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HomeMy WebLinkAboutNC0004979_R. Hennet - Final Allen Expert Report_20160630Expert Report of Remy J.-C. Hennet Allen Steam Station Belmont, North Carolina S.S. PAPADOPULOS & ASSOCIATES, INC. Environmental & Water -Resource Consultants June 30, 2016 7944 Wisconsin Avenue, Bethesda, Maryland 20814-3620 9 (301) 718-8900 Expert Report of Remy J.-C. Hennet Allen Steam Station Belmont, North Carolina Prepared for: Duke Energy Carolinas, LLC Prepared by: Remy J.-C. Hennet, PhD S.S. PAPADOPULOS & ASSOCIATES, INC. Environmental & Water -Resource Consultants June 30, 2016 7944 Wisconsin Avenue, Bethesda, Maryland 20814-3620 9 (301) 718-8900 2.2- bV6VD06nr oe 8F b220CIVIE2' INC' Table of Contents Page Listof Appendices.......................................................................................................................... ii Section1 Introduction................................................................................................................ 1 Section2 Background................................................................................................................ 2 Section 3 Geochemistry of the Ash Basins................................................................................ 4 Section 4 Natural Attenuation in Groundwater......................................................................... 7 Section 5 Cap -in -Place Remedy................................................................................................ 8 Section 6 Excavation and Removal........................................................................................... 9 Section7 Opinions................................................................................................................... 10 Opinion1.................................................................................................................. 10 Opinion2.................................................................................................................. 10 Opinion3.................................................................................................................. 10 Section 8 Bases for Opinions................................................................................................... 11 Opinion1.................................................................................................................. 11 Opinion2.................................................................................................................. 15 Opinion3.................................................................................................................. 18 Appendices 1 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' 4M List of Appendices Appendix A Curriculum Vitae of Remy J.-C. Hennet Appendix B Documents Considered and/or Relied Upon Appendix C Background Concentration Ranges — USGS, Site Data, and Private Wells Appendix D Natural Attenuation — Ash Basins to Compliance Boundary Appendix E Boron and Nitrate — Well AB-14D ii REPORT 2-2- bVbVDObnrO2 9� V22OCIV1E2' JWC' Section 1 Introduction This expert report was prepared by Remy J-C. Hennet. I am a Principal at S.S. Papadopulos & Associates (SSP&A). I hold a Ph.D. degree in geochemistry and a Master's degree in geology from Princeton University, and university degrees in hydrogeology and geology from the University of Neuchatel, Switzerland. My expertise includes the application of geochemistry, hydrogeology and geology to evaluate the origins, fate, and transport of chemicals in the environment and the remediation of environmental problems. I have more than 25 years of research and professional experience. My Curriculum Vitae and list of depositions and trial appearances are provided as Appendix A. The hourly rate charged by SSP&A for my services is $272. I was retained by Duke Energy Carolinas, LLC (Duke Energy) to evaluate the geochemical data that has been collected to characterize the nature and extent of any groundwater contamination from the operation of coal ash basins at the Allen Steam Station, Belmont, North Carolina (the Site), and to evaluate whether impacts have occurred to surface waters and private wells. I was also tasked to analyze and evaluate certain allegations made by Plaintiffs' experts Bedient, Cosler, and Parette with regards to the appropriateness of the remedy that is proposed for the Site, cap -in - place with monitored natural attenuation, and their contention that complete excavation of the ash is the only acceptable remedy. To conduct this evaluation and render my opinions, I relied on my education, research, and professional experience. I reviewed the Comprehensive Site Assessment Report and the Corrective Action Plan Part 1 and Part 2 reports for the Site. I also relied on the peer -reviewed literature and various professional reports cited herein that describe coal ash materials. I retrieved data from publically accessible internet sites (USEPA, USGS, and State web sites). The data, documents and information that I considered are of the type that can be reasonably relied upon to support my opinions. I visited the Site on September 21, 2015. The information that I considered for this report is listed as Appendix B. The opinions presented in this report were reached by applying accepted methodologies in the fields of geochemistry, hydrology, geology, and environmental remediation. The opinions expressed in the report are my own and are based on the data and facts available to me at the time of writing. Should additional relevant information become available, I reserve the right to supplement the discussion and findings presented in this report. 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' Section 2 Background As required by the Coal Ash Management Act of 2014 (CAMA), Duke Energy conducted a series of investigations and studies to characterize the potential for environmental impact from operation of its ash basin system. Duke Energy submitted a Comprehensive Site Assessment Report and Corrective Action Plan Part 1 and Part 2 reports to North Carolina Department of Environment and Natural Resources (NCDENR). The potential source of contamination at the Site is the ash basin system, which consists of the inactive and active ash basins. Ash was disposed of in historical drainage features that were dammed for impoundment. The drainage features were local tributaries to the Catawba River. Site operations started in 1957 and the active basin started operating in 1973. A dike structure separates the active and inactive ash basins. The ash basin system is an integral part of the Site wastewater treatment system. The ash basin system receives discharges from the ash removal system, coal pile runoff, landfill leachate, flue gas desulfurization wastewater, the station yard drain sump, and site storm water. Environmental impacts for groundwater occur when a party causes concentration to exceed the North Carolina Groundwater Quality Standards, as specified in 15A NCAC 2L.0202 (2L Standards). Concentration exceedances to the Interim Maximum Allowable Concentration (IMAC) established by NCDENR pursuant to 15A NCAC 2L.0202(c) are also considered, even though these standards have not been finalized. Surface water impacts are defined by concentration exceedances to the North Carolina Surface Water Quality (213) standards (213 Standards). The 2B Standards depend upon classification of a surface water body. For groundwater, the constituents of interest identified at the Site are: antimony, arsenic, barium, boron, chromium, hexavalent chromium, cobalt, iron, manganese, pH, sulfate, total dissolved solids (TDS), and vanadium. The constituents of interest were identified based on concentrations in groundwater that exceed the 2L Standards and/or IMAC. The available data for the Site includes results from chemical analysis of soil, sediment, rock, ash basin solids, ash basin pore water, groundwater, seepages and surface water samples. Leaching data were collected for samples of ash materials from the basins. The data include information on mineralogical composition of geologic and ash materials, and general physical characteristics for these materials in place (i.e., grain size, porosity, permeability). Site background conditions were characterized through analysis of background soil, rock, and water samples. Additional data and information on coal ash chemistry are available from peer -reviewed literature and specialized professional reports. The extent of groundwater contamination is described in the Comprehensive Site Assessment Report and Corrective Action Plan reports for the Site. The Comprehensive Site Assessment Report concluded that there is no identified imminent hazard to human health or the environment as a result of soil or groundwater contamination at the Site. Additional work is on- going at the Site to further delineate the extent of groundwater contamination where data gaps have been identified. 2 2-2- bVbVDObnr02 9� V220CIV1E2' JWC' The Corrective Action Plan reports further evaluated the hydrology of the Site and the fate and transport of contaminants in the groundwater environment. The reports examined the need for remediation and the feasibility and adequacy of potential remedial measures for Site closure. Based on its evaluation of the available data and information, Duke Energy selected a Cap- in -place remedy for the ash basins, with additional source control measures being considered on an as needed basis. The remedy consists of an engineered cap system over the ash basins and the collection and treatment of storm water, runoff water, and seep water for permitted discharge. The additional source control measures could include hydraulic containment, drains, amendments, and other measures, as necessary to comply with future regulations and to address uncertainties and unforeseen conditions. For the restoration of groundwater, Duke Energy has proposed to rely on monitored natural attenuation. Monitoring after implementation of cap -in -place will provide the basis for assessing the need for additional source control measures for groundwater restoration. Plaintiffs' experts Bedient, Cosler, and Parette have submitted expert reports and opined that a cap -in -place remedy with monitored natural attenuation is inappropriate for the Site. These experts opined that excavation and removal of the ash basins should be the remedy for the Site. 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' Section 3 Geochemistry of the Ash Basins Coal ash is a by-product from the combustion of coal. Under atmospheric conditions, some of the minerals in coal ash are metastable and undergo transformations that lead to the formation of secondary mineral phases that range from amorphous to crystalline (i.e., hydrous aluminosilicates, mullite, calcite, etc.). Over time, the rate of chemical leaching decreases and the formation of amorphous clays and other secondary minerals results in a decrease in coal ash permeability (Jones and Lewis, 1956; Warren and Dudas, 1988; Zevenberg et al., 1999a and 1999b; Bolanz et al., 2012; Fruchter, 1990; Ghuman et al., 1999; Mudd et al., 2004; EPRI, 2009). Depending on their properties, chemicals that are released or leached to pore water during mineral alteration can remain in the pore water and/or can be sequestered in the secondary mineral phases which are immobile. Sequestration in or immobilization onto the mineral phases can be through absorption, adsorption, ion exchange, and secondary mineral precipitation and co - precipitation. The organic carbon content of coal ash, typically measured at the low percent level by weight, provides a substrate for microbial activity. This activity depletes oxygen, making coal ash pore water generally reducing or anaerobic. As for pH conditions, fresh coal ash pore water at the Site is typically alkaline, whereas aged or weathered ash pore water tends to be neutral (reflecting the mineral alterations and prolonged contact with carbon dioxide from the atmosphere). Ash and coal materials that are exposed to atmospheric oxygen can become acidified as a side effect of the oxidation of their sulfidic mineral content. In the ash basins, the water (i.e., sluiced ash water, rain, storm water) that percolates through the ash to groundwater has a distinctive chemical fingerprint. The chemical fingerprint reflects the interaction between water and coal ash materials. Ash pore water is a sodium -calcium - sulfate aqueous solution, meaning that these compounds dominate the dissolved concentrations. Boron, chloride, strontium, magnesium, iron, manganese, and potassium are typically present at part per million level. Aluminum, barium, and arsenic are typically present at the low part per million or less level. Traces, at the part per billion level, are also typical for antimony, cobalt, vanadium and molybdenum. All of the constituents of interest occur in soils, rock, surface water, and groundwater under background conditions. The background range concentrations can be lower, similar, or higher than in the ash basins, depending on the compound considered. This is why it is necessary to account for the background range for evaluating the environmental impacts of the ash basins. For groundwater background concentrations, data is available from the United