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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Economic Extraction and Recovery of REEs and Production of Clean Value-Added Products from Low-Rank Coal Fly Ash

The University of North Dakota (UND) Energy & Environmental Research Center (EERC) teamed with Pacific Northwest National Laboratory (PNNL) , the North Dakota Industrial Commission Lignite Research Program, and commercial partners Basin Electric Power Cooperative, Great River Energy, and Southern Company to execute a Cooperative Agreement funded by the U.S. Department of Energy’s (DOE’s) National Energy Technology Laboratory (NETL) focused on identifying unique pathways and pretreatments to extract rare-earth elements (REEs) from low-rank coal (LRC) ash in a more economical and environmentally benign manner than current methods. The EERC drew upon the unique and deep knowledge of the team regarding LRC geochemistry, ash transformation mechanisms during combustion, and fly ash chemistry in the approach to understand the portioning of REEs in LRC ash. A comprehensive characterization effort was undertaken to fully establish the form, associations, and partitioning of the REEs and other elements/minerals of interest in fly ash, as well as the ash chemistry, mineralogy, and morphology. Using this information, the team tested methods of REE extraction to take advantage of the unique and advantageous properties of LRC ash. Multiple complementary approaches were evaluated that combined both novel and proven methods to develop an extractive process for REEs and other high-value metals from LRC ash that provide technological and economic progress on the current state of the art. Methodologies were also evaluated for the potential to synergistically remove toxic metals while extracting other high-value metals from the ash, generating a clean, safe ash material as a value-added product. This would eliminate waste and offer significant additional revenue potential. Based on laboratory-scale testing, an initial high-level technical and economic analysis to estimate operating expenses and product revenues to guide future phases of technology development was implemented. By focusing on minimizing process steps and consumptive use of extraction solutions, a tunable, economically viable process for REE extraction from LRC ash was developed. The tunable process has the ability to be adjusted to adapt to the differing ash chemical and physical properties that are characteristic of LRC ash. This is key to deployment as a commercial process. In demonstrating the process, the EERC was able to illustrate mixed REE concentration greater than the goal of 2 wt%. High-level economic analysis of the process with LRC ash of moderate REE levels demonstrated the potential of the process, but recovery of just the REEs was insufficient to cover operational costs. With the additional extraction of other high-value metals found in LRC ash, the process economics approach would break even, and it is anticipated that with process optimization, the developed process could potentially be economically sound. The same economic analysis performed utilizing LRC ash with high levels of REEs showed the recovery of the REEs alone would make the process economically viable even without further optimization.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS2016

Ultraviolet Satellite Measurements of Volcanic Ash

Ultraviolet (UV) remote sensing of volcanic ash and other absorbing aerosols from space began with the launch of the first Total Ozone Mapping Spectrometer (TOMS) instrument in 1978. Subsequent UV satellite missions (TOMS, GOME, SCIAMACHY, OMI, GOME-2, OMPS) have extended UV ash measurements to the present, generating a unique multidecadal record. A UV Aerosol Index (UVAI) based on two near-UV wavelengths, equally applicable to multispectral (TOMS, DSCOVR) or hyperspectral (GOME, SCIAMACHY, OMI, GOME-2, OMPS) instruments, has been used to derive a unique absorbing aerosol climatology across multiple UV satellite missions. Advantages of UV ash measurements relative to infrared (IR) techniques include the ability to detect ash at any altitude (assuming no clouds), above clouds, and over bright surfaces, where visible and IR techniques may fail. Disadvantages include the daytime-only restriction and nonspecificity to silicate ash, since UV measurements are sensitive to any UV-absorbing aerosol, including smoke, desert dust, and pollution. However, simultaneous retrieval of sulfur dioxide (SO2) abundance and UVAI provides robust discrimination of volcanic clouds. Although the UVAI is only semiquantitative, it has proved successful at detecting and tracking volcanic ash clouds from many volcanic eruptions since 1978. NASA A-Train measurements since 2006 (eg, CALIOP) have provided much improved constraints on volcanic ash altitude, and also permit identification of aerosol type through sensor synergy. Quantitative UV retrievals of ash optical depth, effective particle size, and ash column mass are possible and require assumptions of ash refractive index, particle size distribution, and ash layer altitude. The lack of extensive ash refractive index data in the UV-visible and the effects of ash particle shape on retrievals introduce significant uncertainty in the retrieved parameters, although limited validation against IR ash retrievals has been successful. In this contribution, we review UV ash detection and retrieval techniques and provide examples of volcanic eruptions detected in the approx. 37 year data record.

