### 1

### 2 2. Synopsis :

2.1. Title: The impact of Coal Combustion Products on the quality of water resources in North Carolina 2.2. Project Type: Research 2.3. Focus Categories: WQL , HYDGEO, TS 2.4. Research Category (required by the USGS): Water Quality 2.5. Keywords : coal ash, water quality, contamination, metals, monitoring and regulations 2.6.Proposed Start Date: 03/01/2011 and End Date : 02/29/2012. 2.7. Investigator(s): PI: Avner Vengosh , Professor, Division of Earth and Ocean Sciences, Nicholas School of the Env ironment, Duke University, Durham, NC 27708; Phone: (919) 681

- 8050; Fax (919) 684

- 5833; E

- mail: vengosh@duke.edu Co

- PI: Heileen Hsu

- Kim

, Assistant Professor, Department of Civil & Environmental Engineering, Pratt Schoo l of Engineering, Duke University, Durham, NC 27708; Phone: (919) 660

- 5109; Fax: (919) 660

- 5219; email: hsukim@duke.edu 2.8. Congressional District of Duke University performing the research: Congressional District 4

2 .9. Abstract: Coal combustion products (CCPs) are known to contain toxic elements such as arsenic, selenium, and mercury. While a subset of CCPs is recycled for beneficial purposes, the majority of the waste is stored in more than 350 landfills and storage ponds across the nation. CCPs are not classified as hazardous waste, and as a result, these landfills and storage ponds are typically unlined and susceptible to leaks and failures. Moreover, discharge of effluents from storage ponds may pose an ecological hazard if they contain toxic elements leached from CCPs. Despite the risks, the hazards stemming from ongoing CCPs waste disposal practices have not been fully evaluated. In a recent nationwide survey of 431 holding ponds, 49 have been assigned a “high haz ard potential” rating by the EPA, and approximately one

- quarter of these are located in North Carolina. The objectives of this project are (1) determine the magnitude of CCPs contamination of associated water resources in NC; (2) evaluate the fate (e.g., r etardation) of key contaminants (arsenic, selenium, boron, strontium, barium, methylmercury) in water resources and the environmental factors that control these variations; (3) establish reliable monitoring tools for evaluating the impact of CCPs on NC wat er resources that can be used for state regulations; and (4) provide the scientific base for possible future state regulation on CCPs storage in NC. The project will include systematic sampling of effluents and affected surface water, pore water in lake se diments and groundwater in the vicinity of CCP storage ponds in NC, measurements of major elements, trace

- metals and boron isotopes composition for tracing leachates generated from CCPs, and modeling of species distribution in the investigated water. An ou tcome of this research will be a scientific evaluation of the environmental impacts of CCPs on the water resources in NC and establishing reliable monitoring tools for state regulation of the fate of contaminants that are generated from CCPs in NC. This in formation will also be needed for future regulatory actions expected from the EPA on CCPs disposal practices.

### 3 3. Project Description 3.1. Title: The impact of Coal Combustion Products on the quality of water resources in North Carolina

3.2. Statem ent of the regional or state water problem(s). Over five hundred power plants nationwide generate approximately 130 million tons of Coal Combustion Products (CCPs) each year, 43% of which is recycled into other materials while the remaining 70 million ton s is stored in 194 landfills and 161 ponds in 47 states [ 2 ]

. CCPs represent the largest industrial waste stream in the U.S.; however, they are not classified as hazardous waste. As a result, disposal storage ponds an d landfills are generally unlined and, in many instances, may not be adequately monitored with respect to their effects to groundwater and surface waters. One of the major potential hazards of coal ash storage ponds is the continuous leaching of contaminan ts and their transport to the hydrological system. Because monitoring results from discharges of holding ponds and landfills are scant, the long

- term environmental impacts of leachates generated from CCPs are unknown. In a recent nationwide survey of 431 holding ponds, 49 have been assigned a “high hazard potential” rating by the EPA [ 3 ] , and approximately one - quarter of these are located in North Carolina (the mos t of any state; Fig. 1). Despite the large amount of CCP wastes that are generated and disposed annually in NC, the risks associated with disposal practices are not well known, particularly in light of a recent coal ash spill at the Tennessee Valley Autho rity (TVA) Kingston Fossil Plant in Harriman, TN. On December 22, 2008, a breach in the retaining wall for the CCP storage pond resulted in the accidental release of approximately 4.1 million m 3 of coal ash onto the surrounding land surface and into the ad jacent Emory and Clinch Rivers [ 4 ] . This disaster w as the largest coal ash spill in U.S. history and brought waste storage practices for CCPs to the nation’s attention [ 5 ]

. Consequently, the EPA has recently reviewed its regulations with respect to the definition of CCPs and modes of its disposal [ 6 ] . In NC, an increasing public awareness has called to impose new regulations on storage and reuse of CCPs (e.g., Sierra Club report, [ 7 ] ).

Table 1: Summary of power plant sites in NC (see location in Fig. 1), energy production, and updated average flow data (million gallons per day, MGD) for ash pond and cooling water discharge s from June 2007 to June 2010. Data was provided by the Division of Water Quality, Surface Water Protection, North Carolina Department of Environment and Natural Resources.

### 4 Nine coal fired plants in North Carolin a (Table 1) discharge a total of 554.1 million gallon per day (MGD) of effluents from ash holding ponds and 431 5

. 4 MGD of cooling water (see distribution in Table 1). This massive discharge has a significant impact on the hydrological balance of the water resources associated with these outflow sites and, moreover, on their water quality. The objective of this project is to provide systematic water quality data for each of these sites. Previous data and our own preliminary measurements (see below) suggest t hat effluents that are discharged from the ash ponds have high contents of contaminants originated from coal ash. In addition, a larger volume of effluent is discharged from the coal

- fired plants as cooling water (Table 1) with an assumption of higher wate r quality, but without any supported data. This project will also provide a systematic analysis of the quality of cooling water effluents, given the huge volume of their discharge to the water resources of NC. The highest volume of ash pond effluents in NC is discharge from the Roxboro Steam Station (average flow of 502 MGD) into Hyco Lake (Fig. 2). A preliminary survey by the Division of Water Quality Surface Water Protection at the North Carolina Department of Environment and Natural Resources (DENR) [ 8 ] has shown that the levels of contaminants, particularly selenium, arsenic, thallium and boron, in the outfall ( NPDES OUTFALL 003) of Roxboro Steam Station (NC0003425) to Hyco Lake i s extremely high. From June 3, 2008 through June 2, 2009, fifty

- three weekly samples were collected from Outfall 03. The data show that the annual Figure 1. Proposed sampling locations of nine surface water sites in North Carolina those receive direct runoff or effluent from CCP storage ponds from coal power plants.