States Geological Survey, the State of North Carolina, and from the samples collected for Site characterization. The Site is located over metamorphosed bedrock consisting of quartz diorite and tonalite, with meta quartz diorite, metadiabase, metagranite, and pegmatite.' Together, and in context, these data ' Geologic Map of the Charlotte P x 2° Quadrangle, North Carolina and South Carolina, 1988, R. Goldsmith, D. J. Milton, and J. W. Horton, Jr., USGS. P 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' �S define the background range for the constituents of interest. Background data information for groundwater is illustrated in Appendix C. The water that percolates from coal ash basins into subsurface soil and rock materials is put in contact with different mineral phases that represent the geological materials onto which the coal ash lies. Water -mineral interactions in the geological materials and mixing with groundwater result in changes in chemical composition. Boron, because of its properties, remains in the water phase and tends to transport conservatively (little or no retardation) with groundwater. Other chemicals that include the constituents of interest, such as iron, manganese, arsenic and other trace compounds in ash pore water, are not conservative and partition between the mineral and aqueous (water) phases. Those reactive chemicals are attenuated in the subsurface environment by immobilization and sequestration through mineral precipitation or co -precipitation and by retardation through sorption and ion exchange processes. Iron is most important for attenuation in the subsurface environment, as it is present at relatively high concentrations in ash and geological materials. Iron minerals and mineral coatings are effective at attenuating (sequestering, immobilizing, and retarding) other chemicals in groundwater (Dixit and Hering, 2003; Dzombak and Morel, 1990; Stumm and Morgan, 1996). Dissolved chemicals are present in groundwater as chemical species. The speciation of a chemical is primarily controlled by the redox and pH conditions in the subsurface and by interactions between chemicals in solution. The different chemical species of a given constituent have different properties. It is therefore important to consider chemical speciation in the evaluation of transport in the groundwater environment. For the compounds that are elevated in the ash pore water and the impacted groundwater beneath and downgradient of the ash basins, the chemical speciation can be derived from the Eh -pH diagrams (Atlas of Eh -pH Diagrams, 2005). Chemical speciation informs whether a chemical can be reduced or oxidized and if its aqueous solubility is controlled by mineral phases and/or other attenuating processes (e.g., sorption and ion exchange). As part of the Site assessment work and studies that were conducted with Site materials, solid -water partition coefficients (KD) were determined for 10 chemicals (arsenic, boron, cadmium, chromium, iron, manganese, molybdenum, selenium, thallium, and vanadium). The chemicals were dissolved in water and interacted with soil materials from the Site. The results were obtained under controlled laboratory conditions and are not directly applicable to the Site groundwater conditions; however, the results demonstrate that with the exception of boron, the chemicals that were tested interact with the Site soil materials. The results demonstrate that chemical attenuation is an active process at the Site for the tested compounds. Natural attenuation for boron is dominated by physical attenuation and takes place principally through the immobilization of the ash pore water and other physical processes that include dilution, diffusion, and dispersion. Groundwater samples from wells screened within the ash contained elevated concentrations of constituents of interest, confirming that attenuation is active with concentration diminishing in the soil and rock materials beneath and downgradient of the ash basins (Appendix D). These observations of concentrations attenuating away from the ash basins support Duke Energy's decision to propose using monitored natural attenuation for the restoration of groundwater as a supplement to the cap -in -place control measures. The limited chemical interaction between boron and soil materials explains why boron is a valid tracer for delineating the extent of the ash basin impacts; boron is typically present at low 5 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' �S concentration in background groundwater (<50 ug/L range) and its presence at high concentration (-1000 ug/L range) in the ash pore water makes it a simple conservative tracer that can be used to delineate the extent of groundwater affected by the ash basins and evaluate the effectiveness of physical attenuation processes that would affect all mobile COI's equally. The results for the other chemicals tested for chemical interactions support the conclusion that natural attenuation, both physically and chemically, is active under Site conditions and that natural attenuation can be considered as a restoration remedy for groundwater after the cap -in -place remedy has been implemented. 2 2-2- bVbVDObnr02 9� V220CIV1E2' JWC' Section 4 Natural Attenuation in Groundwater Natural attenuation results from physical, chemical, and biological processes that act alone or in combination to reduce or decrease the volume of impacted groundwater and compound mass, concentration, toxicity, and/or mobility in groundwater. The major processes that attenuate mass or concentrations in groundwater are dilution, dispersion, absorption, adsorption, ion exchange, precipitation, co -precipitation, complexation to organic substrate, and biomass accumulation. For conservative compounds such as boron in groundwater, dilution and dispersion dominate attenuation. For reactive compounds such as iron, manganese, or arsenic, adsorption, precipitation and co -precipitation processes also attenuate concentrations in addition to dilution and dispersion. USEPA provides guidance for the implementation of natural attenuation as a remedial measure for groundwater contamination by inorganic compounds (EPA, Directive 9283.1-36, August 2015; EPA 600-R-07-139, 2007a; EPA 600-R-07-140, 2007b; EPA 600-R-10-093, 2010; EPA, Directive 9200.4-17P, April 21, 1999). The USEPA guidance provides objectives for the performance of monitored natural attenuation: 1) Demonstrate that natural attenuation is occurring according to expectations; 2) Detect changes in environmental conditions (e.g., hydrogeologic, geochemical, microbiological, or other changes) that may reduce the efficacy of any of the natural attenuation processes; 3) Identify any potentially toxic and/or mobile transformation products; 4) Verify that the plume(s) is not expanding downgradient, laterally or vertically; 5) Verify no unacceptable impact to downgradient receptors; 6) Detect new releases of contaminants to the environment that could impact the effectiveness of the natural attenuation remedy; 7) Demonstrate the efficacy of institutional controls that were put in place to protect potential receptors; and 8) Verify attainment of remediation objectives. As discussed in Section 8 of this report, the Site data indicate that natural attenuation is occurring in the groundwater environment. The cap -in -place remedy will decrease the flux of constituents of concern to groundwater and result in a decrease of the extent of the groundwater impact. Monitored natural attenuation is therefore a valid remedial option for the restoration of groundwater for this Site. Progress toward the restoration of groundwater through natural attenuation will be monitored once the cap -in -place remedy and additional source control measures, if any are necessary, have been implemented. The monitoring data and information will be the basis for selection of the final groundwater remedy for the Site. 7 2-2- bVbVDObnr02 9� V220CIV1E2' JWC' Section 5 Cap -in -Place Remedy The engineered cap -in -place remedy that Duke Energy plans to construct to cover the ash basins will have the effect of greatly reducing the infiltration of water and wastewater through the coal ash. The amount of ash pore water that will recharge to groundwater will be greatly diminished and the flux of chemicals entrained with infiltration water will also decrease. The ash materials have a high water retention capacity, meaning that absent recharge by infiltration water, as under a cap -in -place remedy, the ash pore water is mostly immobile, further decreasing the flux of constituents of interest from the ash materials to groundwater (Tiruta-Barna et al. 2006). Secondary mineral phases will continue to form in the coal ash and in the soil and rock materials beneath the coal ash basin. The permeability of coal ash materials under the cap is expected to continue to decrease over time because of accumulation of secondary minerals in the pore spaces. Groundwater -ash interactions will also decrease because of the lowering of the water table, exposing less of the ash materials to groundwater. If monitoring of the cap -in -place remedy indicates that restoration of groundwater is not taking place, additional source control measures (i.e., drains, pumping, slurry walls) could be implemented to intercept the impacted groundwater and/or to further depress the water table to further isolate the ash materials. The geochemical conditions in the capped coal ash will remain generally reducing and anaerobic from the continuous degradation of the organic substrate in the ash by micro-organisms, with a pH condition near neutral to alkaline, depending on the age and degree of weathering of the ash materials. Under an uncapped condition, atmospheric oxygen is introduced into the ash materials with infiltration water that contains dissolved oxygen. The atmospheric oxygen is consumed for the oxidation of the organic substrate that is present in the ash materials. Consumption of oxygen takes place primarily in the upper portion of the ash materials, as infiltration water progresses toward the water table, and the effect of atmospheric oxygen is typically limited to the shallow ash. Under a cap -in -place condition, the upper portion of the ash might possibly become more reducing. If there was a reduction in atmospheric oxygen because of capping, it would result in more reducing conditions in the pore water at depth in the ash materials. The geochemical result of more reducing conditions would be for some increased sulfide activity from the reduction of sulfate to sulfide. The presence of dissolved sulfide would result in the precipitation of sulfidic or pyritic minerals. Under such reducing conditions, iron, manganese, and other metals dissolved in the pore water would be precipitated or co -precipitated out of the pore water and become immobilized in the solid matrix within the coal ash and beneath. Mineral precipitation and co -precipitation would remove these constituents of interest from the aqueous phase, reduce their flux to groundwater, and contribute to the restoration of groundwater. 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' Section 6 Excavation and Removal The excavation and removal of the ash in the ash basins and a portion of the soil materials beneath the basins was considered by Duke Energy, but determined not to be the preferred remedy for the Site based on environmental, engineering, social, and economic considerations. Excavation is typically conducted using specialized machinery to removed materials that are transported for disposal elsewhere. Excavation of the ash basins would expose subsurface soil and rock materials to geochemical conditions that are different from the conditions with the ash in place. A change in geochemical conditions would result in a rearrangement of the mineralogy in the aquifer, with dissolution and precipitation of secondary mineralogy affecting groundwater chemistry and redistributing the constituents of interest in the subsurface. The geochemical disturbance will induce transient changes in the chemistry of groundwater that would only gradually attenuate, long after the implementation of excavation. The presence of sulfidic minerals in the soil and rock materials beneath the ash basins would become oxidized by contact with infiltration water and atmospheric oxygen. Oxidation of sulfidic minerals (i.e., pyrite) generates acidity, dissolved sulfate, and dissolved metals and metalloids that are trace compounds of the minerals and are put into solution in the process. The acidity released to groundwater would dissolve additional metals and metalloids from the soil and aquifer matrices. The release of acidity to groundwater would decrease natural attenuation in the aquifer and increase the leaching of natural occurring constituents of interest from native materials. Excavation would not remove the impacted groundwater beneath and downgradient of the excavation. The impacted groundwater that is left behind would serve as a long term sources that could sustain the groundwater impacts after excavation. Excavation of the large quantities of materials in the ash basins would take time to implement (i.e., years or decades). During that period of open excavation, precipitation, storm water, and runoff water would enter the excavation in great quantities and infiltrate to groundwater. This added infiltration would introduce additional contamination and force impacted groundwater farther into the aquifer system, therefore increasing the extent of the existing groundwater impacts. Geochemical processes that control aquifer restoration are typically slow and take time to effectively achieve restoration goals. This would be true under both the excavation and cap -in - place remedies. There are anticipated negative effects with regards to groundwater for the excavation and removal remedy advocated by Plaintiffs' experts. These effects have to be considered for a comparative evaluation of the cap -in -place and excavation options. 