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Coal fly ash is a promising alternative source for rare earth elements (REE), which are critical materials in many technologies. REEs are entrained in the aluminosilicate glass of the fly ash particles, hindering their ability to solubilize during acid leaching. The purpose of this research was to test the effectiveness of roasting techniques to improve extraction of REEs from fly ash, determine key parameters controlling REE extraction, and understand trade-offs in reagent use. Representative coal ash samples from major U.S. coal basins (Appalachian, Illinois, and Powder River basins) were roasted using a variety of chemical additives (Na2O2, NaOH, CaO, Na2CO3, CaSO4, (NH4)2SO4). Further experiments investigated the effects of additive:ash ratio, roasting temperature, and leachate pH on REE extraction. We found that NaOH roasting often recovered >90% of total REE content, equivalent to the USGS-recommended method (Na2O2 sintering). Other additives tested recovered 70% REE extraction are a 1:1 NaOH-ash ratio and leaching with 1–2 mol/L HNO3.

The recovery of rare earth elements (REEs) from coal combustion fly ash has recently gained attention as a possible beneficial reuse application that could provide an alternative, low-grade source of REEs in an unstable global supply market. To economically recover REEs, an efficient process needs to be developed to remove them from the ash. This study investigated different methods of leaching REEs from fly ash and other coal combustion ashes. Aqueous acid and alkaline leaching were employed on multiple types of coal fly ash samples (representing coals from three major U.S. coal basin sources) with variable leaching parameters that include extractant type (HCl, NaOH), extractant concentration, leachate-to-ash ratio, and addition of CaO during the leaching process. Acid leaching of high calcium-containing fly ashes such as samples derived from Powder River Basin coals had the highest recoveries of REEs (near 100% of total REE contents), while leaching efficiencies were much lower (

The Kentucky State University heating plant stoker ash, with over 1000 μg/g Rare earth elements + yttrium (REY), was previously shown to be more resistant to acid-extraction than pulverized-coal fly ashes of similar bulk composition. In this study, the petrology and mineralogy of this stoker ash was examined in greater detail as a means to better understand why the REY were relatively inert towards acid extraction. The results showed that this stoker ash is dominated by mullite and quartz/cristobalite with lesser amounts of hematite and magnetite compared to the glass-dominated assemblages of pulverized-coal-combustion fly ashes with similar chemical compositions. On the nanometer to micron scale, La-Ce-Nd-bearing monazite and Ce phosphates (monazite – CePO4 and CeP3O9) are seen to be part of the mineral assemblage. Overall, the results demonstrate that despite the presence of discrete REY-bearing minerals in the sample, their encapsulation within other phases may explain their low extractability.

The increasing occurrence of tetrabromobisphenol A (TBBPA) in the environment is raising questions about its potential environmental health impacts as it has been shown to cause various deleterious effects in humans. The fact that the highest concentrations of TBBPA have been reported in wastewater sludge is concerning as effluent discharge and biosolids land application are likely a route by which TBBPA can be further disbursed to the environment. Our objectives in this study were to evaluate the effect of biochar (BC) and activated carbon (AC) in promoting the biodegradation of TBBPA, and characterize the response of anaerobic sludge microbial communities following amendments. Both carbonaceous amendments were found to promote the reductive debromination of TBBPA. Nearly complete transformation of TBBPA to BPA was observed in the amended reactors ~20 days earlier than in the control reactors. In particular, the transformation of diBBPA to monoBBPA, which appears to be the rate-limiting step, was accelerated in the presence of either amendment. Overall, microbial taxa responding to the amendments, i.e., ‘sensitive responders’, represented a small proportion of the community (i.e., 7.2%), and responded positively. However, although both amendments had a similar effect on TBBPA degradation, the taxonomic profile of the sensitive responders differed greatly from one amendment to the other. BC had a taxonomically broader and slightly more pronounced effect than AC. This work suggests that BC and AC show great potential to promote the biodegradation of TBBPA in anaerobic sludge, and their integration into wastewater treatment processes may be helpful for removing TBBPA and possibly other emerging hydrophobic contaminants.

