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At least 1,315 records · Page 73

Evaluating the combustion reactivity of drop tube furnace and thermogravimetric analysis coal chars with a selection of metal additives

Opportunities exist for effective coal combustion additives that can reduce the carbon content of pulverized fuel ash (PFA) to below 6%, thereby making it saleable for filler/building material applications without the need for postcombustion treatment. However, with only limited combustion data currently available for the multitude of potential additives, catalytic performance under pulverized fuel (PF) boiler conditions has received relatively little attention. This paper therefore compares the reactivity of catalyzed bituminous coal chars from thermogravimetric analysis (TGA) with those generated by devolatilization in a drop tube furnace (DTF). The principal aim was to explore the fundamental chemistry behind the chosen additives' relative reactivities. Accordingly, all eight of the investigated additives increased the TGA burnout rate of the TGA and DTF chars, with most of the catalysts demonstrating consistent reactivity levels across chars from both devolatilization methods. Copper(I) chloride, silver chloride, and copper nitrate were thus identified as the most successful additives tested, but it proved difficult to establish a definitive reactivity ranking. This was largely due to the use of physical mixtures for catalyst dispersion, the relatively narrow selection of additives examined, and the inherent variability of the DTF chars. Nevertheless, one crucial exception to normal additive behavior was discovered, with copper(I) chloride perceptibly deactivating during devolatilization in the DTF, even though it remained the most effective catalyst tested. As a prolonged burnout at over 1000{sup o}C was required to replicate this deactivation effect on the TGA, the phenomenon could not be detected by typical testing procedures. Subsequently, a comprehensive TGA study showed no obvious relationship between the catalyst-induced reductions in the reaction's apparent activation energy and the samples recorded burnout rates.

01 COAL, LIGNITE, AND PEAT↗

Effects of Measurement Materials and Oxygen Partial Pressure on the Viscosity of synthetic Eastern and Western United States Coal Slags

The viscosity of the molten ash (slag) resulting from the mineral constituents in carbon feedstock used in slagging gasifiers is critical for controlling the gasification process. The viscosity of two synthetic slags with compositions resembling the mineral impurities in average eastern and western coal feedstock was examined at temperatures from 1300–1500 °C using a rotating bob viscometer. A few combinations of atmospheres and experimental materials were investigated with respect to one another to determine slag viscosity. A CO/CO{sub 2} atmosphere (CO/CO{sub 2} = 1.8, corresponding to a P{sub O{sub 2}} = 10–8 atm) is required to sustain ferrous ions in FeO-containing slags, an environment that is oxidizing to most metals. Iron oxide in the slag prevents usage of Fe parts. In unpurified Ar, the Fe metal surface oxidizes. Using purified argon prevents iron measurement components from oxidation; however, the metallic surfaces act as nucleation sites for the reduction of the Fe oxide in the slag into metallic Fe. Dissolution of ceramic materials into the slag, including Al{sub 2}O{sub 3} and ZrO{sub 2}, occurs in both atmospheres. Therefore, evaluating slag properties in the laboratory is challenging. The measured viscosities of two synthetic slags in this study diverged depending upon material selection. This difference is likely attributable to container/spindle-slag interactions. Viscosity measurements of the eastern coal slag using all ceramic parts agreed best with FactSage prediction above 1350 °C, with an average activation energy of 271.2 kJ. For western coal slag, the dissolution of container/spindle materials was substantial during the measurement, with precipitation of crystalline phase noted. The experimental viscosity data of the western coal slag agreed best with Kalmanovitch prediction above 1350 °C. The activation energy changed dramatically for both data sets of western coal slag, likely indicating the Newtonian-to-non-Newtonian transition.