0 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' Section 7 Opinions Based on my education and experience, and a detailed review of the available data and information, I have reached the following opinions: Opinion 1. The constituents of interest at the Site are naturally occurring upgradient from the Site at concentrations that are within the background range. Certain constituents of interest are present under background conditions at concentrations that exceed the 2L Standards, IMAC, or 2B Standards. Opinion 2. The cap -in -place remedy will decrease the flux of constituents of interest from the ash basins to groundwater. Natural attenuation is and will continue to be active in the groundwater environment, resulting in a future decrease in the mass and concentration of the constituents of interest that are dissolved in groundwater. The cap -in -place remedy, supplemented by source control measures if necessary, and monitored natural attenuation are a reasonable and adequate remedy for the Site. Opinion 3. Excavation of the ash basins is not necessary for Site groundwater restoration.. Excavation alone cannot achieve the complete removal of the constituents of interest from the subsurface and provides no substantial benefit over a cap -in -place remedy to restore groundwater. I hold these opinions with a reasonable degree of scientific certainty. I reserve the right to modify and supplement these opinions should additional information become available. 10 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' Section 8 Bases for Opinions Opinion 1. The constituents of interest at the Site are naturally occurring upgradient from the Site at concentrations that are within the background range. Certain constituents of interest are present under background conditions at concentrations that exceed the 2L Standards, IMAC, or 2B Standards. The constituents of interest identified in the Comprehensive Site Assessment Report for groundwater are: antimony, arsenic, barium, boron, chromium, hexavalent chromium, cobalt, iron, manganese, pH, sulfate, total dissolved solids, and vanadium. These compounds and parameters are naturally occurring in natural soil and rock materials, surface water, and groundwater. I reviewed the publically accessible USGS data (http://nwis.waterdata.usgs.gov/nwis wdata) for the occurrence of constituents of interest in groundwater across North Carolina and compared that information with the data presented in the Comprehensive Site Assessment Report for the Site. Results are illustrated in Appendix C. The data sets compared include: • Site background wells; • Private water wells in the vicinity of the Site; and • Site monitoring wells. I also evaluated natural attenuation in groundwater using the available Site data. Results are illustrated in Appendices D and E. From this evaluation of the available data I conclude that for the Site: • Boron is present at high concentration (— 1,000 ug/L) in the ash pore water and impacted groundwater and at low concentration in groundwater under background condition (i.e., not detected or < 50 ug/L). Under the redox and pH conditions encountered in the groundwater environment, boron is soluble in water and does not appreciably interact with the solid matrix 2. Boron therefore transports with groundwater with little or no retardation. Under Site conditions in the groundwater environment, boron can be considered a conservative tracer for environmental fate and transport at the Site. Boron is attenuated in groundwater primarily by dilution and dispersion (see Appendix D). • Sulfate is present over a wide range of concentrations in the ash pore water and groundwater beneath and downgradient of the ash basins. Sulfate concentration in background groundwater can vary greatly, but is typically lower than in the impacted groundwater. Sulfate is redox reactive and its concentration in groundwater can be controlled by several processes that include mineral precipitation (i.e., barite, pyrite). Sulfate is attenuated in groundwater primarily by dilution and dispersion. Additional 2 Boron is often detected in septic system effluents, as borates in detergents, soaps, and personal care products can contribute to the presence of boron in groundwater (EPA, 2008). 11 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' attenuation is provided by processes that can include mineral precipitation (i.e., barite) and reduction of sulfate to sulfides under strongly reducing conditions. Iron, manganese, and arsenic are reactive in the groundwater environment and do not behave conservatively in groundwater, as boron does. Iron, manganese, and arsenic can occur within a wide range of concentrations in background groundwater (see Appendix Q. The compounds are present in background soil and rock materials. These compounds are sensitive to attenuation processes in the groundwater environment. Iron, manganese and arsenic attenuate in the groundwater environment (see Appendix D). This demonstrates that these compounds can occur naturally at concentrations that can exceed the standards and are attenuated at the Site. • Trivalent chromium and hexavalent chromium form a redox pair, and both chemical species are present in groundwater under background conditions. When not specified, chromium refers to the sum of all chromium species in a sample. Hexavalent chromium can form from trivalent chromium through oxidation under background conditions (Oze, 2007). The reducing conditions that prevail in the ash and impacted groundwater environments at the Site are not amenable to the formation of hexavalent chromium, and the amount of hexavalent chromium relative to trivalent chromium is small. Chromium and hexavalent chromium are present in background groundwater, soil, and rock materials. Chromium is also present in grout (Hewlett, 1988). There is no groundwater impact for chromium from the ash basins as the reported detections of chromium are within the background range. Antimony, cobalt, and vanadium are present at trace levels that are typically within the groundwater background range. These compounds are present in soil and rock materials as well as in ash materials. There is no impact for antimony or vanadium from the ash basins and the reported trace detections are within the background range. Cobalt concentrations are discussed further in the well by well discussion below. The identified constituents of interest at the Site include pH and total dissolved solids. I reviewed the pH and total dissolved solids data in the context of the available chemical data and mineralogical information. I conclude that: The elevated pH occurrences (i.e. pH > 8.5) in monitoring wells that do not have detectable boron concentrations is most likely a side effect of well construction. For the wells that show elevated pH values with no detectable boron,' the leakage of grout into the wells' sand packs is the simplest and most likely explanation for the elevated pH values, since grout is strongly alkaline (Hewlett, 1988). For the monitoring wells that have detectable concentration of boron, the occurrence of elevated pH can be explained by either grout 'For example, wells with elevated pH and no detectable boron: GWA-113R, AB-20D, AB-34D, AB-36D, GWA-2D, AB-2113R, AB-211), AB-3513R, AB-35D, BG-lD, GWA-113, BG-213R, AB-23BRU, AB-24D, AB-2513R, AB- 25BRU, AB-28D, BG-4D, GWA-14D, GWA-21D, GWA-23D, GWA-2413R, GWA-26D, GWA-26S, GWA-61), GWA-6DA, and AB-14BR 12 2-2- bVbVDObnrO2 9� V22OCIV1E2' JWC' �S leakage and/or by the presence of coal ash leachate impacting groundwater.4 Additional work by Duke Energy is on -going to address well construction issues at the Site. • There are a wells that report acidic pH values (i.e., pH< 5). These wells have no detectable boron (<50 ug/L).5 Low pH values can occur under background conditions (see Appendix D). Acidic values that could be related to Site operations would be associated with runoff from the coal pile. The presence of pyritic materials in coal can be oxidized by contact with rain water and generate an acidic leachate (Stumm and Morgan, 1996). For example, the low pH value at monitoring well GWA-6S, located outside of the ash basins, is likely related to the adjacent coal pile. This is confirmed by the presence of elevated sulfate and other constituents of interest in this well. GWA-7S also reported a low pH value, but boron was not detected in this well. The cause of the low pH value reported for this well is not yet determined with reasonable certainty, and additional characterization is on -going. • Both low and high pH values are reported at GWA-14D. The reason behind these large changes in pH values is unclear, and could reflect well construction or field data quality issues. The absence of detectable boron in that well indicates that groundwater is not impacted by the ash basins in that area. • Total dissolved solids represent the sum of all chemicals that are dissolved in a water sample. This parameter does not inform as to chemical composition, but can be used to appreciate the overall dissolved content in water samples. Total dissolved solids can vary over a large range in background groundwater and exceed the 2L Standard. Total dissolved solids values are elevated in ash pore water and in the impacted groundwater beneath and downgradient of the ash basins. Boron is periodically reported above the background range, but below the 2L Standard, in monitoring well AB-14D. This occurrence is indicative of a moderate water quality impact from the ash basins in that area. The presence of boron in this well is likely related to the localized mounding of the water table near the ash basins. Slight changes in mounding geometry result in the observed boron concentration fluctuations over time. The fluctuation is indicative of relative changes in recharge rates between the nearby ash basin area and the uplands outside of the ash basin. For example, boron concentrations would be expected to increase when the infiltration in the ash basins is higher relative to the uplands recharge. Conversely, boron concentrations would decrease when recharge in the uplands is higher relative to the ash basin area. Concentrations of the constituents of interest other than boron are not distinguishable from the background range and there is no indication of an impact for these compounds. The cap -in -place remedy will result in much less infiltration in the ash basin. The periodic detection of boron concentrations in that area 4 For example, wells with elevated pH and detectable boron: AB-21SL, AB-25SL, AB-24SL, AB-235, AB-29SL, GWA-5BR, GWA-513, AB-2913, GWA-313, AB-26D, GWA-3BR, AB-3113, GWA-5BR, GWA-513, AB-2913, GWA-313, AB-2613, GWA-3BR, and AB-31D 5 For example, wells with acidic pH and no detectable boron: AB-2, AB-125, AB-14D, and GWA-7S. Boron detection limit for well GWA-6S ranged between 500 and 2,500 ug/L, and the level of boron in this well is uncertain. There was no boron data reported for well GWA-14D, in the information reviewed. 