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At least 883 records · Page 49

Integrating biomass quality variability in stochastic supply chain modeling and optimization for large-scale biofuel production

The production of biofuels using second-generation feedstocks has been recognized as an important alternative source of sustainable energy and its demand is expected to increase due to regulations such as the Renewable Fuel Standard. However, the pathway to biofuel industry maturity faces unique, unaddressed challenges. Here, to address this challenges, this article presents an optimization model which quantifies and controls the impact of biomass quality variability on supply chain related decisions and technology selection. We propose a two-stage stochastic programming model and associated efficient solution procedures for solving large-scale problems to (1) better represent the random nature of the biomass quality (defined by moisture and ash contents) in supply chain modeling, and (2) assess the impact of these uncertainties on the supply chain design and planning. The proposed model is then applied to a case study in the state of Tennessee. Results show that high moisture and ash contents negatively impact the unit delivery cost since poor biomass quality requires the addition of quality control activities. Experimental results indicate that supply chain cost could increase as much as 27%–31% when biomass quality is poor. We assess the impact of the biomass quality on the topological supply chain. Our case study indicates that biomass quality impacts supply chain costs; thus, it is important to consider the impact of biomass quality in supply chain design and management decisions.

09 BIOMASS FUELS↗

Reduced alkali-silica reaction damage in recycled glass mortar samples with supplementary cementitious materials

Recycling waste glass aggregate into concrete can reduce environmental impacts but also may lead to serious alkali silica reaction (ASR) damage. This study aims to characterize ASR damage development in the mortar samples containing reactive glass aggregates and investigate the damage reduction effect of the waste supplementary cementitious materials (SCMs), including recycled glass powders and fly ash. The recycled glass aggregate mortar samples with/without SCMs were prepared in this study. The length change tests were first conducted with the prepared mortar samples based on the ASTM C1260 standard. The results demonstrated the added SCMs can largely decrease early-age ASR expansion rate. The optical microscope and Scanning Electron Microscope (SEM) with Energy Dispersive X-ray Spectroscopy (EDS) were further conducted to characterize the ASR damage in mortar samples and investigate the damage mitigation mechanism with added SCMs. The combined SEM imaging and chemical analysis indicated added SCMs can decrease both the alkali and calcium content of the generated ASR gel. In addition, the ASR damage development inside mortar samples were monitored with dynamic micron X-ray CT (μCT) over a reaction period of 63 hour at the temperature of 80°C. The scanning patterns demonstrated the ASR damage can be easily developed from the area with initial cracks and sharp corners. In conclusion, the images of glass power and fly ash samples showed significantly reduced ASR damage. This study showed that adding of SCMs can largely reduce ASR deterioration and thus facilitate the recycling glass particles into concrete.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Effect of supplementary cementitious materials on the degradation of cement-based barriers in radioactive waste repository: A case study in Korea

This study focuses on investigating the chemical degradation characteristics of cementitious barriers used in low- and intermediate-level radioactive waste repository by reactive transport modeling. The impact of the blending with supplementary cementitious materials (SCMs) in the barriers on the chemical degradation was evaluated to find the optimum barrier design. A number of different barrier designs were examined by replacing ordinary Portland cement (OPC) by SCMs (i.e., fly ash, silica fume, and blast-furnace slag). The simulation results showed that silica fume blended barrier has better durability against chemical degradation by rainwater compared to fly ash or blast-furnace slag blended barriers. In addition, the chemical durability of silica fume-based barrier increased with increasing replacement level up to about 20 %. It seems that the amount of formed calcium silicate hydrate (CSH) in the initial cement-based barrier highly affects the overall chemical durability. The newly developed reactive transport model demonstrated its capability for understanding the barrier performance and investigating the optimal design of the barrier system.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Neutron tomography of particulate filters: A non-destructive investigation tool for applied and industrial research

This research describes the development and implementation of high-fidelity neutron imaging and the associated analysis of the images. This advanced capability allows the non-destructive, non-invasive imaging of particulate filters (PFs) and how the deposition of particulate and catalytic washcoat occurs within the filter. The majority of the efforts described here were performed at the High Flux Isotope Reactor (HFIR) CG-1D neutron imaging beamline at Oak Ridge National Laboratory; the current spatial resolution is approximately 50 μm. The sample holder is equipped with a high-precision rotation stage that allows 3D imaging (i.e., computed tomography) of the sample when combined with computerized reconstruction tools. What enables the neutron-based image is the ability of some elements to absorb or scatter neutrons where other elements allow the neutron to pass through them with negligible interaction. Of particular interest in this study is the scattering of neutrons by hydrogen-containing molecules, such as hydrocarbons (HCs) and/or water, which are adsorbed to the surface of soot, ash and catalytic washcoat. Even so, the interactions with this adsorbed water/HC is low and computational techniques were required to enhance the contrast, primarily a modified simultaneous iterative reconstruction technique (SIRT). Lastly, this effort describes the following systems: particulate randomly distributed in a PF, ash deposition in PFs, a catalyzed washcoat layer in a PF, and three particulate loadings in a SiC PF.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

