An investigation of the potential environmental and health impacts in the immediate aftermath of one of the largest coal ash spills in U.S. history at the Tennessee Valley Authority (TVA) Kingston coal-burning power plant has revealed three major findings. First, the surface release of coal ash with high levels of toxic elements (As = 75 mg/kg; Hg = 150 μg/kg) and radioactivity (226Ra + 228Ra = 8 pCi/g) to the environment has the potential to generate resuspended ambient fine particles (<10 μm) containing these toxics into the atmosphere that may pose a health risk to local communities. Second, leaching of contaminants from the coal ash caused contamination of surface waters in areas of restricted water exchange, but only trace levels were found in the downstream Emory and Clinch Rivers due to river dilution. Third, the accumulation of Hg- and As-rich coal ash in river sediments has the potential to have an impact on the ecological system in the downstream rivers by fish poisoning and methylmercury formation in anaerobic river sediments.

An 18 month investigation of the environmental impacts of the Tennessee Valley Authority (TVA) coal ash spill in Kingston, Tennessee combined with leaching experiments on the spilled TVA coal ash have revealed that leachable coal ash contaminants (LCACs), particularly arsenic, selenium, boron, strontium, and barium, have different effects on the quality of impacted environments. While LCACs levels in the downstream river water are relatively low and below the EPA drinking water and ecological thresholds, elevated levels were found in surface water with restricted water exchange and in pore water extracted from the river sediments downstream from the spill. The high concentration of arsenic (up to 2000 µg/L) is associated with some degree of anoxic conditions and predominance of the reduced arsenic species (arsenite) in the pore waters. Laboratory leaching simulations show that the pH and ash/water ratio control the LCACs' abundance and geochemical composition of the impacted water. These results have important implications for the prediction of the fate and migration of LCACs in the environment, particularly for the storage of coal combustion residues (CCRs) in holding ponds and landfills, and any potential CCRs effluents leakage into lakes, rivers, and other aquatic systems.

The combustion of coal to generate electricity produces about 130 million tons of coal combustion residues (CCRs) each year in the United States; yet their environmental implications are not well constrained. This study systematically documents the quality of effluents discharged from CCR settling ponds or cooling water at ten sites and the impact on associated waterways in North Carolina, compared to a reference lake. We measured the concentrations of major and trace elements in over 300 samples from CCR effluents, surface water from lakes and rivers at different downstream and upstream points, and pore water extracted from lake sediments. The data show that CCR effluents contain high levels of contaminants that in several cases exceed the U.S. EPA guidelines for drinking water and ecological effects. This investigation demonstrates the quality of receiving waters in North Carolina depends on (1) the ratio between effluent flux and freshwater resource volumes and (2) recycling of trace elements through adsorption on suspended particles and release to deep surface water or pore water in bottom sediments during periods of thermal water stratification and anoxic conditions. The impact of CCRs is long-term, which influences contaminant accumulation and the health of aquatic life in water associated with coal-fired power plants.

In the U.S., coal fired power plants produce over 136 million tons of coal combustion residuals (CCRs) annually. CCRs are enriched in toxic elements, and their leachates can have significant impacts on water quality. Here we report the boron and strontium isotopic ratios of leaching experiments on CCRs from a variety of coal sources (Appalachian, Illinois, and Powder River Basins). CCR leachates had a mostly negative δ11B, ranging from −17.6 to +6.3‰, and 87Sr/86Sr ranging from 0.70975 to 0.71251. Additionally, we utilized these isotopic ratios for tracing CCR contaminants in different environments: (1) the 2008 Tennessee Valley Authority (TVA) coal ash spill affected waters; (2) CCR effluents from power plants in Tennessee and North Carolina; (3) lakes and rivers affected by CCR effluents in North Carolina; and (4) porewater extracted from sediments in lakes affected by CCRs. The boron isotopes measured in these environments had a distinctive negative δ11B signature relative to background waters. In contrast 87Sr/86Sr ratios in CCRs were not always exclusively different from background, limiting their use as a CCR tracer. This investigation demonstrates the validity of the combined geochemical and isotopic approach as a unique and practical identification method for delineating and evaluating the environmental impact of CCRs.