13 2-2- bVbVDObnrO2 9� V22OCIV1E2' IMC' �S J should decrease in concentration to background concentration. Planned monitoring under the Cap- in -place remedy will determine whether additional measures will be required for remediation. Under an excavation remedy, the boron concentration and extent of impact could increase in that area during the period of excavation, as additional infiltration to groundwater would take place in the ash basin area. It should also be noted that when boron concentrations decrease, nitrate concentrations increase at AB-141) (Appendix E). The reverse correlation indicates that nitrate and elevated boron have different sources. The presence of nitrate or nitrogen compounds and low levels of boron is consistent with residential fertilizer and septic system use in this area. This observation supports the conclusion that groundwater at AB-14D reflects the variable influence of both residential and ash basin waters on the transient composition of groundwater. The cap -in - place remedy will reduce the recharge from the ash basins and under this condition nitrogen concentrations will increase whereas boron concentration will decrease. Elevated nitrogen concentrations (>1,000 ug/L) are reported in several wells in the area (GWA-15S/D, GWA-145, AB-13S/D, AB-4S, AB-37D, GWA-91), AB-2OD, AB-12D). Boron is not detected (<50 ug/L) in the monitoring wells. The absence of detectable boron combined with nitrogen from a source that is not the ash basins is consistent with the conclusion that groundwater flow direction is from west to east (from the residential area toward the ash basins and the river), and not the reverse. Groundwater mounding from the ash basins has a limited influence on groundwater quality and this influence does not extend to the private water supply wells since boron is not detected in those wells. The cap -in -place remedy will suppress the mounding effect and there is no threat to the public water supply wells at the Site under this remedy. Plaintiffs' expert Cosler stated that in his opinion, background wells AB-1R, BG-IS, BG- 1D, BG-2S, BG-2D, and BG-2BR are or might be located downgradient from the ash basins, and that therefore these wells are not representative of background groundwater quality. Cosler opined that the inclusion of these wells in the determination of background exaggerates the background levels. Groundwater in these wells contains no detectable boron, and the chemical fingerprints are not indicative of an ash basin impact. The chemical fingerprints in these wells are consistent with background range conditions. There is no geochemical basis to conclude that these wells are impacted by the ash basins. Cosler used a one-dimensional analytical chemical transport model to support his opinion that the constituents of interest will transport with groundwater past the compliance boundary (located under the Catawba River). Cosler did not provide sufficient documentation and description of his calculations to allow for an evaluation of his model results. Cosler provided no information that would demonstrate that his model was calibrated to Site data. Based on the limited information provided, it appears that Cosler applied his model to boron. Cosler used boron concentrations for well MW-I IS and well GWA-27D. For both wells, Cosler calculated boron concentrations at the downgradient compliance boundary that are above the 2L Standard. There are no groundwater data downgradient from well GWA-27D, and the Cosler results cannot be verified. For the MW-I IS area, the downgradient compliance boundary is at the river shore line or close to the shore line. There are four wells (MW-2OD, MW-2ODR, GWA-225, and GWA- 6 Septic system use in the area of AB-14D could contribute boron to groundwater. The detection of boron at low concentrations in private wells where septic systems are in use, together with elevated nitrate concentrations, are typically indicative of septic system contributions (EPA, 2008). 14 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' 22BRU) located downgradient from the ash basin at the compliance boundary in that area. Boron never exceeded the 2L Standard in those wells (the available data span the period April 2011 to April 2016). This fact alone indicates that Cosler's model results are unreliable and invalid. Cosler provided only an illustration of his model results in the form of a figure for boron and cobalt and a table that contain his calculated model results. The figure provided gives a false impression that the model results support Cosler's opinion. First, Cosler calibrated his model using the results from the Corrective Action Plan transport model which he vehemently criticizes as being wrong and faulty. If the Corrective Action Plan results and model are wrong and faulty, as he claims, he should not have used those to calibrate his own model. This calls into questions the reliability of the conclusions reached by Cosler based on these calculations. Second, for the results on which he provided some details (boron and cobalt based on data for two wells), Cosler failed to consider the fact that cobalt concentration is within the background range in the well (GWA- 4S) he used to support his conclusion for groundwater transport. Third, Cosler failed to consider the fact that boron is not elevated in the well (GWA-5S) he uses to support his opinion on cobalt transport. Fourth, in order to possibly reach the compliance boundary beneath the river, groundwater would have to be deep enough in the aquifer next to the river, otherwise shallow groundwater would discharge to the river since the water table inland is higher than the river stage. Cosler used chemical data from water table wells located next to the river (GWA-4S and GWA- 5S) for his modeling. The chemistry in those wells is not appropriate since the wells do not represent the deeper groundwater that could potentially reach the compliance boundary. If Cosler had used the available chemistry for the deeper wells (i.e., AB-31D, GWA-4D, AB-32D, GWA- 5BR, and GWA-5D), his model calculation would show no exceedances to the standards. Finally, Cosler's model calculations are not validated by any data. Similar flaws likely render unreliable Cosler's model results for all constituents that he calculated transport predictions for. Cosler's model results are therefore not valid, and his opinion that constituents of interest will transport with groundwater past the compliance boundary under the Catawba River is not supported. Concentrations in groundwater that exceed a criterion (2L Standard or IMAC), but that are within the background range, are not indicative of a coal ash impact to groundwater. At the Site, a coal ash impact to groundwater is indicated by the presence of a geochemical fingerprint that includes boron, alone or together with other constituents of interest, at concentrations that are higher than the upper bound of the background range. Opinion 2. The cap -in -place remedy will decrease the flux of constituents of interest from the ash basins to groundwater. Natural attenuation is and will continue to be active in the groundwater environment, resulting in a future decrease in the mass and concentration of the constituents of interest that are dissolved in groundwater. The cap -in -place remedy, supplemented by source control measures if necessary, and monitored natural attenuation are a reasonable and adequate remedy for the Site. The cap -in -place remedy proposed by Duke Energy and additional source control measures that will be implemented, if necessary, will decrease the flux of the constituents of interest from the ash basins to groundwater. This will be beneficial to Site remediation and groundwater restoration. The decrease in flux will be accompanied by a reduction of the extent of the groundwater plume and will allow natural attenuation to proceed at an accelerated rate toward 15 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' �S restoration. The cap -in -place remedy will therefore represent a net improvement for groundwater quality beneath and downgradient of the ash basins. There is no human exposure to the impacted groundwater, and no imminent need for aggressive remediation beyond the actions that Duke Energy is planning for the Site. The addition of monitored natural attenuation to the source control measures will provide the means to follow the progress of groundwater restoration. The remediation planned by Duke Energy has flexibility built in to address unforeseen events or to implement additional remediation at the local scale, should such measures be necessary. For example, the interception of impacted groundwater (i.e., via pump and treat or some form of hydraulic controls) could be implemented in some portions of the ash basins, to complement the cap -in -place remedy if the restoration of groundwater does not occur as anticipated. The constituents of interest attenuate in the groundwater environment. Boron attenuates primarily by dilution and dispersion, and other constituents attenuate by dilution and dispersion and through other processes that include sorption, mineral precipitation, and ion exchange. This is illustrated in Appendix D. Plaintiffs' expert Parette has opined that monitored natural attenuation is not an appropriate remedy for constituents of interest at the Site. Parette apparently based this on statements in the Comprehensive Site Assessment Report and Corrective Action Plan Part 1 and Part 2 reports that he took out of context. Duke Energy's proposed remedy for the Site is to implement a cap -in -place remedy supplemented by source control measures, if necessary, with monitored natural attenuation for groundwater restoration. The performance of the remedy will be evaluated through monitoring, and a final groundwater remedy will be selected based on that information. Furthermore, as discussed in Sections 4 and 5 above, natural attenuation for the constituents of interest is active at the Site, and will remain active upon implementation of the cap -in -place remedy. Parette has opined that the utilization of monitored natural attenuation in combination with a cap -in -place remedy is problematic, as he believes conditions would be less favorable for natural attenuation following capping. First, less favorable conditions do not imply that natural attenuation is not taking place or cannot restore groundwater; and less favorable conditions do not negate the merits of natural attenuation. Second, one main reason given by Parette for this opinion is that capping of the ash basins would lead to more anoxic conditions in the Site groundwater. The coal ash pore water and the impacted groundwater are already depleted of dissolved oxygen (anaerobic). Water that contains atmospheric oxygen and infiltrates into the ash, is readily depleted of its oxygen which is utilized to oxidize the organic content of the ash materials (the organic carbon content is reported to be at the percent level, providing an ample supply of organic substrate to sustain microbial activity in the ash materials). A cap would not change the situation, with the exception of a shallow zone of ash materials where oxygen from infiltration water is utilized to degrade the organic substrate in the ash in the absence of a cap. In the impacted groundwater environment, the conditions are typically reducing and anaerobic, and oxygen does not reach groundwater by infiltration through the ash. Third, some dissolved oxygen is present in the shallow groundwater upgradient from the ash basins; that condition will remain after capping. Furthermore, the available data demonstrate that natural attenuation is active at the Site (see Appendices D and E), and in the portion of the aquifer that has been impacted by the ash basins, the ratio of upgradient 16 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' �S groundwater to the water that percolates through the ash will increase under the cap -in -place remedy. This will increase, not decrease the rate of natural attenuation. Parette opined that the partition coefficients (KD) obtained from the testing of Site materials in the laboratory are biased high because the synthetic groundwater used for the tests did not contain all the chemical species present in Site groundwater. Because of this, Parette appears to imply that because of this alleged bias, monitored natural attenuation is not appropriate for the restoration of groundwater. Even if all chemical species present in Site groundwater had been incorporated in the synthetic groundwater for testing, the main conclusion from the testing would remain valid. The main conclusion from the testing is that the constituents of interest in groundwater do interact with the solid matrix, demonstrating the occurrence of attenuation. Running the tests with all chemical species incorporated in the synthetic groundwater might have decreased somewhat the experimental KD values; however, this effect would not be a basis to negate the conclusion that the dissolved constituents of interest interact with the Site solid matrices that were tested. Boron is the exception, for which the testing showed that attenuation by interaction with the solid matrix does not contribute substantially to attenuation in the groundwater environment. Attenuation for boron in groundwater is primary through dilution and dispersion, as discussed under Section 3 above. Parette opined that vanadium is not attenuated in Site groundwater and that monitored natural attenuation is not adequate. Parette remarked that the experimental data reported a decrease in dissolved vanadium with increasing vanadium concentrations in the solid materials tested. Based on that, Parette opined that vanadium does not attenuate in groundwater at the Site. The apparent trend underlined by Parette can only be scientifically evaluated by considering the details of the experimental procedures. Vanadium, like all constituents of interest, including boron, is attenuated in groundwater by dilution and dispersion (see Appendix D). Some additional attenuation by sorption and ion exchange can be expected for vanadium, but is not quantified for the Site. Vanadium is present in soil, and rock materials at the Site under background conditions, reflecting the vanadium content of the geological materials (USGS, 2013b). Parette has opined that natural attenuation is impaired because of the presence of silica, phosphate, bicarbonate, and dissolved organic carbon, and by the formation of complexes between chemical species in groundwater. Competition between chemicals and complex formation in groundwater does not mean that natural attenuation is not active for the constituents of interest at the Site. The fact that the available data demonstrate that natural attenuation is active at the Site, as discussed above, indicates that these impairments are not important and do not negate natural attenuation. Parette's opinion is therefore not a basis to reject the monitored natural attenuation