01 COAL, LIGNITE, AND PEAT↗

Steam-Coal Gasification Using CaO and KOH for in Situ Carbon and Sulfur Capture

We present experimental results of coal gasification with and without the addition of calcium oxide and potassium hydroxide as dual-functioning catalyst-capture agents. Using two different coal types and temperatures between 700 and 900 °C, we studied the effect of these catalyst-capture agents on (1) the syngas composition, (2) CO 2 and H 2 S capture, and (3) the steam-coal gasification kinetic rate. The syngas composition from the gasifier was roughly 20% methane, 70% hydrogen, and 10% other species when a CaO/C molar ratio of 0.5 was added. We demonstrated significantly enhanced steam–coal gasification kinetic rates when adding small amounts of potassium hydroxide to coal when operating a CaO-CaCO 3 chemical looping gasification reactor. For example, the steam–coal gasification kinetic rate increased 250% when dry mixing calcium oxide at a Ca/C molar ratio of 0.5 with a sub-bituminous coal, and the kinetic rate increased 1000% when aqueously mixing calcium oxide at a Ca/C molar ratio of 0.5 along with potassium hydroxide at a K/C molar ratio of 0.06. In addition, we conducted multi-cycle studies in which CaCO 3 was calcined by heating to 900 °C to regenerate the CaO, which was then reused in repeated CaO-CaCO 3 cycles. The increased steam-coal gasification kinetics rates for both CaO and CaO + KOH persisted even when the material was reused in six cycles of gasification and calcination. The ability of CaO to capture carbon dioxide decreased roughly 2-4% per CaO-CaCO 3 cycle. We also discuss an important application of this combined gasifier-calciner to electricity generation and selling the purge stream as a precalcined feedstock to a cement kiln. In this scenario, the amount of purge stream required is fixed not by the degradation in the capture ability but rather by the requirements at the cement kiln on the amount of CaSO 4 and ash in the precalcined feedstock.

01 COAL, LIGNITE, AND PEAT↗

Volume Flow Rate Estimation for Small Explosions at Mt. Etna, Italy, From Acoustic Waveform Inversion

Rapid assessment of the volume and the rate at which gas and pyroclasts are injected into the atmosphere during volcanic explosions is key to effective eruption hazard mitigation. Here, we use data from a dense infrasound network deployed in 2017 on Mt. Etna, Italy, to estimate eruptive volume flow rates (VFRs) during small gas-and-ash explosions. We use a finite-difference time-domain approximation to compute the acoustic Green's functions and perform a full waveform inversion for a multipole source, combining monopole and horizontal dipole terms. The inversion produces realistic estimates of VFR, on the order of 4 × 10 4 m 3 /s and well-defined patterns of source directivity. This is the first application of acoustic waveform inversion at Mt. Etna. Our results demonstrate that acoustic waveform inversion is a mature and robust tool for assessment of source parameters and holds potential as a tool to provide rapid estimates of VFR in near real time.

58 GEOSCIENCES↗

Analyzing Wildland Fire Smoke Emissions Data Using Compositional Data Techniques

By conservation of mass, the mass of wildland fuel that is pyrolyzed and combusted must equal the mass of smoke emissions, residual char and ash. For a given set of conditions, these amounts are fixed. This places a constraint on smoke emissions data which violates statistical assumptions for many of the methods currently used to analyze these data such as linear regression, analysis of variance, and t-tests. These data are inherently multivariate and non-negative parts of a whole. This paper introduces the field of compositional data analysis to the emissions community and provides examples of appropriate statistical treatment of emissions data. It is shown that modified combustion efficiency should not be used as a predictor variable for other smoke emissions because it is not an independent variable. An alternative method based on compositional linear trends to estimate trace gas composition using CO and CO2 is presented. The data used in this paper resulted from projects the DOD/DOE/EPA Strategic 586 Environmental Research and Development Program projects RC-1648 and 1649. The senior 587 author appreciates the guidance and R scripts provided by Prof. Girty at San Diego State 588 University to estimate linear trends by perturbation. J. P.-A. was supported by the Spanish 589 Ministry of Science, Innovation and Universities under the project CODAMET (RTI2018-590 095518-B-C21, 2019-2021). The data used in this study have been previously published and are 591 available in the original publications. DRW conceived the initial manuscript (70 percent) and 592 performed the bulk of the data analysis. JPA provided statistical guidance and compositional data 593 expertise and contributed 20 percent of the manuscript. TJJ and HJ were extensively involved in 594 the study that provided the data. TJJ provide smoke emissions expertise and HJ provided 595 combustion expertise. The authors declare that they have no conflict of interest. The use of trade 596 or firm names in this publication is for reader information and does not imply endorsement by 597 the U.S. Department of Agriculture of any product or service.

