, cation exchange capacity (CEC), and column test procedures described below required the analysis of aqueous samples for dissolved cations (Ca2+, Mg2+, Na+,

K+ and Sr2+). All samples were shipped to Columbia Analytical Services (Rochester, NY) for analysis by Inductively Coupled Plasma (ICP, EPA Method 200.7). Aqueous sample handling and analytical procedures are summarized in the CAS Quality Assurance Manual, which was included in the QAPP.

Batch Testing Two types of batch tests were performed: (1) batch sorption tests to confirm the effectiveness of the two zeolites to remove Sr2+ from groundwater under competitive cation-exchange conditions, and (2) cation exchange capacity (CEC) tests, which were designed to quantify the sorption capacity of the materials and quantify the initial sorbed concentrations of the cations of interest to this study.

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Laboratory Testing of Zeolitic Materials: November 23, 2009 Sorption tests The intent of the batch sorption testing was to obtain a qualitative confirmation of the ability of the materials to remove strontium from water under competitive conditions, with nonradioactive Sr2+ used as a surrogate for Sr-90. A detailed summary of procedures is included in the QAPP. Duplicate tests were performed for each zeolite at two different solid-liquid ratios.

Synthetic groundwater, similar in cation composition to the WVDP groundwater, was prepared by adding reagent grade salts to deionized water, with the final distribution of major cations given below in Results. Approximately 100 ml of the synthetic groundwater and approximately 10 or 20 grams of the zeolite were combined in Erlenmeyer flasks, yielding liquid:solid ratios of about 10:1 and 5:1, respectively. Duplicate tests were performed for each zeolite and each solid-liquid ratio. In addition, three controls were prepared: (1) one flask containing TMP zeolite and deionized water, (2) one flask containing BR zeolite and deionized water, and (3) one flask containing synthetic groundwater with no zeolite.

The flasks were placed on a mechanical shaker for approximately 2 weeks and visually inspected during this time to verify adequate mixing. At the end of the mixing period, the samples were stored overnight without mixing to allow solid/liquid separation. The aqueous phase was then decanted and filtered using a 0.45 m syringe filter. Samples were submitted to Columbia Analytical Services to be analyzed for the five cations of interest.

CEC tests The most important zeolite property with respect to removal of Sr-90 is its cation exchange capacity (CEC), typically expressed in milliequivalents of exchange capacity per gram of solid (meq/g). Although standardized washing procedures exist for measuring CEC in soils, for high-capacity materials (such as zeolite) these procedures may underestimate the overall CEC because the washing process is a limited-duration approximation of more sustained exposure to a competitive cation exchange environment. Furthermore, standard CEC procedures quantify the overall capacity but do not indicate the concentrations of individual sorbed cations, which are needed to support solute-specific transport modeling. Thus, for this study, a modified procedure was developed to provide the needed information.

The current UB method is loosely based on a study by Cerri et al. (2002), which evaluated alternative procedures specifically for application to clinoptilolite-rich rock similar to the materials under investigation. To assess and improve the performance of the Cerri method, several modifications were evaluated. First, the wash water was not heated, which was supported by correspondence with the authors of the Cerri paper indicating that heating was not believed to substantially affect the measured CEC. Second, the number and duration of washes were varied in an effort to increase the efficiency of cation removal. However, although removal efficiency is expected to increase with repeated washing, it was also desirable to identify a point of diminishing returns to allow the procedure to be completed in a reasonable time frame.

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Laboratory Testing of Zeolitic Materials: November 23, 2009 A detailed summary of the washing procedure is given in the Appendix. The procedure generally consisted of washing a known mass of zeolite repeatedly with a solution containing a very high concentration (1 mole/liter) of ammonium (NH4+). All wash water was retained, combined in a single container, and analyzed for the cations of interest. By applying the known mass:volume relationships, the concentrations of individual cations in the sorbed (exchanged) phase were calculated, and the individual concentrations were summed to estimate the total CEC.

In developing the procedure, several procedural variations were assessed, including:

Pre-washing of some zeolite samples to remove fine particles.

Changes to the number of sequential washes (1, 2, 3, or 4); each wash involved replacing the ammonium solution with a fresh batch.

Changes to the duration of each individual wash, ranging from one to three days.

Variation in the mixing apparatus, which included an end-over-end tumbler and a less aggressive roller.

The relative influence of the procedural variations is discussed in the Results section.

Column Testing The purpose of the column experiments was to determine the ability of the two selected zeolite materials (BR, TMP) to remove Sr2+ from the aqueous component over time and investigate the potential impact of mixing of the zeolite with native soil on Sr2+ sorption. These goals were addressed by conducting experiments linked to the development of a numerical contaminant transport model. Although the primary result from each column test was a plot of the time-dependent effluent concentration, columns were not intended to represent small-scale treatment systems. Rather, the column was operated as a well- controlled physical model designed to support a robust estimation of the geochemical parameters that can subsequently be used to simulate the performance of the PTW in a variety of geometries and flow regimes.

Ten experimental columns (C1 - C10) were operated over durations of 131 days to greater than 180 days, with four of the columns remaining in operation as of this writing. A summary of key column test conditions is given below, with additional details provided in Table 1:

Columns C1-C8 were the primary focus of the work and were designed to provide a side-by-side comparison of the TMP and BR zeolites, as well as an evaluation of the behavior of zeolite:soil mixtures. Each of the four experimental configurations (BR, BR:soil, TMP, TMP:soil) was duplicated.

Four of the column experiments (C2, C4, C6, and C7) were terminated after 142 days of operation to support analysis of the sorbed phase cations, which was expected to further improve quality of the calibrated model.

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Laboratory Testing of Zeolitic Materials: November 23, 2009 Column C9 was considered a control column containing only WVDP soil. Because the observed effluent concentrations remained very similar to the influent source concentrations, the experiment was terminated after 131 days.

Column C10 was considered an exploratory column that included zero-valent iron mixed with BR zeolite and soil; the iron was intended to promote the precipitation of calcium, which in turn would reduce the competition with Sr2+ for sorption sites.

However, observed pH levels and cation concentrations were similar to zeolite:soil mixtures (presumably influenced by zeolite:soil buffering), and the experiment was discontinued after 131 days.

Photographs of the experimental setup are included as Exhibits 1-2. The ten columns and their end caps were constructed of Plexiglas. Each column was 10 cm in length and 3.81 cm in diameter, with column dimensions selected to minimize wall effects (e.g. Mehta and Hawley, 1969) and structural dispersive mixing (Li et al., 2009). Each column was equipped with a water inlet at the base of the column and a built-in diffuser to evenly distribute the flow of incoming synthetic groundwater. Sampling ports located along the column length were not used in this study for aqueous sampling, but facilitated removal of column solids at the end of selected experiments. Further details of the column experimental procedures are provided in the project QAPP. Key experimental design components included:

The column materials were pre-soaked with a low ionic strength solution to reduce the amount of cation exchange during the initial column filling and flushing, which allowed for more accurate specification of initial conditions during model calibration.

Cation concentrations in the synthetic groundwater (Table 2) were prepared to represent the average concentrations observed in WVDP wells, with the exception of Sr2+, which was increased to the approximate maximum observed of 1 mg/L. Midway through the experiments (approximately 100 days), the source concentrations of Ca2+ and Na+ were increased to enhance the sensitivity of transport model parameters to the effluent data and thereby provide for more robust model calibration. For the long-running columns, the influent concentrations were subsequently returned to their initial value after approximately 155 days.

A multi-channel peristaltic pump was utilized to provide steady flow to the columns, with frequent gravimetric flow measurements used to support minor adjustment (if necessary) to the pump settings. The design flow rate of 0.2 ml/min was selected based on natural groundwater flow conditions observed at the site. The resulting Darcy velocity (flow per area) was approximately 0.23 m/day. Based on the results of previous work, these velocities, while near the high end of anticipated field conditions, were considered low enough such that cation exchange process would achieve local equilibrium.

Column effluent samples were collected on an approximately weekly basis, with 1-2 additional weekly samples collected at startup and immediately following changes to the groundwater influent chemistry.

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Laboratory Testing of Zeolitic Materials: November 23, 2009 Following the completion of experiments C2, C4, C6, and C7, the columns were drained and disassembled after carefully after removing the solid materials using stainless steel spatulas. Solids were removed from eight discrete segments located adjacent to the mid-column sampling ports, which were used (with the effluent opening) to facilitate access to the solids. The removed solids were dried and subjected to the washing procedure described in the previous section.

Although not included in the scope of this project, six additional column tests were conducted at the West Valley Demonstration Project (WVDP) by WVES personnel in consultation with UB staff. Test procedures were identical to the UB experiments, with the exception that source groundwater was collected from a well located on the WVDP North Plateau in the vicinity of the proposed PTW. Relevant groundwater cations were similar to the UB study, but the source water also contained Sr-90 at approximately 38,000 pCi/L. In addition to two columns containing 100 percent zeolite (one BR, one TMP), the WVDP experiments included two columns containing an approximately equal mass (50:50) of BR zeolite and soil and two columns containing an 80:20 mixture of BR zeolite and soil. Results from the WVDP columns will be reported elsewhere; some preliminary observations relevant to interpretation of the UB study are given in the Results section.

Modeling Overview Contaminant transport modeling was an integral component of the project, both for interpretation of column results and for extrapolation of zeolite behavior to the field scale in support of preliminary PTW design. Simulations were performed using the MOUSER software, a public domain software package developed and refined at the University at Buffalo; mathematical developments are outlined in a series of papers beginning with Miller and Rabideau (1993), including extension to incorporate multi-solute cation exchange (Rabideau et al., 2005). A description of MOUSER history, capabilities, and extensive publication record is included in the Appendix. Advantages of the MOUSER software relevant to this project include:

Good computational performance, which is provided by a numerical solution procedure built around a flexible grid-based split-operator approach. Problems of interest to this work require several orders of magnitude less computational time than PHREEQC (Parkhurst and Apelo, 1999), the only identified public domain software that can be readily configured for the 5-solute cation exchange system of interest.

Support for numerous boundary condition options for both the domain entrance and exit, including a time-dependent source condition.

Ability to provide output for several simulated variables, including solute concentrations(s), sorbed concentration(s), and total (aqueous plus sorbed) concentration(s).

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Laboratory Testing of Zeolitic Materials: November 23, 2009 Support for several default reaction scenarios, including nonequilibrium sorption, sequential multi-solute parent-daughter decay, and the multi-solute competitive cation exchange that is the focus of this work.

Available utilities that support automated model calibration.

Modeling tasks included multi-solute contaminant transport simulations representing the laboratory columns and a hypothetical field PTW, as well as the automated calibration of MOUSER to quantify key transport and reaction parameters based on laboratory data.

Calibration tasks were performed using OSTRICH, a flexible optimization software package developed at the University at Buffalo. OSTRICH performs calibration and/or optimization for any user-supplied simulation code, using a variety of gradient-based and heuristic optimization procedures. Details regarding the formulation and implementation of OSTRICH calibration algorithms are provided by Matott (2003). Advantages of OSTRICH relative to this project include the ability to select from a wide variety of numerical search algorithms, including hybrid procedures that combine global search procedures (to circumvent local minima) with a gradient based polishing step that improves the solution and generates a variety of regression diagnostics and statistics.

Transport Formulation Both the experimental column system and the field-installed PTW were modeled using the one-dimensional form of the advective-dispersive-reactive equation (ADRE) and application-specified boundary conditions. The general form of the ADRE used in this work is:

C i C 2 Ci S v i D a Ci b i b s S i i = 1, , k t x x 2 n t n (1) where Ci is the dissolved phase resident contaminant concentration of solute i, k is the number of solutes (k = 5 if Sr-90 is absent; k = 6 if Sr-90 is included), t is time, x is distance from the domain entrance, v is the fluid velocity in the x-direction, D is the dispersion coefficient (includes hydrodynamic dispersion and molecular diffusion), a and s are first-order decay coefficients for the aqueous and sorbed phases, respectively, b is the bulk density, n is the porosity, and S is the sorbed phase mass fraction. For this work, S is understood to represent the mass of cation residing in the exchanger phase.

For column applications, x = 0 denotes the beginning of the porous media system at the column entrance and x = L denotes the end of the porous media system at the column exit, which corresponds to the modeled locations of influent and effluent sample collection, respectively.

For the field PTW applications, these entrance/exit locations correspond to the transitions between native aquifer material and emplaced zeolite. For both applications, flow is assumed to be predominantly one-dimensional in the x-direction.

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Laboratory Testing of Zeolitic Materials: November 23, 2009 The form of Eq. (1) allows for consideration of a number of sorption reactions; for this work, the reactions are limited to competitive cation exchange. In the current implementation, binary equilibrium relationships are expressed in terms of the reference solute C1, which was assigned as the monovalent sodium (Na+). For each of the remaining solutes, the governing equilibrium relationship is expressed using the Gaines-Thomas (1953) convention, as formulated by Vulva et al. (2000):

mi a yi K Na ,i Na (2) y Na ai Where KNa,i is the equilibrium constant for solute i, a represents the aqueous phase activity, y is the sorbed phase activity, m is the charge of solute i.

The aqueous phase activity (a) is the product of the concentration and an activity correction based on the Davies equation (e.g., Stumm and Morgan, 1996):

I ai 0.5 zi2 0.3I ci 1 I (3) where zi is the charge associated with cation i, ci is the solute molar concentration and I is the solution ionic strength. Because the dependent variables tracked by MOUSER are typically restricted to the cations of interest, the ionic strength is calculated by:

i k I 0.5 c i z i2 An (4) i 1 where k is the number of modeled cations and An is the background anion ionic strength, which is supplied as input to the model based on the source groundwater.

The sorbed phase activity (y) is calculated using the Gaines-Thomas convention, which assumes that the sorbed phase solute activity is proportional to the solute mole fraction:

qi N i yi Q (5) where q is the sorbed phase mass fraction (moles/kg) of species i, N is the equivalents per mole, and Q is the total cation exchange capacity (eq/kg).

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Laboratory Testing of Zeolitic Materials: November 23, 2009 The cation exchange capacity (Q) is equivalent to the sum of the k sorbed ion concentrations:

i k Q mi q i (6) i 1 Calibration Calibration of MOUSER parameters was performed using the OSTRICH software to automatically adjust selected model parameters to minimize the following objective function:

j nt w Z obs 2 j j Z model j (7) j 1 where is the weighted sum of squares objective function, nt is the total number of observed data points, which included both solute-specific aqueous and sorbed phase concentrations, Zj is the concentration (aqueous or sorbed) for data point j, with the superscripts obs and model denoting observed and simulated, respectively, and wj is the weight assigned to data point j.

Specification of the appropriate weighting factors (w) is guided by several considerations, including data uncertainty, differences in units (e.g., between aqueous and sorbed concentrations) and relevant concentration ranges (e.g., ~100 g/L Sr2+ to ~300 mg/L Na+),

importance relative to project objectives, and apparent sensitivity of the optimization procedure (e.g., Hill and Tiedeman, 2007). Because of the complexity of the highly nonlinear simulation model and the relatively large number of calibration data points (150 - 200 per column),

considerable adjustment of calibration weights was required. In general, most aqueous effluent concentrations were assigned a weight of 1, with higher weights (up to ~5000) assigned to sorbed phase data and Sr2+ effluent concentrations.

Because of the considerable computational time required to generate high-confidence calibrations, the bulk of project effort was dedicated to analyzing results from the BR columns C4 and C8. Column C4 was selected because the data set included both aqueous and sorbed concentrations, and is therefore expected to yield more robust parameter estimates. Column C8, which is still operational, was selected because it includes a zeolite:soil mixture and because observations recorded in August 2009 indicated an increase in Sr2+ effluent concentration. The refinement of model calibrations and the analysis of the full set of column results are ongoing and will be addressed in detail in a journal articles and a forthcoming University at Buffalo doctoral dissertation.

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Laboratory Testing of Zeolitic Materials: November 23, 2009 RESULTS Mechanical Tests Summaries of key results from the mechanical testing are given in Table 3, with the original Geotechnics reports included in the Appendix. Both the TMP and BR materials were classified under the USCS system as poorly graded (or well sorted) due to the low coefficient of uniformity (CU). Constant head permeability tests indicated hydraulic conductivity (K) values of (TMP original) 0.025 cm/s, (TMP 2nd batch) 0.10 cm/s, and (BR) 0.12 cm/s.

The BR and TMP (both batches) materials, which were milled to similar requirements (14x40), differed substantially in terms of the fraction of particles below the specified lower limit; this likely is responsible for the approximately five-fold difference in the measured hydraulic conductivity between the original TMP batch and the BR materials. The BR and 2nd-batch TMP hydraulic conductivities were similar to the range obtained from previous UB laboratory tests for uncompacted TMP materials (0.1 - 0.4 cm/s for 15x50 and 20x50; Rabideau et al., 2005). However, the original TMP value was below this range. These laboratory results for both TMP and BR values are above the results from the field hydraulic conductivity tests (0.001 - 0.003 cm/s) performed within the currently installed pilot PTW, which is composed of TMP zeolite The difference in laboratory results between the first batch TMP and BR materials may be due to the relatively large fraction of below-specification particles for the TMP material, which reflects the more friable nature of the rock and/or inadequate quality control in the preparation of the test material by TMP. It is also noteworthy that the independent XRD analysis indicated that the original TMP material contained a significant clay fraction (10, 12 percent smectite), while no clay was identified in the BR samples.