Multidecadal record↗
DOE OSTI2018

Determining Coal Ash Impacts on Radium and Thorium Background Levels in Soil Using Rare Earth Element Analyses - 18604

One challenge at large remediation sites contaminated with radiological materials is differentiating between low-level site-related contamination and NORM. This is because sites contaminated with radiological materials, such as thorium processing and mining and milling facilities, often generate wastes that contain contaminants that are similar to NORM deposits. For sites in urban areas, this issue is further compounded due to the presence of historic industrial fill (historic fill) containing materials such as fly ash, coal ash, and red brick, that exhibit elevated radioactivity levels. These materials often have activity levels near, or even well above, a site's cleanup goal. At a large Superfund Site in the eastern US (Site), many of the suspected Site-related fill areas are commingled with coal and fly ash. As the cleanup criteria for the radionuclides of concern (ROC), radium (Ra) and thorium (Th), is 5 pico-Curies per gram above background, a four-pronged approach was developed to determine if the coal and fly ash are impacting the background levels of the ROCs. This evaluation included a review of boring logs to visually confirm the presence of historic fill, as well as coal fragments and coal ash; a literature review to establish the typical concentrations of Ra and Th found in coal and fly ash from US sources; the use of rare earth analyses to establish chemical signatures for non-Site related historic fill containing coal ash versus Site-related fill; and a quantitative analysis of Site-related data to determine if the radioactivity levels in historic fill containing coal were elevated. Soil samples were collected from two locations at the Site; fill areas containing coal ash that were not suspected to be impacted by Site activities, as well as fill areas containing coal ash that were associated with the former processing facility. These samples were analyzed for rare earth elements (REE), as well as Ra-228 and Th-232 and the ratios of lanthanum, cerium, and neodymium to Ra-228 and Th-232 were established for each sample. Based on a comparison of these data, a strong correlation was established between the rare earth/thorium decay chain ratios and the classification of material as either Site or non-Site related. These data were used to develop a higher background activity for fill areas containing non-Site related NORM. While the cleanup level defined in the Record of Decision remained unchanged, the higher background derived from the fly ash/coal ash material, as identified by REE analyses, resulted in higher project screening levels, which ensured that excavation activities did not 'chase' material that was not Site-related. To date, use of the coal ash background level has saved millions of dollars in cleanup costs since non-Site related contamination is not being remediated. Use of this approach to determine the appropriate background level for a site is relatively straightforward since it relies on visual observation of the soil for coal and fly ash, along with REE analyses, which is an inexpensive, quick, and established analytical method for soil samples. As long as a good rare earth profile of both contaminated and natural (in this case fly ash and coal ash) material can be established, the results can be quite definitive, which could result in significant volume reduction by minimizing the amount of material excavated and disposed of. This will lead to cost and time savings for what could be an otherwise costly and potentially complex excavation. Anyone performing environmental remediation of NORM contaminated sites may benefit from this paper and presentation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

Lube oil-dependent ash chemistry on soot oxidation reactivity in a gasoline direct-injection engine

Gasoline particulate filters (GPF) are considered an enabling technology to meet stringent particulate matter (PM) regulations for gasoline direct-injection (GDI) engines, which are known to produce significant PM emissions. While ash loading in filters has been recognized to be detrimental in filter performance by increasing back pressure, increased ash fractions in soot were observed to enhance soot oxidation. In this study, GDI soot samples derived from different gasoline/lube oil blends were evaluated to identify potential promoting factors when formulated lube oils were dosed into gasoline fuel. Ca-derived ash enhanced soot oxidation remarkably, while P- and ZDDP-derived ash deteriorated soot oxidation. It is apparent that the promoting effect of lube oil-derived ash is due mainly to the Ca component that is the most abundant among additive components in lube oil. Bulk and surface analyses of these ash compounds indicate that Ca-derived ash would be complex compounds, while the contribution of CaSO 4 , which is one of the most abundant ash compounds from diesel engines, is almost negligible. For the validation of the ash promoting impact in filters, the regeneration experiments were compared for a TWC-coated GPF in a GDI engine before and after ash loading was performed. The pressure drop of the ash-loaded GPF decreased noticeably in the initial regeneration stage and it increased gradually, whereas that of no ash-loaded GPF increased gradually without any reduction. So, it is concluded that the ash layer in the GPF assisted soot oxidation in the early regeneration stage when it was in close contact with soot.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2020