The distribution of Rare Earth elements (REE) in coal-derived fly ashes can have distinctive patterns when fly ashes are produced from different coals within or between basins, such as the Pennsylvanian Class F fly ashes from the Illinois and Central Appalachian basins. Both the Fire Clay coal and a blend of a number of eastern Kentucky coals show strong Gd peaks and an H-type distribution in the Upper Continental Crust-corrected plots. The Fire Clay coal-derived ash has a higher heavy REE concentration than the blended coal-derived ash. The Illinois Basin-derived fly as has an overall lower REE concentration than the latter ashes. Class C fly ash derived from Powder River Basin coals has, with the exception of an Eu peak, a flatter distribution of REE and an overall L-type or indistinct H- versus L-type distribution. The signatures of the REE in fly ashes may be useful in predicting their behavior in the extraction of the REE; simple extrapolations from the basic concentrations and the predicted extraction percentages for ashes from different basins are not necessarily indicative of the actual distribution of the extracted REE.

The feed coal and corresponding ash from a series of stoker boilers burning Pennsylvania anthracite were investigated for their petrographic and chemical characteristics. The coals have low-S and moderate-ash contents with similar major oxide and minor element compositions. The volatile minor elements, such as Zn and As, decrease in concentration from the feed coal to the stoker ash (comparisons on the ash basis). The light rare earth elements (La through Sm) decrease in concentration relative to the heavy rare earth elements (Eu through Lu) from the coal ash to the stoker ash.

This study examined rare earth element (REE) trends for Illinois Basin coal-sourced fly ashes, with the goal of understanding the elemental composition and resource potential for various fly ash fractions. Illinois Basin coals have a high volatile C through A bituminous rank with a moderate ash content (slightly>12% ash (dry basis)), about 3% sulfur, and, in general, lower concentrations of hazardous and other trace elements than many Central Appalachian coals. Fly ash from the combustion of Illinois Basin coals tends to have a high Fe2O3 content owing to the amount of pyrite in the feed coals. The rare earth element (REE) concentrations in Illinois Basin coal-sourced fly ashes are less than that for fly ashes from the combustion of Central Appalachian coals. The Upper continental crust-corrected fly ashes show an H-type enrichment, a positive EuN/EuN*, and, in some cases, a sharp Gd peak. For comparison, a suite of fly ashes from the combustion of a blend of eastern Kentucky coals had an H-type enrichment, a positive EuN/EuN*, but only a minimal Gd peak. In contrast, fly ash from the combustion of the Fire Clay coal, a REE-rich coal, had a negative EuN/EuN* and a sharp Gd peak. These results highlight the importance of feed coal composition on trace element contents of respective combustion fly ash fractions and also the unique REE enrichment patterns of the Illinois Basin fly ashes relative to the better studied fly ashes of eastern Kentucky and Central Appalachia.

Potosí, Bolivia, is the site of centuries of historic and present-day mining of the Cerro Rico, a mountain known for its rich polymetallic deposits, and was the site of large-scale Colonial era silver refining operations. In this study, the concentrations of several metal and metalloid elements were quantified in adobe brick, dirt floor, and surface dust samples from 49 houses in Potosí. Median concentrations of total mercury (Hg), lead (Pb), and arsenic (As) were significantly greater than concentrations measured in Sucre, Bolivia, a non-mining town, and exceeded US-based soil screening levels. Adobe brick samples were further analyzed for bioaccessible concentrations of trace elements using a simulated gastric fluid (GF) extraction. Median GF extractable concentrations of Hg, As, and Pb were 0.085, 13.9, and 32.2% of the total element concentration, respectively. Total and GF extractable concentrations of Hg, As, and Pb were used to estimate exposure and potential health risks to children following incidental ingestion of adobe brick particles. Risks were assessed using a range of potential ingestion rates (50-1000mg/day). Overall, the results of the risk assessment show that the majority of households sampled contained concentrations of bioaccessible Pb and As, but not Hg, that represent a potential health risk. Even at the lowest ingestion rate considered, the majority of households exceeded the risk threshold for Pb, indicating that the concentrations of this metal are of particular concern. To our knowledge, this is the first study to quantify key trace elements in building materials in adobe brick houses and the results indicate that these houses are a potential source of exposure to metals and metalloids in South American mining communities. Additional studies are needed to fully characterize personal exposure and to understand potential adverse health outcomes within the community.