Batch Sorption Tests A summary of the batch test results is given in Table 4, with original lab reports provided in the Appendix. In Table 4, the column labeled initial water refers to the synthetic groundwater that served as the initial condition for each flask, as determined by laboratory analysis of the control sample subjected to the same mixing regime. Each of the tabulated TMP/BR cation concentrations represents an average of duplicate samples after the two-week mixing period. (Duplicate samples gave similar results, with an average difference of two percent.) Also, the differences in aqueous cation concentrations for different liquid/solid ratios were minor, which is consistent with a cation exchange process.

Both zeolite materials demonstrated substantial removal of strontium. Because the final 2+

Sr concentrations for all samples were at or below the laboratory reporting limit (0.1 mg/L), the minor differences among the samples are not considered significant. That is, both materials 13

Laboratory Testing of Zeolitic Materials: November 23, 2009 performed equivalently with respect to strontium removal, exhibiting greater than 90% removal for the conditions of the batch tests.

Although Sr2+ removal was similar, the two zeolite materials produced a different final mix of cations. For TMP, the amounts of aqueous sodium and potassium increased significantly, while calcium and magnesium were removed from the water. For BR, the amounts of aqueous calcium and potassium increased significantly, while sodium and magnesium were removed from the water. The observed cation exchange behavior is consistent with the elemental compositions of the source materials provided by the suppliers (see Appendix). For example, BR contains a considerably higher initial concentration of calcium relative to TMP, whose exchange capacity is dominated by potassium.

CEC Tests Preliminary testing To evaluate the washing procedure, preliminary testing was performed using different numbers and durations of the washing step, different techniques for mixing the samples during the washing period, and prewashing of some samples to reduce the loss of fine particles during washing and more accurately represent column conditions. Results of these tests are summarized in Tables 5-6, with all concentrations reported in units of milliequivalents of cation per gram of solid (meq/g).

The results of different washing procedures were compared with respect to the measured sorbed concentration of each cation, as well as the estimated CEC, which was computed by summing values for the five individual cations. In general, the differences among the washing procedures were relatively consistent, with increased CEC observed for samples that were prewashed and mixed with the more gentle tumbling procedure. It is likely that several factors contributed to the slightly higher CEC observed for prewashed solids, including a lower exchange capacity associated with the removed fine-grained (non-zeolite) materials, as well as improved recovery of solids throughout the multiple wash/filter steps. Similarly, the less aggressive mixing procedure resulted in improved recovery of solids. The relative magnitudes of the calculated CEC for the BR and TMP materials were not ordered consistently by the number or duration of washes, which suggests that variations in the number and duration of washes were less important than the pre-washing and mixing procedures.

The calculated CEC values for the pre-washed BR material (1.43 - 1.59 meq/g) were similar to the range reported by the supplier (1.5 to 1.8 meq/g), while the TMP values (1.06 to 1.28 meq/g) were significantly lower than the supplier-reported value of 1.77 meq/g. For both materials, the independent CEC measurements by Hazen Research were similar to the UB results 14

Laboratory Testing of Zeolitic Materials: November 23, 2009 obtained for samples that were prewashed and mixed by tumbling (roller-mixing yield slightly higher CEC values).

The reason for the inconsistency with the TMP-reported CEC value is unclear, although the sieve analysis of the TMP material indicated a larger-than-anticipated percentage of fine-grained material, which is typically associated with non-zeolite materials. It is noteworthy that the concentrations of total and individual sorbed cations for the TMP material are nearly identical to values measured by Mineral Associates (Brockport NY), using a similar but less aggressive washing procedure followed by cation analysis by ICP (reported by Rabideau et al.,

2005).

Washing of column solids Following the completion of column tests C2, C4, C6, and C7 on July 10, 2009, solids from specified segments of columns C2 and C4 were removed, washed and analyzed for sorbed cations according to the procedure identified in the preliminary work (prewashing and roller-mixing). As summarized in Table 7, both materials exhibited an overall increase in the amount of exchanged Sr2+ relative to the initial conditions, with concentrations decreasing for the column inlet to the exit. Other changes in the distribution of sorbed cations were more complex and influenced by the different initial conditions for the two materials, as well as the specific source water used to flood the columns. For the TMP material, sorbed Ca2+ and Mg2+ increased, while K+ and Na+ decreased. Conversely, for the BR material, sorbed Ca2+ decreased slightly while Na+ increased significantly.

For both TMP and BR, the overall computed CEC values were consistent across the column segments, but were approximately 6-8 percent higher than the values measured for the raw materials (shaded rows in tables 5-6). The difference is attributed to the longer contact time associated with the column flushing, but may also indicate a small initial CEC contribution from cations other than the 5 major cations addressed in this work (e.g., iron, bromide, zinc).

For interpreting the column experiments, the final sorbed cation measurements values were considered more representative of the actual exchange capacity of the zeolites. Therefore, to provide consistent initial conditions for subsequent column modeling, the estimated initial conditions were adjusted by scaling each individual cation concentration to the final measured CEC, as shown in the last row of Table 7.

Summary of washing results Extensive effort was devoted to the development of an experimental procedure for measuring sorbed cations. Based on preliminary testing, a procedure was standardized included three sequential multi-day washes of prewashed solids, using a gentle (roller) mixing, followed by analysis of the collected wash water for the cations of interest. Application of the procedure 15

Laboratory Testing of Zeolitic Materials: November 23, 2009 to the BR and TMP solids yielded internally consistent results and overall CEC values that were slightly higher than independent measurements from an outside laboratory. The higher UB values are attributed to the more extensive washing procedure, which is designed to support the interpretation of long-term column tests. In particular, the scaled initial conditions will provide a consistent amount of sorbed mass between initial and final conditions.

Column Results: General Observations Results from the primary column tests are summarized in the series of plots shown in Figures 1-12. Figures 1-10 show the effluent concentrations as a function of time for the 5 cations (in mg/L, with Sr2+ in g/L). For these plots, concentrations were plotted both in terms elapsed time (days) and number of pore volumes (1 pore volume = vt/L). The computed pore volumes were based on an assumed effective porosity of 0.5 for pure zeolite and 0.25 for zeolite/soil mixtures; although consistent with the range of likely values, pore volumes should be regarded as an approximation for illustrative purposes only. Figures 11-12 show the concentrations of sorbed cations measured for Columns 2 and 4 at the completion of the experiments (in mg/kg). It is noted that many of the effluent measurements for Sr2+ were estimated values between the Method Detection Limit (0.01 mg/L) and laboratory Reporting Limit (0.1).

General observations from the column effluent measurements include the following:

Effluent measurements of pH, turbidity, and conductivity (not shown) were relatively stable and did not exhibit significant trends. Typical values were pH ~ 7.8, turbidity ~

0.1 - 0.2 NTU, and conductivity ~ 2 mS. Changes in the column effluent cation concentrations generally were mirrored by similar (small) changes in effluent conductivity, which is proportional to ionic strength.

Column flow rates were measured gravimetrically and fluctuated within about 10% of the design value of 0.2 mL/min. The resulting groundwater velocity was dependent on the column effective porosity, which varied according to the particular mixture of zeolite:soil (discussed below).

Visual inspection of Columns 1-8 indicated saturated conditions without evident air entrainment or settling. Inspection of Column 9 (WVDP soil only) indicated a small loss of solid material at the upper end of the column, presumably due to the flushing of fine-grained materials. Column 10 (BR:soil/iron) exhibited a small degree of discoloration attributable to biological growth, presumably iron bacteria.

Effluent cation concentrations for Column 9 (WVDP soil only) were virtually identical to the column influent, which supports the assumption that the synthetic groundwater was approximately equilibrated with soil cations and therefore representative of on-site conditions.

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Laboratory Testing of Zeolitic Materials: November 23, 2009 Duplicate columns generated very similar effluent concentration curves (sorbed phase was not analyzed), indicating good reproducibility of results.

Effluent samples from Columns 1-8 exhibited complex behavior typical of transport influenced by competitive cation exchange. Early-time effluent curves (less than ~30 days) differed significantly for the two zeolites, as this period was dominated by the release of initially sorbed cations and the two materials have different initial conditions. Although substantial removal of Sr2+ persisted through the duration of all experiments, columns that contained 20%

WVDP soil began to exhibit a gradual increase in Sr2+ in the column effluent after approximately 100-120 days of operation, with a more pronounced increase noted for the TMP material. For descriptive purposes, the effluent concentrations can be considered in distinct chronological stages that differed slightly for the two zeolites as noted below.

Bear River (BR) columns The BR columns exhibited the following general behavior:

During the first 20-30 days of operation, the zeolite adjusted to the high ionic-strength influent by releasing exchangeable cations, resulting in complex (crossing) effluent curves that eventually stabilized in a quasi-plateau. During the initial adjustment stage, the BR material released substantial amounts of Ca2+ and lesser amounts of Na+.

During the next quasi-plateau phase (20-95 days), effluent concentrations were approximately stable at values similar to the influent concentrations for the non-Sr2+

cations. Effluent Sr2+ concentrations were steady at less than ten percent of the influent level during this period.

All effluent cation concentrations exhibited a small concentration increase immediately following the addition to influent Ca2+ and Na+ that had been implemented at approximately 95 days of operation.

For the 100% BR columns (C3, C4), the effluent Sr2+ concentrations remained steady at the second quasi-plateau until approximately day 120, when they began to fluctuate slightly. However, for 100% BR columns all Sr2+ concentrations were close to the laboratory reporting limit of 0.1 mg/L for the entire duration of the experiments, which suggests that caution should be used in interpreting changes.

For the columns containing the 80:20 BR:soil mixture, the Sr2+ concentration began to gradually increase at approximately day 110, suggesting that the mixture was beginning to approach sorption equilibrium with the groundwater. For the long-running column (C8), the Sr2+ dropped abruptly at approximately day 150 when the source water ionic strength was reduced to its initial value, but then resumed the increasing trend. At the time of this writing, the last Sr2+ measurement of approximately 260 g/L was recorded after 185 days of operation, corresponding to 26 percent of the influent value after almost 2000 pore volumes of operation (based on an assumed effective porosity of 0.25).

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Laboratory Testing of Zeolitic Materials: November 23, 2009 Teague Mineral Products (TMP) columns The TMP columns exhibited qualitatively similar behavior, with the following differences:

During the first 20-30 days of operation, the zeolite adjusted to the high ionic-strength influent by releasing exchangeable cations, resulting in complex (crossing) breakthrough curves that eventually stabilized in a quasi-plateau. In contrast to the BR material, the TMP material released large amounts of both K+ and Na+ but did not release Ca2+.

During the next quasi-plateau phase (20-95 days), effluent concentrations were approximately stable at values similar to the influent concentrations for the non-Sr2+

cations. In contrast to the BR material, effluent Sr2+ concentrations exhibited a more complex pattern of a gradual increase (to approximately 18 percent of the influent level) followed by a gradual decrease to concentrations below the reporting limit of 0.1 mg/L.

The initial increase in Sr2+ is attributed to its higher initial concentrations in the TMP zeolite, including its possible presence in the non-zeolitic portion of the rock.

For the 100% TMP columns (C1, C2), the effluent Sr2+ concentrations after day 95 remained steady at concentrations close to the reporting limit of 0.1 mg/L. Thus, except for the early time TMP increase-then-decrease, all columns containing 100% zeolite exhibited Sr2+ concentrations close to the laboratory reporting limit of 0.1 mg/L for the entire duration of the experiments, which suggests that caution should be used in interpreting small fluctuations.

For the columns containing the 80:20 TMP:soil mixture (C5, C6), the Sr2+ concentrations began to gradually increase at approximately day 90, suggesting that the mixture was beginning to approach sorption equilibrium with the groundwater. These trends were similar to the BR:soil columns (C7,C8), but the concentration increases were more pronounced. For the long-running column (C5), the Sr2+ concentration dropped abruptly at approximately day 150 when the source water ionic strength was reduced to its initial value, but then resumed the increasing trend. At the time of this writing, the last Sr2+

measurement of approximately 430 g/L was recorded after 185 days of operation, corresponding to 43 percent of the influent value after almost 2000 pore volumes of operation (based on an assumed effective porosity of 0.25).

Summary of column results Taken as a whole, the results of the column tests support the following general observations about the performance of the natural zeolites for removal of Sr2+ from groundwater:

Columns containing only TMP or BR zeolite effectively removed Sr2+ from groundwater by cation exchange. For both systems, substantial increases in effluent Sr2+ were not observed during the flushing periods of 750-900 pore volumes. Plateau Sr2+concentrations fluctuated around the laboratory reporting limit of 0.1 mg/L, which is approximately ten percent of the source concentration (1 mg/L). Effluent concentrations exhibited minor adjustments in response to changes in the influent Na+ and Ca2+

concentrations.

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Laboratory Testing of Zeolitic Materials: November 23, 2009 Columns containing 80:20 mixtures of zeolite/soil exhibited an increase in effluent Sr2+

near the end of experimental period. The increase began slightly earlier for TMP (~95 days versus ~120 days for BR) and progressed more rapidly, resulting in higher Sr2+

concentrations at the end of the 190-day experimental period (0.43 mg/L TMP, 0.25 BR).

The reason for the earlier TMP increase is attributable to a lower cation exchange capacity, higher water velocity (due to lower effective porosity) or a combination of both.

Modeling interpretation of selected columns is described in the next section. Some preliminary observations from the WVDP columns are also given in the Discussion section.

Column Results: Model Calibration Interpretation of the column results was performed using the MOUSER software to simulate the transport and exchange of the five cations of interest. Model parameterization was based on a combination of direct measurement, engineering judgment, and calibration as summarized in Table 10, with key assumptions outlined below:

Column flow rates were based on the average values of multiple measurements performed throughout the duration of the experiments. The corresponding Darcy velocity (flow per area) is a straightforward calculation based on the known column dimensions.

For columns containing 100 percent zeolite, the specified bulk density was based on the measured mass of zeolite loaded into the column.

For zeolite:soil mixtures, the bulk density was treated as a calibration parameter and interpreted as the effective zeolite density, i.e., the mass of zeolite per volume that is available for cation exchange. This approach can account for a possible reduction in exchange capacity due to a masking of zeolite capacity by fine soil particles.

The dispersion coefficient was scaled to the velocity using an effective dispersivity calculated as 5 percent of the column length (D = 0.05 v). The assumed dispersivity was similar to values measured in similar studies (Rabideau et al., 2005) and is not expected to significantly influence solute transport, which is dominated by the processes of advection and cation exchange.

Specified flux (3rd-type) entrance boundary conditions were assigned based on the average concentrations measured for the synthetic groundwater during each of the three distinct source periods.

The initial sorbed cation concentrations were assigned by scaling the values measured in batch CEC tests, as described previously. The overall CEC was calculated as the sum of the five sorbed cations.

The four Gaines-Thomas selectivity coefficients were treated as calibration parameters for all simulations.

Due to the relatively large amount of water absorption by zeolites (relative to soil systems), the effective (mobile phase) porosity was treated as a calibration parameter.

19

Laboratory Testing of Zeolitic Materials: November 23, 2009 In contrast to groundwater flow models, the automated calibration of reactive transport models has not received extensive attention in the scientific literature because it is very difficult to obtain robust parameter estimates in a cost-effective manner (for a recent discussion, see Matott and Rabideau, 2008). Calibration of the column experiments was challenged by the usual difficulties, including considerable computational time needed to complete a calibration run (hours to days on a desktop computer), integration of multiple data types (aqueous and sorbed) over relatively large concentration ranges, and the existence of multiple plausible parameter sets.

Furthermore, the simultaneous consideration of multiple columns in the calibration process was not computationally tractable, even with state-of-the-science tools used in this study. Thus, a single best parameter was not achievable; instead the calibration effort is an ongoing iterative process of successive adjustment and refinement. To provide support for the preliminary PTW design process, efforts to date have focused on columns containing the BR zeolite, particularly C4 (which includes sorbed concentration data) and C8 (the longest running zeolite:soil mixture).

Despite the limitations identified above, the calibration process identified a number of model configurations that exhibited reasonable consistency in the estimated cation exchange selectivity coefficients, which were the primary concern of the project. Plots of the fitted models are shown along with the measured data in Figures 13-15, with calibrated parameters included in the Table 8 summary. Model fits for column C4 were considered very good and captured all significant trends in the data. The calibrated selectivity coefficients were consistent with the expected ordering (Sr2+ >> Ca2+ > Mg+ > K+) and the calibrated porosity (0.53) is consistent with expectations for relatively homogeneous PTW materials. Calibration diagnostics did not indicate significant parameter correlation, which increases confidence in a unique parameter set.