NOvA: Current Status and Future Reach

NO@nA, the NuMI Off-Axis @n_e Appearance experiment will study @n_@m->@n_e oscillations, characterized by the mixing angle @q_1_3. A complementary pair of detectors will be constructed ~14 mrad off beam axis to optimize the energy profile of the neutrinos. This system consists of a surface based 14 kTon liquid scintillatior tracking volume located 810 km from the main injector source (NuMI) in Ash River, Minnesota and a smaller underground 222 Ton near detector at the Fermi National Accelerator Laboratory (FNAL). The first neutrino signals at the Ash River site are expected soon after the completion of 2012 Fermilab accelerator upgrades. In the meantime, a near detector surface prototype has been completed and neutrinos from two sources at FNAL have been observed using the same highly segmented PVC and liquid scintillator detector system that will be deployed in the full scale experiment. With the recent measurements of @q_1_3 as input, updated sensitivities of NO@nA@?s capability to ultimately determine the ordering of the neutrino masses and measure CP violation in neutrino oscillations will be provided. Additionally, design and initial performance characteristics of the surface prototype system along with implications for the full NO@nAprogram will be presented.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Influence of particle size on NIR spectroscopic characterization of sorghum biomass for the biofuel industry

NIR spectroscopy is a rapid and accurate green technology for high-throughput biomass characterization, including sorghum (Sorghum bicolor), a promising energy crop for the biofuel industry. This study assessed the influence of particle size on NIR spectroscopic analysis (wavelength range: 867–2535 nm) of sorghum biomass composition. Grown under field conditions, a total of 113 types of genetically diverse sorghum accessions were dried, ground, and sieved (<250, 250–600, 600–850, and > 850 µm particle size) for developing partial least square regression (PLSR) prediction models for moisture, ash, extractive, glucan, xylan, acid-soluble lignin (ASL), acid-insoluble lignin (AIL), and total lignin (ASL + AIL). Overall, smaller particle sizes provided better model performance, while no single particle size provided the best performance for all the selected components. With only 9 selected bands and 4 latent variables (LVs), the best PLSR model was obtained for moisture with particle size of 600–850 µm with the square root of the coefficient of determination (R) of 0.85, the ratio of prediction to deviation (RPD) of 2.2, and the root mean square error (RMSE) of 0.46 % in external validation. Similar model performances were also obtained for ash, extractive, glucan, and xylan. This study showed that size reduction could effectively improve NIR spectroscopic analysis for lipid-producing sorghum biomass for the biofuel industry.

09 BIOMASS FUELS↗

Characterizing value-added pellets obtained from blends of miscanthus, corn stover, and switchgrass

The current pellet industry primarily relies on woody biomass. Inclusion of a diverse feedstock, such as herbaceous biomass, is necessary to meet the rising demand for pellets in heat and power generation, and for biofuel production. This study was motivated by the need to densify biomass, improving its naturally low energy density, to reach the required pellet standards for biofuel conversion. Here, we developed value-added miscanthus pellets blended with different ratios of corn stover and switchgrass and analyzed their chemical, physical, and mechanical properties. Pure miscanthus pellet durability index (PDI) was less than 85 %, well below the ISO 17225-6 standard for herbaceous pellets. While increasing switchgrass and corn stover ratios increases durability beyond 94 %, it also increases ash content from 1.6 % to 4.6 %, a quality unfavorable for biofuel conversion. The moisture content of the blended pellets varied from 7.12 % to 12.45 %, and positively correlated with the durability of the pellets. Pure miscanthus pellets had the highest bulk density, 633 kg/m 3 , while pellets containing 75 % miscanthus and 25 % corn stover had the lowest density, 564 kg/m 3 . The findings of this study also identified a decrease in the pellet bulk density with the increase in ash content and pellet diameter.