### 5 discharge had Se concentrations in the range of 5 to 23 ppb, mostly above 5 ppb, which is the EPA Criterion C ontinuous Concentration (CCC) for aquatic life. The As concentrations varied from 5 to 16 ppb relative to 10 ppb, which is Maximum Contaminant Level (MCL) for drinking water. Thallium (Tl) concentrations yielded a mean of 3.8 ppb (the North Carolina Water Quality Standard/ Environmental Protection Agency Criteria for Tl is 0.24 ppb and for Water Supply waters and Human Health based on fish consumption is 0.47 ppb). Boron concentrations varied from 500 to 1100 ppb, which is much higher as compared to typical streams and rivers in NC (<50 ppb) [ 8 ]

. The DENR study from Hyco Lake also revealed high concentrations of Se and As in fish tissues. The median concentration of Se in the fish s amples (n=21) collected in 2009 of was 2.7 mg/kg

, with 15 of 21 fish tissue sample results above the EPA Subsistence Fisherman Contaminant Level of 2.457 mg/Kg

, and 6 of 21 were above the EPA Criteria for Wildlife Protection Contaminant Level of 3.0 mg/kg. For arsenic all of 44 samples had As levels above the EPA Recreational Fisherman concentration of 0.026 mg/kg [ 8 ]

. Discharge of mercury is known to occur; however, the fate of Hg i n Hyco Lake is less certain. Mercury differs from other contaminants (e.g., arsenic, selenium) in that this metal is a concern if converted to methylmercury in benthic sediments of lakes and streams and bioaccumulated in the food web. Mercury analyses in t he DENR study [ 8 ] did not use the most sensitive methodology; thus, mercury was not detected in the discharge to Hyco Lake (<200 ng/L). However, in process water effluents, Progress Energy (the operator of the Roxboro plant) reported concentrations up to 747 ng/L, much greater than EPA surface water guidelines (< 12 ng /L). While mercury is released directly to Hyco Lake, significant bioaccumulation in recreational fish was not observ ed [ 8 ] . Coal ash wastes are expected to contain forms of mercury that are bioavailable to sediment microorganisms that methylate mercury (mainly sulfate

- reducing bacteria). In additi on, our previous work demonstrated that CCPs contain large quantities of leachable sulfate [ 5 ] that is capable of stimulating methylmercury production, particularly in freshwater settings. While mercury methylation may be active in receiving water sediments; food web accumulation in Hyc o Lake may be confounded by excess selenium, which is known to counteract trophic transfer of mercury. In light of these unknowns, additional data on methylmercury levels in the receiving waters of CCP storage pond effluents is needed understand the overal l risks associated with Hg in CCPs.

3.2.1. Preliminary results from Hyco Lake, NC As the first stage to evaluate the quality of water resources in NC that are affected by direct discharge of effluents from coal ash holding ponds and cooling water, we i nitiate a preliminary sampling (November 2009, February 2010, August 2010) of Hyco Lake (Fig. 1). Hyco Lake receives a large volume of effluents from Roxboro Steam Station (Table 1). Time series analysis of the three sampling campaigns reveals that the co ncentrations of leachable coal ash contaminants (LCACs) [ 5 ] such as boron vary significantly with time, showing high levels during relatively low lake levels (Fig. 2). These variations indicate that an assessment of the contribution of coal ash effluents to the water quality of surface waters in NC should consider both variations in the effluent composition and hydrological conditions, such as water level (i.e., dilution factor). A detailed investigation of the lake water chemistry in August 2010 indicates that the LCACs in Hyco Lake can be divided into two groups based on their geochemical variations: (1) elements that behave conservatively in the lake water (Ca, Mg, B, Se, Li, Sr, Cr) and their concentrations are depended on the mass balance between the coal ash effluents and pristin e water (Fig. 3); and (2) elements that associated with the redox state of the water (As, Ba, Mn) and show relatively high concentrations in anoxic deep water during thermal stratification of the lake (Fig. 4). These results are consistent with similar tre nds in leachable LCACs in areas impacted by the TVA coal ash spill in Kingston, TN that observed in our previous investigations

### 6 [ 5 ] . Consequently, low redox potential at the la ke bottom water after seasonal thermohaline stratification of the water column can enhance mobilization of tra ce elements that are retained by the lake sediments under oxic conditions.

It should be noted that the high boron concentrations (~1000 ppb) we found in Hyco Lake is associated with relatively low arsenic (2

- 7 ppb) and se lenium (1

- 2.5 ppb) contents. However, the consistent variations of As and Mn with depth and redox condition (Fig. 4) indicates that reductive dissolution of Mn

- oxides (and possibly Fe

- oxides) releases As to the bottom lake water. This phenomenon can explai n the apparent inconsistency; low As in the lake water relative to high As in fish tissues from the lake [ 8 ]. We therefore propose that As enrichment and bioaccumulation may occur in reduced zones in affected lakes (bottom water, pore water) due to the sensitivity of As to redox conditions and speciation (see in Section 3.6). The notion that CCP storage pond impact can simply be quantified by measurements at the receiving water surface may not be fully approp riate. The overall impact of coal ash effluents on water resources will be the focus of this proposed project. We propose to investigate temporal (changes of hydrological conditions) and spatial (depth profile, pore water) Figure 2

. Variation of boron concentrations as compared to water level (USGS data) changes in Hyco Lake. Note that high boron contents were recorded during periods of low lake levels.

Figure 3

. Variations of boron and selenium versus calcium contents in Hyco Lake as measured during August 2010. Simil ar linear correlations were observed for Mg, Sr, Li, and Cr, which suggest that the concentrations of these elements depend on mixing relationships between coal ash effluents and pristine water.

### 7 water quality variations that wil l ensure a reliable assessment of this potential impact.

Finally, we measured the boron isotope composition of Hyco Lake. The δ 11 B results (see section 3.6 for explanation of the definition of δ 11 B) was

- 2.4 ‰, which is consistent with our previous res earch [ 5 ]

, in areas impacted by the TVA coal ash spill (i.e., elevated boron and negative δ 11 B value). These observations indicate that boron isotopes may be useful as a tracer of oxyanions (As and Se) released by CCP s’ storage ponds.

3.3. Statement of results or benefits The proj ect aims to provide an assessment on the water quality status of water resources that are associated with long

- term discharge of effluents from major CCP holding ponds and storage sites in NC. The study will provide a scientific evaluation for the fate of contaminants that are generated in CCPs holding ponds and transported into the environment. The results of the study will address some of the key questions related to the impact of CCPs on water resources in NC:

• What is the extent and magnitude of contamin ation of water resources in NC by long

- term and unmonitored discharge of effluents from the major CCP holding ponds in NC?

• What is the impact of the large volume of cooling water discharged from coal fired plants on water resources in NC? Can we assume tha t cooling water has low levels of contaminants?

• Is mixing and dilution the key process that controls the actual contaminant concentrations in the affected lakes and rivers?

• What are the other biogeochemical processes that cause differential distribution of contaminants in the affected water resources?

• What are the ecological and water management risks that are associated with continued discharge of CCP effluents to water resources in NC?

• Would changes in water availability (e.g., increased upstream use , consecutive droughts induced from climate change) and/or environmental conditions (e.g., rise in temperature, redox conditions) in the affected water resources increase the contamination risks of these resources?

Given that the EPA is reconsidering was te disposal requirements for CCPs (i.e., Figure 4

. Variations of dissolved (< 0.45 μ m) manganese, arsenic, and barium concentrations with water depth at Hyco Lake during August 2010. The relatively enrichment of these elements with depth is associated with reducing conditions and thermohaline stratification of the lake water, which

sugge sts that reductive dissolution of Mn

- oxides and release of As to the lake

water.

### 8 reclassification as hazardous materials) and effluent discharge from CCP holding ponds might require much more rigorous permission procedures that includes water quality assessments, this project will provide DENR a nd other state and federal agencies the scientific basis for adequate monitoring tools for tracing the impact of CCP contaminants on water resources. The project is also designed to evaluate the changes of each of the contaminants that is associated with C CP’s discharge, delineate the geochemical processes that affect contaminant distribution, and provide a theoretical framework for predicting their abundance under different environmental conditions (pH, redox state, salinity).