Although a number of other parameter sets yielded comparable visual agreement with the data, the magnitudes of the calibrated selectivity coefficients were similar.

Model fits for Column C8 were less satisfactory, showing general agreement with trends, but more significant deviations in concentration magnitudes. The calibrated porosity (0.25) was much smaller than for the pure material (0.53 for C4), which is attributed to the less uniform size distribution of the mixture and the presence of fine soil particles. To replicate the Sr2+

concentration increase that occurred near the end of the experimental period, it was necessary to decrease the effective zeolite bulk density from the measured value of 0.9 g/cm3 to approximately 0.5 g/cm3. The reason for the required decrease was unclear, although a plausible explanation is that the mixing of zeolite with soil results in a reduction of the fraction of zeolite available for cation exchange. Such a reduction could result from fine soil particles masking zeolite exchanges surfaces or restricting solute access to zeolite micropores. Regardless of the underlying mechanism, the column mixing conditions probably represent a worst case cation exchange environment because of the thorough mixing of zeolite:soil that had been implemented to ensure homogeneous column conditions.

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Laboratory Testing of Zeolitic Materials: November 23, 2009 Extrapolation to Field Conditions The experimental columns represent a physical model constructed at approximately 10 percent of the anticipated field scale (10-cm column versus 1-meter PTW). However, for the pure zeolite columns, the durations of column experiments were not sufficient to generate substantial levels of Sr2+ in the effluent, and the lifetime of the PTW cannot be directly estimated from the column data alone. Extrapolation of column results to assess PTW performance was therefore accomplished by reconfiguring the one-dimensional transport model to reflect a domain geometry and groundwater flow field consistent with anticipated field conditions (Figure 16), while retaining the geochemical parameters determined from the columns. However, it is important to recognize that conditions affecting the installed PTW will vary considerably along its considerable length of several hundred feet. That is, the one-dimensional simulations represent hypothetical snapshots of PTW behavior as influenced by a particular combination of localized flow conditions, source strength, groundwater geochemistry, and emplacement conditions. Thus, the simulations described below are presented to demonstrate the use of mathematical model for performance assessment, and should not be interpreted as definitive depictions of specific design scenarios.

The field PTW simulations are presented in terms of simulated Sr-90 effluent curves for an assumed source scenario, which can then be referenced to performance criteria for the PTW effluent. The rationale for the hypothetical simulations is summarized in Table 9. At the time of this writing, the scenario designated as Case 2 is considered a conservative reference case based on specified flow and zeolite CEC conditions drawn from the midrange of observed conditions. Potential variations in groundwater flow conditions were explored in Case 1 and Case 3 by adjusting the local groundwater flow velocity consistent with locations across the PTW cross-section, drawing on the results of site wide groundwater flow modeling by the project design team. Cases 4-5 represent Case 2 conditions with the zeolite CEC adjusted over the range of variability suggested by the BR supplier specification. Case 6 represents a very conservative mixing scenario referenced to laboratory column C8; it is presented here to demonstrate the flexibility of the model, not as a plausible field scenario.

Results from six illustrative simulations are shown in Figures 17-18, with the model parameters summarized in Table 10. Important assumptions include:

An installed PTW thickness of three feet of BR zeolite was used for all scenarios.

Groundwater flow was assumed to be perpendicular to the PTW, which likely underestimates the effective thickness of the treatment zone for the non-perpendicular conditions believed to characterize most of the PTW extent.

21

Laboratory Testing of Zeolitic Materials: November 23, 2009 Groundwater cation concentrations were assigned based on average values of North Plateau field measurements, consistent with the initial source concentrations used for the column tests.

A constant Sr-90 source activity of 50,000 pCi/L was assumed (equivalent to 3.64 x 10-7 mg/L based on a Sr-90 specific activity of 1.37 x 108 pCi/g), which was a conservative representation of average conditions along the PTW extent. Actual PTW entrance concentrations may be lower and/or may increase gradually depending on future conditions and whether/when source removal and decommissioning measures are implemented.

An effective porosity of 0.35 was assumed for all simulations, which was expected to represent a conservative (low) estimate based on the assumption of moderate compaction and/or mixing with native soil.

Cation exchange selectivity coefficients were assigned based on the calibrated values from column C4. Initial sorbed concentrations were assigned based on the scaled measurements from the batch CEC tests.

Except for Case 6, the zeolite bulk density was specified at 0.9 g/cm3 based on the high end of the loose packing density listed by the supplier. For Case 6, the bulk density and porosity were adjusted to the conditions of Column C8, which are interpreted to represents a worst case mixing scenario that might occur near the edges of the PTW.

The hypothetical results shown in Figures 17-18 are plausible depictions of potential PTW performance under various assumed conditions, but are not intended to represent actual design scenarios. Interpretation of this type of figure in the context of performance assessment would require several additional assumptions, including refinement of the assumed flow, source, and zeolite packing conditions, as well as determination of an appropriate metric for acceptable effluent concentration. Furthermore, it is important to recognize that individual one-dimensional simulations represent local conditions rather than an integrated picture of the entire PTW system; simulation results are also strongly influenced by the conservative assumptions identified previously, including flow oriented perpendicular to the barrier axis and a uniform Sr-90 activity of 50,000 pCi/L entering the PTW during the entire simulation period.

Discussion As detailed in the Introduction and Methods sections, it is not practical to operate experimental columns for a duration equivalent to the anticipated PTW lifetime under typical groundwater flow conditions. For example, use of an accelerated flow velocity is likely to introduce nonequilibrium sorption effects that violate modeling assumptions necessary to provide an accurate interpretation of geochemical data. Thus, the design of sorbing barriers in general, and zeolite barriers in particular, typically depend on the extrapolation of experimental behavior to field conditions using mathematical models (for an extended discussion of these 22

Laboratory Testing of Zeolitic Materials: November 23, 2009 issues, see Rabideau et al., 2001). These modeling predictions necessarily involve a degree of uncertainty; however several factors (discussed below) provide insight into the possible range of uncertainty affecting field predictions, and ongoing work continues to improve the understanding of the behavior of natural zeolite sorbents under conditions relevant to PTW applications.

PTW field performance is driven by three general factors: (1) overall sorption capacity of the zeolite, (2) selectivity of sorption for Sr-90 relative to other cations, and (3) rate of groundwater flow through the PTW. The third factor (flow) is primarily determined by field conditions and is readily represented in the mathematical model by specification of the PTW thickness and groundwater velocity. As such, model sensitivity analysis is a straightforward component of design process, as illustrated by the hypothetical simulations shown in Figure 17 and discussed above.

The overall PTW sorption capacity is affected by both the CEC and emplaced bulk density of the zeolite material. The in-place bulk density is difficult to assess a priori with confidence, as the proposed emplacement technique has not been utilized in a full-scale system with the candidate materials. Consequently, field simulations were based on the assumption of a loose packing bulk density which underestimates the emplaced condition, which will likely experience some degree of compaction. The simulations, therefore, provide a conservative (underestimate) of PTW performance.

Confidence in the overall PTW sorption capacity is enhanced, however, by the fact that the CEC of the candidate zeolite can be measured directly and independently of column tests.

Measurements of the CEC for the BR material fell within a relatively narrow range and were consistent with both the suppliers specifications and measurements by an outside laboratory.

Furthermore, the sensitivity analysis presented in Figure 18 indicates that the extrapolated PTW performance is relatively insensitive to CEC variation over the range of reasonably expected values. Also, anticipated QA/QC measures to monitor the clinoptilolite fraction of the installed natural zeolite will further reduce the uncertainty associated with the overall sorption capacity.

Estimation of the CEC for the TMP material is associated with less confidence, in part because of the differences between measured and supplier-reported values, and in part because of inconsistencies noted in the mineral composition of the supplied test specimens.

Confidence in the zeolite selectivity for Sr-90 is subject to greater uncertainty, but is supported by several factors. First, preliminary observations from the ongoing WDVP columns have indicated that, for the two pure zeolite columns, the fractional removal of Sr-90 is greater than the removal of Sr2+. This relationship is consistent with the fact that both zeolites contain a small amount of initial sorbed Sr2+, which is released during the early period of column operation. Furthermore, observations from columns containing zeolite:soil mixtures indicate similar fractional removal of Sr-90 and Sr2+. A more complete analysis of the WVDP columns 23

Laboratory Testing of Zeolitic Materials: November 23, 2009 will be presented elsewhere (after more extended operation of the columns), but these preliminary observations strongly support the use of Sr2+ as a surrogate contaminant.

In addition to specifying the overall zeolite CEC and emplaced bulk density, models of field PTW performance also require specification of the four cation exchange selectivity coefficients, which are calibrated from column data. As is common with complex geochemical models of this type, it is possible to generate approximately similar model predictions of column behavior using different combinations of selectivity coefficients, which are difficult or impossible to measure one-at-a-time. To enhance confidence in the calibrated parameter sets, a number of procedures were utilized, including:

The duration of the UB experimental columns (~ 6 months, with some columns continuing) significantly exceeds all previous published studies of natural zeolite sorbents.

Several aspects of the experimental design were implemented to reduce the potential for parameter correlation and nonuniqueness, including the perturbation of the influent groundwater cation concentrations and the labor intensive measurement of sorbed cations at the end of selected column tests.

The availability of robust and computationally efficient calibration software has established, with high confidence, that calibrated parameter sets represent globally optimal best fit parameters for a particular set of modeling assumptions and data weights.

Although refinement of model calibrations continues, the results presented in the report represent the results of dozens of computationally intensive calibrations performed under a variety of assumptions related to column conditions (e.g., effective porosity, dispersivity), data weighting, and numerical search procedure (to locate the best fit).

The model calibrations described in the previous sections (e.g., Figures 13-15) represent the best fit selectivity coefficients based on the most likely configuration of measured/estimated column conditions. However, the multiple exploratory calibrations generated other plausible parameter sets that produced comparable or slightly inferior agreement with experimental data.

These alternative parameter sets were used to perform additional field simulations (not shown) for the Case 2 configuration discussed above. In general, model predictions based on the alternative sets of selectivity coefficients produced Sr-90 effluent plots centered around the previous Case 2 scenario, comparable to the relatively small range of predictions associated with the CEC variations in Cases 4-5 (but not Case 6) shown in Figure 18.

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Laboratory Testing of Zeolitic Materials: November 23, 2009

SUMMARY

AND CONCLUSIONS The experimental program has generated a considerable amount of new information on the performance of zeolitic materials for removing strontium from groundwater. These data are significant both in terms of their scope (multiple material combinations, multiple tests) and for the extended duration of column tests (some > 200 days) beyond previous tests of approximately 60 day duration. Of particular importance for PTW design, the extended column experiments provided more robust estimates of cation exchange selectivity coefficients, and the new batch CEC tests have provided a more complete picture of the initial distribution of zeolite cations, an important component of simulation modeling.

Removal of Sr-90 by Natural Zeolite Taken as whole, the tests confirmed the ability of the candidate zeolites to remove Sr2+

(and by extrapolation, Sr-90) from groundwater similar to WVDP conditions by the process of cation exchange. For both candidate zeolites (BR, TMP), approximately 90 percent Sr2+ removal was consistently observed through the entire duration of the 200-day study for columns with 100 percent zeolite. Although a significant increase in Sr2+ effluent did not occur during the study period, the high quality data set supports the estimation of cation exchange parameters for use in design simulations.

For both zeolites, columns constructed of zeolite/soil mixtures began to exhibit a gradual increase in effluent Sr2+ concentrations after approximately 100 days of operation (the precise timing is complicated by a concurrent increase in the influent ionic strength). The Sr2+ increases began earlier and were more pronounced for the TMP:soil columns relative to BR:soil.

However, because of numerous complexities associated with the mixture systems, a comprehensive modeling interpretation was not achievable. In general, the Sr2+ increases were attributed to the lower overall CEC associated with the mixture, lower effective porosity due to the less uniform particle size distribution (resulting in higher velocity), and a possible masking of zeolite exchange sites by fine soil particles. However, because the zeolite/soil columns were assembled by a complete mix procedure designed to produce homogeneous column conditions, they likely represent an unrealistic worst case mixing scenario.

Comparison of Candidate Zeolites Considering the full suite of mechanical, batch, and column tests, several clear advantages of the BR zeolite relative to the TMP material are evident:

The TMP material is more friable and both batches provided by the suppler contained a relatively large percentage of particles finer than the design specification. Although the first batch of TMP material may have been influenced by quality control issues, the more 25

Laboratory Testing of Zeolitic Materials: November 23, 2009 friable nature of the material suggests that some of the fine particles are likely generated during post-milling handling. Also, XRD analysis revealed a significant clay fraction (10-12 percent) in the TMP samples, but none in the BR material. The inclusion of clay minerals and the finer particle fraction is potentially problematic because it could lead to reduced porosity and hydraulic conductivity in the field. In this regard, the BR material, which is also much less friable when handled, is clearly superior.

The BR material consistently exhibits a higher cation exchange capacity than TMP, regardless of the test protocol. The range of CEC values reported by the supplier (1.5 -

1.8 meq/g) is reasonably consistent with measurements from the UB study and an outside laboratory. In contrast, TMP CEC measurements were consistently 20-30 percent lower than BR values, which is also consistent with the lower clinoptilolite fraction measured by an outside laboratory (0.67 for TMP, 0.87 for BR). Thus, the BR material exhibits a clear advantage in terms of expected Sr2+ removal capacity.

Significant differences between the two materials were not evident during column tests conducted with 100 percent zeolite, presumably because the durations of the tests were not sufficient to achieve elevated Sr2+ effluent concentrations for either material.

For column experiments conducted with zeolite/soil mixtures, Sr2+ concentrations began to gradually increase near the end of the experimental period. The observed increase began earlier and progressed further for the TMP:soil columns relative to the BR:soil columns; however interpretation of these differences is complicated by the multiple effects of soil mixing, including changes to the column porosity and bulk density, as well as possible masking effects of small particles. Although not conclusive, the results are consistent with a larger Sr2+ removal capacity for the BR material.

Mixing of Zeolite with Soil The inclusion of zeolite/soil mixtures was intended to provide insight into possible mixing that would occur during PTW construction using a trencher apparatus. Because field mixing is likely to occur at the outer edges of an installed PTW rather than uniformly throughout its cross section, the column configurations represent an unrealistic worst case mixing environment, applicable to only a small portion of an installed system. However, the results suggest that for regions subject to near-complete mixing, the presence of soil could inhibit Sr-90 removal more substantially than would be predicted by treating the soil as an inert material that simply dilutes the amount of zeolite in the mixture zone. Although modeling of the zeolite/soil system is still at early stage of development, it appears that mixing effects could be approximately represented by appropriate adjustment (reduction) to the estimated zeolite bulk density. From a PTW construction standpoint, the zeolite emplacement should be conducted in a manner that minimizes mixing of native soil into the treatment zone.

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Laboratory Testing of Zeolitic Materials: November 23, 2009 Implications for PTW Design For a PTW system constructed of the BR material, the experimental program has provided estimated values for important geochemical parameters that include the total cation exchange capacity, the initial distribution of sorbed cations, and the Gaines-Thomas selectivity coefficients. Other important design variables include the treatment zone thickness, effective porosity and zeolite bulk density of the installed PTW, local groundwater flow rates, the time-dependent concentration of Sr-90 entering the treatment zone, and the target effluent concentration. Appropriate specification of these variables will result in simulations of PTW performance with significantly increased confidence relative to previous projects (e.g., Hanford, Chalk River, West Valley pilot) that were based on very limited experimental data sets.

A limited set of PTW simulations based on hypothetical but realistic field conditions suggest that the local groundwater flow velocity is probably the most important factor influencing the longevity of the zeolite at a particular PTW cross-section. In general, the expected time reach a specified Sr-90 effluent concentration is approximately proportional to the local flow velocity, although the influence of Sr-90 decay will increase as the local residence time within the PTW increases (as the groundwater velocity is decreased). Similarly, the estimated PTW life is approximately proportional to the effective zeolite CEC, but the expected range of variation is much smaller than the local groundwater velocity.

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Laboratory Testing of Zeolitic Materials: November 23, 2009 REFERENCES Aloysis, D. L. (1995). Sorbent material testing and evaluation for passive filter wall design, report submitted to West Valley Nuclear Services, Dames & Moore, Orchard Park, NY.

Biedermann, C. A. (2009). Letter DW:11285 to B.C. Bower, Response to U.S. Department of Energy (DOE) West Valley Demonstration Project (DOE-WVDP) Surveillance S09-021E, North Plateau Plume Subcontract Oversight of Lab Work, dated September 3, 2009.

Cantrell, K. (1996). A permeable reactive wall composed of clinoptilolite for containment of Sr-90 in Hanford groundwater, Proceedings of the International Topical Meeting on Nuclear and Hazardous Waste Management, 1358-1365, American Nuclear Society, Inc., La Grange Park, Il.