simplex, compositional data analysis, balance, log↗

Informed Multi‐Scale Approach Applied to the British Columbia Fires of Late Summer 2017

Abstract Pyrocumulonimbus (PyroCb) clouds have a complex origin dependent on fire dynamics and meteorological conditions. When a pyrocumulonimbus cloud develops and is maintained over a period of time, it can inject significant aerosol into the troposphere and lower stratosphere, resulting in a longer‐term (months to years) occurrence of aerosol in the stratosphere. In this work, we investigate the British Columbia wildfires on 12–13 August 2017 using a multi‐scale simulation framework. We use the output of a physics‐based wildfire model (FIRETEC) with parameterized energy, particle, and gas emissions to drive the upper atmospheric aerosol mass injection within a regional cloud resolving model (HIGRAD). We demonstrate that vertical motions produced by latent heat release of the condensation of ice and cloud particles within the PyroCbs induce another 5 km of lifting of the simulated aerosol plume. Primary black carbon and organic aerosols (OAs) alone may not be enough to explain the observed aerosol burden, thus we show that secondary OA produced via condensation of gases by the fires, ash, and possibly dust can enhance lofted aerosol mass. A simulation with all emission mechanisms active, driven by the observed fuel load and environmental conditions, reasonably reproduces an aerosol profile inferred from observational data.

54 ENVIRONMENTAL SCIENCES↗

A role for subducting clays in the water transportation into the Earth’s lower mantle

Subducting sedimentary layer typically contains water and hydrated clay minerals. The stability of clay minerals under such hydrous subduction environment would therefore constraint the lithology and physical properties of the subducting slab interface. Here we show that pyrophyllite (Al 2 Si 4 O 10 (OH) 2 ), one of the representative clay minerals in the alumina-silica-water (Al 2 O 3 -SiO 2 -H 2 O, ASH) system, breakdowns to contain further hydrated minerals, gibbsite (Al(OH) 3 ) and diaspore (AlO(OH)), when subducts along a water-saturated cold subduction geotherm. Such a hydration breakdown occurs at a depth of ~135 km to uptake water by ~1.8 wt%. Subsequently, dehydration breakdown occurs at ~185 km depth to release back the same amount of water, after which the net crystalline water content is preserved down to ~660 km depth, delivering a net amount of ~5.0 wt% H 2 O in a phase assemblage containing δ-AlOOH and phase Egg (AlSiO 3 (OH)). Our results thus demonstrate the importance of subducting clays to account the delivery of ~22% of water down to the lower mantle.

58 GEOSCIENCES↗

Environmental degradation of high-temperature protective coatings for ceramic-matrix composites in gas-turbine engines

Abstract The need for higher efficiencies and performance in gas-turbine engines that propel aircraft in the air, and generate electricity on land, is pushing the operating temperatures of the engines to unprecedented levels. Replacing some of the current hot-section metallic components with ceramic-matrix composites (CMCs) is making that possible. A high-temperature ceramic coatings system, that includes environmental-barrier coatings (EBCs), are needed to protect CMCs. However, these coatings undergo degradation in the highly hostile environment of the gas-turbine engine consisting of a combination of high gas temperatures, pressures, and velocities. In addition, there is the ubiquitous presence of steam (a combustion by-product) and occasional ingestion of calcia-magnesia-aluminosilicates (CMASs) in the form of dust, sand, or ash from the environment. Steam can cause corrosion of EBCs, and the molten CMAS deposits can react with the EBCs resulting in their failure. This article provides a perspective on the understanding of these degradation mechanisms, and possible approaches, guided by that understanding, for mitigating the degradation. An outlook on the future challenges and opportunities is presented.