3.4. Nature, scope, and obje ctives of research This project aims to evaluate the impact of Coal Combustion Products (CCPs) on the quality of water resources in North Carolina by integration of existing database and generating additional field

- based water quality data. For several dec ades CCPs have been stored in landfills and holding ponds in NC (Fig. 1) without systematic evaluation of the impact of leachates generated from CCPs on associated water resources. The literature and our own previous investigations [ 9

- 18 ] have shown that leachates that are generated from CCPs are enriched in contaminants such as arsenic, selenium, boron, strontium, thallium, and barium that could affect the ecological sy stem upon migration into the environment. The objectives of this project are (1) determine the magnitude of contamination of impacted water resources in NC by effluents discharged from CCPs holding ponds and cooling water; (2) evaluate the fate (e.g., ret ardation) of key contaminants (arsenic, selenium, boron, strontium, barium, methylmercury) in water resources and the environmental factors that control these variations; (3) establish reliable monitoring tools for evaluating the impact of CCPs on NC water resources that can be used for state regulations; and (4) provide the scientific basis for possible future state regulation on CCP storage in NC. We hypothesize that (1) the geochemical tracers we have developed in our previous investigation of the TVA co al ash spill in Kingston TN [4

- 5] , which consist of trace metals (arsenic, selenium, boron, strontium, barium) and boron isotope composition [ 5

, 9 ] , are capable of elucidating contaminants that originate from CCP s leachate s in affected water resources; and (2) the environmental conditions (pH, redox state) control the species distribution of oxyanions (arsenic, selenium, boron) [1, 10

- 11] and mercury [19

- 20] in the water and thus their reactivity with the host sediments (lake) or aquifer rocks (groundwater). We will test these hypotheses by systematic sampling of water bodies located in the vicinity of CCP storage ponds in NC (Fig. 1), quantifica tion of major elements, trace

- metals and boron isotopes, and modeling of species distribution in the investigated water. The fieldwork will include in

- situ measurements (pH, temperature, DO, EC, redox potential) and systematic sampling of surface water and groundwater (Fig. 1). In the lake sites, we will also collect water column, sediment and sediments pore water at different depths and distances from the effluent discharge areas. Groundwater samples will be collected from wells located both upstream and d ownstream from CCPs holding ponds. We will collect water and sediment samples using standard procedures for trace metal analyses. In filtered (0.45 mm) and unfiltered grab samples, we will quantify major and trace metals (Ca, Mg, Fe, Li, B, V, Cr, Mn, As, Co, Ni, Zn, Se, Rb, Sr, Mo, Cd, Sb, Ba, TI, Pb,Th, and U) by ICP

- MS and major anions by ion chromatography and integrate new data with the existing state database of the Division of Water Quality of DENR . We will also quantify isotopic compositions of bor on by thermal ionization mass spectrometry (TIMS) . Total Hg and methylmercury (MeHg) concentration will be determined by atomic fluorescence spectroscopy using standard EPA methods. We will utilize chemical equilibrium models (e.g., MINEQL+ ) to
assess aque ous phase speciation and saturation index. In particular, we will investigate how the species distribution of arsenic (As V and As III ), selenium (Se VI and Se IV ), boron (B(OH) 3 and B(OH) 4 - ), and methylmercury are controlled by environmental factors (redox, pH). We will use boron isotopes to verify and quantify the impact of CCPs on the investigated water resources.

### 9 We plan to perform a field sampling at each of the major sites in NC (Table 1) as the first stage of the research. For some sites, (e.g., Hyco la ke) we will collect water samples on a monthly basis to monitor possible seasonal changes in both effluents and affected water compositions. Since we have already established our field and analytical procedures, we will be able to begin the research as soo n as the first month of the project period.

3.5. Methods, procedures, and facilities We will perform systematic measurements of surface waters and groundwater associated with CCP holding ponds in North Carolina coal

- fired plants (Figure 1, and Table 1) . The EPA reported in a recent survey of 431 holding ponds in the nation, 49 have been assigned a “high hazard potential” rating, and approximately one

- quarter of these are located in North Carolina (the most of any state). We propose 9 field sessions for one

- year project at 9 different sites that receive effluent or runoff from holding ponds at coal

- fired plants (Figure 1; Table 1). Fieldwork and sampling will be coordinated with staff of the Division of Water Quality, Surface Water Protection, North Caro lina Department of Environment and Natural Resources (DENR). We have already established effective and productive working relations with DENR (see attached support letter), which will guarantee the successful operational and data assimilation that will be generated in this project. The fieldwork will include in

- situ measurements (pH, temperature, DO, EC, redox potential) and systematic sampling of surface water at different water depths, pore water extracted from lake and river sediments, sediments in lake s and rivers in the vicinity of the discharge areas, and groundwater in affected areas (Asheville site). In the lake sites, we will collect pore water and sediments with Wildco Box core (25 cm depth) and Russian Peat core (up to 1 meter depth) from differe nt depths and distances from the effluent discharge areas. Groundwater samples will be collected from wells located both upstream and downstream from CCP holding ponds. We will follow standard quality assurance practices for the collection and analysis of water and sediment samples for trace element determination. These protocols including polyethylene or polycarbonate containers rinsed overnight in an acid bath followed by rinsing with ultrapure water. For mercury, fluoropolymer or glass containers will be used. Trace

metal grade acids will be used to preserve samples. Samples will be collected using clean hands protocols, stored in plastic bags, and refrigerated during transport. In the laboratory, open sample containers will be handled in a HEPA

- filtered laminar flow hood. Sample analyses will be based on standard calibrations (performed daily) and verified with NIST

- certified reference materials. The acceptance criteria for data quality will vary depending upon the type of data collected. In general, a r elative standard deviation of less than 10% for replicate chemical analyses would indicate good precision. Bias ( i.e. , systematic error) will be determined for each method of analyses by method blanks, equipment blanks, and matrix spike recoveries. Precisi on will be analyzed through replicate samples and specified by the percent relative standard deviation. The effluents of holding ponds will be collected by either direct access (as we have done with TVA) or through sampling in the receiving water directly downstream of discharge points. In filtered (0.45 mm) and unfiltered grab samples, we will quantify major and trace metals by ICP

MS, major cations by DCP, and major anions by ion chromatography. Total Hg concentration will be determined by cold vapor ato mic fluorescence spectroscopy (EPA Method 1631). Methylmercury (MeHg) concentration in water and sediments will be determined by distillation, ethylation, chromatographic separation followed by atomic fluorescence spectroscopy (EPA method 1630) [22]

. We will measure the isotopic compositions of boron ( 11 B/ 10 B) by thermal ionization mass spectrometry (TIMS) technique at Duke University.

### 10 3.5.1. Facilities, Equipment, and Other Resources at Duke University: 1) Tr ace Metals, and thermal ionization mass spectrometer (Avner Vengosh)

Facilities in the Division of Earth and Ocean Sciences Division at the Nicholas School of the Environment at Duke includes a VG PlasmaQuad

- 3 inductively

- coupled

- plasma mass spectrometer ( ICP

- MS) equipped with the S

- option pump for increased sensitivity and a UC laser

- ablation microprobe for spot analyses to 6 microns (for ultra

- trace element spot analyses in the ppb levels). Detection limits (defined as peak:blank ratios of 3:1) have been demonstrated at <1 ppt for heavier elements (mass ratio greater than 80) and <5 ppt for most lighter elements. The ICP

- MS is capable of measurements with high precision and accuracy for a large range of trace metals in the ppb level. For boron isotope mea surements a Thermo Scientific TRITON thermal ionization mass spectrometer (TIMS) in a dedicated facility. The TRITON is a new TIMS with the most precise and accurate isotope ratios for positive and negative ions. The instrument was installed in February 20 08. 2) Environmental Engineering Laboratory (Hsu

- Kim) include the following equipment relevant to the proposed research:

• Leeman Labs Prism Inductively

- Coupled Plasma Optical Emission Spectrometer (ICP

OES) for element analysis at ppb levels or higher

• Agi lent 7700 Series ICP

- MS with helium collision cell capability for removal of polyatomic interferences during detection of trace elements at parts

- per

- trillion levels.