Mercury stable isotope abundances were used to trace transport of Hg-impacted river sediment near a coal ash spill at Harriman, Tennessee, USA. δ(202)Hg values for Kingston coal ash released into the Emory River in 2008 are significantly negative (-1.78 ± 0.35‰), whereas sediments of the Clinch River, into which the Emory River flows, are contaminated by an additional Hg source (potentially from the Y-12 complex near Oak Ridge, Tennessee) with near-zero values (-0.23 ± 0.16‰). Nominally uncontaminated Emory River sediments (12 miles upstream from the Emory-Clinch confluence) have intermediate values (-1.17 ± 0.13‰) and contain lower Hg concentrations. Emory River mile 10 sediments, possibly impacted by an old paper mill has δ(202)Hg values of -0.47 ± 0.04‰. A mixing model, using δ(202)Hg values and Hg concentrations, yielded estimates of the relative contributions of coal ash, Clinch River, and Emory River sediments for a suite of 71 sediment samples taken over a 30 month time period from 13 locations. Emory River samples, with two exceptions, are unaffected by Clinch River sediment, despite occasional upstream flow from the Clinch River. As expected, Clinch River sediment below its confluence with the Emory River are affected by Kingston coal ash; however, the relative contribution of the coal ash varies among sampling sites.

Mountaintop mining (MTM) is the primary procedure for surface coal exploration within the central Appalachian region of the eastern United States, and it is known to contaminate streams in local watersheds. In this study, we measured the chemical and isotopic compositions of water samples from MTM-impacted tributaries and streams in the Mud River watershed in West Virginia. We systematically document the isotopic compositions of three major constituents: sulfur isotopes in sulfate (δ 34 S SO4 ), carbon isotopes in dissolved inorganic carbon (δ 13 C DIC ), and strontium isotopes ( 87 Sr/ 86 Sr). The data show that δ 34 S SO4 , δ 13 C DIC , Sr/Ca, and 87 Sr/ 86 Sr measured in saline-and selenium-rich MTM impacted tributaries are distinguishable from those of the surface water upstream of mining impacts. These tracers can therefore be used to delineate and quantify the impact of MTM in watersheds. High Sr/Ca and low 87 Sr/ 86 Sr characterize tributaries that originated from active MTM areas, while tributaries from reclaimed MTM areas had low Sr/Ca and high 87 Sr/ 86 Sr. Leaching experiments of rocks from the watershed show that pyrite oxidation and carbonate dissolution control the solute chemistry with distinct 87 Sr/ 86 Sr ratios characterizing different rock sources. We propose that MTM operations that access the deeper Kanawha Formation generate residual mined rocks in valley fills from which effluents with distinctive 87 Sr/ 86 Sr and Sr/Ca imprints affect the quality of the Appalachian watersheds.

Selenium (Se) in coal ash spills poses a threat to adjacent ecosystems because of its potential to mobilize and bioaccumulate in aquatic organisms. Given that the mobility and bioavailability of Se is controlled by its valence states, we aimed to define Se speciation in coal ash solids and examine the relationships between Se speciation and the magnitude of its mobilization from coal ash. We used coal ash samples from the Tennessee Valley Authority (TVA)-Kingston fossil plant and the site of a coal ash spill that occurred in 2008 in Tennessee. Results of X-ray absorption spectroscopic analyses showed that Se in coal ash samples was a mixture of elemental Se(0) and Se oxyanions. The amount of leachable Se increased with an increase of pH from 3 to 13. At the natural pH of coal ash samples (from pH 7.6 to 9.5), the leachable Se was comprised of Se oxyanions, mainly selenite. This was observed by both direct quantification of Se oxyanions in the leachate and the corresponding loss of Se oxyanions in the solid phase. At pH 12, however, the Se release appeared to derive from both desorption of Se oxyanions and oxidative dissolution of elemental Se(0). Our results indicate that Se oxyanions are the most labile species; however, the magnitude of Se mobilization will increase if the waste material is subjected to alkaline conditions.

Hexavalent chromium [Cr­(VI)] is a known pulmonary carcinogen. Recent detection of Cr­(VI) in drinking water wells in North Carolina has raised public concern about contamination of drinking water wells by nearby coal ash ponds. Here we report, for the first time, the prevalence of Cr and Cr­(VI) in drinking water wells from the Piedmont region of central North Carolina, combined with a geochemical analysis to determine the source of the elevated Cr­(VI) levels. We show that Cr­(VI) is the predominant species of dissolved Cr in groundwater and elevated levels of Cr and Cr­(VI) are found in wells located both near and far (>30 km) from coal ash ponds. The geochemical characteristics, including the overall chemistry, boron to chromium ratios, and strontium isotope (87Sr/86Sr) variations in groundwater with elevated Cr­(IV) levels, are different from those of coal ash leachates. Alternatively, the groundwater chemistry and Sr isotope variations are consistent with water–rock interactions as the major source for Cr­(VI) in groundwater. Our results indicate that Cr­(VI) is most likely naturally occurring and ubiquitous in groundwater from the Piedmont region in the eastern United States, which could pose health risks to residents in the region who consume well water as a major drinking water source.