Distribution of rare earth elements in fly ash derived from the combustion of Illinois Basin coals

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 Fe 2 O 3 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 Eu N /Eu N * , 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 Eu N /Eu N * , 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 Eu N /Eu N * and a sharp Gd peak. Finally, 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.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2015

Leaching characteristics of toxic constituents from coal fly ash mixed soils under the influence of pH

Highlights: • The impact of pH on the leaching of elements and metals from fly ash mixed soils. • Generally Ca, Cd, Mg, and Sr follows a cationic leaching pattern. • The leaching of As and Se shows an oxyanionic leaching pattern. • The leaching behavior of elements does not change based on material type. • Different fly ash types show different abilities in immobilizing trace elements. - Abstract: Leaching behaviors of Arsenic (As), Barium (Ba), Calcium (Ca), Cadmium (Cd), Magnesium (Mg), Selenium (Se), and Strontium (Sr) from soil alone, coal fly ash alone, and soil-coal fly ash mixtures, were studied at a pH range of 2–14 via pH-dependent leaching tests. Seven different types of soils and coal fly ashes were tested. Results of this study indicated that Ca, Cd, Mg, and Sr showed cationic leaching pattern while As and Se generally follows an oxyanionic leaching pattern. On the other hand, leaching of Ba presented amphoteric-like leaching pattern but less pH-dependent. In spite of different types and composition of soil and coal fly ash investigated, the study reveals the similarity in leaching behavior as a function of pH for a given element from soil, coal fly ash, and soil-coal fly ash mixtures. The similarity is most likely due to similar controlling mechanisms (e.g., solubility, sorption, and solid-solution formation) and similar controlling factors (e.g., leachate pH and redox conditions). This offers the opportunity to transfer knowledge of coal fly ash that has been extensively characterized and studied to soil stabilized with coal fly ash. It is speculated that unburned carbon in off-specification coal fly ashes may provide sorption sites for Cd resulting in a reduction in concentration of these elements in leachate from soil-coal fly ash mixture. Class C fly ash provides sufficient CaO to initiate the pozzolanic reaction yielding hydrated cement products that oxyanions, including As and Se, can be incorporated into.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2012

Fish Bioaccumulation Studies Associated with the Kingston Fly Ash Spill, Spring 2009 – Fall 2010