The unintended release of coal ash to the environment is a concern due to the enrichment of contaminants such as arsenic (As) and selenium (Se) in this solid waste material. Current risk assessments of coal ash disposal focus on pH as the primary driver of leaching from coal ash. However, redox speciation of As and Se is a major factor for their mobilization potential and has received much less attention for risk assessments, particularly in disposal scenarios where coal ash will likely be exposed to microbially-driven redox gradients. The aim of this study was to demonstrate the differences of aerobic and anaerobic conditions for the leaching of As and Se from coal ash. Batch sediment-ash slurry microcosms were performed to mimic an ash spill scenario and were monitored for changes in As and Se speciation and mobilization potential. The results showed that the dissolved As concentrations were up to 50 times greater in the anaerobic microcosms relative to the aerobic microcosms during the two week incubation. This trend was consistent with As redox speciation determined by X-ray absorption spectroscopy, which indicated that 55% of the As in the solid phase at the end of the experiment was present as As(III) (a more leachable form of arsenic relative to As(V)). In the aerobic microcosms, only 13% of the As was As(III) and the rest was As(V). More than half of the Se was present as Se(IV) in the original fly ash and in the aerobic microcosms, while in the anaerobic microcosms Se was gradually transformed to less soluble Se(0) species. Likewise, dissolved Se concentrations were up to 25 times greater in the aerobic microcosms relative to anaerobic conditions. While the overall observations of As and Se mobilization potential from coal ash were consistent with expectations for aqueous and solid phase speciation of these elements, the findings directly show the relevance of these processes for coal ash disposal. These results highlight the need to select appropriate environmental parameters to include in risk assessments as well as provide potential geochemical monitoring tools through the use of dissolved Se/As ratios to determine the redox conditions of ash storage and spill sites.

Coal combustion ash and pre-combustion coal refuse are currently under consideration as potential sources of rare earth elements. One of the early steps in recovering REEs from coal by-products is often acid leaching, which can result in low pH leachates with complex aqueous chemistry. The aim of this work was to understand the connection between REE solubility, pH, and major elemental components of leachates for coal by-products. To accomplish this, we investigated the effects of solids concentration (i.e., pulp density) and pH adjustment on REE solubility in acid leachates of coal fly ashes from the Powder River Basin (PRB) and Appalachian Basin in the United States, and a coal processing refuse from the Southwestern U.S. For PRB ashes, the concentrations of soluble REEs generally increased with increasing pulp density; however, at pulp density values above 80–100 g/L, the soluble REE concentrations in the leachates were markedly lower. Similarly, the soluble concentrations of other major solutes (Fe, Al, Si) that leached from PRB fly ashes were also non-linear with pulp density. These major elements tended to reach maximum concentration values at 60–70 g/L pulp density. In contrast, for the Appalachian fly ashes and the coal by-product, soluble concentrations of REE and major elements in leachates increased linearly with pulp density. Chemical equilibria calculations of mineral saturation indices indicated that trends in soluble REE concentrations could be explained by saturation conditions for Fe and Al-(hydr)oxides and possibility sulfate minerals, but not lanthanide hydroxides. Furthermore, pH adjustment of the acid leachates showed that REEs and many major solutes were removed from solution at pH values above 4.5, also consistent with Fe- and Al-(hydr)oxide precipitation. These results highlight the importance of understanding the chemical composition of leachates when designing REE recovery processes for low-grade geologic feedstocks and that precipitation of hydr(oxide) or sulfate minerals of major elements rather than discreet formation of REE mineral phases could be used for process optimization.