Cerri, G., Langella, A., Pansini, M., and Cappelletti, P. (2002). Methods of determining cation exchange capacities for clinoptilolite rich rocks of the Logoduro region of Northern Sardinia, Italy, Clays and Clay Minerals, 50(1), 127-135.

Furhmann, M., Aloysius, D., and Zhou, H. (1995). Permeable, subsurface sorbent barrier for 90 Sr: Laboratory studies of natural and synthetic materials, Waste Management, 15(7), 485-493.

Gaines, G.L., and Thomas, H.C. (1953). Adsorption studies of clay minerals. II. A formulation of the thermodynamics of exchange adsorption, Journal of Chemical Physics, 21, 714-718.

Geomatrix Consultants (2001a). Pilot permeable treatment wall hydraulic evaluation report, prepared for West Valley Nuclear Services LLC., Buffalo NY.

Geomatrix Consultants (2001b). Pilot permeable treatment wall engineering evaluation report, prepared for West Valley Nuclear Services LLC., Buffalo NY.

Hill, M. C., and Tiedeman, C. R. (2007). Effective groundwater model calibration: With analysis of data, sensitivities, predictions, and uncertainty, Wiley Interscience, New York, NY.

Lee, D. R., Smith, D. J., Shikaze, S. G., Jowett, R., Hartwig, D. S., and Milloy, C. (1998).

Wall-and-curtain for passive collection/treatment of contaminant plumes, Proceedings of the First International Conference on Remediation of Chlorinated and Recalcitrant Compounds, Battelle Press, Columbus, OH.

Lia, M., Wang, T., and Teng, S. (2009). Experimental and numerical investigations of effect of column length on retardation factor determination: A case study of cesium transport in crushed granite, Journal of Hazardous Materials, 162, 530-535.

28

Laboratory Testing of Zeolitic Materials: November 23, 2009 Matott, L.S. (2003). OSTRICH: An Optimization Software Tool, Department of Civil Structural, and Environmental Engineering, University at Buffalo, Buffalo, NY (available from http://www.groundwater.buffalo.edu).

Matott, L. S., and Rabideau, A. J. (2008). Calibration of subsurface reactive transport models involving complex biogeochemical processes, Advances in Water Resources, (3192), 269 - 286, doi:10.1016/j.advwatres.2007.08.005.

Mehta, D., and Hawley, M. C. (1969). Wall effect in packed columns, Industrial Engineering and Chemical Processes Design and Development, 8 (2), 280-282, DOI: 10.1021/i260030a021.

Miller, C.T., and Rabideau, A.J. (1993). Development of split-operator Petrov-Galerkin methods for simulating transport and diffusion problems, Water Resources Research, 29 (7),

2227- 2240.

Moore, H. R., Steiner, R. E., Fallon, E., Repp, C. L., Hemann, M. R., and Rabideau, A. J. (2000).

Permeable treatment wall pilot project at the West Valley Demonstration Project, proceedings of Waste Management 2000, 27 February - 2 March, 2000, Tucson, AZ.

Parkhurst, D.K., and Appelo, C.A.J., (1999). Users Guide to PHREEQC (Version 2) a computer program for speciation, batch reaction-path, one-dimensional transport, and inverse geochemical calculations, U.S. Geological Survey Water Resources Investigations Report, Reston VA, pp. 99-4259.

Rabideau, A. J., Van Benschoten, J. E., Khandelwal, A., Patel, A., and Repp, C. L. (2001).

Sorbing vertical barriers, in Physical/chemical subsurface remediation, Smith, J. and Burns, S.

(eds.), Kluwer Publishers.

Rabideau, A. J., Van Benschoten J., Bandilla, K., and Patel, A. (2005). Performance assessment of a zeolite treatment wall for removing Sr-90 from groundwater, Journal of Contaminant Hydrology, 79(1 - 2), 1 - 24, doi:10.1016/j.jconhyd.2005.04.003.

Rabideau, A. J., Bronner, C. E., and Seneca, S. (2009). Quality Assurance Project Plan, Laboratory testing of zeolitic materials, Number 1, Revision 0, Department of Civil, Structural, and Environmental Engineering, University at Buffalo, Buffalo NY.

Stumm, W., and Morgan, J.J. (1996). Aquatic chemistry. Wiley, New York, NY.

Vulva, V. M., Kretschmar, R. , Rusch, U., Grolimund, D., Westall, J. C., and Borkovec, M.

(2000). Cation competition in a natural subsurface material: Modeling of sorption equilibria, Environmental Science and Technology, 34 (11) 2149-2155.

West Valley Nuclear Services Co., Inc. (WVNSCO) (2007). Sampling and analysis plan for characterization of the North Plateau plume area, WVDP-465, West Valley, NY.

29

Table 1: Scope of Column Experiments Column Duration Samples Description

1. (days) * = not analyzed C1 TMP zeolite only ongoing 39 effluent C2 Duplicate of C1 142 31 effluent, 8 zeolite segments C3 BR zeolite only ongoing 39 effluent C4 Duplicate of C3 142 31 effluent, 8 zeolite segments C5 TMP zeolite combined with 20% WVDP soil ongoing 39 effluent C6 Duplicate of C5 142 31 effluent, 8* zeolite segments C7 BR zeolite combined with 20% WVDP soil 142 31 effluent, 8* zeolite segments C8 Duplicate of C7 ongoing 39 effluent C9 WVDP soil only 131 28 effluent C10 BR zeolite, WVDP soil (20%), iron (10%) 131 28 effluent 1

Table 2: Groundwater cation concentrations Groundwater conc.

Synthetic Synthetic Synthetic from 11 on-site groundwater groundwater groundwater wells (mg/l)

Cation 2/19 - 5/28 5/28 - 8/4 8/4 - current Mean Maximum (mean, mg/l) (mean, mg/l) (mean, mg/l)

Ca2+ 167 230 160.8 205.6 162.4 Mg2+ 26 36 26.5 25.4 26.7 K+ 3 6 5.0 5.0 5.0 Na+ 185 273 178.8 217.8 176.4 Sr2+ 0.3 1 1.0 1.0 1.0

Table 3. Selected results of mechanical (Geotechnics Inc.)

Parameter TMP (original) TMP (2nd batch) BR D60 0.8 mm 0.8 mm 1.2 mm D30 0.5 mm 0.5 mm 0.8 mm D10 0.3 mm 0.3 mm 0.5 mm Percent < 0.425 (#40 sieve) 25.2% 17.3% 1.6%

Coefficient of curvature (CC) 1.0 1.1 1.0 1

Coefficient of uniformity (CU) 2.9 2.6 2.3 Hydraulic conductivity 0.025 cm/s 0.10 cm/s 0.12 cm/s 1

Calculated as D60/D10 by Geotechnics, differences are due to roundoff

Table 4. Batch sorption test results Initial TMP TMP BR BR Cation water finala finala final a finala Sample numberb 130 122, 123 126, 127 124, 125 128, 129 Liquid:solid NA 10:1 5:1 10:1 5:1 Na+(mg/L) 174.0 267.5 244.0 75.3 86.9 K+ (mg/L) 5.0 74.3 72.0 38.4 36.6 Mg2+ (mg/L) 24.9 5.1 7.1 14.0 15.7 Ca2+ (mg/L) 159.0 70.5 76.8 246.0 225.5 Sr2+ (mg/L) 1.1 0.1 0.1 c

< 0.1 < 0.1c a

Average of two samples, b Sample numbers refer to CAS reports (Appendix) c less than method reporting limit of 0.1 mg/L

Table 5. Preliminary CEC test results (TMP)

Days Num.

Pre- Ca2+ Mg2+ K+ Na+ Sr2+ CEC per of Mixing wash (meq/g) (meq/g) (meq/g) (meq/g) (meq/g) (meq/g)

Wash washes 15 No Tumbler 0.27 0.01 0.66 0.19 2.06E-0 3 1.14 24 No Tumbler 0.27 0.01 0.66 0.19 2.07E-0 3 1.13 33 No Tumbler 0.27 0.02 0.63 0.19 2.20E-0 3 1.11 42 No Tumbler 0.27 0.01 0.58 0.19 2.23E-0 3 1.06 34 Yes Tumbler 0.28 0.02 0.70 0.20 1.04E-0 4 1.21 43 Yes Tumbler 0.29 0.02 0.69 0.20 1.59E-0 4 1.20 33 Yes Tumbler 0.29 0.02 0.65 0.21 1.34E-0 4 1.17 3,4,3 3 Yes Tumbler 0.30 0.02 0.70 0.20 1.59E-0 4 1.22 34 Yes Roller 0.28 0.02 0.69 0.21 2.17E-0 3 1.19 43 Yes Roller 0.31 0.02 0.73 0.25 2.48E-0 3 1.31 33 Yes Roller 0.32 0.02 0.70 0.25 2.49E-0 3 1.28 3,4,3 3 Yes Roller 0.38 0.02 0.69 0.24 2.45E-0 3 1.28 Average of prewashed/roller (4 samples) 0.31 0.02 0.70 0.23 2.40E-03 1.27 Rabideau et al. (2005), analysis by 0.23 0.02 0.64 0.26 2.00E-0 3 1.14 Mineral Associates (Brockport, NY)

TMP supplier data sheet 1.77 Hazen Research (Golden, CO) 1.16

Table 6. Preliminary CEC test results (BR)

Days Num.

Pre- Ca2+ Mg2+ K+ Na+ Sr2+ CEC per of Mixing wash (meq/g) (meq/g) (meq/g) (meq/g) (meq/g) (meq/g)

Wash washes 15 No Tumbler 0.62 0.05 0.52 0.06 1.37E-03 1.25 24 No Tumbler 0.65 0.07 0.51 0.06 1.47E-03 1.29 33 No Tumbler 0.71 0.08 0.56 0.07 1.59E-03 1.42 42 No Tumbler 0.73 0.06 0.54 0.05 1.22E-03 1.38 34 Yes Tumbler 0.72 0.08 0.61 0.07 1.68E-03 1.48 43 Yes Tumbler 0.70 0.08 0.59 0.07 1.69E-03 1.45 33 Yes Tumbler 0.76 0.07 0.53 0.07 1.74E-03 1.43 3,4,3 3 Yes Tumbler 0.75 0.08 0.57 0.07 1.78E-03 1.47 34 Yes Roller 0.78 0.09 0.62 0.08 1.82E-03 1.58 43 Yes Roller 0.82 0.09 0.60 0.08 1.79E-03 1.59 33 Yes Roller 0.80 0.08 0.54 0.08 1.79E-03 1.50 3,4,3 3 Yes Roller 0.78 0.09 0.56 0.08 1.79E-03 1.52 Average of prewashed/roller (4 samples) 0.79 0.09 0.58 0.08 1.79E-03 1.55 BR supplier data sheet 1.5-1.8 Hazen Research (Golden, CO) (average of two) 1.48

Table 7. Sorbed cation concentrations at end of experiment (cations and CEC in meq/g)

Distance from Column inlet (cm) Ca2+ Mg 2+ K+ Na + Sr 2+

CEC C2 (TMP) 0.00 - 1.25 0.82 0.098 0.20 0.28 2.78E-0 2 1.38 C2 (TMP) 1.25 - 2.50 0.82 0.07 0.22 0.28 2.12E-0 2 1.40 C2 (TMP) 2.50 - 3.50 0.80 0.06 0.25 0.27 1.37E-0 2 1.38 C2 (TMP) 3.50 - 5.0 0.66 0.06 0.26 0.22 6.99E-0 3 1.20 C2 (TMP) 5.00 - 6.00 0.74 0.06 0.33 0.25 4.85E-0 3 1.38 C2 (TMP) 6.00 - 7.25 0.68 0.06 0.36 0.23 3.71E-0 3 1.33 C2 (TMP) 7.25 - 8.50 0.67 0.06 0.40 0.23 3.38E-0 3 1.36 C2 (TMP) 8.50 - 10.00 0.65 0.06 0.41 0.23 2.80E-0 3 1.36 C2 (TMP) average CEC 1.35 TMP measured initial condition 0.31 0.02 0.70 0.23 2.40E-0 3 1.27 TMP scaled initial condition1 0.33 0.02 0.75 0.25 2.46E-0 3 1.35 C4 (BR) 0.00 - 1.25 0.96 0.13 0.20 0.30 2.80E-0 2 1.61 C4 (BR) 1.25 - 2.50 0.97 0.13 0.22 0.31 2.18E-0 2 1.65 C4 (BR) 2.50 - 3.50 1.00 0.14 0.26 0.32 1.33E-0 2 1.72 C4 (BR) 3.50 - 5.0 0.93 0.12 0.31 0.30 6.22E-0 3 1.67 C4 (BR) 5.00 - 6.00 0.87 0.12 0.38 0.29 3.43E-0 3 1.66 C4 (BR) 6.00 - 7.25 0.84 0.12 0.42 0.28 2.50E-0 3 1.66 C4 (BR) 7.25 - 8.50 0.86 0.12 0.48 0.30 2.21E-0 3 1.75 C4 (BR) 8.50 - 10.00 0.79 0.11 0.50 0.27 1.91E-0 3 1.68 C4 (BR) average CEC 1.67 BR measured initial condition 0.79 0.09 0.58 0.08 1.79E-0 3 1.57 BR scaled initial condition1 0.86 0.10 0.63 0.09 1.93E-0 3 1.67 1

Scaled initial conditions were calculated by increasing individual cation concentrations to yield the column CEC while maintaining the originally measured proportions.

Table 8. Column simulation parameters Model parameter C4 C8 Comment (100% BR) (BR:soil)

Domain length 0.1 meters 0.1 meters Column dimension Porosity 0.53 0.25 Calibrated Bulk density (effective) 0.88 g/mL 0.51 g/mL C4 = measured; C8 = calibrated Based on measured column flow rate and Water velocity 0.53 m/d 1.25 m/d calibrated effective porosity Dispersivity 0.005 m 0.005 m Typical value based on 5% of domain length Influent conditions Table 2 Table 2 Measured Zeolite CEC 1.67 meq/g 1.67 meq/g Measured C4 final column value Initial sorbed cations Table 7 Table 7 Measured and scaled to CEC Cation exchange selectivity coefficients KK,Na 30 44 Calibrated KMg,Na 197 369 Calibrated KCa,Na 425 376 Calibrated KSr,Na 6111 5412 Calibrated

Table 9. PTW simulation scenarios Scenario Flow Cation exchange Comment Representative of conditions with Case 1 High: v = 1.7 ft/d Mid: CEC = 1.65 meq/g higher groundwater velocity along eastern PTW segment Case 2 Mid: v = 1 ft/d Mid: CEC = 1.65 meq/g Reference scenario for comparison Representative of conditions with Case 3 Low: v = 0.5 ft/d Mid: CEC = 1.65 meq/g lower groundwater velocity along central PTW segment Case 4 Mid: v = 1 ft/d Low: CEC = 1.50 meq/g CEC from low end of BR range Case 5 Mid: v = 1 ft/d High: CEC = 1.80 meq/g CEC from high end of BR range Zeolite density reduced to represent Case 6 Mid: v = 1 ft/d Mid: CEC = 1.65 meq/g worst case mixing with native soil

Table 10. PTW simulation parameters Model parameter Value Com ment Wall thickness 3 feet AMEC, based on trencher capability Wall porosity 0.35 AMEC, conservative (low) estimate Groundwater velocity 1 ft/d AMEC, middle (Case 2, 4-7) 1.7 ft/d AMEC, high (Case 1) 0.5 ft/d AMEC, low (Case 3)

Zeolite bulk density 0.96 g/mL Loose packing from BR spec (Cases 1-5) 0.51 g/L Worst case mixing scenario from C8 (Case 6)

Dispersivity 0.15 ft Typical value based on 5% PTW thickness Entrance Sr-90 50,000 pCi/L Constant source scenario Entrance Sr2+ 0.30 mg/L High end of field range Entrance Ca2+ 170 mg/L High end of field range Entrance Mg2+ 27 mg/L High end of field range Entrance Na2+ 185 mg/L High end of field range Entrance K+ 5 mg/L High end of field range Zeolite CEC 1.65 meq/g Column C4 and middle of BR spec (Case 1-3, 6) 1.5 meq/g Low end of BR spec (Case 4) 1.8 meq/g High end of BR spec (Case 5)

Initial sorbed cations (5 values) Based on UB lab measurements (Table 7), scaled to CEC Selectivity coefficients (4 values) Based on UB column calibration (Table 8)

Sr90 decay rate 6.59 x 10-5 day-1 Literature value, sorbed and aqueous phases

Figure 1. Effluent concentrations for Column C1 (TMP zeolite); some values for Sr2+ fall between the Method Detection Limit (0.01 mg/L) and the Reporting Limit (0.1 mg/L).

Pore Volumes (n=0.5) 0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 500 475 450 Effluent Concentration (mg/L) 425 Ca2+ Mg2+

400 375 K+ Na+

350 325 Sr2+

300 275 250 Strontium Conc. (g/L 225 200 175 150 125 100 75 50 25 0

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 Time (days)

Figure 2. Effluent concentrations for Column C2 (TMP zeolite); some values for Sr2+ fall between the Method Detection Limit (0.01 mg/L) and the Reporting Limit (0.1 mg/L).