In December 2008, an ash dike at the Tennessee Valley Authority (TVA) Kingston Fossil Plant ruptured, releasing over one billion gallons of coal fly ash into the Emory and Clinch Rivers. Coal fly ash may contain several contaminants of concern, but of these selenium (Se) and arsenic (As) have been highlighted because of their toxicity and tendency to bioaccumulate in aquatic food chains. To assess the potential impact of the spilled fly ash on humans and the environment, a comprehensive biological and environmental monitoring program was established, for which resident aquatic organisms (among other sample media) are collected to determine contaminant exposure and evaluate the risk to humans and wildlife. Studies on bioaccumulation and fish health are major components of the TVA Biological Monitoring Program for the Kingston fly ash project. These studies were initiated in early Spring 2009 for the purposes of: (1) documenting the levels of fly ash-associated metals in various tissues of representative sentinel fish species in the area of the fly ash spill, (2) determining if exposure to fly ash-associated metals causes short, intermediate, or long-term health effects on these sentinel fish species, (3) assessing if there are causal relationships between exposure (to metals) and effects on fish, (4) evaluating, along with information regarding other ecological and physicochemical studies, the nature and route of contaminant transfer though food chains into higher level consumers, (5) providing important information for the Ecological Risk Assessment (ERA) for the Kingston fly ash project, and (6) serving as an important technology transfer or model study focused on how to best evaluate the environmental effects of fly ash, not only at the Kingston site, but also at sites on other aquatic systems where coal-fired generating stations are located. This report summarizes the bioaccumulation results from the first two years of study after the fly ash spill, including four seasonal collections: Spring 2009, Fall 2009, Spring 2010, and Fall 2010. Both the Spring and Fall studies have focused on 3-4 sentinel fish species that represent different feeding habits, behaviors, and home ranges. In addition to bioaccumulation studies, the Spring investigations also included evaluation of fish health and reproductive integrity on the same fish used for bioaccumulation. Two associated reports present the fish health (Adams et al 2012) and reproductive studies (Greeley et al 2012) conducted in 2009 and 2010. The fish health study conducted in conjunction with the bioaccumulation and reproductive study is critical for assessing and evaluating possible causal relationships between contaminant exposure (bioaccumulation) and the response of fish to exposure as reflected by the various measurements of fish health. This report emphasizes evaluation of arsenic and selenium bioaccumulation in fish and consists of four related studies (Sections 2-5) including, (1) bioaccumulation in liver and ovaries, (2) bioaccumulation in whole body gizzard shad (Dorosoma cepedianum), (3) bioaccumulation in muscle tissue or fillets, and (4) a reconstruction analysis which establishes the relationship between selenium in muscle tissue and that of the whole body of bluegill (Lepomis machrochirus). Metals other than arsenic and selenium are evaluated separately in Section 6. This report focuses on selenium and arsenic for the following reasons: (1) based on baseline studies conducted in early 2009 in the Emory and Clinch River, only two potentially fly-ash related metals, selenium and arsenic, appeared to be elevated above background or reference levels, (2) selenium and arsenic are two of the metals in coal ash that are known to bioaccumulate and cause toxicity in wildlife, and (3) based on bioaccumulation studies of bluegill and carp (Cyprinus carpio) in the Stilling Pond during Spring 2009, which would represent a worst case situation for metal bioaccumulation, selenium and arsenic were the only two metals consistently elevated above background levels in fish. Each of the four selenium and arsenic evaluations presented in this report include an approach section, a results section which addresses primarily spatial and temporal patterns in bioaccumulation, an interpretation and discussion section, and a synthesis section which provides the main summary points of each study. Other metals in fish from near the spill site are evaluated by comparison with reference sites and evaluation of spatial and temporal trends. Statistical approaches to data analysis will be conducted after the third year of bioaccumulation monitoring when there is a larger n size available for analysis, there has been sufficient time for food-chain driven bioaccumulation (2009 data was likely closer to pre-spill exposures), and data correction factors for selenium and mercury (because of poor analytical recoveries for some samples) have been fully codified by the study team.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2016

Ash reduction strategies in corn stover facilitated by anatomical and size fractionation

There is growing interest internationally to produce fuels from renewable biomass resources. Inorganic components of biomass feedstocks, referred to collectively as ash, damage equipment and decrease yields in thermal conversion processes, and decrease feedstock value for biochemical conversion processes. Decreasing the ash content of feedstocks improves conversion efficiency and lowers process costs. Because physiological ash is unevenly distributed in the plant, mechanical processes can be used to separate fractions of the plant based on ash content. This study focuses on the ash separation that can be achieved by separating corn stover by particle size and anatomical fraction. Baled corn stover was hand-separated into anatomical fractions, ground to <19.1 mm, and size separated using six sieves ranging from 9.5 to 0.150 mm. Size fractions were analyzed for total ash content and ash composition. Particle size distributions observed for the anatomical fractions varied considerably. Cob particles were primarily 2.0 mm or greater, while most of the sheath and husk particles were 2.0 mm and smaller. Particles of leaves greater than 0.6 mm contained the greatest amount of total ash, ranging from approximately 8 to 13% dry weight of the total original material, while the fractions with particles smaller than 0.6 mm contained less than 2% of the total ash of the original material. As a result, based on the overall ash content and the elemental ash, specific anatomical and size fractions can be separated to optimize the feedstocks being delivered to biofuels conversion processes and minimize the need for more expensive ash reduction treatments.

09 BIOMASS FUELS↗
DOE OSTI2013

Environmental and technical assessments of the potential utilization of sewage sludge ashes (SSAs) as secondary raw materials in construction