• Brooksrand MERX cold vapor atomic fluorescence spectrophotometer for total mercury detec tion at 0.5 ng/L or greater

• Milestone Direct Mercury Analyzer (for Hg in solids and sediments)

• BrooksRand distillation, purge

- and

- trap, cryogenic gas chromatogaph apparatus for methylmercury analysis in water and sediment

• Total Organic Carbon Analyzer (Shi madzhu)

• UV

- Vis spectrophotometer with integrating sphere

• Varian high performance liquid chromatograph (HPLC) system with photodiode array and fluorescence detectors

• Two trace metal

- clean HEPA

- filtered laminar flow work stations

• COY anaerobic vinyl glove bo x

• numerous fume hoods

• Barnstead Nanopure water filtration system (>18 M Ω

- cm resistivity).

3.6. Related research
3.6.1. Introduction Toxic elements are capable of leaching from CCPs storage locations, either through continuous discharge of effluents (e.g ., holding ponds) or from accidental releases (e.g., TVA coal ash spill) that affect the quality of associated receiving waters. In some cases, however, contaminants are not readily leached from CCPs. Such instances depend on the type and/or origin (e.g., bottom versus fly ash) and composition of the CCPs, the concentration of trace metals in the original coal source, combustion process parameters, treatment (e.g., flue gas desulfurization (FGD) for removing sulfur dioxide), and environmental conditions for disposal (e.g., storage pond water chemistry, redox condition). CCPs generally represent a mixture of solid wastes from various stages of coal combustion and flue gas treatment (e.g., bottom ash, fly ash, boiler slag, FGD material). CCP wastes that are di sposed in holding ponds and landfills typically consist mostly of fly ash and bottom ash [ 23 ]

.

### 11 3.6.2. Metals and metalloids mobilization from CCPs: the dependence on species distribution Numerous studies have shown that coal ash contains high levels of toxic metals and metalloids that can harm the enviro nment. Some of these elements are soluble in water and easily extracted in aquatic systems [10, 16

- 17, 24

- 31] . Our previous investigation of the TVA coal ash spill in Kingston, TN [ 5

, 9 ] and Hyco Lake in NC showed relatively high levels of As, Se, B, Ba, and Sr in water associated with CCP discharge . This proposal focuses particularly on evaluating the reactivity of these elements and Hg and the conditions that could enhance their mo bilization and bioavailability in aquatic systems. Arsenic and selenium mobilization: Mobilization of arsenic and selenium from CCPs and their contents in CCP leachates depend on the environmental conditions (acidity, redox, solids/liquids ratio, time, tem perature), the chemical composition of the water medium and the properties of ash itself (content of metals, acidity) [ 11

, 32 ] . As and Se leaching from acidic ashes are likely controlled by the formation of surface complexes with Fe

- and Mn

- o xides, while the leaching from alkaline ashes are controlled by the solubility of calcium coprecipitates in the ash [ 14 ] . Previous studies have also shown that arsenic in CCPs exist predominantly as the oxidized As(V) species while selenium exists as the intermediate valence Se(IV) [1, 12

- 13, 15, 33] . W ang et al. [ 11 ] have shown (and we have confirmed by our preliminary leaching experiments) that As and Se contents in leachates vary with pH, in accordance to sorption trends typical for oxyanions: low and high pH conditions induce higher As and Se mobilization relative to neutral pH (Figure 5). The species distribution of As and Se leached into solution will depend not only on pH, but also on redox conditions. Under reducing conditions, arsenic species consist of arsenite (As III ), which occurs as the uncharged species H 3 AsO 3 at neutral pH and dissociates to H 2 AsO 3 - under high pH conditions (pK a =9.3). Under oxic conditions, arsenate (As V ) is composed of arsenic acid (H 3 AsO 4 0 ) with pK a dissociation constants of 2.3, 6.8 and 11.3 ( [ 1 ] ; Figure 5). Selenium species distribution also depends on pH and redox. In reducing conditions, selenium occurs in natural systems as Se IV or Se 0 while in oxidizing conditions selenium occurs as Se VI (selenate). Se VI is found as H 2 SeO 3 0 , HSeO 3 - , and SeO 3 2

- with acid dissociation constants of 2.6 and 8.3 ( [ 1 ] ; Figure 5). Se(0) readily forms an insoluble elemental Se precipitate. At low pH (less than pH ~2) uncharged H 3 AsO 3 0 and H 2 SeO 3 0 species are predominant (Figure 5), which results in high mobi lization of both As and Se. Under near neutral pH, the charged anion species adsorb more strongly to mineral oxides; thus, their mobilization is limited. At high pH values, deprotonation of hydroxyl groups on mineral surfaces and increased competition from OH - ions results in an overall decrease in As and Se anion sorption. However at higher pH values, both AsO 4 3

- and SeO 3 2

- are capable of precipitating with Ca

Figure 5. Modeling of the distribution of arsenic, selenium and boron species in fresh water conditions as a function of pH, based on literature values [ 1 ] of the dissociation constants of the weak acids of arsenic, selenium and boron. Note the distinction between reduced and oxidized states of a rsenic.

### 12 compounds (e.g., Ca

- arsenate [ 34 ] ), and thus, their mobilization would be dependent on the Ca content of the solution. Consequently, Wang et al. [ 11 ] showed that sub

- bituminous coal ashes leached more Ca than the bitum inous coal ashes, which resulted in significantly lower As and Se leaching from sub

- bituminous coal ash. Our preliminary results confirm this phenomenon, particularly with the coal ash from the Duke University coal power plant. Compared to the TVA Kingston ash, the lime

- treated Duke ash contained more leachable Ca, causing a reduction of dissolved As and Se at high pH leaching conditions. Boron mobilization: Similar to As and Se, boron in aquatic solution occurs as the uncharged boric acid (B(OH) 3 0 ) and bor ate ion ((B(OH) 4 - ), depending on solution pH (Figure 5), salinity, and temperature. The adsorption of boron on oxides and clay minerals show maximum adsorption (i.e., less leaching) in the pH range 8

- 9, indicating that the borate anion adsorbs more signifi cantly than the uncharged boric acid species [ 35

- 38 ] . Under high pH conditions, high concentrations of hydroxide ions compete with borate ions for adsorption sites. Si nce the dissociation of boric acid depends on salinity and temperature, the relative proportion of boron species in the solution would affect boron mobilization from CCPs. At high pH conditions borate can condense onto CCP particles through the formation o f ion

- pairs with Na, Ca, and Mg [ 35

- 38 ] , resulting in removal of boron from solution and a decrease in apparent boron reactivity with leachates. The similarity of boro n reactivity and species distribution to those of As and Se makes boron a unique tracer that can potentially mimic the mobilization of these oxyanions. In this study, we will use an approach that combines total boron content in leachates and boron isotope fractionation to delineate the role of species distribution on the mobilization of As and Se from CCPs. We will use the known dissociation constant of boric acid and its variation with salinity and temperature [ 39 ] to model the boron species distribution under the controlled experiments and predic t the isotopic composition of dissolved boron in the leachates. These models would provide a better assessment of the reactivity of boron in the natural conditions and a direct evaluation of the retardation of boron and its reactivity with sediments or aqu ifer materials. 3.6.4. Fate of metals and metalloids in the environment: the role of acidity and redox state

CCPs are not classified as hazardous waste; thus, discharge from landfills and holding ponds is not always controlled or monitored. Accumulation of As, Se, B, Hg, and other metals in leachates originating from CCPs may therefore pose an ecological risk if the waste is improperly disposed of or accidentally released to the environment. Consequently, the conditions prevailing in holding ponds and landf ills would control the reactivity of these elements and their fate in the environment. The literature shows that acidity and redox potential are two water chemistry variables that are critical to the fate of these elements. However, most hazard assessments of CCP waste materials only address leaching related to acidity. Much less is known concerning transformations induced by redox gradients. As shown earlier, the speciation of As, Se, B, and Hg would control the mobilization of these elements from CCPs an d would also determine their fate in the environment. For example, As in CCPs occurs in the As(V) form, but could be converted to the more mobile As(III) form under anaerobic conditions [ 45 ] (e.g., landfill, sediments with high organic content). Likewise, the adsorption of Se (IV) would decrease with pH as the fraction of selenium as SeO 3 2