Padture, Nitin P. (ORCID:0000000166228559)↗

Direct observation of permafrost degradation and rapid soil carbon loss in tundra

Evidence indicates that 5–15% of the vast pool of soil carbon stored in northern permafrost ecosystems could be emitted as greenhouse gases by 2100 under the current path of global warming. Yet, direct measurements of changes in soil carbon remain scarce, largely because ground subsidence that occurs as the permafrost soils begin to thaw confounds the traditional quantification of carbon pools based on fixed depths or soil horizons. This issue is overcome when carbon is quantified in relation to a fixed ash content, which uses the relatively stable mineral component of soil as a metric for pool comparisons through time. We applied this approach to directly measure soil carbon pool changes over five years in experimentally warmed and ambient tundra ecosystems at a site in Alaska where permafrost is degrading due to climate change. We show a loss of soil carbon of 5.4% per year (95% confidence interval: 1.0, 9.5) across the site. Our findings point to lateral hydrological export as a potential pathway for these surprisingly large losses. This research highlights the potential to make repeat soil carbon pool measurements at sentinel sites across the permafrost region, as this feedback to climate change may be occurring faster than previously thought.

54 ENVIRONMENTAL SCIENCES↗

Direct observation of ion acceleration from a beam-driven wave in a magnetic fusion experiment

According to the article, efficiently heating a magnetically confined plasma to thermonuclear temperatures remains a central issue in fusion energy research. One well-established technique is to inject beams of neutral particles into the plasma, a process known as neutral beam injection. In the classical picture, fast ions generated from neutral beam injection predominantly heat electrons as they are slowed by friction. This electron heat is then collisionally coupled to the plasma ions, which comprise the fusion fuel. Fast ions can also drive plasma waves, which divert energy from the fuel and can degrade confinement. Here we present new observations from a field reversed configuration plasma in which a beam-driven wave in the open field line region couples directly to fuel ions, drawing a high-energy tail on subcollisional timescales that dramatically enhances the fusion rate. This mode therefore allows the beam energy to bypass the electron channel and does so without having a deleterious effect on global plasma confinement. Our results demonstrate a means of directly and non-destructively coupling energy from fast ions to plasma ions, which may pave the way for improved neutral beam injection heating efficiency or the prevention of ash accumulation with alpha channelling.

Physics↗

Predicting wind-driven spatial deposition through simulated color images using deep autoencoders

Abstract For centuries, scientists have observed nature to understand the laws that govern the physical world. The traditional process of turning observations into physical understanding is slow. Imperfect models are constructed and tested to explain relationships in data. Powerful new algorithms can enable computers to learn physics by observing images and videos. Inspired by this idea, instead of training machine learning models using physical quantities, we used images, that is, pixel information. For this work, and as a proof of concept, the physics of interest are wind-driven spatial patterns. These phenomena include features in Aeolian dunes and volcanic ash deposition, wildfire smoke, and air pollution plumes. We use computer model simulations of spatial deposition patterns to approximate images from a hypothetical imaging device whose outputs are red, green, and blue (RGB) color images with channel values ranging from 0 to 255. In this paper, we explore deep convolutional neural network-based autoencoders to exploit relationships in wind-driven spatial patterns, which commonly occur in geosciences, and reduce their dimensionality. Reducing the data dimension size with an encoder enables training deep, fully connected neural network models linking geographic and meteorological scalar input quantities to the encoded space. Once this is achieved, full spatial patterns are reconstructed using the decoder. We demonstrate this approach on images of spatial deposition from a pollution source, where the encoder compresses the dimensionality to 0.02% of the original size, and the full predictive model performance on test data achieves a normalized root mean squared error of 8%, a figure of merit in space of 94% and a precision-recall area under the curve of 0.93.