Highlights: ► We used sewage sludge ashes in ready-mix concrete recipe. ► SSAs were used as a substitution of cement. ► Compressive strength of ready-mix concrete incorporating SSAs were similar as blank one. ► Contaminants leaching from concrete monoliths were above threshold limits. - Abstract: Ashes produced by thermal treatments of sewage sludge exhibit common properties with cement. For example, major elements present in SSA are the same of major elements of cement. Hydraulic properties of SSA are quite the same of cement ones. They may therefore be used to substitute part of cement in concrete or other cementitious materials, provided that technical prescriptions are satisfied and that environmental risks are not significantly increased. The objective of the present study was to determine the appropriate substitution ratios to satisfy both technical and environmental criteria. In a first step, the elemental composition and particle size distribution of the ashes were measured. Then the ashes were used along with Portland cement and sand at different ratios of substitution to produce mortar and concrete which were cured for up to 90 days into parallelepipedic or cylindrical monoliths. The mechanical properties of the monoliths were measured using standard procedures for flexural and compressive strengths, and compared to blanks containing no ashes. The environmental criteria were assessed using leaching tests conducted according to standard protocols both on the ashes and the monoliths, and compared to the blanks. Results showed that the characteristics of the ashes ranged between those of cement and sand because of their larger particle size and higher content in SiO{sub 2} as compared to cement. The monoliths made with the highest substitution ratios exhibited a significant decrease in flexural and compressive strengths. However, when the ashes were used in partial substitution of cement at appropriate ratios, the concrete monoliths exhibited similar compressive strengths as the blank samples. The most appropriate ratios were found to be 10% substitution of cement and 2% substitution of sand. The leaching tests conducted on the ashes in their powdery form revealed that amongst the potential contaminants analyzed only Mo and Se were leached at concentrations above the threshold limits considered. The leaching tests conducted on concrete monoliths showed however that none of the contaminants monitored, including Mo and Se, were leached above the limits. In addition, whether concrete recipe incorporated ashes or not, similar concentrations were measured for each potential contaminant in the leachates. This result indicated that mixing ash with cement and sand to produce mortar or concrete induced a stabilization of Mo and Se and thereby constituted in itself a good treatment of the ashes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2012

Trophic structure and metal bioaccumulation differences in multiple fish species exposed to coal ash-associated metals

On December 22, 2008 a dike containing coal fly ash from the Tennessee Valley Authority Kingston Fossil Plant near Kingston Tennessee USA failed and resulted in the largest coal ash spill in U.S. history. Coal ash, the by-product of coal combustion, is known to contain multiple contaminants of concern, including arsenic and selenium. The purpose of this study was to investigate the bioaccumulation of arsenic and selenium and to identify possible differences in trophic dynamics in feral fish at various sites in the vicinity of the Kingston coal ash spill. Elevated levels of arsenic and selenium were observed in various tissues of largemouth bass, white crappie, bluegill and redear sunfish from sites associated with the Kingston coal ash spill. Highest concentrations of selenium were found in redear sunfish with liver concentrations as high as 24.83 mg/kg dry weight and ovary concentrations up to 10.40 mg/kg dry weight at coal ash-associated sites. To help explain the elevated selenium levels observed in redear sunfish, investigations into the gut pH and trophic dynamics of redear sunfish and bluegill were conducted which demonstrated a large difference in the gut physiology between these two species. Redear sunfish stomach and intestinal pH was found to be 1.1 and 0.16 pH units higher than in bluegill, respectively. In addition, fish from coal ash-associated sites showed enrichment of 15N & 13C compared to no ash sites, indicating differences in food web dynamics between sites. These results imply the incorporation of coal ash-associated compounds into local food webs and/or a shift in diet at ash sites compared to the no ash reference sites. Based on these results, further investigation into a broader food web at ash-associated sites is warranted.

Otter, Ryan↗
DOE OSTI2019

Wear and Why? How Ash Elements Can Help Define Wear Profiles of Biomass Feedstocks

Biomass feedstocks have been shown to cause high wear rates on biomass processing equipment, including grinders, pneumatic conveyance systems, and screw feeders. Previously, wear rates were positively correlated with ash concentrations. Physical and chemical properties, including ash content, vary across the anatomy of plants in biomass feedstocks. To better understand biomass tissues that cause the most wear, anatomical fractions of pine forest residues were tested for wear properties. Fractions were tested in the Accelerated Wear Testing Apparatus using steel coupon mass loss to evaluate wear rates. Extrinsic ash was extracted and characterized. Total ash content of the forest residue was 0.80wt%. Anatomical fractions showed varied amounts of ash with highest concentrations in bark and needles (2.33wt%, 3.52wt%, respectively). The wear rate of the forest residue was 2.36mg loss per kg biomass. Low ash fractions, including whitewood and cambium, caused little wear. Bark had lower ash than the needles but resulted in more wear (8.63 vs 5.57mg loss per kg biomass). Bark contained the most extrinsic ash and largest ash particle size, while needles contained the least extrinsic ash and smallest ash particle size. These findings indicate that total ash content (intrinsic plus extrinsic), soil contamination, and elemental analysis can provide information related to wear properties of biomass materials; however, these analyses do not fully explain the differences observed in the wear rates of bark and needles. Additional testing is to determine other parameters of importance.