aspect of the planned remedy for the Site. Parette also opined that the partition coefficients (KD) obtained from the testing of Site materials in the laboratory are biased high because the synthetic groundwater used for the tests did not contain all the chemical species present in Site groundwater. Because of this, Parette appears to imply that monitored natural attenuation is not appropriate for the restoration of groundwater. Even if all chemical species present in Site groundwater had been incorporated in the synthetic groundwater for testing, the main conclusion from the testing would remain valid. The main conclusion from the testing is that the constituents of interest in groundwater do interact with the solid matrix, demonstrating the occurrence of attenuation. Boron is the exception, for which testing showed that attenuation by interaction with the solid matrix does 17 2-2- bVbVDObnr02 9� V220CIV1E2' JWC' not contribute substantially to attenuation. Attenuation for boron is primary through dilution and dispersion, as discussed under Section 3 above. Parette opined that monitored natural attenuation should not be selected to remedy arsenic at the Site and that the cap -in -place remedy would likely increase the mobility of arsenic in groundwater. There are several reasons why the cap -in -place remedy does not negate the use of natural attenuation for the restoration of groundwater at the Site. Arsenic is amenable to natural attenuation in the groundwater environment, as discussed above. The reduction of the infiltration flux through the ash materials relative to the flux of groundwater from upgradient is expected to increase arsenic attenuation in groundwater, not the reverse. In addition, more reducing conditions in the ash materials would result in increased sulfide activity leading to the precipitation or co - precipitation of arsenic with sulfide minerals. This sequestration of arsenic in the ash materials would further decrease the arsenic flux from the ash to groundwater. Parette opined that monitored natural attenuation should not be selected to remedy antimony, boron, chromium, hexavalent chromium, cobalt, and vanadium at the Site. Antimony, chromium, hexavalent chromium, cobalt and vanadium are within the groundwater background range and do not require active remediation at the Site. Parette's opinions on these constituents are therefore irrelevant. The exception is for cobalt in the area of the coal pile, and this occurrence would not be addressed by either the cap -in -place or excavation remedies. As for boron in groundwater, the elevated concentrations will decrease under the planned source control measures because of a reduction in the flux of boron from the capped ash basins and through attenuation (primarily dilution and dispersion). There is no risk of exposure to unsafe level of boron at the Site and its vicinity, now, or in the future. Opinion 3. Excavation of the ash basins is not necessary for Site groundwater restoration. Excavation alone cannot achieve the complete removal of the constituents of interest from the subsurface and provides no substantial benefit over a cap -in -place remedy to restore groundwater. The excavation and removal of the ash in the ash basins and a portion of the soil materials beneath the basins was evaluated by Duke Energy and determined not to be the best remedy for the Site. Cap -in -place control measures with monitored natural attenuation combined with additional control measures, if necessary, was selected as a better remedy for the Site. The determination is based on a technical evaluation of the merits and limitations of these two options. Excavation and complete removal of ash and shallow soil materials from the ash basins is the remedy that Plaintiffs' experts advocate for the Site. I disagree with that conclusion for the following major reasons (see also Sections 5 and 6 above): • The engineered cap -in -place control measures that Duke Energy plans to construct to cover the ash basins will have the effect of greatly reducing the infiltration of water and wastewater through the coal ash. The amount of ash pore water that will recharge to groundwater will be greatly diminished and the flux of chemicals entrained with infiltration water will decrease. 2-2- bVbVDObnr02 9� V220CIV1E2' IMC' �S • Natural attenuation will provide for a gradual restoration of the impacted groundwater under either the cap -in -place and excavation scenarios. Geochemical processes that control aquifer restoration will be slow and gradual and will require a long period of time (i.e., years or decades) under both the excavation and cap -in -place remedies. • Excavation would not remove all the ash materials. It is simplistic to assume that excavation at the scale promoted by Plaintiffs' experts would be able to remove the totality of the ash at the Site. Ash materials were placed on bare soils for several decades, and some ash most likely penetrated deeper in the subsurface than can be reached by the excavation promoted by Plaintiffs' experts. • Excavation would not remove the impacted groundwater beneath and downgradient of the excavation. The residual mass of ash materials and the impacted groundwater would serve as long term sources and sustain the groundwater impacts. • Excavation will disturb large volumes of coal ash and expose chemically reduced materials to atmospheric oxygen and water. A change in geochemical conditions would result in a rearrangement of the mineralogy of the aquifer, with dissolution and precipitation of secondary mineralogy affecting groundwater chemistry and redistributing the constituents of interest in the subsurface. The geochemical disturbance would induce transient changes in the chemistry of groundwater that would only gradually and slowly attenuate long after the implementation of excavation. • Excavation of the large quantities of materials in the ash basins would take time to implement (i.e., years or decades). During that period of open excavation, precipitation, storm water, and runoff water would enter the excavation in great quantities and infiltrate to groundwater. This added infiltration would introduce additional contamination and force impacted groundwater farther into the aquifer system, thereby increasing the extent of the existing groundwater impacts. Plaintiffs' expert Bedient advocates excavation and removal, coupled with additional measures such as hydraulic groundwater containment, to prevent coal ash contaminants from migrating across the compliance boundary and into the Catawba River for the foreseeable future. If hydraulic control is necessary to control the migration of contaminants, as argued by Bedient, it could be implemented without excavation and removal, for example under a cap -in -place source control. Duke Energy's proposed cap -in -place source control remedy for the Site has the flexibility to implement additional measures to control contaminant transport, if necessary. Bedient wrongly assumes that the source of contamination would be entirely removed by the excavation remedy. The excavation would not remove the impacted groundwater. The excavation would not remove the mass of contaminants that is stored by sorption and mineral coatings in the soil, rock and aquifer materials that could not be excavated. The excavation would also not remove the naturally occurring compounds of concern that are components of the native soil and rock materials. Furthermore, the excavation would not remove residual ash materials that could have penetrated into the subsurface beyond the extent of the excavation. Cosler and Parette advocate excavation and removal because they believe it would result in a reduction of the clean-up time for groundwater by a factor 2.5 to 5 relative to the cap -in -place source control remedy. The uncertainty on estimating clean-up rates for groundwater is very large, 19 2-2- bVbVDObnr02 9� V220CIV1E2' JWC' �S and predictions based on such estimates are highly uncertain and unreliable. The time factor improvement claimed by Cosler and Parette for clean-up under the excavation scenario fails to account for the time it would take to excavate the ash basins. Several years would be required to excavate the ash basins and accounting for this would delay the onset of the groundwater cleanup. The time factor improvement claimed by Cosler and Parette for clean-up under the excavation scenario would provide little benefit since there is no imminent risk of exposure to unsafe contaminant levels at the Site. In addition, the flux of contaminants from the ash basins will decrease under the cap -in -place remedy (and the additional source control measures that will be implemented, if necessary), and the extent of contamination will be reduced. Natural attenuation will provide for gradual groundwater restoration, further reducing the need for aggressive excavation and removal of the ash basins. 20 APPENDICES Appendix A Curriculum Vitae of Remy J.-C Hennet 2.2- bV6VD06nr oe 8F b220CIVIE2' INC' REMY J.-C. RENNET Geochemist AREAS OF EXPERTISE ■ Geochemistry, Hydrogeology, Geology ■ Origin, Fate, and Transport of Chemicals in the Environment SUMMARY OF QUALIFICATIONS A geochemist with 25 years of research and professional experience, Dr. Hennet specializes in evaluating the origin, fate, and transport of organic and inorganic chemicals in the environment. Dr. Hennet is often retained as an expert witness for litigation in providing services to industry, law firms, and the U.S. Department of Justice. His areas of expertise include the analysis of geochemical fingerprints, the evaluation of the timing of chemical releases, allocation of responsibilities, geochemical modeling, and the evaluation and application of novel on -site technologies to solve environmental problems. He is a member of the American Academy of Forensic Sciences, the American Chemical Society, and the Association of Groundwater Scientists and Engineers. He was awarded the Woods Hole Oceanographic Institution's Postdoctoral Scholarship in 1987 and has numerous publications in the fields of inorganic and organic geochemistry. REPRESENTATIVE EXPERIENCE S.S. Papadopulos & Associates, Inc., Bethesda, Maryland ■ Environmental Forensics ■ Litigation Support U.S. Department of Justice — Served as an expert witness for several environmental litigation cases. Examples of this work include: the quantification of the history of benzene flux from the subsurface to ambient air following the release of military jet fuel; the evaluation of multi -source petroleum hydrocarbon releases and their individual extent; the evaluation of the impact of bleaching agent when released in a desert environment; the impact and duration of large herbicides, and other products); and the origin, fate, chlorinated solvents at several military bases. YEARS OF EXPERIENCE: 25+ EDUCATION PhD - Geochemistry, Princeton University, 1987 MA -Geology, Princeton University, 1983 Diplome - 3eme Cycle, Hydrogeologie, Universite de Neuchatel, 1981 Diplome - Geologie, Sciences Exactes, Universite de Neuchatel, 1980 REGISTRATIONS Certified Professional Geological Scientist: No. 10572, American Institute of Professional Geologists Licensed Professional Geoscientist: Texas No. 425 PROFESSIONAL HISTORY S.S. Papadopulos & Associates, Inc.: Principal, 1989 to present Woods Hole Oceanographic Institution: Postdoctoral Scholar, 1987-1989 Princeton University: Research Assistant, 1983-1987; Teaching Assistant, 1982-1985 Universite de Neuchatel: Research Assistant, 1980-1981 scale pesticide applications (fumigants, transport, and timing of the release of Atlantic Richfield Company, Montana —Provided technical support for natural resource damage litigation and testified as an expert witness. For the Anaconda tailings ponds site, collected data for a modeling simulation of the fate and transport of dissolved arsenic and cadmium in the alluvium beneath and down -gradient of the ponds. For the Butte mining district, evaluated the background condition for metals, arsenic, and sulfur chemical species. For the Montana Pole wood treatment site, evaluated the mobility of arsenic and pentachlorophenol (PCP) in the groundwater environment. For the Milltown Reservoir on the Clark Fork River; evaluated the background conditions and the mobility of metals and arsenic chemical species in sediments accumulated behind the reservoir. ■ Allocation of Responsibility and Costs (Confidential Clients), Nationwide — Reviewed and interpreted large volumes of information to support multi -party allocation models. 2.2- bV6VD06nr oe 8F b220CIVIE2' INC' REMY J.