Coal byproducts represent an abundant and untapped potential source of critical rare earth elements (REEs). In this study, we tested the efficacy of a biosorption-based approach to recover REEs from leachate solutions derived from North Dakota lignite coal and Powder River Basin (PRB) coal fly ash. A pairwise comparison was performed using a range of cell densities of two distinct bacteria, including an Escherichia coli strain previously genetically engineered for cell surface display of lanthanide binding tags, and Arthrobacter nicotianae, a native bacterium that exhibits high REE adsorption capacity. At optimal cell densities, we observed a recovery efficiency of 80% for total REEs and > 90% for middle and heavy REEs from the lignite leachate. Higher cell densities were required to achieve a similar total REE recovery efficiency in the PRB leachate due to its higher non-REE content, which negatively impacted light REE recovery. Despite the chemical complexity of both feedstocks, separation factors ≥ 30 were observed for Nd relative to nearly all non-REE metals after a single adsorption/desorption cycle, highlighting the high adsorption selectivity for REEs. Quantification of impurities in the extracted metal solutions revealed that Ca and Mg content in the leachate solutions play a dominant role in both the REE recovery yield and purity. The Mg/Ca impurities can be further reduced by incorporation of a low pH wash step between the adsorption and desorption steps, yielding extracted concentrates with a REE purity (mass fraction REE of total metals) of 80% and 50% for lignite and PRB, respectively. Thermodynamic speciation analysis of the REE-enriched eluents from both feedstocks suggests that at a post-biosorption hydroxide precipitation step can be employed to yield high purity total REE precipitates. Collectively, these results highlight the utility of biosorption for selective REE recovery from coal byproducts and pave the way for a sustainable route to diversify the REE supply chain.

Coal ash is one of the largest industrial waste streams in the United States and contains elevated concentrations of hazardous elements that could pose environmental and human health risks. Due to the relatively high strontium concentrations in coal ash and the distinctive 87Sr/86Sr ratios, strontium isotopes have been utilized to trace coal ash contaminants in impacted water resources. While previous studies have characterized the Sr isotope ratios for the water-soluble Sr derived from coal ash, the strontium isotopic composition of the bulk coal ash has not been systematically evaluated. In the current study, we report the 87Sr/86Sr ratios of bulk and water-soluble Sr in fly ash derived from coals of the three major coal-producing basins in the U.S., the Appalachian Basin, Illinois Basin, and Powder River Basin. The data show a wide range of 87Sr/86Sr ratios in the bulk fly ash samples (0.710788–0.722311), with the most radiogenic 87Sr/86Sr ratios in fly ash originating from Illinois Basin coals (0.718029 ± 0.003365; n = 16), followed by those from Appalachian Basin coals (0.712641 ± 0.000860; n = 16), and those from Powder River Basin coals (0.711663 ± 0.000489; n = 7). The 87Sr/86Sr ratios in the water leachates are significantly lower than the 87Sr/86Sr ratios of the bulk fly ash for Illinois Basin and Appalachian Basin (0.711660 ± 0.001172 and 0.710694 ± 0.000317, respectively, p-value

The extensive use of silver nanoparticles (AgNPs) in manufactured products will inevitably increase environmental exposure, highlighting the importance of accurate toxicity assessments. A frequent strategy to estimate AgNP cytotoxicity is to use absorbance or fluorescent-based assays. In this study we report that AgNPs – with or without surface functionalizations (polyvinyl pyrrolidone or gum arabic), and of different sizes (2–15 nm) – can interfere with the spectrometric quantification of different dyes commonly used in cytotoxicity assays, such as 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT), neutral red (NR), Hoechst, and Resazurin. Some AgNP types caused more interference than others, which was dependent on the assay. Overall most AgNPs caused the direct reduction of MTT, as well as Hoechst and NR fluorescence quenching, and absorbed light at the same wavelength as NR. None of the AgNPs tested caused the direct reduction of Resazurin; however, depending on AgNP characteristics and concentration, they may still promote fluorescence quenching of this dye. Our results show that AgNPs with different size and coatings can interfere with spectroscopy-based assays to different degrees, suggesting that their cytotoxicity may be underestimated or overestimated. We suggest that when using any spectroscopy-based assay it is essential that each individual nanoparticle formulation be tested first for potential interferences at all intended concentrations.