Lacey, Jeffrey A.↗
DOE OSTI2012

Treatment of fly ash for use in concrete

A process for treating fly ash to render it highly usable as a concrete additive. A quantity of fly ash is obtained that contains carbon and which is considered unusable fly ash for concrete based upon foam index testing. The fly ash is mixed with a quantity of spray dryer ash (SDA) and water to initiate a geopolymerization reaction and form a geopolymerized fly ash. The geopolymerized fly ash is granulated. The geopolymerized fly ash is considered usable fly ash for concrete according to foam index testing. The geopolymerized fly ash may have a foam index less than 40%, and in some cases less than 20%, of the foam index of the untreated fly ash. An optional alkaline activator may be mixed with the fly ash and SDA to facilitate the geopolymerization reaction. The alkaline activator may contain an alkali metal hydroxide, carbonate, silicate, aluminate, or mixtures thereof.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Understanding the Effects of Ash Content on Various Pretreatment Technologies for the Bioconversion of Corn Stover

Here, the study aimed to examine the effects of adding biomass ash on the biochemical processes involved in fermentable sugar production. Corn stover was pretreated using several methods—hot water, dilute acid, alkaline, γ-valerolactone, and ionic liquid methods, each examined with ash loadings of 7.18% and 21.07%. The findings demonstrated that increased ash content adversely affected both pretreatment and enzymatic hydrolysis. Specifically, the total sugar yield was 3 to 16% lower at the higher ash content across all pretreatment methods, and up to 4.01% lower during enzymatic hydrolysis. For acidic pretreatment, the sugar yield decreased as ash content increased. In contrast, ash content had a lesser impact on alkaline pretreatment compared to acidic pretreatment. For example, using corn stover with an ash content as high as 22.65% resulted in only a 2.90% decrease in total sugar yield compared to corn stover without added ash. Further, the primary reasons for the reduced sugar yield in higher ash biomass during acidic pretreatments were likely the neutralizing effect of the ash and decreased acid access to the substrates. During enzymatic hydrolysis, ash reduced the sugar yield by limiting enzyme access to cellulose.

09 BIOMASS FUELS↗
DOE OSTI2018

Effects of roasting additives and leaching parameters on the extraction of rare earth elements from coal fly ash

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 (Na 2 O 2 , NaOH, CaO, Na 2 CO 3 , CaSO 4 , (NH 4 ) 2 SO 4 ). Further experiments investigated the effects of additive:ash ratio, roasting temperature, and leachate pH on REE extraction. We found here that NaOH roasting often recovered >90% of total REE content, equivalent to the USGS-recommended method (Na 2 O 2 sintering). Other additives tested recovered <50% of total REE content; the 450 °C sinter temperature, which was well below the melting points of these agents, may have been a contributing factor. Decreasing the NaOH-ash ratio did not significantly inhibit in REE recoveries, while increasing the leachate pH led to a sharp decline. There was a strong positive correlation between REE extraction and leachate H + molarity. Recoveries of ~100% were observed for the Powder River Basin ash sample regardless of the roasting agent and additive:ash ratio used. This suggests that acid leaching alone is sufficient for recovering REEs from more soluble Powder River Basin ashes. For Appalachian and Illinois Basin ashes, the recommended roasting conditions for >70% REE extraction are a 1:1 NaOH-ash ratio and leaching with 1–2 mol/L HNO 3 .