-C. RENNET Geochemist Page 2 • Atlantic Richfield/BP, California, Nevada — Provided a detailed evaluation of the design and performance of abatement measures at closed sulfur and copper mines. Applied geochemical fingerprints and performed modeling to evaluate the origin fate and transport of contamination. ■ Rhone Poulenc Corporation, Pennsylvania, California, and New Jersey — Studied arsenic fixation in soil material by various physicochemical treatments as part of a collaborative effort with Pennsylvania State University, with a focus on understanding the processes that control the fixation of arsenic in soils. Advised on the interpretation of data to characterize the mobility of arsenic chemical species at the Bay Road Site in the San Francisco Bay area, and at the Factory Lane Site in New Jersey. ■ Panhandle Eastern Pipeline Company — Evaluated and characterized the fate, transport, and distribution of polychlorinated biphenyls (PCBs) in the subsurface at several sites along a major pipeline system. Pipeline liquid condensate was discharged to unlined pits located at pumping stations spread along the system. The condensate contained PCBs from the operational bleeding of oil from gas pressurization turbines. The disposal of condensate resulted in surface and subsurface contamination by PCBs and light hydrocarbon compounds. Provided guidance in site characterization, site remediation, and to the site closure process. • Envirosafe Services Landfill, Toledo, Ohio —Reviewed detailed organic, inorganic, and isotope data to evaluate the integrity of a large active landfill complex located in an area characterized by historical waste disposal activity. ■ Lone Pine Superfund Site, Freehold, New Jersey —Performed data collection and interpretation to predict chemical composition for the design of a treatment facility. ■ Heleva Superfund Site, Allentown, Pennsylvania —Conducted specialized sampling to assess trace amount of chlorinated hydrocarbons in acetone -rich groundwater. Acquired isotope and nutrient data to characterize subsurface conditions for natural attenuation and design of the treatment plant. • Love Canal, Niagara Falls, New York, and Stringfellow, Glen Avon, California, Superfund Sites — Performed detailed data interpretations to assess the validity of expert witness' testimonies related to the fate, behavior, and migration of toxic chemicals in the subsurface. ■ Tyson Superfund Site, Pennsylvania — Conducted a detailed technical investigation of the performance of a large vacuum -extraction system consisting of more than 250 individual extraction wells. The extraction of volatile organic compounds was impeded by subsurface heterogeneities and the presence of residual non -aqueous phase liquids in the subsurface. ■ Little Mississinewa River Superfund Site, Union City, Indiana, — Several miles of river sediments were contaminated with waste oil containing elevated PCBs, and PCTs, PAHs, and metals. The main sources of contamination consisted of two major industrial outflows that discharged to the river over a period of several decades. Using chromatograms and raw electronic instrument response data from the analysis of about 200 samples, characterized the chemical fingerprints of both sources and quantified relative contributions. ■ Coronet Company, Florida —Provided a detailed evaluation of the fate and transport of arsenic, boron, radium, polonium, and other chemicals in soil, ponds sediment, and groundwater at a former phosphate mining and fertilizer processing plant. Conducted geochemical modeling. • White Pine Sash Superfund Site, Missoula, Montana —The release of wood treatment product containing pentachlorophenol (PCP) in diesel resulted in contamination of the vadose zone above a major water supply aquifer. Chlorinated-dioxins/furans were also detected in soil samples. Concurrently with the PCP product release(s), diesel/fuel oil No 2 had been released from underground storage tanks in the area. Evaluated and delineated the extent of impact of the diesel/fuel oil No 2 release independently of the PCP -diesel release(s). 2.2- bV6VD06nr oe 8F b220CIVIE2' INC' REMY J.-C. RENNET Geochemist Page 3 • CSX Transportation, Florida — Evaluated the origin(s) fate and transport of arsenic in the environment. • Titan Tire Corporation, Iowa — Evaluated the origin of PCB contamination and conducted a detailed review of laboratory data packages. ■ Uranium Mine Tailings, New Mexico —Evaluated tailings piles (from the processing of uranium ore) for water balance, dewatering, contaminant flux to groundwater, the progress of groundwater plume development, and the effects of remedial measures. Recommended dose reconstruction in water wells. ■ Citizens about Rushton Rezoning, Inc., South Lyon, Michigan — Analyzed the potential environmental and hydrogeological impacts of water -treatment lagoons and infiltration spraying fields. Calculated the fate and transport of nitrogen and phosphorous in the soil and groundwater. [The lagoons and spraying fields were selected as a wastewater treatment for a large residential development. The spraying fields were located on sloped glacial till that has limited permeability and capacity. Regulated surface -water bodies were located adjacent to the spraying fields and lagoons.] Woods Hole Oceanographic Institution, Woods Hole, Massachusetts Studied the organic and inorganic chemistry of the Guaymas Basin hydrothermal system. Performed detailed trace analyses of metals and petroleum hydrocarbons. The research included the use of the research submarine Alvin for in -situ parameter measurements and sampling. Researched and studied the formation of natural petroleum and the effects of organic molecules degradation and migration on the formation of geopressured zones. Princeton University, Princeton, New Jersey As Research Assistant, studied metal -organic interaction in natural settings, and served as Senior Thesis Advisor for an experimental study of lead -organic complexing and for an experimental study of trichloroethane in groundwater. Served as Teaching Assistant in Historical Geology and Geomorphology. Universite de Neuchatel, Centre d'Hydrologie, Switzerland Studied tritium in groundwater and performed related laboratory work. Conducted geochemical fingerprinting in carbonate terrains as applied to the development of water resources. PROFESSIONAL SOCIETIES American Academy of Forensic Sciences American Chemical Society American Institute of Professional Geologists Geological Society of America National Ground Water Association — Association of Ground Water Scientists and Engineers HONORS & AWARDS Postdoctoral Scholar, Woods Hole Oceanographic Institution, 1987-1989 Princeton University Fellowship, 1982-1987 Swiss National Science Foundation Fellowship at Princeton University, 1981-1982 Mention Bien, Geologie, Universite de Neuchatel, 1980 2.2- bV6VD06nr oe 8F b220CIVIE2' INC' REMY J.-C. RENNET Geochemist Page 4 APPOINTMENTS 2002-2005: Geological Sciences Advisory Board, University of Alabama. 1996-2001: Member of Governing Board, Association of Princeton Graduate Alumni. 2000: Convenor, THEIS 2000 Conference: Iron in Groundwater, National Ground Water Association. 1993-1999: Technical Advisory Board, Xetex Corporation. 1989-1992: Member of Steering Committee, Working Group 91, Scientific Commission for Oceanic Research. PUBLICATIONS Soderberg, K., D.P. McCarthy, and R. J.-C. Hennet, 2015. Volatilization of Polychlorinated Biphenyls: Implication for their Distribution, Forensics and Toxicity in Urban Environments. Presentation at the Geological Society of America Annual Meeting, November 1-4, 2015, Baltimore, MD. Soderberg, K. and R.J.-C. Hennet, 2014. Detection of Pharmaceuticals in the Environment: History of Use as a Forensic Tool. in Goldstein, W. ed. Pharmaceutical Accumulation the Environment: Prevention, Control, Health Effects and Economic Impact. CRC Press: Boca Raton, FL. 262 p. Hennet, R.J.-C, 2010. PCBs in the Interstate Natural Gas Transmission System — Status and Trends. White Paper prepared for the Interstate Natural Gas Association of America. Hennet, R.J.-C, 2010. Working with Lawyers: The Expert Witness Perspective. United States Attorneys' Bulletin, v. 58, no. 1, pp. 14-17. Soderberg, K., and R.J.-C. Hennet, 2007. Uncertainty and Trend Analysis -- Radium in Groundwater and Drinking Water. Ground Water Monitoring and Remediation, v. 27, no. 4, pp. 122-127. Soderberg, K., R. Hennet, and C. Muffels, 2005. Uncertainty and Trend Analysis for Radium in Groundwater and Drinking Water (abstract). Presentation at the 2005 National Ground Water Association Conference on Naturally Occurring Contaminants: Arsenic, Radium, Radon, and Uranium, February 24-25, 2005, Charleston, SC. in Abstract Book, pp. 30-44. Hennet, R.J.-C, 2002. The Application of Stable Isotope Ratios in Environmental Forensics. in American Academy of Forensic Sciences Proceedings, pp. 103-104. Hennet, R.J.-C, 2002. Life is Simply a Particular State of Organized Instability. in Fundamentals of Life, G. Palyi et al., eds. Paris, France: Elsevier, pp. 109-110. Hennet, R.J.-C., and L. Chapp, 2001. Using the Chemical Fingerprint of Pharmaceutical Compounds to Evaluate the Timing and Origin of Releases to the Environment. in Proceedings of the American Academy of Forensic Sciences, v.4, no. 1, p. 101. Vlassopoulos, D., C. Andrews, R. Hennet, and S. Macko, 1999. Natural Immobilization of Arsenic in the Shallow Groundwater of a Tidal Marsh, San Francisco Bay. Presentation at the American Geophysical Union Spring Meeting, Boston, MA, May 31-June 4, 1999. Hennet, R.J.-C, D. Carleton, S. Macko, and C. Andrews, 1997. Environmental Applications of Carbon, Nitrogen, and Sulfur Stable Isotope Data: Case Studies (abstract). Invited speaker at the Geological Society of America Annual Meeting, Salt Lake City, UT, November. Jiao, J., C. Zheng, and R. Hennet, 1997. Analysis of Under -pressured Reservoirs for Waste Disposal. Hydrogeology Journal, v.5, no. 3, pp. 19-31. 2.2- bV6VD06nr oe 8F b220CIVIE2' INC' REMY J.-C. RENNET Geochemist Page 5 Jiao, J., C. Zheng, and R. Hennet, 1995. Study of the Feasibility of Liquid Waste Disposal in Underpressured Geological Formations. Proceedings of the American Geophysical Union Spring Meeting, Baltimore, MD, May 30—June 2, 1995. in Eos Supplement, v. 76, no. 17, S137. Vlassopoulos, D., P. Lichtner, W. Guo, and R. Hennet, 1995. Long -Term Controls on Attenuation of Mine -Waste Related Contamination in Alluvial Aquifers: The Role of Aluminosilicate Clay Minerals. Proceedings of the American Geophysical Union Spring Meeting, Baltimore, MD, May 30-June 2, 1995. in Eos Supplement, v. 76, no. 17, S150. Feenstra, S., and R. Hennet, 1993. Assessment of Performance Limitations on Soil Vapor Extraction (SVE) in Variable Soils. The Newsletter of the Association of Ground Water Scientists and Engineers, v. 9, no. 3, pp. 112-113. Hennet, R.J.-C., and S. Feenstra, 1993. Assessment of Performance Limitations on Soil Vapor Extraction (SVE) in Variable Soils (abstract). Presentation at the Symposium on Chlorinated Volatile Organic Compounds in Ground Water, National Ground Water Association 45th Annual Convention, Kansas City, MO, October 17-20, 1993. in Ground Water, v. 31, no. 5, pp. 828-829. Hennet, R.J.-C., and C. Andrews, 1993. PCB Congeners as Tracers for Colloid Transport in the Subsurface —A Conceptual Approach. in Manipulation of Groundwater Colloids for Environmental Restoration. Ann Arbor, MI: Lewis Publishers, pp. 241-246. Hennet, R.J.-C, 1992. Abiotic Synthesis of Amino Acid Under Hydrothermal Conditions and the Origin of Life: A Perpetual Phenomenon? Invited speaker at the Gordon Research Conference on Organic Geochemistry, New Hampshire. Hennet, R.J.-C, N. Holm, and M. Engel, 1992. Abiotic Synthesis of Amino Acid Under Hydrothermal Conditions and the Origin of Life: A Perpetual Phenomenon? Naturwissenschaften, v. 79, pp. 361-365. Hennet, R.J.-C, and N. Holm, 1992. Hydrothermal Systems: Their Varieties, Dynamics, and Suitability for Prebiotic Chemistry. in Origins of Life and Evolution of the Biosphere, Netherlands, v. 22, pp. 15-31. Holm, N., A. Cairns -Smith, R. Daniel, J. Ferris, R. Hennet, E. Shock, B. Simoneit, and H. Yanagawa, 1992. Future Research. in Origins of Life and Evolution of the Biosphere, v. 22, pp. 181-190. Hunt, J.M., and R. Hennet, 1992. Modeling Petroleum Generation in Sedimentary Basins. in Productivity, Accumulation, and Preservation of Organic Matter Recent and Ancient Sediments. J. Whelan and J. Farrington, eds. New York: Columbia University Press, pp. 20-52. Hunt, J.M., M. Lewan, and R. Hennet, 1991. Modeling Oil Generation with Time -Temperature Index Graphs Based on the Arrhenius Equation. AAPG Bulletin, v. 75, no. 4, pp. 795-807. Hennet, R.J.-C, D. Crerar, and J. Schwartz, 1988. The Effect of Carbon Dioxide Partial Pressure on Metal Transport in Low -Temperature Hydrothermal Systems. Chemical Geology, v. 69, pp. 321- 330. Hennet, R.J.-C, D. Crerar, and J. Schwartz, 1988. Organic Complexes in Hydrothermal Systems: Economic Geology, v. 83, pp. 742-767. Hennet, R.J.-C, and F. Sayles, 1988. Effect of Dissolved Organic Compounds on Trace Metal Mobility in Low -Temperature Hydrothermal Systems (abstract). Presentation at the Joint Oceanographic Assembly, Acapulco, Mexico, August 23-31, 1988. in Journal of Arboriculture, v. 14, Mexico 88, p. 43. 2.2- bV6VD06nr oe 8F b220CIVIE2' INC' REMY J.-C. RENNET Geochemist Page 6 Hennet, R.J.-C, and J.K. Whelan, 1988. In -Situ Chemical Sensors for Detecting and Exploring Ocean Floor Hydrothermal Vents. Woods Hole Oceanographic Institution Technical Report WHOI-88-53, p. 69. Hennet, R.J.-C, 1987. The Effect of Organic Complexing and Carbon Dioxide Partial Pressure on Metal Transport in Low -Temperature Hydrothermal Systems. Unpublished PhD thesis, Department of Geochemistry, Princeton University. 308 p. Hennet, R.J.-C, D. Crerar, E. Brown, and J. Schwartz, 1986. Transport of Base Metals in Hydrothermal Brines by Organic and Possible Thiocarbonate Complexes: The Genesis of Stratiform Sediment -Hosted Lead and Zinc Deposits. Conference Proceedings. in Geological Science, Stanford University, v. 20, pp. 197-198. Hennet, R.J.