In the United States, aquatic mercury contamination originates from point and non-point sources to watersheds. Here, we studied the contribution of mercury in urban runoff derived from historically contaminated soils and the subsequent production of methylmercury in a stream-wetland complex (Durham, North Carolina), the receiving water of this runoff. Our results demonstrated that the mercury originated from the leachate of grass-covered athletic fields. A fraction of mercury in this soil existed as phenylmercury, suggesting that mercurial anti-fungal compounds were historically applied to this soil. Further downstream in the anaerobic sediments of the stream-wetland complex, a fraction (up to 9%) of mercury was converted to methylmercury, the bioaccumulative form of the metal. Importantly, the concentrations of total mercury and methylmercury were reduced to background levels within the stream-wetland complex. Overall, this work provides an example of a legacy source of mercury that should be considered in urban watershed models and watershed management.

Detailed Spanish records of mercury use and silver production during the colonial period in Potosi, Bolivia were evaluated to estimate atmospheric emissions of mercury from silver smelting. Mercury was used in the silver production process in Potosi and nearly 32,000 metric tons of mercury were released to the environment. AERMOD was used in combination with the estimated emissions to approximate historical air concentrations of mercury from colonial mining operations during 1715, a year of relatively low silver production. Source characteristics were selected from archival documents, colonial maps and images of silver smelters in Potosi and a base case of input parameters was selected. Input parameters were varied to understand the sensitivity of the model to each parameter. Modeled maximum 1-h concentrations were most sensitive to stack height and diameter, whereas an index of community exposure was relatively insensitive to uncertainty in input parameters. Modeled 1-h and long-term concentrations were compared to inhalation reference values for elemental mercury vapor. Estimated 1-h maximum concentrations within 500 m of the silver smelters consistently exceeded present-day occupational inhalation reference values. Additionally, the entire community was estimated to have been exposed to levels of mercury vapor that exceed present-day acute inhalation reference values for the general public. Estimated long-term maximum concentrations of mercury were predicted to substantially exceed the EPA Reference Concentration for areas within 600 m of the silver smelters. A concentration gradient predicted by AERMOD was used to select soil sampling locations along transects in Potosi. Total mercury in soils ranged from 0.105 to 155 mg kg −1 , among the highest levels reported for surface soils in the scientific literature. The correlation between estimated air concentrations and measured soil concentrations will guide future research to determine the extent to which the current community of Potosi and vicinity is at risk of adverse health effects from historical mercury contamination.

One of the primary goals of hypolimnetic oxygenation systems (HOx) from a drinking water perspective is to suppress sediment-water fluxes of reduced chemical species (e.g., manganese and iron) by replenishing dissolved oxygen (O 2 ) in the hypolimnion. Manganese (Mn) in particular is becoming a serious problem for water treatment on a global scale. While it has been established that HOx can increase sediment O 2 uptake rates and subsequently enhance the sediment oxic zone via elevated near-sediment O 2 and mixing, the influence of HOx on sediment-water fluxes of chemical species with more complicated redox kinetics like Mn has not been comprehensively evaluated. This study was based on Mn and O 2 data collected primarily in-situ to characterize both the sediment and water column in a drinking-water-supply reservoir equipped with an HOx. While diffusive Mn flux out of the sediment was enhanced by HOx operation due to an increased concentration driving force across the sediment-water interface, oxygenation maintained elevated near-sediment and porewater O 2 levels that facilitated biogeochemical cycling and subsequent retention of released Mn within the benthic region. Results show that soluble Mn levels in the lower hypolimnion increased substantially when the HOx was turned off for as little as ∼48 h and the upper sediment became anoxic. Turning off the HOx for longer periods (i.e., several weeks) significantly impaired water quality due to sediment Mn release. Continual oxygenation maintained an oxic benthic region sufficient to prevent Mn release to the overlying source water.