09 BIOMASS FUELS↗

Inorganic characterization of switchgrass biomass using laser-induced breakdown spectroscopy

The inorganic characterization of 74 samples of switchgrass using laser-induced breakdown spectroscopy (LIBS) was undertaken. Determination of ash and inorganic elements content in biomass materials is vital for feedstock screening for bioconversion processes. Hierarchical models using principal component analysis (PCA) and partial least square analysis (PLS) were used to determine the presence of specific elemental micronutrients that are important in determining plant health for robust biomass production. LIBS uses a 532 nm laser with 45 mJ of laser power to excite the samples of switchgrass plant material and the emission of all the elements present in the plant samples were recorded in single spectra with a wide wavelength range of 200–800 nm. The results were compared to the laboratory standard technique, e.g., ICP-OES technique, to determine the true values for major micronutrients such as, silicon (Si), potassium (K), calcium (Ca), magnesium (Mg), phosphorus (P), and sulfur (S). Overall, our objectives were: 1) To determine the spectral features of switchgrass containing different amounts of these elements and 2) To examine the viability of this technique for determining the quality of the feedstock in terms of its inorganic composition. Cross-validation results showed that the broad-based model developed is promising for inorganics prediction in switchgrass. The LIBS validation prediction for the micronutrient elements mentioned here have been obtained. The regression coefficients for Si, were obtained to be 0.995, 0.994 for calibration and validation respectively, in case of Ca the regression coefficients were, 0.994 and 0.992 for calibration and validation. Similarly, in the case of Mg and K these were calculated to be 0.992 and 0.985, and 0.994 and 0.993 respectively. The regression coefficients are not as good as those for the elements mentioned, in case of the two elements S and P. They are 0.957, and 0.878, and 0.952 and 0.894 respectively for calibration, validation for the two elements. This demonstrates that LIBS-based techniques are inherently well suited for diverse environmental applications. Furthermore, LIBS along with PLS model can show capability in determining the viability of switchgrass as a biomass in the production of biofuels and survivability of switchgrass in processes associated with climate change. LIBS can help determining which switchgrass would be appropriate for a specific conversion process that favors low ash content overall or low value of specific inorganics.

59 BASIC BIOLOGICAL SCIENCES↗

Historical releases of mercury to air, land, and water from coal combustion

Coal combustion is one of the largest contemporary sources of anthropogenic mercury (Hg). It releases geologically sequestered Hg to the atmosphere, and fly ash can contaminate terrestrial and aquatic systems. We estimate that coal combustion has released a cumulative total of 38.0 (14.8–98.9, 80% C.I.) Gg (gigagrams, 10 9 g or thousand tonnes) of Hg to air, land, and water up to the year 2010, most of which (97%) has occurred since 1850. The rate of release has grown by two orders of magnitude from 0.01 Gg yr -1 in 1850 to 1 Gg yr -1 in 2010. Geographically, Asia and Europe each account for 32% of cumulative releases and an additional 18% is from North America. About 26.3 (10.2–68.3) Gg, 71% of the total, were directly emitted to the atmosphere, mostly from the industrial (45%) and power generation (36%) sectors, while the remainder was disposed of to land and water bodies. While Europe and North America were the major contributing regions until 1950, Asia has surpassed both in recent decades. By 2010, Asia was responsible for 69% of the total releases of Hg from coal combustion to the environment. Control technologies installed on major emitting sources capture mainly particulate and divalent Hg, and therefore the fraction of elemental Hg in emissions from coal combustion has increased over time from 0.46 in 1850 to 0.61 in 2010. About 11.8 (4.6–30.6) Gg of Hg, 31% of the total, have been transferred to land and water bodies through the disposal or utilization of Hg-containing combustion waste and collected fly ash/FGD waste; approximately 8.8 Gg of this Hg have simply been discarded to waste piles or ash ponds or rivers.

01 COAL, LIGNITE, AND PEAT↗

Subsurface microbial communities as a tool for characterizing regional-scale groundwater flow

Subsurface microbial community distribution patterns are influenced by biogeochemical and groundwater fluxes and may inform hydraulic connections along groundwater-flow paths. This study examined the regional-scale microbial community of the Death Valley Regional Flow System and evaluated whether subsurface communities can be used to identify groundwater-flow paths between recharge and discharge areas. Samples were collected from 36 sites in three groundwater basins: Pahute Mesa–Oasis Valley (PMOV), Ash Meadows (AM), and Alkali Flat–Furnace Creek Ranch (AFFCR). Microbial diversity within and between communities varied by location, and communities were separated into two overall groups that affiliated with the AM and PMOV/AFFCR basins. Network analysis revealed patterns between clusters of common microbes that represented groundwaters with similar geochemical conditions and largely corroborated hydraulic connections between recharge and discharge areas. Null model analyses identified deterministic and stochastic ecological processes contributing to microbial community assemblages. Most communities were more different than expected and governed by dispersal limitation, geochemical differences, or undominating processes. However, certain communities from sites located within or near the Nevada National Security Site were more similar than expected and dominated by homogeneous dispersal or selection. Overall, the (dis)similarities between the microbial communities of DVRFS recharge and discharge areas supported previously documented hydraulic connections between: (1) Spring Mountains and Ash Meadows; (2) Frenchman and Yucca Flat and Amargosa Desert; and (3) Amargosa Desert and Death Valley. However, only a portion of the flow path between Pahute Mesa and Oasis Valley could be supported by microbial community analyses, likely due to well-associated artifacts in samples from the two Oasis Valley sites. This study demonstrates the utility of combining microbial data with hydrologic, geologic, and water-chemistry information to comprehensively characterize groundwater systems, highlighting both strengths and limitations of this approach.