-C, 1985. Partial Pressure of Carbon Dioxide and Base Metal Solubility: A Model for the Genesis of Hydrothermal Ore Deposits. Poster presentation at the Gordon Research Conference on Inorganic Geochemistry of Hydrothermal Deposits, New Hampshire. Hennet, R.J.-C, D. Crerar, and E. Brown, 1985. Base Metal Transport by Organic Complexing in Ore -Forming Brines (abstract). in Proceedings of the Second International Symposium on Hydrothermal Reactions. The Pennsylvania State University, p. 43. Hennet, R.J.-C, D. Crerar, and J. Schwartz, 1985. Metal -Organic Complexes in Ore -Forming Brines. Presentation at the1901h National Meeting of the American Chemical Society, Division of Environmental Chemistry, Chicago, IL, September 9, 1985. Hennet, R.J.-C, 1983. Formation Constants of Lead and Zinc Metal -Organic Complexes Using Polarography (ASV, DPP), Specific Ion Electrodes (ISE), and Nuclear Magnetic Resonance Spectroscopy (NMR). Unpublished MA thesis, Princeton University. Hennet, R.J.-C, D. Crerar, J. Schwartz, and T. Giordano, 1983. New Ligand-Bond Mechanisms for the Transport of Zinc in the Genesis of Mississippi Valley -Type Ore Deposits. Eos, v. 64, no. 45, p. 885. Flury, F.R., R. Hennet, and A. Matthys, 1981. Developpement des resources en eaux de la Ville de Delemont (Jura, Suisse). Unpublished Diplome d'Hydrogeologie. Centre d'Hydrogeologie. Universite de Neuchatel, Switzerland. Hennet, R.J.-C, 1980. Cartographie de la Region Neuchatel-Valangin: Etude de la Mineralogie par Diffraction-X, de la Stratigraphie et des Microfacies du Valanginien. Discussion de Stratotype de Valangin. Unpublished Diplome de Geologie. University de Neuchatel, Switzerland. DEPOSITION AND TESTIMONY EXPERIENCE DEPOSITIONS 2016 Tri-Realty Company v. Ursinus College. The United States District Court for the Eastern District of Pennsylvania. Civil Action No. 2:11-cv-05885-GP. April 20. 2015 Duke Energy Progress, Inc. v. N.0 Department of Environment Resources, et al. State of North Carolina, Wake County in the Office of Administrative Hearings. Case No. 15 HER 02581. July 9. 2014 United States of America v. Richard Middleton, Circle Environmental, Inc., BSJR, LLC, and WaterPollutionSolutions.com, Inc. The United States District Court for the Middle District of Georgia Albany Division. Case No. 1:11-cv-00127-WLS. November 3. 2.2- bV6VD06nr oe 8F b220CIVIE2' INC' REMY J.-C. RENNET Geochemist Page 7 2014 Santa Fe Pacific Gold Corporation vs. United Nuclear Corporation vs. The Travelers Indemnity Company, et al, State of New Mexico, County of Cibola Eleventh Judicial District. No. CV-97-13911. February 6. 2013 State of New Mexico ex rel. vs. Kerr-McGee Corporation et al. State of New Mexico, County of Cibola Thirteenth Judicial District Court. No. CB-83-190-CV & CB-83-220-CV (Consolidated). April24-26. 2012 Grant Neibaur and Sons Farms, et al vs. The United States of America. U.S. District Court for the District of Idaho. No. CIV 4:11 -cv-001 59-BLW. September 19. 2012 State of New Mexico ex rel. vs. Kerr-McGee Corporation et al. State of New Mexico, County of Cibola Thirteenth Judicial District Court. No. CB-83-190-CV & CB-83-220-CV (Consolidated). September 11-14. 2012 Commissioner of the Department of Planning and Natural Resources, et al. vs Century Aluminum Company, et al. District Court of the Virgin Islands Division of St. Croix. Civil No. 2005-0062. June 26. 2012 Commissioner of the Department of Planning and Natural Resources, et al. vs Century Alumina Company, et al. District Court of the Virgin Islands Division of St. Croix. Civil No. 2005-0062. June 25. 2012 ExxonMobil Oil Corporation vs Nicoletti Oil, Inc., et al. U.S. District Court Eastern District of California. No. 1:09-cv-01498-A WI-DLB. June 14. 2012 United States of America vs Dico Inc. and Titan Corporation. U.S. District Court Southern District of Iowa. No. 4:10-cv-00503-RP-RAW. January 20. 2011 Joseph A. Pookatas, Donald L.Michel and the Confederated Tribes of the Colville Reservation and the State of Washington (Plaintiff Intervenor) vs Teck Cominco Metals, LTD. U.S. District Court Eastern District of Washington at Yakima. CB-04-0256-LRS. June 10. 2010 United States Virgin Islands Department of Planning and Natural Resources vs. St. Croix Renaissance Group, L.L.L.P., et al. District Court of the Virgin Islands Division of St. Croix. Civil No. 2007/114. October 20. 2010 In the Matter of the Application for Water Rights of Leadville Water, JV., in Park County, Colorado. District Court, Water Division No. 1, State of Colorado. 07CW251. September 22-23. 2009 Timm Adams et al. vs. United States of America et al. U.S. District Court, District of Idaho. 03-0049-E-BLW. January 15. 2008 Pennsauken Solid Waste Management Authority vs. Devoe et al. New Jersey Superior Court, Camden County, Law Division. No. L-13345-91. October 15. 2007 Arbitration in the Issue of PCB Contamination in the Little Mississinewa River, Union City, Indiana. Pittsburgh, Pennsylvania. August 22. 2007 San Diego Unified Port District vs. TDY Industries, Inc.; Ryan Aeronautical Company; Teledyne Ryan Company; Teledyne Ryan Aeronautical Company; Teledyne Industries, Inc; Allegheny Teledyne, Inc.; Allegheny Technologies, Inc. United States District Court, Southern District of California. Case Number 03 CV 1146-B (POR). January 5. 2006 Sierra Club, Natural Resources Defense Council, and Natural Parks Conservation Association vs. Robert B. Flowers, Chief of Engineers, United States Army Corps of 2.2- bV6VD06rlr'02 8F b220CIVIE2' INC' REMY J.-C. RENNET Geochemist Page 8 Engineers et al. U.S. District Court, Southern District of Florida. Case No. 03-23427-CIV- Hoeveler. October 31 and November 17. 2003 Linda Akee et al. vs. The Dow Chemical Company et al., Dole Food Company, Inc., Third - Party Plaintiffs vs. The United States of America, Third -Party Defendant. U.S. District Court for the District of Hawaii. Civil Action No. CV00-00382 BMK. August 25. 2000 Chevy Chase Bank, FSB, Plaintiff/Counter-Defendant vs. Shell Oil Company and Motiva Enterprises, LLC, Defendants/Counter-Plaintiffs. U.S. District Court for the District of Maryland, Southern Division. December 14. 1999 Textron vs. Ashland, Inc. et al. Superior Court of New Jersey. 1999 McMahon vs. The United States of America. U.S. District Court, Southern District of Texas, Laredo Division. Case No. L-99-009. December 1. 1998 Kay Bettis et al. vs. Ruetgers-Nease Corp. et al. U.S. District Court for the Northern District of Ohio Eastern Division. Case No. 4:90 CV 0502. 1996 State of Montana vs. Atlantic Richfield Company. U.S. District Court, District of Montana, Helena Division. Case No. CV-83-317-HLN-PGH. 1996 Kenneth Bowers vs. The United States and Tenco Services, Inc. U.S. District Court for the District of South Carolina. Case No. 2:95-5568. 1995 Reichhold Chemicals, Inc. vs. Textron Inc. et al. U.S. District Court, Northern District of Florida. Case No. 92-30393RV. TESTIMONY 2015 United Nuclear Corporation vs. London Insurance Companies. Eleventh Judicial District Court. County of McKinley, State of New Mexico. No. D-1 1 13-CV-9700139. January 21 and 22. 2013 United States of America vs Dico Inc. and Titan Corporation. U.S. District Court Southern District of Iowa. No. 4:10-cv-00503-RP-RAW. December 4. 2009 Timm Adams et al. vs. United States of America and E.I. DuPont de Nemours and Company, a Delaware corporation. U.S. District Court, District of Idaho. Case No. CIV-03- 0049-E-BLW. August 4, 5, 6. 2008 Attorney General of the State of Oklahoma and Oklahoma Secretary of the Environment vs. Tyson Foods, Inc., et al. U.S. District Court for the Northern District of Oklahoma. 4:05-CV- 00329-TCK-SAJ. March 7. 2006 Sierra Club, Natural Resources Defense Council, and Natural Parks Conservation Association vs. Robert B. Flowers, Chief of Engineers, United States Army Corps of Engineers et al. U.S. District Court, Southern District of Florida. Case No. 03-23427-CIV- Hoeveler. November 28 and 29. 2004-2005 Universal Waste, Inc. and Clearview Acres, Ltd. Regarding Delisting Petition for Site Number 0633009. Adjudicatory Hearing by New York Department of Environmental Conservation, Office of Hearings and Mediation. Site Number 0633009. October 27 and February 3. 2004 Part 31, City of South Lyon and the Citizens About Rushton Rezoning, Inc., Permit No.: M 00994; and Permit No: GW186300602. State of Michigan, Department of Environmental Quality, Office of Administrative Hearings, Lansing, MI. May 20, 21, and 27. 2.2- bV6VD06nr oe 8F b220CIVIE2' INC' REMY J.-C. RENNET Geochemist Page 9 2003 Robert McMahon vs. The United States of America. U.S. District Court, Southern District of Texas. Case No. L-99-009. February. 2001 Bolinder et al. vs. United States. U.S. District Court, District of Utah. Case No. 2:97CV0912. May. 1998 State of Montana vs. Atlantic Richfield Company. 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Mechanism and Conditions of Clay Formation During Natural Weathering of MSWI Bottom Ash: Clays and Clay Minerals 44, no. 4: 546-552. 0 Appendix C Background Concentration Ranges - USGS, Site Data, and Private Wells 2.2- bV6VD06nr oe 8F b220CIVIE2' INC' Appendix C Explanation Sheet Background concentration cumulative distribution plots were created for the following analytes: • Boron • Chromium • Sulfate • Antimony • Arsenic • Vanadium • Iron • Cobalt • Manganese • pH • Barium • Total Dissolved Solids The cumulative distribution plots illustrate the differences in the range of concentrations sampled from different locations. Locations (site background wells, private wells, and USGS wells) can be compared by the relationships between their sample concentrations at different percentiles. Data Sources The site background data was obtained from the from the Duke Energy MANAGES environmental database, queried on 6/23/2016 by Tim Hunsucker. USGS well dataset was obtained from the USGS National Water Information System' (NWIS). The NWIS was queried on 6/10/2016 for all groundwater data from North Carolina wells for the analytes listed above. The NWIS query results did not contain data for total boron or total vanadium. The private well data was obtained from the NC DEQ websitez from the document "Full Well Water Testing Results For Posting 8.2031,. Estimated values (J qualifier) were omitted from the analysis for the private well data. Data Handling The following site wells were considered background wells for the calculations: • AB-111 • BG-3S • GWA-17S • BG-1D • BG-4BR • GWA-19D • BG-1S • BG-4D • GWA-19S • BG-2BR • BG-4S • GWA-21D • BG-2D • GWA-16D • GWA-21S • BG-2S • GWA-16S • BG-3D • GWA-17D All non -detects samples in the site background and private wells datasets were set to one half their detection limit. 1 http://nwis.waterdata.usgs.gov/nwis/qwdata z https://deg.nc.gov 3 https://ncdenr.s3.amazonaws.com/s3fs-public/document- Iibra ry/Full%20WeII%20Water%20Testing%20Results%20For%2OPosting%208.20.pdf 2.2- bV6VD06nr'o2 8F b220CIVIE2' INC' The USGS dataset sample values were averaged by well after sAMlues to one half their detection limit, in an effort to try to avoid unnecessary spatial bias in sites sampled more frequently. Sites where all the values in the average calculation were non -detects were considered non -detects for plotting purposes. For percentile calculations and plotting, all non -detect values for a given analyte were set to the lowest non -detect value in that dataset. This ensured non -detect samples would be the top (highest) ranks for the percentile calculation. This was necessary because they cannot be assumed to be greater than any detected value. 