Pore Volumes (n=0.5) 0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 500 475 450 Effluent Concentration (mg/L) 425 Ca2+ Mg2+

400 375 K+ Na+

350 325 Sr2+

300 275 250 Strontium Conc. (g/L 225 200 175 150 125 100 75 50 25 0

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 Time (days)

Figure 3. Effluent concentrations for Column C3 (BR zeolite); some values for Sr2+ fall between the Method Detection Limit (0.01 mg/L) and the Reporting Limit (0.1 mg/L).

Pore Volumes (n=0.5) 0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 500 475 450 Effluent Concentration (mg/L) 425 Ca2+ Mg2+

400 375 K+ Na+

350 325 Sr2+

300 275 Strontium Conc. (g/L 250 225 200 175 150 125 100 75 50 25 0

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 Time (days)

Figure 4. Effluent concentrations for Column C4 (BR zeolite); some values for Sr2+ fall between the Method Detection Limit (0.01 mg/L) and the Reporting Limit (0.1 mg/L).

Pore Volumes (n=0.5) 0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 500 475 450 Effluent Concentration (mg/L) 425 Ca2+ Mg2+

400 375 K+ Na+

350 325 Sr2+

300 275 250 Strontium Conc. (g/L 225 200 175 150 125 100 75 50 25 0

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 Time (days)

Figure 5. Effluent concentrations for Column C5 (TMP zeolite with 20% WV soil); some values for Sr2+ fall between the Method Detection Limit (0.01 mg/L) and the Reporting Limit (0.1 mg/L).

Pore Volumes (n=0.25) 0 100 200 300 400 500 600 700 800 900 10001100120013001400150016001700180019002000 500 475 450 Effluent Concentration (mg/L) 425 Ca2+ Mg2+

400 375 K+ Na+

350 325 Sr2+

300 275 250 Strontium Conc. (g/L 225 200 175 150 125 100 75 50 25 0

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 Time (days)

Figure 6. Effluent concentrations for Column C6 (TMP zeolite with 20% WV soil); some values for Sr2+ fall between the Method Detection Limit (0.01 mg/L) and the Reporting Limit (0.1 mg/L).

Pore Volumes (n=0.25) 0 100 200 300 400 500 600 700 800 900 1000110012001300140015001600170018001900 500 475 450 Effluent Concentration (mg/L) 425 Ca2+ Mg2+

400 375 K+ Na+

350 325 Sr2+

300 275 Strontium Conc. (g/L 250 225 200 175 150 125 100 75 50 25 0

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 Time (days)

Figure 7. Effluent concentrations for Column C7 (BR zeolite with 20% WV soil); some values for Sr2+ fall between the Method Detection Limit (0.01 mg/L) and the Reporting Limit (0.1 mg/L).

Pore Volumes (n=0.25) 0 100 200 300 400 500 600 700 800 900 100011001200130014001500160017001800 500 475 450 Effluent Concentration (mg/L) 425 Ca2+ Mg2+

400 375 K+ Na+

350 325 Sr2+

300 275 250 Strontium Conc. (g/L 225 200 175 150 125 100 75 50 25 0

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 Time (days)

Figure 8. Effluent concentrations for Column C8 (BR zeolite with 20% West Valley soil);

some values for Sr2+ fall between the Method Detection Limit (0.01 mg/L) and the Reporting Limit (0.1 mg/L).

Pore Volumes (n=0.25) 0 100 200 300 400 500 600 700 800 900 1000110012001300140015001600170018001900 500 475 450 425 Effluent Concentration (mg/L)

Ca2+ Mg2+

400 375 K+ Na+

350 325 Sr2+

300 275 250 Strontium Conc. (g/L 225 200 175 150 125 100 75 50 25 0

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 Time (days)

Figure 9. Effluent concentrations for Column C9 (WV Soil); all values for Sr2+ fall between the Method Detection Limit (0.01 mg/L) and the Reporting Limit (0.1 mg/L).

Pore Volumes (n=0.25) 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 500 475 450 425 Effluent Concentration (mg/L)

Ca2+ Mg2+

400 375 K+ Na+

350 325 Sr2+

300 275 250 225 200 175 150 125 100 75 50 25 0

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 Time (days)

Figure 10. Effluent concentrations for Column C10 (BR zeolite with 20% WV soil and 10% iron); some values for Sr2+ fall between the Method Detection Limit (0.01 mg/L) and the Reporting Limit (0.1 mg/L).

Pore Volumes (n=0.25) 0 100 200 300 400 500 600 700 800 900 1000110012001300140015001600170018001900 500 475 450 425 Effluent Concentration (mg/L)

Ca2+ Mg2+

400 375 K+ Na+

350 325 Sr2+

300 275 250 Strontium Conc. (g/L 225 200 175 150 125 100 75 50 25 0

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 Time (days)

Figure 11. Sorbed cations at end of experiment for Column C2 (100% TMP)

Figure12. Sorbed cations at end of experiment for Column C4 (100% BR)

Figure 13. Calibrated effluent concentrations for Column C4 (100% BR)

Figure 14. Calibrated sorbed concentrations for Column C4 (100% BR)

Figure 15. Calibrated effluent concentrations for Column C8 (80/20 BR soil)

Figure 16 Conceptual model for PTW simulations Groundwater flow x=0 x=L Sr-90 plume PTW Confining layer

Figure 17. Hypothetical PTW simulations: flow variation Figure 18. Hypothetical PTW simulations: zeolite variation Exhibit 1. UB doctoral candidate Shannon Seneca with zeolite experimental columns Exhibit 2. UB experimental columns C2 (left, 100% TMO) and C3 (right, 100%BR)

TEAGUE MINERAL PRODUCTS 1925 Hwy 201 S. Adrian OR 97901 Phone 541/339-3940 541/339-4385 Phone or Fax TM CH Chrisman Hill NATURAL ZEOLITE ANALYSES These analyses represent the chemical composition and physical characteristics of commercially available products. The CH Zeolite analysis represents a bulk sample of the entire bed thickness. These are typical analyses, not specifications. Natural occurring minerals vary. TMP mines only high purity raw materials with continuous quality control to ensure minimal variation from shipment to shipment.

Whole Rock Chemistry: XRF, Dry Weight Basis, Normalized to 100%

SiO 67.9 2

Al²0³ 10.6 Weight Ti0² 0.29 Percent Fe²0³ 2.58 Oxides Ca0 1.27 Mg0 .21 Na²0 .81 K²0 4.75 PO 2 5

.27 TiO 2

.29 BaO .16 S <.05 Cation Exchange Capacity (CEC): Ammonium Acetate Method meq/100g - 177 Bulk Density: pounds/foot³ - 20 x 50 mesh granules loose 48.67 packed 53.04 Water Absorbance: 20 x 50 mesh granules, saturated, drained - 70%

Color: off white Brightness: 67 Zeolite Species: Clinoptilolite Approximate Zeolite Content by XRD: 70 - 80%

Note* Individual samples may vary from this analysis and should not be considered a certified sample unless stated as such.

DISCLAIMER THE INFORMATION CONTAINED IN THIS BULLETIN IS , TO OUR BEST KNOWLEDGE, TRUE AND ACCURATE. ALL RECOMMENDATIONS OR SUGGESTIONS ARE MADE WITHOUT GUARANTEE, SINCE THE CONDITIONS OF USE ARE BEYOND OUR CONTROL. TEAGUE MINERAL PRODUCTS DISCLAIMS ANY LIABILITY INCURRED IN CONJUCTION WITH USE OF THESE DATA OR SUGGESTIONS. NOTHING HEREIN IS A RECOMMENDATION TO USE ANY PRODUCT IN CONFLICT WITH EXISTING PATENTS COVERING ANY MATERIAL OR ITS USE. TEAGUE MINERAL PRODUCTS SHALL NOT BE LIABLE FOR ANY LOSS OR DAMAGE DIRECTLY OR INDIRECTLY ARISING FROM THE USE OF THE PRODUCT AND WE ASSUME NO OBLIGATION OR LIABILITY FOR RELIANCE ON THE INFORMATION CONTAINED HEREIN, OR OMISSIONS HEREFROM.

Copyright © 2000-2009. Teague Mineral Products. All rights reserved

BRZ Specifications, natural clinoptilolite with high cation exchange capacity. http://www.bearriverzeolite.com/brz-specifications.htm A WHOLLY OWNED SUBSIDIARY OF THE UNITED STATES ANTIMONY CORPORATION PUREST 406-827-3523 or tfl3543@blackfoot.net NATURAL ZEOLITE PRODUCTS SPECIFICATIONS HOME SALES CONTACTS APPLICATIONS Zeolites are a group of volcanic minerals that are hydrated calcium USAC CORPORATE potassium sodium aluminosilicates in which water is held in channel ways by absorption. The lattices are negatively charged, and they loosely hold positively charged cations such as calcium, sodium, potassium, and ammonium. Their ability to exchange one cation for another is known as their cation exchange capacity or CEC. Once the ammonium ion is in the lattice, it is not water-soluble. They chemically filter out the ammonium.

BEAR RIVER ZEOLITE (BRZ') SPECIFICATIONS GENERAL CHEMICAL COMPOSITION CERTIFICATION MATERIAL SAFETY DATA SHEET (MSDS) 1 of 3 4/24/2009 10:23 AM

BRZ Specifications, natural clinoptilolite with high cation exchange capacity. http://www.bearriverzeolite.com/brz-specifications.htm GENERAL:

Mineral Component: 85% Clinoptilolite balance opaline silica Cation Exchange Capacity: 1.5 to 1.8 meq/gram ( as ammonium, -N)

Maximum Water Retention: >55 WT %

Overall Surface Area: 24.9 square meters/gram Bulk Density (Weight) Approx. 55 - 60 pounds per cubic foot Hardness Mohs no. 4 Color Pale green Sizes 3/8 x 1/4. 4 x 8, 4 x 14, 14 x 40, 40 x 100, -100, -40 mesh Mine and Processing Plant 4323 East Glendale Road, Preston, Idaho 83263 Headquarters and Sales Office 1250 Prospect Creek Road, Thompson Falls, MT 59873 Telephone 406-827-3523 Fax 406-827-3543 email tfl@blackfoot.net Transportation: Truck or Rail Reserve: Approximately 200,000,000 tons CHEMICAL COMPOSITION:

Cations:

Potassium: 3.47%

Calcium: 1.60%

Sodium: <0.5%

Other Elements:

Cu 25ppm Zn 35ppm Rb 120ppm Fe 1.3%

Zr 480ppm Y 55ppm Nb 40ppm Sr 560ppm Nd 45ppm La 55ppm Ba 1200ppm Ce 130ppm Pb <30ppm Rock Analytical Data:

SiO2 67.4%

2 of 3 4/24/2009 10:23 AM

BRZ Specifications, natural clinoptilolite with high cation exchange capacity. http://www.bearriverzeolite.com/brz-specifications.htm AI2O3 10.6%

FE2O3 1.7%

MgO 0.45%

CaO 2.23%

Na2O 0.59%

K2O 4.19%

TiO2 0.27%

P2O5 0.10%

MnO <0.01%

LOI @925C 11.4%

CERTIFICATION:

U.S. Food and Drug Administration (FDA) Registration 17000178052 Canadian Animal Feed registration No. 990643 Swimming Pools & Spas-ANSI/NSF standard 50 (ZeoSand),

Drinking Water Treatment-ANSI/NSF standard 60 (ChemSorb Sorbent Powder),

Drinking Water-ANSI/NSF standard 61 (ChemSorb Filter Granules)

GRAS (generally regarded as safe) under 21 CFR Part 182.2729, 40 CFR Part 180.1001 General Physical Attributes: non dusting, resistant to attrition, non clouding in liquids (due to absence of clays), good permeability, relatively high density, high water retention.

Applications: Fertilizer and soil amendments; water and other liquid purification and clarification; odor abatement; oxygen production and gas separations; ion exchange; absorption and adsorption; nitrogen (ammonia/ammonium) abatement; hydrocarbon abatement; abatement of certain toxic waste and acid wastes; fillers; desiccants; construction materials; aquaculture water treatment; radioactive waste management; animal feed additive supplements; catalysts substrates; wastewater treatment; oil spill sorbent; biological and animal waste management; and many others.

HOME SALES CONTACTS APPLICATIONS Copyright © 2007 Bear River Zeolite Web design by Beaver Creek Consultants 3 of 3 4/24/2009 10:23 AM

Appendix: Zeolite Characterization procedure, June 1 2009 Scope:

This test will be used to characterize the distribution of sorbed cations on the zeolite materials collected from the installed permeable treatment wall (PTW).

Process:

Cations will be flushed from the zeolite material using a modified version of the standard batch exchange method described by Cerri et al. in their journal article in Clay and Clay Minerals Vol. 50 No. 1, 127135, 2002. General process steps are as follows:

1. For samples of dry unprocessed material, a prewashing step is recommended to remove fine particles that would be lost during subsequent handling (this step is omitted for samples from the field or completed column tests). Regardless of preliminary processing, dry the zeolite (e.g., overnight at 103 degrees Celsius).

2. Weigh out a specified mass of dried zeolite (mz). Recommended: 9 grams;

3. Prepare a 1 M NH4+ solution using NH4Cl;

4. Combine specified amount of zeolite and solution in test tube. Recommended: 1:10 solid liquid ratio = 9 grams of zeolite and 90 grams of NH4Cl solution;

5. Place cap on test tube and tape to seal;

6. Place test tube(s) on rotator to slowly mix over a specified period of time. Recommended =

4 days;

7. Separate rinsate by vacuum filtration followed by syringe filtration using a 0.45 µm filter;

8. Collect rinsate in a beaker;

9. Carefully remove all solid material (from filter and glassware) and replace in test tube.

10. Repeat steps 4 through 6 twice (i.e., three separate rinses with 90 g of solution, each with 4 days of mixing). All rinsate (for each zeolite sample) is combined in a single beaker.

Carefully measure and record total volume of collected rinsate (VT);

11. Store rinsate in prepreserved labeled sample containers until delivered to laboratory for cation analysis.

These steps will be followed by analysis of the rinsate for the following cations: Ca2+, Mg2+, Na+, K+ and Sr2+.

The concentration of each sorbed cation is computed as follows; CiVT qi =

mz where qi is the sorbed concentration of cation i (mg/kg), Ci is the concentration of cation i in the rinsate (mg/L), VT is the total volume of rinsate (mL, typically 270 mL), and mz is the mass of zeolite (g, typically 9 g).

MOUSER MOderately USEr-friendly Reactive transport model Version 2 Overview of key features prepared for West Valley Nuclear Services, LLC Department of Civil, Structural, and Environmental Engineering State University of New York at Buffalo Buffalo, New York 14260 www.groundwater.buffalo.edu DRAFT July 03, 2009

MOUSER Version 2: July 2, 2009 1 INTRODUCTION 1.1 Overview and history This report provides an overview of the MOUSER software, with an emphasis on its history, capabilities, and evaluation. MOUSER implements solutions to the one-dimensional advective-dispersive-reactive equation (ADRE) for a variety of boundary conditions and reaction scenarios. Although MOUSER was originally developed to simulate subsurface barrier systems (slurry walls and permeable reactive barriers), it simulation capability is applicable to any problem defined by the one-dimensional ADR equation, including advection- or diffusion-dominated laboratory columns and field-scale transport along a streamline.

The original developments that formed the basis for current MOUSER were initiated during Dr. Alan Rabideaus 1994 Ph.D. dissertation. In particular, the split-operator finite element approach to contaminant transport modeling was introduced by Miller and Rabideau (1993) and has remained the basis for the underlying numerical engine. During the period 1994 - 1999, the first user-oriented software implementation was developed under the sponsorship of DuPont, who utilized an early version of the program (TRANS1D) for research and the analysis of site-specific groundwater containment systems. After the completion of the DuPont project, MOUSER was developed as a new public domain research tool designed to support an expanded set of reaction scenarios, using methods refined and tested under the DuPont program, and released to the public in 2003. Subsequently, MOUSER has been updated on a periodic basis to support new groundwater contaminant reaction scenarios, with an emphasis on decay and sorption processes. Significant extensions included the development of a multi-solute cation exchange to support the design of a permeable treatment wall (PTW) at the West Valley Demonstration project, and the recent expansion of the sorption isotherm capability to include several multi-parameter dual mode models.

1.2 Capabilities MOUSER solves the governing ADR equation for a two-compartment system consisting of an immobile solid phase (porous media) and a mobile pore fluid phase. The required input parameters for MOUSER include information regarding physical and chemical properties of the contaminant(s) and porous media. Preparation of input is readily accomplished using a text editor. Detailed discussions of the required input parameters are contained in a separate users guide.