- increases [ 1 ] (Figure 2 and 3). Thus at pH>7.5, the mobility of Se (IV) in pore water is expected to be high, unless SeO 3 2

- is precipitated into calcium selenates in the presence of high Ca contents in CCPs [ 11 ] . Under strongly reducing conditions such as those found in organic matter

- rich wetland sediments, Se is often immobilized by conversion to an elemental Se(0) solid phase (e.g., [ 46 ] ). Further reduction to Se(

- II) would result in insoluble metal selenides (Fe

selenides, Cu

- selenides, HgSe). In contrast, boron speciation would not be affected by the redox state, only by the pH conditions. Our preliminary results from the NSF RAPID projec t

### 13 confirm this model. Data from pore water extracted from sediments in which ash has accumulated due to the TVA coal ash spill in the Clinch River, downstream from the spill area, show significantly high As/Se ratios relative to both laboratory experiments and surface water contamination in the tributar y area (the Cove ). The high As/Se ratios are associated with predominance of the reduced As(III) and low of dissolved oxygen, inferring anaerobic conditions. In the proposed project we will model the relation ships between As, Se, and B species, for predicting their behaviors under given temperature, pH, and redox conditions.

3.6.5.Boron isotope as a tracer of CCPs Boron has two stable isotopes ( 11 B/ 10 B ratio ~4), which has a large variation in nature due to t he large fractionation of relatively light isotopes. The boron isotope ratio has been used to trace groundwater contaminants such as agricultural runoff, wastewater, and petroleum waste [ 47

- 50 ]

. Williams and Hervig [ 51 ] studied B isotopic values of different coals in the U.S. and determined that 11 B was highly depleted in coal compared to most terrestrial rocks. Thus, coal is characterized by negative δ 11 B values (as low as

- 70‰) relativ e to the international standard ( δ 11 B is defined as [( 11 B/ 10 B) sample / ( 11 B/ 10 B) NIST

- SRM951 - 1] × 1000 where the units are reported in per mil). Limited data on the boron isotope ratios in CCPs suggest that coal ash has δ 11 B values (ranging from

- 4 to

- 19‰) th at are similar to the coal [ 47

, 52 ] , although the direct relationship between the composition of co

- existing coal and CCPs, nor the mechanisms that control boron isotopic fractionation in CCPs, have not ye t been established. The boron isotope fractionation depends on the distribution of boron species [ 53 ] , which in turn is controlled by the salinity, temperature, and pH. Boric acid is en riched in 11 B while the borate anion is enriched in 10 B. The dependence of boron isotope variations on pH and salinity could be used to determine the conditions in which CCP leachate

- derived boron interacts with sediments or aquifer rocks and as an indirec t proxy for the mobilization of Se and As, which also depends on pH conditions. Our leaching experiments of the TVA ash showed depleted δ 11 B values, in the range of

- 14 to

- 18‰, which is consistent with results from surface water in a region of limited water exchange (“Cove” in Figure 4) from the TVA spill area of low δ 11 B values of

- 13‰. These isotope ratios are significantly different fr om upstream Emory River (+10 to +15‰), which represents meteoric boron. Slightly contaminated river water downstream from the ash spill in Emory and Clinch R ivers showed intermediate δ 11 B values of 0 to +5‰. These results clearly demonstrate the sensitivi ty of boron isotopes for tracing dissolved boron that is derived from CCPs leaching in aquatic systems.

3.7. Training potential. This project is based on the research of two graduate students from the Nicholas School of Environment ( Laura Ruhl ) and Prat t School of Engineering ( Amrika Deonarine) . In addition, we expect 2

- 3 more undergraduate students to be involved in this study as part of their honors thesis. Furthermore, the research will be the based of the course “ Coal Combustion Products and Their Im pact on the Environment: Exploration of the coal ash spill in Kingston Tennessee” that is given to master’s students as part of the Master of Environmental Management (MEM) at the Nicholas School of Environment. Students in this course will visit the prop osed field sites as part of the class.

### 14 4. References Cited : 1. Plant, J.A., et al., Arsenic and Selenium , in Treatise on Geochemistry , D.H. Heinrich and K.T. Karl, Editors. 2003, Pergamon: Oxford. p. 17

- 66. 2. Lombardi, K. Coal A sh: The hidden story; How Industry and the EPA Failed To Stop a Growing Environmental Disaster 2009; Available from: http://www.publicintegrity.org/articles/entry/1144

. 3. U.S. Environmental Protection Agency. Coal Combustion Residues (CCR)

- Surface Impoundments with High Hazard Potential Ratings . 2009 7/12/10]; Available from: http://www.epa.gov/waste s/nonhaz/industrial/special/fossil/ccrs

- fs/index.htm

. 4. Tennessee Valley Authority. Corrective action plan for the TVA Kingston fossil plant ash release . 2009; Available from: http://www.tva.gov/kingsto n/index.htm

. 5. Ruhl, L., et al., Survey of the potential environmental and health impacts in the immediate aftermath of the coal ash spill in Kingston, Tennessee. Environmental Science & Technology, 2009. 43 : p. 6326

– 6333. 6. U.S. Environmental Protectio n Agency. Hazardous and Solid Waste Management System; Identification and Listing of Special Wastes; Disposal of Coal Combustion Residuals From Electric Utilities . 2010 7/13/2010 7/12/10]; June 21, 2010 [Available from: http://www.epa.gov/epawaste/nonhaz/industrial/special/fossil/ccr

- rule/index.htm

. 7. Sierra Club, N.C.C., Unlined Landfills? 2010. 8. Smith, S.D.a.R., A., Hyco Lake Roanoke River Basin Person County : Roxboro steam electric plant NPDES final outfall data analysis , N.D.o.W.Q.S.W. Protection, Editor. 2010: Raleigh, NC. 9. Ruhl, L.S., A. Vengosh, and G. Dwyer. Boron and Strontium Isotope proxies for tracing the environmental impact of the TVA coal ash sp ill, Kingston, TN . in Geological Society of America Annual Meeting . 2009. Portland, OR. 10. Yudovich, Y.E. and M.P. Ketris, Arsenic in coal: a review. International Journal of Coal Geology, 2005. 61 : p. 141

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- 2966. 12. Huggins, F.E., et al., Selenium and Arsenic Speciation in Fly Ash from Full

- Scale Coal

Burning Utility Plants. Environmental Science & Technology, 2007. 41 (9): p. 3284

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- amended soils using ion chromatography inductively coupled plasma mass spectrometry. Environmental Science & Technology, 1999. 33 : p . 270

- 275. 14. van der Hoek, E.E. and R.N.J. Comans, Modeling arsenic and selenium leaching from acidic fly ash by sorption on iron (hydr)oxide in the fly ash matrix. Environmental Science & Technology, 1996. 30 : p. 517

- 523. 15. Narukawa, T., et al., Inves tigation on chemical species of arsenic, selenium and antimony in fly ash from coal fuel thermal power stations. Journal of Environmental Monitoring, 2005. 7 (12): p. 1342

- 1348. 16. Hower, J.C., et al., Major and minor element distribution in a coal

- fired u tility boiler in KY. Energy Sources, 2006. 28 (A): p. 79

- 95. 17. Meij, R., Trace elements behavior in coal fired power plants. Fuel, 1994. 39 : p. 199

- 217. 18. Swaine, D.J. and F. Goodarzi, Environmental aspects of trace elements in coal . 1995, Dordrecht, Th e Netherlands: Kluwer Academic Publishers. 19. Fleming, E.J., et al., Mercury methylation from unexpected sources: Molybdate

- inhibited freshwater sediments and an iron

- reducing bacterium. Applied and Environmental Microbiology, 2006. 72 (1): p. 457

- 464. 20. Gilmour, C.G., E.A. Henry, and R. Mitchell, Sulfate stimulation of mercury methylation in freshwater sediments. Environmental Science & Technology, 1992. 26 (11): p. 2281

- 2287.