54 ENVIRONMENTAL SCIENCES↗

Biomass Feedstocks for Renewable Fuel Production: A review of the impacts of feedstock and pretreatment on the yield and product distribution of fast pyrolysis bio-oils and vapors

Renewable transportation fuels from biomass have the potential to substantially reduce greenhouse gas emissions and diversify global fuel supplies. Thermal conversion by fast pyrolysis converts up to 75% of the starting plant material (and its energy content) to a bio-oil intermediate suitable for upgrading to motor fuel. Woody biomass, by far the most widely-used and researched material, is generally preferred in thermochemical processes due to its low ash content and high quality bio-oil produced. However, the availability and cost of biomass resources, e.g. forest residues, agricultural residues, or dedicated energy crops, vary greatly by region and will be key determinates in the overall economic feasibility of a pyrolysis-to-fuel process. Formulation or blending of various feedstocks, combined with thermal and/or chemical pretreatment, could facilitate a consistent, high-volume, lower-cost biomass supply to an emerging biofuels industry. However, the impact of biomass type and pretreatment conditions on bio-oil yield and quality, and the potential process implications, are not well understood. This literature review summarizes the current state of knowledge regarding the effect of feedstock and pretreatments on the yield, product distribution, and upgradability of bio-oil.

09 BIOMASS FUELS↗

Isolation and characterization of new lignin streams derived from extractive-ammonia (EA) pretreatment

One of the key challenges facing lignin conversion to fuels and chemicals is related to the level of carbohydrate and ash impurities found in extracted lignin. Structural modifications of lignin may also occur as a result of biomass pretreatment and harsh lignin extraction protocols. Extractive-Ammonia (EA) is a new pretreatment technology that uses liquid ammonia to cleave lignin–carbohydrate complexes, decrystallize cellulose, solubilize lignin, and selectively extract lignin from lignocellulosic biomass, enabling better utilization of both lignin and carbohydrate components in a biorefinery. The EA-based biorefinery produces two different lignin-rich streams, with different properties, that could potentially be upgraded to fuels and chemicals using green processes. Here, a water/ethanol-based fractionation method was developed to enrich the ammonia-soluble extractives, resulting in a major product stream containing 92% lignin. Detailed characterization of the various streams resulting from EA treatment, including compositional analysis, structural characterization by nuclear magnetic resonance (NMR) spectrometry, elemental analysis, molecular weight analysis, and thermo-gravimetric analysis provides a broad evaluation of the EA-derived lignin product stream structures and properties, assessing their potential for commercial applications. In conclusion, EA-derived lignins preserve much of lignin's functionality, including the sensitive β-aryl ether units. Furthermore, we observed nitrogen incorporation in the lignin-rich streams, notably due to the presence of hydroxycinnamoyl amides formed during ammonia pretreatment.

09 BIOMASS FUELS↗

Novel aqueous amine looping approach for the direct capture, conversion and storage of CO 2 to produce magnesium carbonate

Designing novel integrated chemical pathways for the capture, conversion, and storage of CO 2 is a crucial need for advancing sustainable energy conversion. The accelerated conversion of CO 2 to water-insoluble and stable magnesium carbonate is a thermodynamically downhill route for permanently storing CO 2 . However, a practical constraint of carbon mineralization is the slow kinetics at low CO 2 concentrations. In this study, we investigate a direct integrated mineralization approach, whereby CO 2 , amine solvents (such as monoethanolamine, MEA), water and alkaline Mg-bearing solids are reacted in a slurry reaction environment. About 70% conversion of magnesium oxide to magnesium carbonate was achieved at 50 °C after 3 hours. The looping of amine-bearing solvents between the CO 2 loaded and release states, facilitates the accelerated conversion of magnesium-bearing oxides to magnesium carbonate. Hydrated magnesium carbonate and magnesium hydroxide phases were noted when less than complete conversion of magnesium oxide was achieved. The morphological features were determined using in operando ultra-small and small angle X-ray scattering (USAXS/SAXS) and grazing incidence-small angle X-ray scattering (GI-SAXS) measurements. The proposed pathway is an adaptive, low temperature, single-step approach for the direct capture, conversion and storage of CO 2 . By demonstrating the effectiveness of aqueous alkaline amine looping approach for the accelerated carbon mineralization of MgO, we aim to expand this approach to include heterogeneous alkaline industrial residues such as coal fly ash and steel slag and naturally occurring minerals such as magnesium silicate and calcium silicate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct analysis of cotton swipes for plutonium isotope determination by microextraction-ICP-MS