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2014

Trace element partitioning in ashes from boilers firing pure wood or mixtures of solid waste with respect to fuel composition, chlorine content and temperature

Highlights: • Different solids waste incineration is discussed in grate fired and fluidized bed boilers. • We explained waste composition, temperature and chlorine effects on metal partitioning. • Excessive chlorine content can change oxide to chloride equilibrium partitioning the trace elements in fly ash. • Volatility increases with temperature due to increase in vapor pressure of metals and compounds. • In Fluidized bed boiler, most metals find themselves in fly ash, especially for wood incineration. - Abstract: Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of fly ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature. Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

Speciation of Selenium, Arsenic, and Zinc in Class C Fly Ash

A major environmental concern associated with coal fly ash is the mobilization of trace elements that may contaminate water. To better evaluate proper use of fly ash, determine appropriate disposal methods, and monitor postdisposal conditions, it is important to understand the speciation of trace elements in fly ash and their possible environmental impact. The speciation of selenium, arsenic, and zinc was determined in five representative Class C fly ash samples from combustion of sub-bituminous Powder River Basin coal using synchrotron-based X-ray absorption spectroscopy to provide an improved understanding of the mechanisms of trace element association with the fly ash. Selenium in all fly ash samples occurs predominantly as Se(IV), with the exception of one sample, in which there was a minor amount of Se(0). Se(0) is likely associated with the high content of unburned coal in the sample. Arsenic exists in the fly ash as a single phase most consistent with calcium pyroarsenate. In contrast, zinc occurs as two distinct species in the silicate glass matrix of the fly ash. This work demonstrates that residual carbon in fly ash may reduce potential Se mobility in the environment by retaining it as less soluble elemental Se instead of Se(IV). Further, this work suggests that As and Zn in Class C fly ash will display substantially different release and mobilization behaviors in aquatic environments. While As release will primarily depend upon the dissolution and hydrolysis of calcium pyroarsenate, Zn release will be controlled by the dissolution of alkaline aluminosilicate glass in the ash.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Composition and Plume Gas Interaction Control Iron Fractional Solubility More Than Particle Size in Volcanic Ash: Implications for Fertilization of the North Atlantic

Deposition of volcanic ash is thought to impact marine biogeochemical cycling by adding soluble iron (Fe) to the surface ocean. The magnitude of this input is a function of the amount of ash deposited, the total Fe content in the ash, and ash‐derived Fe's fractional solubility. However, the relative importance of chemical composition, acidic processing by the volcanic plume, and ash particle size in determining solubility is unclear. We paired an aerosol leach meant to provide an upper limit for fractional Fe solubility with chemical analyses of ash from the Cumbre Vieja (CV) and La Soufrière eruptions, which both impacted the North Atlantic in 2021. Fe in the ash samples is <6% soluble, but Fe fractional solubility in CV ash is approximately triple that of La Soufrière ash. Compared to La Soufrière, a larger proportion of the Fe in CV ash is in silicate rather than oxide minerals, which release more soluble Fe. Elevated levels of surficial fluorine (F) also suggest that CV ash was subjected to a more fluorine‐rich eruption plume and underwent more acidic processing. Particle size does not appear to be a primary control on Fe release. We estimate that the CV eruption had a much larger impact on dissolved Fe (DFe) concentration in the surface ocean than the La Soufrière eruption because of differences in soluble Fe content and particle deposition velocity. These differences may help explain why some eruptions elicit a biological response in the ocean while others do not.

Elliott, Hope E. [Univ. of Miami, FL (United State↗
DOE OSTI2020

Distribution of Lanthanides, Yttrium, and Scandium in the Pilot-Scale Beneficiation of Fly Ashes Derived from Eastern Kentucky Coals

In this study, Central Appalachian coal-derived fly ashes from two power plants were beneficiated in a pilot-scale facility in order to produce a product with a relatively consistent concentration of rare earth elements (REE). The <200-mesh final fly ash product was produced by removing the carbon- and Fe-rich particles prior to screening at 200 mesh (75 µm). The Plant D fly ash had high concentrations of CaO and SO3, which were diminished through the two months when the ash was being beneficiated, representing a consequence of the heat, humidity, and excessive rainfall in the Kentucky summer. The high CaO and SO3 concentrations through the early runs likely contributed to the lower REE in the <200-mesh products of those runs. Of the non-REE minor elements, Ba, V, Mn, Zn, and As showed the greatest between-run variations within the runs for each plant. The overall REE concentrations proved to be similar, both on a between-run basis for the individual fly ash sources and on a between-plant basis. Variations in fly ash quality will occur in larger-scale operations, so on-going attention to the fly ash quality and the response of the fly ash to beneficiation is necessary. Changes in the Plant D fly ash with time imply that both the freshness of the original ash and the length and conditions of its storage at the site of beneficiation could be factors in the quality and consistency of the processed fly ash.

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