### 15 21. U.S. Environmental Protection Agency, Method 1631, Revision D: Mercury in W ater by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectroscopy . 2001: Washington, D.C. 22. U.S. Environmental Protection Agency, Method 1630; Methyl Mercury in water by Distillation, Aqueous Ethylation, Purge and Trap, and CVAFS . 2001: Washington, DC. 23. American Coal Ash Association. 2008 Coal Combustion Product (CCP) Production and Use Survey Report . 2009; Available from: http://www.acaa

- usa.org

. 24. Elseewi, A.A., A.L. Page, and S.R. Grimm, Chem ical characterization of fly

- ash aqueous systems. Journal of Environmenal Quality, 1980. 9 : p. 424

- 428. 25. Querol, X., J.L. Fernandez

- Turiel, and A. Lopez

- Soler, Trace elements in coal and their behavior during combustion in a large power station. Fuel, 1 995. 71 (3): p. 331

- 343. 26. Cornelis, G., et al., Leaching mechanisms of oxyanionic metalloid and metal species in alkaline solid wastes: A review. Applied Geochemistry, 2008. 23 : p. 955

- 976. 27. Hower, J.C., et al., Association of the sites of heavy metal s with nanoscale carbon in a Kentucky electrostatic precipitator fly ash. Environmental Science & Technology, 2008. 42 : p. 8471

- 8477. 28. Hower, J.C., et al., Characteristics of coal combustion products (CCP's) from Kentucky power plants, with emphasis on mercury content. Fuel, 2005. 84 : p. 1338

- 1350. 29. Sakulpitakphon, T., et al., Tracking mercury from the mine to the power plant: geochemistry of the Manchester coal bed, Clay County, Kentucky. International Journal of Coal Geology, 2004. 57 (2): p. 127

- 141

. 30. Mardon, S.M. and J.C. Hower, Impact of coal properties on coal combustion by

- product quality: examples from a Kentucky power plant. International Journal of Coal Geology, 2004. 59 : p. 153

- 169. 31. Jankowski, J., et al., Mobility of trace elements fro m selected Australian fly ashes and its potential impact on aquatic ecosystems. Fuel, 2006. 85 : p. 243

- 256. 32. Iwashita, A., et al., Leaching characteristics of boron and selenium for various coal fly ashes. Fuel, 2005. 84 (5): p. 479

- 485. 33. Goodarzi, F. and F.E. Huggins, Improved characterization of inorganic components in airborne particulate matter. Journal of Environmental Monitoring, 2001. 3 : p. 1

- 6. 34. Bothe, J.V. and P.W. Brown, Arsenic immobilization by calcium arsenate formation. Environmental S cience & Technology, 1999. 33 (21): p. 3806

- 3811. 35. Sims, J.R. and F.T. Bingham, Retention of boron by layer silicates, sesquioxides, and soil materials: II. Sesquioxides. Soil Sci. Soc. Am. Proc, 1968. 32 : p. 364

- 369. 36. Keren, R. and R.G. Gast, Boron i n water, soils and plants , in Advances in soil science, Volume I . 1985, Springer

- Verlag: New York. 37. Keren, R., R.G. Gast, and B. Bar

- Yosef, pH dependent boron adsorption by Na

Montmorillonite. Soil Science Society of America Journal, 1981. 45 : p. 45

- 48. 38. Keren, R. and U. Mezuman, Boron adsorption by clay minerals using a phenomenological equation. Clays Clay Mineral, 1981. 29 : p. 198

- 204. 39. Dickson, A.G., Thermodynamics of the dissociation of boric acid in synthetic seawater from 273.15 to 318.15 K. Deep

- Sea Ressearch, 1990. 37 : p. 755

- 766. 40. Xin, M., M.S. Gustin, and K. Ladwig, Laboratory study of air

- water

- coal combustion product (fly ash and FGD solid) mercury exchange! Fuel, 2006. 85 (16): p. 2260

- 2267. 41. Pavlish, J.H., et al., Status review o f mercury control options for coal

- fired power plants. Fuel Processing Technology, 2003. 82 : p. 89

- 165. 42. Barnett, M.O., et al., Formation of mercuric sulfide in soil. Environmental Science & Technology, 1997. 31 (11): p. 3037

- 3043. 43. Noel, J.D., P. Bis was, and D.E. Giammar, Evaluation of a sequential extraction process used for determining mercury binding mechanisms to coal combustion byproducts. Journal of the Air & Waste Management Association, 2007. 57 (7): p. 856

- 867.

### 16 44. Bool III, L., E. and J.J. He lble, A laboratory study of the partitioning of trace elements during pulverized coal combustion. Energy & Fuels, 1995. 9 : p. 880

- 887. 45. Yan, X., R. Kerrich, and M.J. Hendry, Distribution of arsenic(III), arsenic(V) and total inorganic arsenic in porewat ers from a thick till and clay

- rich aquitard sequence, Saskatchewan, Canada. Geochimica et Cosmochimica Acta, 2000. 64 (15): p. 2637

- 2648. 46. Weres, O., A.

- R. Jaouni, and L. Tsao, The distribution, speciation, and gochemical cycling of selenium in a sedime ntary environment, Kesterson Reservoir, California, U.S.A. . Applied Geochemistry, 1989. 4 : p. 543

- 563. 47. Davidson, G.R. and R.L. Bassett, Application of boron isotopes for identifying contaminants such as fly ash leachate in groundwater. Environmental S cience & Technology, 1993. 27 : p. 172

- 176. 48. Vengosh, A., et al., Boron isotope application for tracing sources of contamination in groundwater. Environmental Science & Technology, 1994. 28 : p. 1968

- 1974. 49. Bassett, R.L., et al., Identification of groundwater solute sources using boron isotopic composition. Environmental Science & Technology, 1995. 29 : p. 2915

- 2922. 50. Hogan, J.F. and J.D. Blum, Boron and lithium isotopes as groundwater tracers: a study at the Fresh Kills Landfill, Staten Island, New York, USA. Applied Geochemistry, 1999. 18 : p. 615

- 627. 51. Williams, L.B. and R.L. Hervig, Boron isotope composition of coals: a potential tracer of organic contaminated fluids. Applied Geochemistry, 2004. 19 : p. 1625

- 1636. 52. Spivack

- Brindorf, L.J. and B.W. Stewart. Use of boron isotopes to track the interaction of coal utilization byproducts with water and the environment . in American Geological Society Annual Meeting . 2006. Philadephia, PA. 53. Vengosh, A., et al., Coprecipitation an d isotopic fractionation of boron in modern biogenic carbonates. Geochimica et Cosmochimica Acta, 1991. 55 : p. 2901

- 2910.

### 17 5. CVs of the investigators:

______________________________ Avner Vengosh, PhD________

_______ _____________ P rofessor, Nicholas School of the Environment Telephone: (919) 681

- 8050 Division of Earth & Ocean Sciences Fax: (919) 684

- 5833 Duke University E

- mail: vengosh@duke.edu Box 90227, Durham, NC 27708

- 0235

_____________________________________ _____________________________________ ___________________ EDUCATION 1984 B.Sc., Hebrew University of Jerusalem, Jerusalem, Israel, Geology 1986 M.Sc., Hebrew University of Jerusalem, Jerusalem, Israel, Geology 1990 Ph.D., Australian National University, Canber ra, Australia, Environmental Geochemistry ACADEMIC APPOINTMENTS

1991

- 1999 Research Scientist (Senior Lecturer), Hydrological Service, Jerusalem, Israel. 1996

- 1997 Visiting scientist (sabbatical leave), Institute of Earth and Marine Sciences, University of California, Santa Cruz, California. 1999

- 2005 Associate Professor, Deaprtment of Geological and Environmental Sciences, Ben Gurion University, Beer Sheva, Israel. 2003

- 2004 Visiting Professor (sabbatical leave), Department of Deaprtment of Geological and Environmental Scien ces, Stanford University, California. 2005

- 2010 Associated Professor, Division of Earth and Ocean Sciences, Nicholas School of Environment, Duke University, Durham, North Carolina. 2009

- Associated Professor ( Secondary Appointment), Department of Civil an d Environmental Engineering, Pratt School of Engineering, Duke University, Durham, North Carolina. 2010

- Professor, Division of Earth and Ocean Sciences, Nicholas School of Environment, Duke University, Durham, North Carolina.