This study demonstrates a method for determining the isotopic composition of low-level (sub-pg) plutonium (Pu) directly from a cotton swipe. Environmental sample (ES) swipes are routinely employed as a tool for monitoring activities in nuclear facilities. Traditional ES swipe analysis, as employed in nuclear safeguards, utilizes laborious ashing, digestion, and chemical separation procedures prior to mass spectrometric (MS) analysis. Here, an innovative sample introduction technique employing a microextraction probe to extract Pu directly from the swipe surface is described. The microextraction probe lowers onto the swipe surface, seals on a small area (8 mm 2 ), and delivers solvent (2% HNO 3 ) to extract actinide material that may be present. The extracted analyte is subsequently directed into a sector field inductively coupled plasma (ICP)-MS for isotope ratio determination. This microextraction-ICP-MS method successfully determined the isotopic composition ( 240 Pu/ 239 Pu and 242 Pu/ 239 Pu) of three Pu certified reference materials (CRM 136, 137, and 138) that were deposited (1 pg) onto ES swipes. The percent relative difference from the certified value, uncorrected for instrumental fractionation, was <2% for the 240 Pu/ 239 Pu ratio on all three CRMs and <10% for the 242 Pu/ 239 Pu ratio on CRM 136 and 138. Here, the percent relative standard deviation, an estimate of the sample-to-sample isotopic precision, was <4% for the 240 Pu/ 239 Pu and <15% for the 242 Pu/ 239 Pu. Method limits of detection were determined, based on measurements of an enriched 244 Pu material, to be ~7 fg. Additionally, a mixed uranium (U) and Pu deposition was made to determine the method's ability to simultaneously extract U and Pu and determine the isotopic composition of both analytes.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

A portable fiber optic sensor for the luminescent sensing of cobalt ions using carbon dots

Cobalt is critical to energy-relevant technologies, and demand for cobalt will increase significantly with growing global adoption of renewables. However, supply chain stability is threatened by economic and geopolitical factors, incentivizing domestic cobalt production from alternative resources such as coal, coal utilization byproducts (e.g., ash, acid mine drainage) and electronic waste. Rapid, inexpensive, and portable characterization techniques are needed to reduce production costs associated with cobalt prospecting and process monitoring. Here, in this research, we develop a compact, portable fiber optic luminescent probe for cobalt using phosphorus and nitrogen co-doped carbon dots as the sensing material. The carbon dot emission overlaps well with the cobalt absorption band at ~510 nm, leading to a selective decrease in emission as a function of cobalt concentration. The system responds nearly instantly to the presence of cobalt, with detection limits of 0.7 and 3.5 ppm in water and pH 1.68 buffer, respectively, providing comparable performance to a commercial spectrometer at a significantly lower cost. Moreover, the sensor is selective for cobalt in the presence of 13 of the most common metal ions encountered in coal utilization byproducts and is responsive to cobalt when spiked into an acid mine drainage leachate sample, highlighting the sensor's potential for real-world deployment in challenging matrices. In addition, integrating the carbon dots with a filter paper substrate produced ‘test strip’ sensors that exhibited a selective and sensitive visual response to cobalt using a handheld UV lamp. Taken together, the sensing system represents a significant step forward in the development of low-cost practical sensors for high-value metals in complex streams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Cement Changes and Aggregate System on Mechanical Properties of Concrete

In this paper, mechanical properties of concrete mixtures containing different cementitious combinations and two aggregate systems were investigated under plastic and drying conditions. Emphasis was laid on durability and shrinkage of concrete. Life Cycle Analysis was also conducted by using Green Concrete LCA Webtool. Results indicated that the presence of larger aggregate sizes tend to enhance durability of concrete. The presence of nanosilica also imparted superior mechanical properties to concrete. A cementitious combination containing Portland Limestone Cement and fly ash with larger aggregate sizes emerged as a better performing mixture in terms of mechanical properties and with minimum environmental impact.

36 MATERIALS SCIENCE↗