The MOUSER output consists of calculated values of the contaminant(s) aqueous concentration, instantaneous flux and cumulative mass released per area, and/or sorbed/total concentrations. The output is written in space-delimited ASCII format to a text file, which may be easily imported into a spreadsheet or graphing program. Output is provided for the dependent variables in terms of a temporal profile (time-varying output for a specified location) or a spatial profile (output for multiple spatial locations at a single time).

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MOUSER Version 2: July 2, 2009 The contaminant aqueous concentration (ML-3) is expressed as a volume-averaged (i.e., resident) concentration in terms of mass of aqueous solute per volume of pore fluid, although interpretation as a flux-averaged concentration is possible under some circumstances. The instantaneous contaminant flux (MT-1A-2) is defined as the rate of contaminant mass exiting a plane normal to the direction of advective transport, expressed in units of solute mass per cross-sectional area per time. The cumulative mass per area (MA-2) is simply the summation of the total mass of contaminant released from the domain during the simulation period, with units of mass per cross-sectional area (normal to direction of advection). When applicable, the sorbed concentration is expressed as the mass of sorbed solute per mass of solid material, and the total concentration (includes pore fluid) is expressed as the combined mass of solute in the aqueous and sorbed phases per mass of solid material.

In addition to the above general information, separate user documentation provides governing equations solved by the models, detailed instructions for the preparation of input files, general discussions of ADR modeling and parameter selection for a variety of applications, benchmarking and example problems, details of the numerical implementation of the ADR solutions, and an annotated bibliography of published journal articles related to the development or application.

1.3 Unique features MOUSER contains some features that are similar to other public domain one-dimensional ADR codes such as CXTFIT (Parker and van Genuchten, 1984) and PHREEQC (Parkhurst and Appolina, 2000), but emphasizes the following distinctives:

For many problems of interest, three alternative solution methods are available:

(1) analytical (closed form), (2) semi-analytical, based on the numerical inversion of Laplace-transformed solutions, and (3) numerical, using several algorithms built around a flexible grid-based split-operator approach.

Numerous boundary condition options are provided for both the domain entrance and exit.

In addition to the solute concentrations(s), the program can provide output for the following derived variables: instantaneous flux per area, cumulative mass per area, sorbed concentration, and total (aqueous plus sorbed) concentration.

A variety of reaction options are supported, including nonequilbirum sorption, sequential multi-solute parent-daughter decay, and multi-solute competitive cation exchange. Prototype versions of other reaction system have also been developed, but are not currently available with comprehensive documentation.

A number of utilities are available to support automated calibration using the public domain OSTRICH software.

Instructions are available for modeling customized reaction scenarios by developing FORTRAN source code compatible with the other MOUSER modules (currently by request only).

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MOUSER Version 2: July 2, 2009 1.4 Evaluation Since its inception, MOUSER has been extensively tested and benchmarked. Much of this work has been conducted in an ad hoc fashion, through the work of graduate students who have adapted MOUSER to solve specific problems related to a thesis or dissertation. Major evaluation methods include the following:

Beginning with the TRANS1D development and continuing through the lifetime of MOUSER, a series of benchmark problems has been maintained to support comparisons between the numerical solution and various analytical and semi-analytical solutions to the ADRE. In all cases, two or three different methods are implemented to solve the same problem. The most recent technical memorandum includes 20 test problems that cover a range of advection- and diffusion-dominated transport, several combinations of boundary conditions, and various sorption/decay reactions. In general, comparisons with analytical solutions are possible for linear sorption/decay and idealized boundary conditions.

During the period of TRANS1D development, the software was subjected to internal QA/QC review by DuPont, including application under regulatory supervision to site-specific design of containment systems.

A variety of internal procedures are utilized by MOUSER to limit potential errors.

For example, spatial and temporal discretization parameters are checked against standard Peclet/Courant guidance to alert users to possible inaccuracies. For all simulations, a numerical mass balance is calculated for use in determining the appropriate discretization.

Numerical procedures and applications of MOUSER have been published in first-tier journals that require extensive peer-review. An annotated list of relevant publications is given below.

The multi-solute cation exchange formulation developed to evaluate a zeolite-based permeable treatment wall for the West Valley Demonstration Project (Rabideau et al., 2005) was recently benchmarked against the PHREEQC reactive transport model distributed by the U.S. Geological Survey (Parkhurst and Appolina, 2000). Despite significant differences in notation and numerical implementation, the two programs yielded comparable results for test problems based on the WVDP application. However, the computational time required by the MOUSER model was significantly shorter, thus facilitating a much more detailed set of modeling analyses.

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MOUSER Version 2: July 2, 2009 1.5 Annotated bibliography Discussions of some of the technical issues related to MOUSER applications can be found in the following peer-reviewed journal articles and conference papers, which are available by request from the authors.

1. Miller, C. T., and Rabideau, A. J. (1993). Development of split-operator, Petrov-Galerkin methods to simulate transport and diffusion problems, Water Resources Research, 29(7), 2227 - 2240. Original development of the one-dimensional split-operator finite algorithm, with application to transport coupled with spherical diffusion, including benchmarking against the orthogonal collocation method.

2. Rabideau, A. J. (1996). Contaminant transport modeling, in Assessment of Barrier Containment Technologies, Rumer, R.; Mitchell, J., Eds., prepared under the auspices of U. S. Department of Energy, U. S. Environmental Protection Agency, DuPont Company, NTIS PB96-180583, 1996. An overview of modeling issues relevant to barrier technology.

3. Khandelwal, A., Rabideau, A. J., and Su. J. (1997). Development of contaminant transport model for the design of vertical barriers, Land contamination and reclamation, 5(3),97-101, from 1997 International Containment Technology Conference. An overview of an early version of the TRANS1D model with application to column experiments performed with soil/bentonite slurry wall materials.

4. Khandelwal, A., Rabideau, A. J. (1996). Modeling of diffusion-dominated transport in soil/bentonite slurry walls, Proceedings of the twenty-eighth Mid-Atlantic Conference on Hazardous and Industrial Waste, Buffalo, NY, July 1996. An overview of an early version of TRANS1D, with preliminary results from column experiments.

5. Khandelwal, A., Rabideau, A. J., Shen, P. (1998). Analysis of diffusion and sorption of organic solutes in soil/bentonite barrier walls, Environmental Science &

Technology, 32(9), 1333-1339. Results and TRANS1D model interpretation of laboratory column experiments performed with organic solutes and soil/bentonite barrier materials.

6. Rabideau, A. J., and Khandelwal, A. (1998). Analysis of nonequilibrium sorption in soil/bentonite barriers, Journal of Environmental Engineering, 124(4), 329-335.

Derivation of the single-solute finite layer model used in MOUSER, with discussion of the role of nonequilibrium sorption in soil/bentonite slurry walls.

7. Rabideau, A. J., and Khandelwal, A. (1998). Boundary conditions for modeling transport in vertical barriers," Journal of Environmental Engineering, 124(11), 1135-1141. Recommendations for boundary conditions for modeling slurry walls, including the new concept of mixing zone conditions. Illustrative calculations utilize TRANS1D/MOUSER.

8. Rabideau, A. J., Shen, P., and Khandelwal, A. (1999). Feasibility of amending slurry walls with zero-valent iron, Journal of Geoenvironmental and Geotechnical Engineering 125 (4), 1135-330-334. Analysis the potential performance of soil/bentonite slurry wall materials amended with zero-valent iron. Illustrative calculations utilized TRANS1D/MOUSER.

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MOUSER Version 2: July 2, 2009

9. Khandelwal, A., and Rabideau, A. J. (1999). Transport of sequentially decaying reaction products influenced by linear nonequilibrium sorption, Water Resources Research. Derivation and testing of several multi-solute finite layer models that are implemented in MOUSER, with discussion of applications to iron-based treatment walls.

10. Khandelwal, A., and Rabideau, A. J. (2000). Amendment of soil/bentonite slurry walls with natural humus, Journal of Contaminant Hydrology, 25, 267 - 282.

Results and TRANS1D model interpretation of laboratory column experiments performed with organic solutes and soil/bentonite barrier materials amended to promote sorption.

11. Rabideau, A. J., Suribhatla, R., and Craig, J. R. (2005). Analytical models for the design of iron-based permeable reactive barriers J. Env. Eng., 131(11), 1589 -

1597. Development of new analytical solutions for transport sequential parent-daughter decay, benchmarked against MOUSERs numerical formulation.

12. Rabideau, A. J., Van Benschoten J., Bandilla, K., and Patel, A. (2005). Performance assessment of a zeolite treatment wall for removing Sr-90 from groundwater J.

Cont. Hyd., 79(1 - 2), 1 - 24. Laboratory and modeling studies of natural zeolites used in the West Valley Demonstration Project permeable treatment wall, including development of MOUSERs competitive cation exchange module.

13. Bartelt-Hunt, S., Culver, T. B., Smith, J. A., Matott, L. S., and Rabideau, A. J. (2006).

Optimal design of a compacted soil liner containing sorptive amendments, J. Env.

Eng., 132(7), 769 - 776, application of MOUSER to the optimal design of sorpbing landfill liners.

14. Matott, L. S., Bartelt-Hunt, S., Rabideau, A. J., and Fowler, K. (2006). Application of heuristic optimization techniques and algorithm tuning to multi-layered sorptive barrier design, Env. Sci. & Tech., 40, 6354 - 6360, further application of MOUSER to the optimal design of sorbing landfill liners.

15. Matott, L. S., and Rabideau, A. J. (2008). Calibration of subsurface reactive transport models involving complex biogeochemical processes, Adv. Water Res.,

(3192), 269 - 286. MOUSER was used to benchmark a new software package (NIGHTHAWK) for solving complex reactive transport problems.

16. Bandilla, K., Rabideau, A. J., and Jankovic, I. (2008). A parallel mesh-free multi-solute reactive contaminant transport model based on the Analytic Element Method and the Streamline Method, Adv. Water Res., MOUSER was used to benchmark a new software package (ROBIN) that extended the one-dimensional split-operator approach to multiple dimensions via a streamtube algorithm.

17. Matott, L. S., and Rabideau, A. J., NIGHTHAWK: a program for subsurface transport modeling incorporating equilibrium and kinetic biogeochemistry, Computers & Geosciences (in press). Further use of MOUSER to benchmark the NIGHTHAWK software package for solving complex reactive transport problems.

18. Matott, L. S., Bandilla, K., and Rabideau, A. J., Incorporating nonlinear isotherms into robust multilayer sorptive barrier design, Advances in Water Resources (in press). Additional application of MOUSER and NIGHTHAWK to the design of sorbing landfill liners.

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CAS Sample TMP-Teague Mineral Products, BR-Bear River, SGW-synthetic groundwater Number Date Sample Details 1 2/21 Synthetic influent groundwater 2 2/21 Column 1 - 100% TMP zeolite 3 2/21 Column 2 - 100% TMP zeolite 4 2/21 Column 3 - 100% BR zeolite 5 2/21 Column 4 - 100% BR zeolite 6 2/21 Column 5 - TMP zeolite with 20% WV soil 7 2/21 Column 6 - TMP zeolite with 20% WV soil 8 2/21 Column 7 - BR zeolite with 20% WV soil 9 2/21 Column 8 - BR zeolite with 20% WV soil 10 2/21 Column 9 - 100% WV soil 11 2/21 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 12 2/23 Synthetic influent groundwater 13 2/23 Column 1 - 100% TMP zeolite 14 2/23 Column 2 - 100% TMP zeolite 15 2/23 Column 3 - 100% BR zeolite 16 2/23 Column 4 - 100% BR zeolite 17 2/23 Column 5 - TMP zeolite with 20% WV soil 18 2/23 Column 6 - TMP zeolite with 20% WV soil 19 2/23 Column 7 - BR zeolite with 20% WV soil 20 2/23 Column 8 - BR zeolite with 20% WV soil 21 2/23 Column 9 - 100% WV soil 22 2/23 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 23 2/25 Synthetic influent groundwater 24 2/26 Synthetic influent groundwater 25 2/26 Column 1 - 100% TMP zeolite 26 2/26 Column 2 - 100% TMP zeolite 27 2/26 Column 3 - 100% BR zeolite 28 2/26 Column 4 - 100% BR zeolite 29 2/26 Column 5 - TMP zeolite with 20% WV soil 30 2/26 Column 6 - TMP zeolite with 20% WV soil 31 2/26 Column 7 - BR zeolite with 20% WV soil 32 2/26 Column 8 - BR zeolite with 20% WV soil 33 2/26 Column 9 - 100% WV soil 34 2/26 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 35 2/28 Column 1 - 100% TMP zeolite 36 2/28 Column 2 - 100% TMP zeolite 37 2/28 Column 3 - 100% BR zeolite 38 2/28 Column 4 - 100% BR zeolite 39 2/28 Column 5 - TMP zeolite with 20% WV soil 40 2/28 Column 6 - TMP zeolite with 20% WV soil 41 2/28 Column 7 - BR zeolite with 20% WV soil 42 2/28 Column 8 - BR zeolite with 20% WV soil 43 2/28 Column 9 - 100% WV soil 44 2/28 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 45 3/3 Synthetic influent groundwater 46 3/3 Column 1 - 100% TMP zeolite

CAS Sample TMP-Teague Mineral Products, BR-Bear River, SGW-synthetic groundwater Number Date Sample Details 47 3/3 Column 2 - 100% TMP zeolite 48 3/3 Column 3 - 100% BR zeolite 49 3/3 Column 4 - 100% BR zeolite 50 3/3 Column 5 - TMP zeolite with 20% WV soil 51 3/3 Column 6 - TMP zeolite with 20% WV soil 52 3/3 Column 7 - BR zeolite with 20% WV soil 53 3/3 Column 8 - BR zeolite with 20% WV soil 54 3/3 Column 9 - 100% WV soil 55 3/3 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 56 3/4 Synthetic influent groundwater 57 3/5 Synthetic influent groundwater 58 3/5 Column 1 - 100% TMP zeolite 59 3/5 Column 2 - 100% TMP zeolite 60 3/5 Column 3 - 100% BR zeolite 61 3/5 Column 4 - 100% BR zeolite 62 3/5 Column 5 - TMP zeolite with 20% WV soil 63 3/5 Column 6 - TMP zeolite with 20% WV soil 64 3/5 Column 7 - BR zeolite with 20% WV soil 65 3/5 Column 8 - BR zeolite with 20% WV soil 66 3/5 Column 9 - 100% WV soil 67 3/5 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 68 3/7 Synthetic influent groundwater 69 3/7 Column 1 - 100% TMP zeolite 70 3/7 Column 2 - 100% TMP zeolite 71 3/7 Column 3 - 100% BR zeolite 72 3/7 Column 4 - 100% BR zeolite 73 3/7 Column 5 - TMP zeolite with 20% WV soil 74 3/7 Column 6 - TMP zeolite with 20% WV soil 75 3/7 Column 7 - BR zeolite with 20% WV soil 76 3/7 Column 8 - BR zeolite with 20% WV soil 77 3/7 Column 9 - 100% WV soil 78 3/7 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 79 3/9 Synthetic influent groundwater 80 3/9 Column 1 - 100% TMP zeolite 81 3/9 Column 2 - 100% TMP zeolite 82 3/9 Column 3 - 100% BR zeolite 83 3/9 Column 4 - 100% BR zeolite 84 3/9 Column 5 - TMP zeolite with 20% WV soil 85 3/9 Column 6 - TMP zeolite with 20% WV soil 86 3/9 Column 7 - BR zeolite with 20% WV soil 87 3/9 Column 8 - BR zeolite with 20% WV soil 88 3/9 Column 9 - 100% WV soil 89 3/9 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 90 3/12 Column 1 - 100% TMP zeolite 91 3/12 Column 2 - 100% TMP zeolite 92 3/12 Column 3 - 100% BR zeolite