PROFESSIONAL SERVICE 2001

- 2005 Associate Editor for the international journal Water Resources Research. 2007

- Associate Editor of the international journal Applied Geochemistry.

Publications (Vengosh’s graduate students indicated by *) 1) Ruhl, L.*, Vengosh. A., Dwyer, G.S., Hsu

- Kim, H., Deonarine, A., Bergin, M., Kravchenko, J. (2009). Survey of the potential environmental and health impacts in the immediate aftermath of the coal ash spill in Kingston, Tennessee. Environmental Science and Technology

, 43, 6326

– 6333. 2) Vengosh, A. , Hirschfeld, D*., Vinson, D.S*., Dwyer, G.S. Raanan, H*., Rimawi, O., Al

- Zoubi, A., Akkawi, E., Marie, A., Haquin, G., Zaarur, S., and Ganor, J. (2009) High Naturally Occurring Radioactivity in Fossil Groundwater in the Middle East. Environmental Scienc e and Technology (DOI: 10.1021/es802969r). 3) Vinson, D.S.*, Vengosh, A., Hirschfeld, D*. and Dwyer, G.S. (2009). Relationships between radium and radon occurrence and hydrochemistry in fresh groundwater from fractured crystalline rocks, North Carolina (US A). Chemical Geology

, 260, 159

- 171. 4) Raanan, H.*, Vengosh, A., Paytan, A., and Nishri, A. (2009) Quantifying saline groundwater flow into a fresh water lake using the Ra isotope quartet: A case study from the Sea of Galilee (Lake Kinneret), Israel. Limon ology and Oceanograpghy, 54(1), 119

– 131

.

### 18 5) Pratson, E., Vengosh, A., Dwyer, G., Pratson, L. and Klein, E. (2010). The Effectiveness of Arsenic Remediation from Groundwater in a Private Home. Ground Water Monitoring and Remediation , 30, 87

- 93. 6) Kloppmann , W., Vengosh, A. Guerrot, K., Millot, R., and Parnkaratov, I. (2008) Isotope and ion selectivity in reverse osmosis desalination: Geochemical tracers for man

- made freshwater. Environmental Science and Technology, 42 (13), 4723

– 4731, 10.1021/es7028894

. 7) Vengosh, A., Hening, S.*, Ganor, J., Mayer, B., Weyhenmeyer, C.E., Bullen. T.D. , and Paytan, A. (2007). New isotopic evidence for the origin of groundwater from the Nubian Sandstone Aquifer in the Negev, Israel. Applied Geochemistry , 22, 1052

- 1073

. 8) F arber, E.*, Vengosh, A., Gavrieli, I., Marie, A., Bullen, T.D., Mayer, B., Holtzman, R.*, Segal, M.*, and Shavit, U. (2004) The origin and mechanisms of salinization of the Lower Jordan River. Geochimica Cosmochimica Acta, 68, 1989

- 2006. 9) Vengosh, A., Kl oppmann, W., Marie, A., Livshitz, Y., Gutierrez, A., Banna, M., Guerrot, C., Pankratov, I., Ranan, H., (2005). Sources of salinity and boron in the Gaza Strip: Natural contaminant flow in the southern Mediterranean Coastal aquifer. Water Resources Research

, 41, W01013, doi:10.1029/2004WR003344. 10) Vengosh, A. (2003). Salinization and Saline Environments . In: Sherwood Lollar, B. (ed.), Environmental geochemistry (volume 9), Treatise in Geochemistry . Executive Editors: Holland, H.D. and Turekian, K.T., Elsev ier Science.

SYNERGISTIC ACTIVITIES (last 3 years)

2009 Chair of the session “Future Impacts on Hydrogeological Resource Potential and Quality: Global Change and Implications for the Future of Water Resources in Arid and Semi

- Arid Regions”, Goldschmidt 20 09, Davos, Switzerland, June, 2009. 2009 Testimony to the Subcommittee on Water Resources & Environment, U.S. House of Representatives

- Tennessee Valley Authority's Kingston Ash Slide: Potential Water Quality Impacts of Coal Combustion Water Storage. Washi ngton DC, March 2009 ( http://transportation.house.gov/hearings/hearingDetail.aspx?NewsID=834 ). 2008 Keynote speakers at University Council on Water Resources/ National Ins ititue for Water Research annual conference “ International water resources: Challenges for the 21 st century” , Durham, NC, July 2008. 2007 Chair of a special session ( Pardee Keynote Symposia ) of the Geological Society of America, entitled “ Middle Eastern Water Resources in Times of Crisis ”, 2007 GSA Annual Meeting & Exposition, Denver, October 28

- 31, 2007. 2007 Chair of a session entitled “ Natural Contaminants in Groundwater Resources: Occurrence, Geochemistry, Health, and Remediation “, American Geophysica l Union [ 32 ] , Joint Assembly Meeting, Acapulco, Mexico, May 22

- 25, 2007. 2007

- Member of the Environment Surveillance Committee of th e N.C. Radiation Protection Commission. 2006 Chair of a Workshop on “ Radon Occurrence, Health Risks and Policy

, with an Emphasis on Radon in Ground Water Drinking Supplies” , Duke Garnens, Duke University, Durham, NC, ( http://www.nicholas.duke.edu/radon/ ), October 4, 2006.

### 19 Heileen Hsu

- Kim, Ph.D. Assistant Professor Phone: (919) 660

- 5109 Duke University Fax: (919) 660

- 5219 Civil & Environmental Engineering E

- mail: hsukim@duke.edu 127A Hudson Hall, Box 90287 Durham, NC 27708

Education and Training Massachusetts Institute of Technology Environmental Engineering Science B.S. 1998 University of California, Berkeley Environmental Engineering M.S. 1999 University of California, Berkeley Environmental Engineering Ph.D. 2004 University of Delaware Marine Science, Post

- Doctoral Fellow 200 5

Research and Professional Experience Duke University, Civil & Environmental Engineering. Assistant Professor 2005

- present University of Delaware, College of Marin e Studies. Postdoctoral Fellow 2004

- 2005 University of California, Berkeley. Graduate Student Instructor Fall 1999 Lawrence Livermore National Laboratory, Student researcher Summer 1998, 1999

Journal Publications 1. Zhang T. and Hsu

- Kim H. (2010). Phot olytic degradation of methylmercury enhanced by binding to natural organic ligands. Nature Geoscience

. 3 , 473

- 476. DOI: 10.1038/NGEO892 2. Gondikas A.P., Jang E.K., Hsu

- Kim H. (2010). Influence of amino acids cysteine and serine on aggregation kinetics of zin c and mercury sulfide colloids. J Coll Interf Sci. 347 , 167

- 171. 3. Ruhl L., Dwyer G.S., Deonarine A., Hsu

- Kim H., Bergin M., Kravchenko J., Vengosh A. (2009). Survey of the potential environmental and health impacts in the immediate aftermath of the coal ash spill in Kingston, Tennessee. Environ. Sci. &Technol

. 43 , 6323

- 6333. 4. Deonarine A. and Hsu

- Kim H. (2009). Precipitation of mercuric sulfide nanoparticles in NOM

- containing water: Implications for the natural environment. Environ. Sci. &Technol