100% 90% 80% 70% 60% c 50% L 40% 30% 20% 10% 0% Site Background Wells/Private Wells for Allen - Boron (Unfiltered) Site Background Wells Boron pg/L n = 83 Private Wells Boron pg/L n = 105 Site Background Wells Non -detect Private Wells Non -detect NC 2L Standard, 700 fag/L f I= 10 Concentration pg/L 100 1000 Site Background Wells/USGS Wells/Private Wells for Allen - Sulfate (Unfiltered) • Site Background Wells Sulfate mg/L n = 83 • USGS Wells Sulfate, Averaged by Location mg/L n =60 Private Wells Sulfate mg/L n = 121 Site Background Wells Non -detect USGS Wells Non -detect Private Wells Non -detect 100% 90% 80% 70% 60% a� 50% 40% 30% 20% 10% 0% 0.01 0.10 NG 2L Standard, 25U 1.00 10.00 Concentration mg/L • 100.00 1000.00 100% 90 % 80 % 70% 60% a� 40% 30 20% 10% 0% 0.01 Site Background Wells/USGS Wells/Private Wells for Allen - Arsenic (Unfiltered) • Site Background Wells Arsenic pg/L n = 83 • USGS Wells Arsenic, Averaged by Location pg/L n =122 Private Wells Arsenic pg/L n = 110 Site Background Wells Non -detect USGS Wells Non -detect Private Wells Non -detect 0.10 NG 1L Standard, 10 1.00 10.00 Concentration pg/L 100.00 1000.00 100% 90% 80% 70% 60% a� c 50% ^L♦ ^W I..L 40% 30% 20% 10% 0% Site Background Wells/USGS Wells/Private Wells for Allen - Iron (Unfiltered) • Site Background Wells Iron pg/L n = 83 • USGS Wells Iron, Averaged by Location pg/L n =2221 Private Wells Iron pg/L n = 115 Site Background Wells Non -detect USGS Wells Non -detect Private Wells Non -detect NC 2L Standard, 300 p/L ® MM • •• •• • • 0.1 1.0 10.0 100.0 1000.0 Concentration pg/L 10000.0 100000.0 1000000.0 100% 90% 80% 70% 60% a� 40% 30% 20% 10% 0% Site Background Wells/USGS Wells/Private Wells for Allen - Manganese (Unfiltered) • Site Background Wells Manganese fag/L n = 83 • USGS Wells Manganese, Averaged by Location pg/L n =813 Private Wells Manganese pg/L n = 100 Site Background Wells Non -detect USGS Wells Non -detect Private Wells Non -detect INU « bianaara, au F •i 0.01 0.10 1.00 10.00 100.00 Concentration pg/L •• • • _ _'dmo • 400046000010 ' 1000.00 10000.00 100000.00 100% 90 % 80% 70 % 60% a� 40% 30% 20% 10% 0% 1 Site Background Wells/USGS Wells/Private Wells for Allen - Barium (Unfiltered) • Site Background Wells Barium fag/L n = 83 • USGS Wells Barium, Averaged by Location pg/L n =77 Private Wells Barium pg/L n = 125 Site Background Wells Non -detect USGS Wells Non -detect Private Wells Non -detect 10 NU 2L Standard, NU 100 Concentration pg/L 1000 10000 100% 90% 80% 70% 60% a� 40% 30% 20% 10% 0% Site Background Wells/USGS Wells/Private Wells for Allen - Chromium (Unfiltered) • Site Background Wells Chromium pg/L n = 83 • USGS Wells Chromium, Averaged by Location pg/L n =124 Private Wells Chromium pg/L n = 113 Site Background Wells Non -detect USGS Wells Non -detect Private Wells Non -detect NU 1L Standard, 10 0.01 0.10 1.00 10.00 Concentration pg/L 100.00 1000.00 100% 90% 80% 70% 60% c 50% L 40% 30% 20% 10% 0% Site Background Wells/USGS Wells/Private Wells for Allen - Antimony (Unfiltered) Site Background Wells Antimony pg/L n = 83 USGS Wells Antimony, Averaged by Location fag/L n =61 Private Wells Antimony fag/L n = 100 Site Background Wells Non —detect USGS Wells Non —detect Private Wells Non —detect iNU nwHU 5tanaara, -i 0.01 0.10 1.00 10.00 100.00 Concentration pg/L 100% 90% 80% 70% 60% a� 50% a 40% 30% 20% 10% 0% 0.1 Site Background Wells/Private Wells for Allen - Vanadium (Unfiltered) • Site Background Wells Vanadium pg/L n = 70 Private Wells Vanadium pg/L n = 117 Site Background Wells Non -detect Private Wells Non -detect NC IMAC Standard, 0.3 pg/L •• i • s® = rr• 1.0 Concentration pg/L 10.0 100.0 100% 90% 80% 70% 60% a� 40% 30% 20% 10% 0% 0.01 Site Background Wells/USGS Wells/Private Wells for Allen - Cobalt (Unfiltered) • Site Background Wells Cobalt pg/L n = 70 • USGS Wells Cobalt, Averaged by Location pg/L n =2 Private Wells Cobalt pg/L n = 102 Site Background Wells Non -detect USGS Wells Non -detect Private Wells Non -detect NC IMAC Standard, 1 /L S •• •• •_ • 0.10 Concentration pg/L 1.00 10.00 100% 90% 80% 70% 60% a� 40% 30% 20% 10% 0% Site Background Wells/USGS Wells/Private Wells for Allen - pH • Site Background Wells pH n = 42 • USGS Wells pH, Averaged by Location n =875 Private Wells pH n = 125 Site Background Wells Non -detect USGS Wells Non -detect Private Wells Non -detect N[; 91 Stgndgrd R 5 - R 5 • • • • • • • • • • • • • 2 4 6 8 10 12 14 16 18 20 pH 100% 90% 80% 70% 60% a� 40% 30% 20% 10% 0% Site Background Wells/USGS Wells/Private Wells for Allen - Total Dissolved Solids (Filtered) • Site Background Wells Total Dissolved Solids mg/L n = 83 • USGS Wells Dissolved solids, Averaged by Location mg/L n =2014 Private Wells Total Dissolved Solids mg/L n = 126 Site Background Wells Non -detect USGS Wells Non -detect Private Wells Non -detect NC 2L Standard, 500 m /L ago"* N • •f '' Q • • M 1 10 100 1000 Concentration mg/L 10000 100000 Appendix D Natural Attenuation — Ash Basins to Compliance Boundary 2.2- bV6VD06nr oe 8F b22OCIVIE2' INC' Appendix D Explanation Sheet Box plots were created for boron, sulfate, arsenic, iron, manganese, vanadium, barium, chromium, antimony, cobalt, pH, and total dissolved solids (TDS) to illustrate concentration changes that occur from the ash basins to the compliance boundary. Box plots were created for ash pore -water data, wells within the waste boundary, and wells outside the waste boundary but within the compliance boundary. Any sample event in which boron was not detected (>50 ug/L) was excluded from the analysis since it would not be indicative of groundwater impacted by the ash basins. For comparison purposes box plots of the Site background data, private drinking water supply well (<0.5 mile radius from site), and USGS data are included, even if boron was not detected during the sampling event. The Site background and USGS data are included in the illustration for comparison and are referenced in Appendix C. Ash porewater, inside waste boundary, and outside waste boundary groups only included concentrations if boron was detected (>50 ug/L) at that well for the sample date. Groups in which samples have been screened for boron detects are colored differently from groups which use all sample results regardless if boron was detected. Estimated values (J qualifier) were omitted from the analysis for the private well data. The box plots were constructed to show the median with the upper and lower "hinges" corresponding to the first and third quartiles (25th and 75th percentiles). Values for non -detects are set at half of the detection limit. All data analyzed for unfiltered samples to allow for comparison to the 2L standards and IMAC. The exception is for TDS which requires filtration. The box plots contain two categories of six groups, and are defined as follows: Wells with boron detected > 50 ug/L in sample Ash Porewater — Wells screened within the ash Inside Waste Boundary— Wells screened below the ash, within the waste boundary Outside Waste Boundary — Wells screened outside the waste boundary, downgradient from ash All wells, regardless if boron was detected in sample Site Background — Wells screened outside compliance boundary, up -gradient of ash basin Private Water Supply — All private drinking wells samples within 0.5-mile radius of the Site' USGS Groundwater— North Carolina USGS well data' The following table is a list of all Site wells used for the box plot analysis and which group they were sorted in. No wells were excluded from the private water supply data or USGS groundwater. ' https://ncdenr.s3.amazonaws.com/s3fs-public/document- libra ry/Full%20WeII%20Water%20Testing%20Res ults%20For%20Posting%208.20.pdf Z http://nwis.waterdata.usgs.gov/nwis/qwdata queried downloaded on 6/10/2016 and included all data from North Carolina for the analytes listed above 2.2- bV6VD06nr oe 8F b22OCIVIE2' INC' Allen Box Plot Well Group List All Wells Wells with Boron > 50 ug/L Background Porewater Inside Waste Outside Waste AB-1R AB-20S AB-20D AB-10D GWA-51D BG-1D AB-21S AB-21BR AB-10S GWA-5S BG-1S AB-21SL AB-21D AB-11D GWA-6BR BG-2BR AB-23S AB-22D AB-12D GWA-61D BG-2D AB-24S AB-22S AB-12S GWA-6S BG-2S AB-24SL AB-23BRU AB-13D GWA-71D BG-3D AB-25S AB-24D AB-13S GWA-7S BG-3S AB-25SL AB-25BR AB-14D GWA-81D BG-4BR AB-27S AB-25BRU AB-1R GWA-8S BG-4D AB-28S AB-26D AB-2 GWA-91D BG-4S AB-29S AB-26S AB-21D GWA-9S GWA-16D AB-29SL AB-27D AB-4S AB-14BR GWA-16S AB-30S AB-28D AB-5 AB-4BR GWA-17D AB-35S AB-29D AB-6A AB-41D GWA-17S AB-39S AB-30D AB-6R CIF GWA-19D GWA-19S GWA-21D GWA-21S AB-31D AB-91D GWA-18D AB-31S AB-9S GWA-18S AB-32D GWA-14D GWA-22D AB-32S GWA-14S GWA-22S AB-33D GWA-15D GWA-23D AB-33S GWA-15S GWA-23S AB-34D GWA-1BR GWA-24BR AB-34S GWA-11D GWA-24D AB-35BR GWA-1S GWA-26D AB-35D GWA-26S GWA-61DA AB-36D GWA-2D PH WELL AB-36S GWA-2S AB-1 AB-37D GWA-3BR AB-8 AB-38D GWA-31D GWA-4S AB-39D GWA-3S GWA-5BR AB-23D GWA-41D AB-37S AB-38S Antimony (Unfiltered) - Allen 15- J 1:1110- • • s= • O O U • C O U • • 5- _ • • • • • 0- Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells USGS n=55 Boundary Boundary Background n=100 Groundwater n=52 n=61 n=83 n=61 Sample Location Type. Red Line: NC IMAC Standard (1 ug/L) 10.0 — • • °� i • i Cn • • • O • J _ I = • J - C - O (6 C 0 0.1 — c = O _ U - Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells USGS n=55 Boundary Boundary Background n=100 Groundwater n=52 n=61 n=83 n=61 Sample Location Type. Red Line: NC IMAC Standard (1 ug/L) Arsenic (Unfiltered) - Allen 9101ilz m 100 O J M U • • • 0 Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells USGS n=55 Boundary Boundary Background n=110 Groundwater n=52 n=73 n=83 n=122 Sample Location Type. Red Line: NC 2L Standard (10 ug/L) • • Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells n=55 Boundary Boundary Background n=110 n=52 n=73 n=83 Sample Location Type. Red Line: NC 2L Standard (10 ug/L) • USGS Groundwater n=122 Barium (Unfiltered) - Allen 1500 - J • • 0) 1000 - • s= O • • c O U C O • U 500 - mom 0- Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells USGS n=55 Boundary Boundary Background n=125 Groundwater n=52 n=73 n=83 n=77 Sample Location Type. Red Line: NC 2L Standard (700 ug/L) 1000 — N - M U - U) 0) O J — J - C O (6 C v 10 — c = O _ U I Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells n=55 Boundary Boundary Background n=125 n=52 n=73 n=83 Sample Location Type. Red Line: NC 2L Standard (700 ug/L) USGS Groundwater n=77 Boron (Unfiltered) - Allen 6000 - J 1 p 4000 c CD U C O U • 2000 - M 10000 — 100 — Ash Porewater Inside Waste Outside Waste Site Groundwater n=55 Boundary Boundary Background n=52 n=71 n=83 Sample Location Type. Red Line: NC 2L Standard (700 ug/L) 1 Ash Porewater Inside Waste Outside Waste Site Groundwater n=55 Boundary Boundary Background n=52 n=71 n=83 Sample Location Type. Red Line: NC 2L Standard (700 ug/L) Private Wells n=105 Private Wells n=105 Chromium (Unfiltered) - Allen 250 - 200 - • J 0 150- C • O c • 1100 - C • 0 U 50- • • i • � t 0- Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells USGS n=55 Boundary Boundary Background n=113 Groundwater n=52 n=73 n=83 n=124 Sample Location Type. Red Line: NC 2L Standard (10 ug/L) 100 — U - W 0) O J J 1 C O U Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells n=55 Boundary Boundary Background n=113 n=52 n=73 n=83 Sample Location Type. Red Line: NC 2L Standard (10 ug/L) • USGS Groundwater n=124 Cobalt (Unfiltered) - Allen 600 - 400 - J 1 C O C O U C O U 200 - • 0 100 — Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells USGS n=55 Boundary Boundary Background n=102 Groundwater n=52 n=35 n=70 n=2 Sample Location Type. Red Line: NC IMAC Standard (1 ug/L) Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells n=55 Boundary Boundary Background n=102 n=52 n=35 n=70 Sample Location Type. Red Line: NC IMAC Standard (1 ug/L) USGS Groundwater n=2 Iron (Unfiltered) - Allen 3e+05 - 2e+05 - C O U C U 1 e+05 - i Oe+00 • Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells USGS n=55 Boundary Boundary Background n=115 Groundwater n=52 n=73 n=83 n=2221 Sample Location Type. Red Line: NC 2L Standard (300 ug/L) 1e+05 — N U O J ;.1e+03- J 1 C O U C _ O U 1e+01 — Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells USGS n=55 Boundary Boundary Background n=115 Groundwater n=52 n=73 n=83 n=2221 Sample Location Type. Red Line: NC 2L Standard (300 ug/L) Manganese (Unfiltered) - Allen 30000 - J 20000 - C O U 10000 - 0 10000 — C - a> _ U - C - O _ U I i Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells USGS n=55 Boundary Boundary Background n=100 Groundwater n=52 n=73 n=83 n=813 Sample Location Type. Red Line: NC 2L Standard (50 ug/L) Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells n=55 Boundary Boundary Background n=100 n=52 n=73 n=83 Sample Location Type. Red Line: NC 2L Standard (50 ug/L) USGS Groundwater n=813 pH (Unfiltered) - Allen 12.5 - 5.0 - IN am A • Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells n=30 Boundary Boundary Background n=125 n=28 n=70 n=42 Sample Location Type. Red Line: NC 2L Standard (6.5 - 8.5) t t ' • . USGS Groundwater n=875 . Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells USGS n=30 Boundary Boundary Background n=125 Groundwater n=28 n=70 n=42 n=875 Sample Location Type. Red Line: NC 2L Standard (6.5 - 8.5) Sulfate (Unfiltered) - Allen 400 - ill J E C O 20 200 - WA GDOM m 100 — 0) - O J J E C O Ash Porewater n=55 • • • S • Inside Waste Outside Waste Site Groundwater Private Wells USGS Boundary Boundary Background n=121 Groundwater n=52 n=73 n=83 n=60 Sample Location Type. Red Line: NC 2L Standard (250 mg/L) i Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells n=55 Boundary Boundary Background n=121 n=52 n=73 n=83 Sample Location Type. Red Line: NC 2L Standard (250 mg/L) • USGS Groundwater n=60 Total Dissolved Solids (Filtered) - Allen 25000 - 20000 - 8 1 J 15000 - • O C i coi 10000 - c o = U 5000 - • • 0- Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells USGS n=55 Boundary Boundary Background n=126 Groundwater n=52 n=73 n=83 n=2014 Sample Location Type. Red Line: NC 2L Standard (500 mg/L) 10000 — a> _ M U _ C� 01 O J E - • C MOMO - 23 L 100 = o - • U - C - O - U _ ; • Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells USGS n=55 Boundary Boundary Background n=126 Groundwater n=52 n=73 n=83 n=2014 Sample Location Type. Red Line: NC 2L Standard (500 mg/L) Vanadium (Unfiltered) - Allen 75 - 25 U 100 — N M C O O = U - Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells n=55 Boundary Boundary Background n=117 n=52 n=35 n=70 Sample Location Type. Red Line: NC IMAC Standard (0.3 ug/L) Ash Porewater Inside Waste Outside Waste Site Groundwater Private Wells n=55 Boundary Boundary Background n=117 n=52 n=35 n=70 Sample Location Type. Red Line: NC IMAC Standard (0.3 ug/L) Appendix E Boron and Nitrate — Well AB-14D Appendix E: Historic Boron and Nitrate Concentrations Versus Time for AB-14D 140 120 100 60 40 Boron NO3 20 Jan-11 Jan-12 Jan-13 Date Jan-14 Jan-15 4000 3500 3000 J M 7 C O L 2500 U C O U N (9 L z 2000 1500 -1 1000 Jan-16