CAS Sample TMP-Teague Mineral Products, BR-Bear River, SGW-synthetic groundwater Number Date Sample Details 93 3/12 Column 4 - 100% BR zeolite 94 3/12 Column 5 - TMP zeolite with 20% WV soil 95 3/12 Column 6 - TMP zeolite with 20% WV soil 96 3/12 Column 7 - BR zeolite with 20% WV soil 97 3/12 Column 8 - BR zeolite with 20% WV soil 98 3/12 Column 9 - 100% WV soil 99 3/12 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 100 3/18 Synthetic influent groundwater 101 3/18 Column 1 - 100% TMP zeolite 102 3/18 Column 2 - 100% TMP zeolite 103 3/18 Column 3 - 100% BR zeolite 104 3/18 Column 4 - 100% BR zeolite 105 3/18 Column 5 - TMP zeolite with 20% WV soil 106 3/18 Column 6 - TMP zeolite with 20% WV soil 107 3/18 Column 7 - BR zeolite with 20% WV soil 108 3/18 Column 8 - BR zeolite with 20% WV soil 109 3/18 Column 9 - 100% WV soil 110 3/18 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 111 3/19 Synthetic influent groundwater 112 3/12 T1A - 9g BR in 90 ml 1 M NH4Cl soak 1 day on tumbler, repeat 4X (3 soaks) 113 3/15 T1B - 9g BR in 90 ml 1 M NH4Cl soak 1 day on tumbler, repeat 4X (2 soaks) 114 3/13 T2A-9g BR in 90 ml 1 M NH4Cl soak 2 days on tumbler, repeat 3X (2 soaks) 115 3/17 T2B-9g BR in 90 ml 1 M NH4Cl soak 2 days on tumbler, repeat 3X (2 soaks) 116 3/15 T4 - 9g BR in 90 ml 1 M NH4Cl soak 4 days on tumbler, repeat 1 times 117 3/12 T5A-9g TMP in 90 ml 1M NH4Cl soak 1 day on tumbler, repeat 4X (3 soaks) 118 3/15 T5B-9g TMP in 90 ml 1M NH4Cl soak 1 day on tumbler, repeat 4X (2 soaks) 119 3/13 T6A-9g TMP in 90 ml 1M NH4Cl soak 2 day on tumbler, repeat 3X (2 soaks) 120 3/17 T6B-9g TMP in 90 ml 1M NH4Cl soak 2 day on tumbler, repeat 3X (2 soaks) 121 3/15 T8 - 9g TMP in 1 M NH4Cl soak 4 days on tumbler, repeat 1 times 122 3/15 B1 - 20g TMP zeolite in 100 ml SGW on shaker table 2 weeks 123 3/15 B2 - 20g TMP zeolite in 100 ml SGW on shaker table 2 weeks 124 3/15 B3 - 20g BR zeolite in 100 ml SGW on shaker table 2 weeks 125 3/15 B4 - 20g BR zeolite in 100 ml SGW on shaker table 2 weeks 126 3/15 B5 - 10g TMP zeolite in 100 ml SGW on shaker table 2 weeks 127 3/15 B6 - 10g TMP zeolite in 100 ml SGW on shaker table 2 weeks 128 3/15 B7 - 10g BR zeolite in 100 ml SGW on shaker table 2 weeks 129 3/15 B8 - 10g BR zeolite in 100 ml SGW on shaker table 2 weeks 130 3/15 B9 - 100 ml synthetic groundwater on shaker table 2 weeks 131 3/25 Synthetic influent groundwater 132 3/25 Column 1 - 100% TMP zeolite 133 3/25 Column 2 - 100% TMP zeolite 134 3/25 Column 3 - 100% BR zeolite 135 3/25 Column 4 - 100% BR zeolite 136 3/25 Column 5 - TMP zeolite with 20% WV soil 137 3/25 Column 6 - TMP zeolite with 20% WV soil 138 3/25 Column 7 - BR zeolite with 20% WV soil

CAS Sample TMP-Teague Mineral Products, BR-Bear River, SGW-synthetic groundwater Number Date Sample Details 139 3/25 Column 8 - BR zeolite with 20% WV soil 140 3/25 Column 9 - 100% WV soil 141 3/25 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 142 3/14 T3 - 9g BR in 90 ml 1 M NH4Cl soak 3 days on tumbler, repeat 2 times 143 3/14 T7 - 9g TMP in 90 ml 1 M NH4Cl soak 3 days on tumbler, repeat 2 times 144 3/31 Synthetic influent groundwater 145 4/1 Column 1 - 100% TMP zeolite 146 4/1 Column 2 - 100% TMP zeolite 147 4/1 Column 3 - 100% BR zeolite 148 4/1 Column 4 - 100% BR zeolite 149 4/1 Column 5 - TMP zeolite with 20% WV soil 150 4/1 Column 6 - TMP zeolite with 20% WV soil 151 4/1 Column 7 - BR zeolite with 20% WV soil 152 4/1 Column 8 - BR zeolite with 20% WV soil 153 4/1 Column 9 - 100% WV soil 154 4/1 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 155 4/1 B11- 10 g BR zeolite in 100 ml nanopure water on shaker table 2 weeks 156 4/2 Synthetic influent groundwater 157 4/6 Synthetic influent groundwater 158 4/8 Column 1 - 100% TMP zeolite 159 4/8 Column 2 - 100% TMP zeolite 160 4/8 Column 3 - 100% BR zeolite 161 4/8 Column 4 - 100% BR zeolite 162 4/8 Column 5 - TMP zeolite with 20% WV soil 163 4/8 Column 6 - TMP zeolite with 20% WV soil 164 4/8 Column 7 - BR zeolite with 20% WV soil 165 4/8 Column 8 - BR zeolite with 20% WV soil 166 4/8 Column 9 - 100% WV soil 167 4/8 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 168 4/1 B10- 10 g TMP zeolite in 100 ml nanopure water on shaker table 2 wks.

169 4/9 Synthetic influent groundwater 170 4/14 Synthetic influent groundwater 171 4/15 Column 1 - 100% TMP zeolite 172 4/15 Column 2 - 100% TMP zeolite 173 4/15 Column 3 - 100% BR zeolite 174 4/15 Column 4 - 100% BR zeolite 175 4/15 Column 5 - TMP zeolite with 20% WV soil 176 4/15 Column 6 - TMP zeolite with 20% WV soil 177 4/15 Column 7 - BR zeolite with 20% WV soil 178 4/15 Column 8 - BR zeolite with 20% WV soil 179 4/15 Column 9 - 100% WV soil 180 4/15 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 181 4/16 Synthetic influent groundwater 182 4/22 Column 1 - 100% TMP zeolite 183 4/22 Column 2 - 100% TMP zeolite 184 4/22 Column 3 - 100% BR zeolite

CAS Sample TMP-Teague Mineral Products, BR-Bear River, SGW-synthetic groundwater Number Date Sample Details 185 4/22 Column 4 - 100% BR zeolite 186 4/22 Column 5 - TMP zeolite with 20% WV soil 187 4/22 Column 6 - TMP zeolite with 20% WV soil 188 4/22 Column 7 - BR zeolite with 20% WV soil 189 4/22 Column 8 - BR zeolite with 20% WV soil 190 4/22 Column 9 - 100% WV soil 191 4/22 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 192 4/23 Synthetic influent groundwater 193 4/30 Synthetic influent groundwater 194 4/30 Column 1 - 100% TMP zeolite 195 4/30 Column 2 - 100% TMP zeolite 196 4/30 Column 3 - 100% BR zeolite 197 4/30 Column 4 - 100% BR zeolite 198 4/30 Column 5 - TMP zeolite with 20% WV soil 199 4/30 Column 6 - TMP zeolite with 20% WV soil 200 4/30 Column 7 - BR zeolite with 20% WV soil 201 4/30 Column 8 - BR zeolite with 20% WV soil 202 4/30 Column 9 - 100% WV soil 203 4/30 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 204 5/1 T1-9g pre-washed TMP in 90 ml 1 M NH4Cl 3 days on tumbler, repeat 3X 205 5/1 T2-9g pre-washed TMP in 90 ml 1 M NH4Cl 4 days on tumbler, repeat 2X 206 5/1 T3-9g pre-washed TMP in 90 ml 1 M NH4Cl 3 days on tumbler, repeat 2X 207 5/1 T4-9g pre-washed TMP in 90 ml 1 M NH4Cl on tumbler, soaked 3, 4, 3 days 208 5/1 T5-9g pre-washed BR in 90 ml 1 M NH4Cl 3 days on tumbler, repeat 3X 209 5/1 T6-9g pre-washed BR in 90 ml 1 M NH4Cl 4 days on tumbler, repeat 2X 210 5/1 T7-9g pre-washed BR in 90 ml 1 M NH4Cl 3 days on tumbler, repeat 2X 211 5/1 T8-9g pre-washed BR in 90 ml 1 M NH4Cl on tumbler, soaked 3, 4, 3 days 212 5/7 Synthetic influent groundwater 213 5/7 Column 1 - 100% TMP zeolite 214 5/7 Column 2 - 100% TMP zeolite 215 5/7 Column 3 - 100% BR zeolite 216 5/7 Column 4 - 100% BR zeolite 217 5/7 Column 5 - TMP zeolite with 20% WV soil 218 5/7 Column 6 - TMP zeolite with 20% WV soil 219 5/7 Column 7 - BR zeolite with 20% WV soil 220 5/7 Column 8 - BR zeolite with 20% WV soil 221 5/7 Column 9 - 100% WV soil 222 5/7 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 223 5/14 Synthetic influent groundwater 224 5/14 Column 1 - 100% TMP zeolite 225 5/14 Column 2 - 100% TMP zeolite 226 5/14 Column 3 - 100% BR zeolite 227 5/14 Column 4 - 100% BR zeolite 228 5/14 Column 5 - TMP zeolite with 20% WV soil 229 5/14 Column 6 - TMP zeolite with 20% WV soil 230 5/14 Column 7 - BR zeolite with 20% WV soil

CAS Sample TMP-Teague Mineral Products, BR-Bear River, SGW-synthetic groundwater Number Date Sample Details 231 5/14 Column 8 - BR zeolite with 20% WV soil 232 5/14 Column 9 - 100% WV soil 233 5/14 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 234 5/15 Synthetic influent groundwater 235 5/20 Synthetic influent groundwater 236 5/21 Column 1 - 100% TMP zeolite 237 5/21 Column 2 - 100% TMP zeolite 238 5/21 Column 3 - 100% BR zeolite 239 5/21 Column 4 - 100% BR zeolite 240 5/21 Column 5 - TMP zeolite with 20% WV soil 241 5/21 Column 6 - TMP zeolite with 20% WV soil 242 5/21 Column 7 - BR zeolite with 20% WV soil 243 5/21 Column 8 - BR zeolite with 20% WV soil 244 5/21 Column 9 - 100% WV soil 245 5/21 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 246 5/28 Synthetic influent groundwater 247 5/28 Column 1 - 100% TMP zeolite 248 5/28 Column 2 - 100% TMP zeolite 249 5/28 Column 3 - 100% BR zeolite 250 5/28 Column 4 - 100% BR zeolite 251 5/28 Column 5 - TMP zeolite with 20% WV soil 252 5/28 Column 6 - TMP zeolite with 20% WV soil 253 5/28 Column 7 - BR zeolite with 20% WV soil 254 5/28 Column 8 - BR zeolite with 20% WV soil 255 5/28 Column 9 - 100% WV soil 256 5/28 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 257 5/28 Synthetic influent groundwater - Phase II 258 5/29 Synthetic influent groundwater - Phase II 259 5/29 Column 1 - 100% TMP zeolite 260 5/29 Column 2 - 100% TMP zeolite 261 5/29 Column 3 - 100% BR zeolite 262 5/29 Column 4 - 100% BR zeolite 263 5/29 Column 5 - TMP zeolite with 20% WV soil 264 5/29 Column 6 - TMP zeolite with 20% WV soil 265 5/29 Column 7 - BR zeolite with 20% WV soil 266 5/29 Column 8 - BR zeolite with 20% WV soil 267 5/29 Column 9 - 100% WV soil 268 5/29 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 269 5/31 Synthetic influent groundwater - Phase II 270 5/31 Column 1 - 100% TMP zeolite 271 5/31 Column 2 - 100% TMP zeolite 272 5/31 Column 3 - 100% BR zeolite 273 5/31 Column 4 - 100% BR zeolite 274 5/31 Column 5 - TMP zeolite with 20% WV soil 275 5/31 Column 6 - TMP zeolite with 20% WV soil 276 5/31 Column 7 - BR zeolite with 20% WV soil

CAS Sample TMP-Teague Mineral Products, BR-Bear River, SGW-synthetic groundwater Number Date Sample Details 277 5/31 Column 8 - BR zeolite with 20% WV soil 278 5/31 Column 9 - 100% WV soil 279 5/31 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 280 6/1 Synthetic influent groundwater - Phase II 281 6/3 Synthetic influent groundwater - Phase II 282 6/3 Column 1 - 100% TMP zeolite 283 6/3 Column 2 - 100% TMP zeolite 284 6/3 Column 3 - 100% BR zeolite 285 6/3 Column 4 - 100% BR zeolite 286 6/3 Column 5 - TMP zeolite with 20% WV soil 287 6/3 Column 6 - TMP zeolite with 20% WV soil 288 6/3 Column 7 - BR zeolite with 20% WV soil 289 6/3 Column 8 - BR zeolite with 20% WV soil 290 6/3 Column 9 - 100% WV soil 291 6/3 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 292 6/5 Synthetic influent groundwater - Phase II 293 6/6 Synthetic influent groundwater - Phase II 294 6/6 Column 1 - 100% TMP zeolite 295 6/6 Column 2 - 100% TMP zeolite 296 6/6 Column 3 - 100% BR zeolite 297 6/6 Column 4 - 100% BR zeolite 298 6/6 Column 5 - TMP zeolite with 20% WV soil 299 6/6 Column 6 - TMP zeolite with 20% WV soil 300 6/6 Column 7 - BR zeolite with 20% WV soil 301 6/6 Column 8 - BR zeolite with 20% WV soil 302 6/6 Column 9 - 100% WV soil 303 6/6 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 304 6/8 Synthetic influent groundwater - Phase II 305 6/8 Synthetic influent groundwater - Phase II 306 6/9 Synthetic influent groundwater - Phase II 307 6/9 Column 1 - 100% TMP zeolite 308 6/9 Column 2 - 100% TMP zeolite 309 6/9 Column 3 - 100% BR zeolite 310 6/9 Column 4 - 100% BR zeolite 311 6/9 Column 5 - TMP zeolite with 20% WV soil 312 6/9 Column 6 - TMP zeolite with 20% WV soil 313 6/9 Column 7 - BR zeolite with 20% WV soil 314 6/9 Column 8 - BR zeolite with 20% WV soil 315 6/9 Column 9 - 100% WV soil 316 6/9 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 317 6/12 Synthetic influent groundwater - Phase II 318 6/12 Column 1 - 100% TMP zeolite 319 6/12 Column 2 - 100% TMP zeolite 320 6/12 Column 3 - 100% BR zeolite 321 6/12 Column 4 - 100% BR zeolite 322 6/12 Column 5 - TMP zeolite with 20% WV soil

CAS Sample TMP-Teague Mineral Products, BR-Bear River, SGW-synthetic groundwater Number Date Sample Details 323 6/12 Column 6 - TMP zeolite with 20% WV soil 324 6/12 Column 7 - BR zeolite with 20% WV soil 325 6/12 Column 8 - BR zeolite with 20% WV soil 326 6/12 Column 9 - 100% WV soil 327 6/12 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 328 6/15 Synthetic influent groundwater - Phase II 329 6/15 Column 1 - 100% TMP zeolite 330 6/15 Column 2 - 100% TMP zeolite 331 6/15 Column 3 - 100% BR zeolite 332 6/15 Column 4 - 100% BR zeolite 333 6/15 Column 5 - TMP zeolite with 20% WV soil 334 6/15 Column 6 - TMP zeolite with 20% WV soil 335 6/15 Column 7 - BR zeolite with 20% WV soil 336 6/15 Column 8 - BR zeolite with 20% WV soil 337 6/15 Column 9 - 100% WV soil 338 6/15 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 339 6/23 SC-9g pre-washed TMP in 90 ml 1 M NH4Cl soak 3 days on roller, repeat 3X 340 6/23 SC2-9g pre-washed TMP in 90 ml 1 M NH4Cl soak 4 days on roller, repeat 2X 341 6/23 SC3-9g pre-washed TMP in 90 ml 1 M NH4Cl soak 3 days on roller, repeat 2X 342 6/23 SC4- 9g pre-washed TMP in 90 ml 1 M NH4Cl on roller, soaked 3, 4, 3 days 343 6/23 SC5- 9g pre-washed BR in 90 ml 1 M NH4Cl soak 3 days on roller, repeat 3X 344 6/23 SC6- 9g pre-washed BR in 90 ml 1 M NH4Cl soak 4 days on roller, repeat 2X 345 6/23 SC7- 9g pre-washed BR in 90 ml 1 M NH4Cl soak 4 days on roller, repeat 1X 346 6/23 SC8- 9g pre-washed BR in 90 ml 1 M NH4Cl on roller, soaked 3, 4, 3 days 347 6/19 Synthetic influent groundwater - Phase II 348 6/22 Synthetic influent groundwater - Phase II 349 6/22 Column 1 - 100% TMP zeolite 350 6/22 Column 2 - 100% TMP zeolite 351 6/22 Column 3 - 100% BR zeolite 352 6/22 Column 4 - 100% BR zeolite 353 6/22 Column 5 - TMP zeolite with 20% WV soil 354 6/22 Column 6 - TMP zeolite with 20% WV soil 355 6/22 Column 7 - BR zeolite with 20% WV soil 356 6/22 Column 8 - BR zeolite with 20% WV soil 357 6/22 Column 9 - 100% WV soil 358 6/22 Column 10 - BR zeolite with 20% WV soil and 10% iron filings 359 6/25 Synthetic influent groundwater - Phase II 360 6/29 Synthetic influent groundwater - Phase II 361 6/30 Column 1 - 100% TMP zeolite 362 6/30 Column 2 - 100% TMP zeolite 363 6/30 Column 3 - 100% BR zeolite 364 6/30 Column 4 - 100% BR zeolite 365 6/30 Column 5 - TMP zeolite with 20% WV soil 366 6/30 Column 6 - TMP zeolite with 20% WV soil 367 6/30 Column 7 - BR zeolite with 20% WV soil 368 6/30 Column 8 - BR zeolite with 20% WV soil