. 43

, 2368

- 23 73. 5. Lau B. and Hsu

- Kim H. (2008). Precipitation and growth of zinc sulfide nanoparticles in the presence of thiol

- containing natural organic ligands. Environ. Sci. &Technol

. 42 , 7236

- 7241. 6. Hsu

- Kim H. (2007). Stability of Metal

- Glutathione Complexes During Oxidation by Hydrogen Peroxide and Cu

- Catalysis. Environ. Sci. &Technol

. 41 , 2338

- 2342. 7. Hsu

- Kim H., Mullaugh KM., Tsang J.J., Yucel M., Luther G.W. (2008). Formation of Zn

- and Fe

- sulfides near hydrothermal vents at the Eastern Lau Spreading Center: Impli cations for sulfide bioavailability to chemoautotrophs. Geochem. Transactions . 9:6. 8. Tsang J.J., Rozan T.F., Hsu

- Kim H., Mullaugh K.M., Luther G.W. (2006). Pseudopolarographic determination of Cd 2+ complexation in freshwater. Environ. Sci. &Technol

. 40 , 53 88

- 5394. 9. Hsu

- Kim H. and Sedlak D.L. (2005). Similarities between inorganic sulfide and the strong Hg

- complexing ligands in municipal wastewater effluent. Environ. Sci. &Technol. 39 , 4035

- 4041. 10. Hsu H. and Sedlak D.L. (2003). Strong mercury complexation in w astewater effluent and surface waters. Environ. Sci. &Technol. 37 , 2743

- 2749

. Honors National Science Foundation Ridge2K Postdoctoral Fellowship, “Metal sulfide speciation and cluster formation at deep

- sea hydrothermal vents”, 2004 ACS Environmental Che mistry Division Graduate Student Paper Award, 2003 National Physical Science Consortium Graduate Student Fellowship, 1998

- 2004 UC

- Berkeley Outstanding Graduate Student Instructor Award, 1999

- 2000

### 20 NSF Graduate Research Fellowship, finalist (declined for NPSC award), 1998 Synergistic Activities

• Guest co

- editor for special issue of Environmental Science and Technology : Nanoscale

NOM

- Metal Interactions; publication for spring 2011

• NSF Center for Environmental Implications of NanoTechnology: Co

- Investigator o f

Theme 1 (Exposure, Transport and Transformations in Laboratory Systems) and Core B (Natural and Incidental Nanomaterials in the Environment)

• Patterson Award Committee member (2008

- 2011), Geochemical Society

• Faculty advisor for FEMMES (Females Excelling More in Math, Engineering, and

Science): Duke education outreach program for 4 th

- 6 th grade students.

Professional Affiliations Memberships: American Chemical Society, American Geophysical Union, Association of Environmental Engineering and Science Professo rs, Geochemical Society Academic honor societies: Tau Beta Pi, Chi Epsilon, and Phi Beta Kappa
Teaching CE/ENV 242 Environmental Aquatic Chemistry . (graduate level) F 2005

- 08, 10 CE120L Chemical Processes in Environmental Engineering . (undergrad Sp 07

- 08, F08

- 10 CE265 Instrumental Methods of Environmental Pollutants (graduate) Sp 2008 CE265 Aquatic Geochemistry (graduate) Sp 2009

- 10 Collaborators (recent 48 months) G. Aiken (USGS

- Boulder), M. Auffan (CEREGE), M. Deshusses (Duke), R. DiGiulio (Duke), M. Ho chella (Virginia Tech), J. Hower (Kentucky), T. Johnson (UIUC), J. Little (Virginia Tech), G. Lowry (Carnegie Mellon), A. Masion (CEREGE), T. Phelps (ORNL), J. Rose (CEREGE), N. Robins (NCSU), J. Ryan (CU

- Boulder), M. Wiesner (Duke), A. Vengosh (Duke).

Cur rent Research Advisees Postdoctoral Scholar: Lee Bryant (2010

- present) Ph.D. Students: Amrika Deonarine (2005

- present), Tong Zhang (2007

- present), Andreas Gondikas (2008

- present) Undergraduate Student Researchers: Brian Au (CEE, 2012), Marianne Leonhard t (CEE, 2012)

Former Research Advisees Boris Lau (Postdoctoral Associate 2007

- 2008), Patrick Canning (Undergraduate researcher 2008

- 09) , Natalya Polishchuk (Summer REU Researcher 2007), Eileen Jang (high school student, 2008

- 2009), Avi Agaarwaal (high sc hool student 2010) Former Mentors : D. Sedlak (graduate, UC Berkeley); G. Luther (postdoctoral, U. Delaware)

### 21 6. Other Information

6.1. Information transfer: A ssimilation of the data generated in this study will be conducted by working closely w ith the staff of the Division of Water Quality, Surface Water Protection, North Carolina Department of Environment and Natural Resources (DENR). We have already established effective and productive working relations with DENR (see attached support letter). In addition we plan to present the data in national and international conferences (e.g., the results of the NSF

supported project on the TVA coal ash spill were presented in nine national and international conferences in the USA during 2009 and 2010). We plan to present the data also to NC Environmental Management Commission in order to enhance discussion for possible legislations changes in NC concerning coal ash disposal and water monitoring. Finally, we plan to publish the data in professional peer

- revi ewed journals.

6.2. Progress review: This is a new WRRI project.



### 7. Closely Related Proposals: involving the PI and/or co

- PIs

Vengosh and Hsu Kim:

Agency: NSF ; project: The impact of coal combustion products on the environment: geochemical and isotopic prospective

. Budget : $ 336,017. This proposal seeks to evaluate the overall impact of coal combustion products on the environment and involves systematic leaching experiments of major coal ash from the USA. While the WRRI proposal seeks to evaluate the act ual impact on water resources in NC, the NSF proposal is much more general and aims to evaluate the overall risks of coal ash impact on the environment and mechanisms of contaminants leaching from coal ash

.

### 22 8. Letters of support or co llaboration

### 23

### 24

### 25

### 26 9. Budget Justification

Graduate Student Researcher: Funds are requested to support three months salary of a graduate student for this project. The student will be responsible for fieldwork, lab measurements, and data interpretation. The compensation rate per full

- time student is $25,245 per year. Duke University Ph.D. student wages are determined by the Graduate School in consultation with the faculty, department heads, deans, and the University administration, based on considerati on of living costs and the competitive market for top

- quality Ph.D. students. Fringe Benefits: Fringe benefits at Duke are based on the fiscal year and as such they may differ based on the time period over which they are calculated. In accordance with D uke University guidelines, the fringe benefits rate for the graduate student researcher is 8.4% per
year. Travel: Funds in the amount of $12,000 are requested to support travel expenses for the student and PIs. The funds will be used to cover travel to CCP storage pond sites and associated water resources in NC. The travel funds will also be used to support travel for either the PI or graduate student to present project results at a national scientific conference (e.g., Goldschmidt, American Geological Soci ety, American Geophysical Union). Materials, Supplies, and Consumables: Funds in the amount of $28,049 are requested to purchase laboratory supplies that are needed for this project. These supplies include items such as chemicals, glassware, sampling bot tles, pipette tips, tubing, consumable parts for metals analyses, compressed gases, consumables for laboratory instruments, and other water and mineral analyses. In addition these funds include cost for ICP

- MS instrument time ($35 per sample). We expect t o collect about 100 to 150 water samples during the course of the project. Equipment : No funds are requested for the purchase of equipment. All major equipment to be used for this project has already been purchased.
Other Direct Cost: For the 2010

- 2011 a cademic year, summer Semester tuition remission for Ph.D. research assistants is set at $2,755 per semester ($8,265 annually). These rates are set by the Graduate School and are applied consistently across the University, regardless of funding source.