CAS Sample TMP-Teague Mineral Products, BR-Bear River, SGW-synthetic groundwater Number Date Sample Details pw-pre-washed 369 7/5 Synthetic influent groundwater - Phase III 370 7/6 Column 1 - 100% TMP zeolite 371 7/6 Column 2 - 100% TMP zeolite 372 7/6 Column 3 - 100% BR zeolite 373 7/6 Column 4 - 100% BR zeolite 374 7/6 Column 5 - TMP zeolite with 20% WV soil 375 7/6 Column 6 - TMP zeolite with 20% WV soil 376 7/6 Column 7 - BR zeolite with 20% WV soil 377 7/6 Column 8 - BR zeolite with 20% WV soil 378 7/7 Synthetic influent groundwater - Phase III 379 6/26 LTS1-9g pw TMP in 90 ml 1M NH4Cl 1 wk on roller, repeat 3X (2 soaks) 380 7/3 LTS2-9g pw TMP in 90 ml 1M NH4Cl 1 wk on roller, repeat 3X (2 soaks) 381 6/26 LTS3- 9g pw BR in 90 ml 1 M NH4Cl 1 wk on roller, repeat 3X (2 soaks) 382 6/26 LTS4- 9g pw BR in 90 ml 1 M NH4Cl 1 wk on roller, repeat 3X (2 soaks) 383 7/10 LTS1-9g pw TMP in 90 ml 1M NH4Cl 1 wk on roller, repeat 3X (2 soaks) 384 7/10 LTS3- 9g pw BR in 90 ml 1 M NH4Cl 1 wk on roller, repeat 3X (2 soaks) 385 7/10 LTS4- 9g pw BR in 90 ml 1 M NH4Cl 1 wk on roller, repeat 3X (2 soaks) 386 7/10 NB1- 9g TMP zeolite in 90 ml SGW phase II on roller 2 weeks 387 7/10 NB2- 9g TMP zeolite in 90 ml SGW phase II on roller 2 weeks 388 7/10 NB3- 9g BR zeolite in 90 ml SGW phase II on roller 2 weeks 389 7/10 NB4- 9g BR zeolite in 90 ml SGW phase II on roller 2 weeks 390 7/10 Synthetic influent groundwater - Phase III 391 7/13 Column 1 - 100% TMP zeolite 392 7/13 Column 2 - 100% TMP zeolite 393 7/13 Column 3 - 100% BR zeolite 394 7/13 Column 4 - 100% BR zeolite 395 7/13 Column 5 - TMP zeolite with 20% WV soil 396 7/13 Column 6 - TMP zeolite with 20% WV soil 397 7/13 Column 7 - BR zeolite with 20% WV soil 398 7/13 Column 8 - BR zeolite with 20% WV soil 399 7/19 Synthetic influent groundwater - Phase III 400 7/20 Column 1 - 100% TMP zeolite 401 7/20 Column 3 - 100% BR zeolite 402 7/20 Column 5 - TMP zeolite with 20% WV soil 403 7/20 Column 8 - BR zeolite with 20% WV soil 404 7/21 Synthetic influent groundwater - Phase III 405 7/15 Column 2 - TMP section 1 (bottom to port A) solids characterization 406 7/15 Column 2 - TMP section 2 (port A to port B) solids characterization 407 7/15 Column 2 - TMP section 3 (port B to port C) solids characterization 408 7/15 Column 2 - TMP section 4 (port C to port D) solids characterization 409 7/15 Column 2 - TMP section 5 (port D to port E) solids characterization 410 7/15 Column 2 - TMP section 6 (port E to port F) solids characterization 411 7/15 Column 2 - TMP section 7 (port F to port G) solids characterization 412 7/15 Column 2 - TMP section 8 (port G to top) solids characterization 413 7/16 Column 4 - BR section 1 (bottom to port A) solids characterization 414 7/16 Column 4 - BR section 2 (port A to port B) solids characterization

CAS Sample TMP-Teague Mineral Products, BR-Bear River, SGW-synthetic groundwater Number Date Sample Details pw-pre-washed 415 7/16 Column 4 - BR section 3 (port B to port C) solids characterization 416 7/16 Column 4 - BR section 4 (port C to port D) solids characterization 417 7/16 Column 4 - BR section 5 (port D to port E) solids characterization 418 7/16 Column 4 - BR section 6 (port E to port F) solids characterization 419 7/16 Column 4 - BR section 7 (port F to port G) solids characterization 420 7/16 Column 4 - BR section 8 (port G to top) solids characterization 421 7/10 LTS2-9g pw TMP in 90 ml 1M NH4Cl 1 wk on roller, repeat 3X (2 soaks) 422 7/23 Synthetic influent groundwater - Phase III 423 7/27 Column 1 - 100% TMP zeolite 424 7/27 Column 3 - 100% BR zeolite 425 7/27 Column 5 - TMP zeolite with 20% WV soil 426 7/27 Column 8 - BR zeolite with 20% WV soil 427 7/29 Synthetic influent groundwater - Phase III 428 7/31 Synthetic influent groundwater - Phase III 429 8/4 Synthetic influent groundwater - Phase III 430 8/4 Column 1 - 100% TMP zeolite 431 8/4 Column 3 - 100% BR zeolite 432 8/4 Column 5 - TMP zeolite with 20% WV soil 433 8/4 Column 8 - BR zeolite with 20% WV soil 434 8/5 Synthetic influent groundwater - Phase III 435 8/6 Column 1 - 100% TMP zeolite 436 8/6 Column 3 - 100% BR zeolite 437 8/6 Column 5 - TMP zeolite with 20% WV soil 438 8/6 Column 8 - BR zeolite with 20% WV soil 439 8/10 Synthetic influent groundwater - Phase III 440 8/10 Column 1 - 100% TMP zeolite 441 8/10 Column 3 - 100% BR zeolite 442 8/10 Column 5 - TMP zeolite with 20% WV soil 443 8/10 Column 8 - BR zeolite with 20% WV soil 444 8/14 Synthetic influent groundwater - Phase III 445 8/17 Synthetic influent groundwater - Phase III 446 8/17 Column 1 - 100% TMP zeolite 447 8/17 Column 3 - 100% BR zeolite 448 8/17 Column 5 - TMP zeolite with 20% WV soil 449 8/17 Column 8 - BR zeolite with 20% WV soil

COLUMBIA ANALYTICAL SERVICES, INC.

Analytical Report Client: University of Buffalo Service Request: R0904198 Project: Jarvis Hall Date Collected: 7/15/09 - 7/16/09 Sample Matrix: Water Date Received: 7/29/09 Prep Method: EPA 3010A Units: µg/L Analysis Method: 200.7 Basis: NA Calcium, Total Dilution Date Date Sample Name Lab Code Result Q MRL MDL Factor Extracted Analyzed 405 R0904198-001 582000 10000 2000 10 7/30/09 8/4/09 13:07 406 R0904198-002 577000 10000 2000 10 7/30/09 8/4/09 13:36 407 R0904198-003 555000 10000 2000 10 7/30/09 8/4/09 13:41 408 R0904198-004 467000 10000 2000 10 7/30/09 8/4/09 13:45 409 R0904198-005 522000 10000 2000 10 7/30/09 8/4/09 13:49 410 R0904198-006 467000 1000 200 1 7/30/09 8/4/09 16:21 411 R0904198-007 463000 1000 200 1 7/30/09 8/4/09 16:26 412 R0904198-008 454000 1000 200 1 7/30/09 8/4/09 16:30 413 R0904198-009 682000 10000 2000 10 7/30/09 8/4/09 14:14 414 R0904198-010 668000 10000 2000 10 7/30/09 8/4/09 14:18 415 R0904198-011 690000 10000 2000 10 7/30/09 8/4/09 14:23 416 R0904198-012 640000 10000 2000 10 7/30/09 8/4/09 14:27 417 R0904198-013 618000 10000 2000 10 7/30/09 8/4/09 14:31 418 R0904198-014 586000 10000 2000 10 7/30/09 8/4/09 14:35 419 R0904198-015 591000 10000 2000 10 7/30/09 8/4/09 14:40 420 R0904198-016 549000 10000 2000 10 7/30/09 8/4/09 14:44 Method Blank R0904198-MB 1000 U 1000 200 1 7/30/09 8/4/09 12:29

COLUMBIA ANALYTICAL SERVICES, INC.

Analytical Report Client: University of Buffalo Service Request: R0904198 Project: Jarvis Hall Date Collected: 7/15/09 - 7/16/09 Sample Matrix: Water Date Received: 7/29/09 Prep Method: EPA 3010A Units: µg/L Analysis Method: 200.7 Basis: NA Magnesium, Total Dilution Date Date Sample Name Lab Code Result Q MRL MDL Factor Extracted Analyzed 405 R0904198-001 29300 1000 100 1 7/30/09 8/4/09 15:34 406 R0904198-002 28700 1000 100 1 7/30/09 8/4/09 15:55 407 R0904198-003 26300 1000 100 1 7/30/09 8/4/09 16:00 408 R0904198-004 26200 1000 100 1 7/30/09 8/4/09 16:04 409 R0904198-005 24700 1000 100 1 7/30/09 8/4/09 16:17 410 R0904198-006 23700 1000 100 1 7/30/09 8/4/09 16:21 411 R0904198-007 23100 1000 100 1 7/30/09 8/4/09 16:26 412 R0904198-008 23900 1000 100 1 7/30/09 8/4/09 16:30 413 R0904198-009 56300 1000 100 1 7/30/09 8/4/09 16:35 414 R0904198-010 54200 1000 100 1 7/30/09 8/4/09 16:39 415 R0904198-011 59400 1000 100 1 7/30/09 8/4/09 16:44 416 R0904198-012 51500 1000 100 1 7/30/09 8/4/09 16:48 417 R0904198-013 52800 1000 100 1 7/30/09 8/4/09 16:53 418 R0904198-014 50000 1000 100 1 7/30/09 8/4/09 16:57 419 R0904198-015 48000 1000 100 1 7/30/09 8/4/09 17:21 420 R0904198-016 45800 1000 100 1 7/30/09 8/4/09 17:25 Method Blank R0904198-MB 1000 U 1000 100 1 7/30/09 8/4/09 12:29

COLUMBIA ANALYTICAL SERVICES, INC.

Analytical Report Client: University of Buffalo Service Request: R0904198 Project: Jarvis Hall Date Collected: 7/15/09 - 7/16/09 Sample Matrix: Water Date Received: 7/29/09 Prep Method: EPA 3010A Units: µg/L Analysis Method: 200.7 Basis: NA Potassium, Total Dilution Date Date Sample Name Lab Code Result Q MRL MDL Factor Extracted Analyzed 405 R0904198-001 263000 20000 1000 10 7/30/09 8/4/09 13:07 406 R0904198-002 302000 20000 1000 10 7/30/09 8/4/09 13:36 407 R0904198-003 334000 20000 1000 10 7/30/09 8/4/09 13:41 408 R0904198-004 357000 20000 1000 10 7/30/09 8/4/09 13:45 409 R0904198-005 459000 20000 1000 10 7/30/09 8/4/09 13:49 410 R0904198-006 494000 20000 1000 10 7/30/09 8/4/09 13:53 411 R0904198-007 544000 20000 1000 10 7/30/09 8/4/09 13:57 412 R0904198-008 561000 20000 1000 10 7/30/09 8/4/09 14:10 413 R0904198-009 265000 20000 1000 10 7/30/09 8/4/09 14:14 414 R0904198-010 294000 20000 1000 10 7/30/09 8/4/09 14:18 415 R0904198-011 346000 20000 1000 10 7/30/09 8/4/09 14:23 416 R0904198-012 419000 20000 1000 10 7/30/09 8/4/09 14:27 417 R0904198-013 511000 20000 1000 10 7/30/09 8/4/09 14:31 418 R0904198-014 569000 20000 1000 10 7/30/09 8/4/09 14:35 419 R0904198-015 649000 20000 1000 10 7/30/09 8/4/09 14:40 420 R0904198-016 681000 20000 1000 10 7/30/09 8/4/09 14:44 Method Blank R0904198-MB 2000 U 2000 100 1 7/30/09 8/4/09 12:29

COLUMBIA ANALYTICAL SERVICES, INC.

Analytical Report Client: University of Buffalo Service Request: R0904198 Project: Jarvis Hall Date Collected: 7/15/09 - 7/16/09 Sample Matrix: Water Date Received: 7/29/09 Prep Method: EPA 3010A Units: µg/L Analysis Method: 200.7 Basis: NA Sodium, Total Dilution Date Date Sample Name Lab Code Result Q MRL MDL Factor Extracted Analyzed 405 R0904198-001 227000 10000 1000 10 7/30/09 8/4/09 13:07 406 R0904198-002 222000 10000 1000 10 7/30/09 8/4/09 13:36 407 R0904198-003 212000 10000 1000 10 7/30/09 8/4/09 13:41 408 R0904198-004 182000 1000 100 1 7/30/09 8/4/09 16:04 409 R0904198-005 202000 10000 1000 10 7/30/09 8/4/09 13:49 410 R0904198-006 182000 1000 100 1 7/30/09 8/4/09 16:21 411 R0904198-007 181000 1000 100 1 7/30/09 8/4/09 16:26 412 R0904198-008 184000 1000 100 1 7/30/09 8/4/09 16:30 413 R0904198-009 248000 10000 1000 10 7/30/09 8/4/09 14:14 414 R0904198-010 249000 10000 1000 10 7/30/09 8/4/09 14:18 415 R0904198-011 251000 10000 1000 10 7/30/09 8/4/09 14:23 416 R0904198-012 238000 10000 1000 10 7/30/09 8/4/09 14:27 417 R0904198-013 232000 10000 1000 10 7/30/09 8/4/09 14:31 418 R0904198-014 220000 10000 1000 10 7/30/09 8/4/09 14:35 419 R0904198-015 233000 10000 1000 10 7/30/09 8/4/09 14:40 420 R0904198-016 215000 10000 1000 10 7/30/09 8/4/09 14:44 Method Blank R0904198-MB 1000 U 1000 100 1 7/30/09 8/4/09 12:29

COLUMBIA ANALYTICAL SERVICES, INC.

Analytical Report Client: University of Buffalo Service Request: R0904198 Project: Jarvis Hall Date Collected: 7/15/09 - 7/16/09 Sample Matrix: Water Date Received: 7/29/09 Prep Method: EPA 3010A Units: µg/L Analysis Method: 200.7 Basis: NA Strontium, Total Dilution Date Date Sample Name Lab Code Result Q MRL MDL Factor Extracted Analyzed 405 R0904198-001 43200 1000 100 10 7/30/09 8/4/09 13:07 406 R0904198-002 32600 1000 100 10 7/30/09 8/4/09 13:36 407 R0904198-003 21000 1000 100 10 7/30/09 8/4/09 13:41 408 R0904198-004 10900 1000 100 10 7/30/09 8/4/09 13:45 409 R0904198-005 7500 1000 100 10 7/30/09 8/4/09 13:49 410 R0904198-006 5600 1000 100 10 7/30/09 8/4/09 13:53 411 R0904198-007 5100 1000 100 10 7/30/09 8/4/09 13:57 412 R0904198-008 4260 100 10 1 7/30/09 8/4/09 16:30 413 R0904198-009 43600 1000 100 10 7/30/09 8/4/09 14:14 414 R0904198-010 33000 1000 100 10 7/30/09 8/4/09 14:18 415 R0904198-011 20200 1000 100 10 7/30/09 8/4/09 14:23 416 R0904198-012 9400 1000 100 10 7/30/09 8/4/09 14:27 417 R0904198-013 5300 1000 100 10 7/30/09 8/4/09 14:31 418 R0904198-014 3800 100 10 1 7/30/09 8/4/09 16:57 419 R0904198-015 3330 100 10 1 7/30/09 8/4/09 17:21 420 R0904198-016 2890 100 10 1 7/30/09 8/4/09 17:25 Method Blank R0904198-MB 100 U 100 10 1 7/30/09 8/4/09 12:29 Comments:

Printed 8/5/09 16:44 Form 1A

\\Inflow2\Starlims\LimsReps\AnalyticalReport.rpt SuperSet

Reference:

09-0000114388 rev 00

WVDP-506 Rev. 0 WVDP RECORD OF REVISION Revision On Rev. No. Description of Changes Pagels) Dated 0 Original Issue All 12/14/2009 The State University of New York at Buffalo (UB) Department of Civil, Structural, and Environmental Engineering under contract to WVES conducted the testing of zeolite materials for potential application in mitigation of North Plateau Strontium-90 groundwater contam inatio n.

WV-1807. Rev. 0 (DCIP-I 01) 1