54 ENVIRONMENTAL SCIENCES↗

A biosorption-based approach for selective extraction of rare earth elements from coal byproducts

Coal byproducts could be a promising feedstock to alleviate the supply risk of critical rare earth elements (REEs) due to their abundance and REE content. Herein, we investigated the economic and environmental potential of producing REEs from coal fly ash and lignite through an integrated process of leaching, biosorption, and oxalic precipitation based on experimental data and modeling results. Two microbe immobilization systems (PEGDA) microbe beads and Si sol-gels) were examined for their efficiency in immobilizing Arthrobacter nicotianae to selectively recover REEs. Techno-economic analysis revealed that North Dakota lignite could be a profitable feedstock when Si sol-gel is used due to its high cell loading and REE adsorption capacity. Life cycle analysis revealed that Si sol-gel based biosorption could be more environmental friendly than the prevailing REE production in China due to use of less toxic chemicals. However, fly ash sourced from Powder River Basin coals was neither profitable or environmentally sustainable, primarily due to low solublity of high-value scandium at an economical pulp density (100 ash/L). To further improve the proposed biotechnology, future research could focus on scandium recovery, leaching efficiency, and microbe carriers.

20 FOSSIL-FUELED POWER PLANTS↗

Quaternary tephra from the Valles caldera in the volcanic field of the Jemez Mountains of New Mexico identified in western Canada

A fine-grained, up to 3-m-thick tephra bed in southwestern Saskatchewan, herein named Duncairn tephra (Dt), is derived from an early Pleistocene eruption in the Jemez Mountains volcanic field of New Mexico, requiring a trajectory of northward tephra dispersal of ~1500 km. An unusually low CaO content in its glass shards denies a source in the closer Yellowstone and Heise volcanic fields, whereas a Pleistocene tephra bed (LSMt) in the La Sal Mountains of Utah has a very similar glass chemistry to that of the Dt, supporting a more southerly source. Comprehensive characterization of these two distal tephra beds along with samples collected near the Valles caldera in New Mexico, including grain size, mineral assemblage, major- and trace-element composition of glass and minerals, paleomagnetism, and fission-track dating, justify this correlation. Two glass populations each exist in the Dt and LSMt. The proximal correlative of Dt1 is the plinian Tsankawi Pumice and co-ignimbritic ash of the first ignimbrite (Qbt1g) of the 1.24 Ma Tshirege Member of the Bandelier Tuff. Finally, the correlative of Dt2 and LSMt is the co-ignimbritic ash of Qbt2. Mixing of Dt1 and Dt2 probably occurred during northward transport in a jet stream.

58 GEOSCIENCES↗

Power and particle exhaust for the ARC fusion power plant

To successfully show that fusion is an attractive energy source, the ARCTM fusion power plant will need to operate with a robust, integrated power and particle exhaust solution. To maximise ARC’s fusion power output while avoiding excessive erosion of the plasma-facing components, we will need to radiatively dissipate most of the power crossing the last-closed flux surface, injecting radiating impurities such as argon or neon to access divertor detachment. Divertor detachment will need to be integrated with a high-performance core plasma, and with efficient impurity pumping to prevent the accumulation of helium ash in the core. To access and control detachment in high-performance plasmas, we have designed ARC with up–down-symmetric divertors, with secondary X-points in long, tightly baffled outer legs. Using a core-edge modelling workflow, we predict that with this divertor design, ARC will access detachment with modest argon seeding in the divertor (c Ar,div ∼0.9%), which should have minimal impact on the core ( Z eff,core <0.5) for reasonable argon enrichment (c Ar,div /c Ar,core =6). Due to the high predicted divertor neutral pressure (p div ∼20 Pa), we predict that ARC will sufficiently pump helium to limit ash accumulation in the core (c He,core <2%) for a helium enrichment of c He,div /c He,core =0.4. ARC’s divertor design is expected to increase the stability of a detachment front in the outer divertor leg, helping to prevent divertor reattachment during smaller heat-flux transients such as scrape-off-layer filaments associated with the quasi-continuous exhaust regime. However, this buffering will not be sufficient to prevent divertor reattachment during large type-I edge-localised modes (ELMs), and as such these will need to be avoided on ARC. Experiments on SPARC will be used to select an integrated scenario which avoids or mitigates type-I-ELMs while maintaining access to detachment, good core fusion performance and sufficient impurity exhaust. SPARC experiments will also be used to finalise ARC’s divertor design, by studying the impact of magnetic and first-wall geometry on detachment stability, impurity enrichment and neutral baffling under conditions similar to those expected for ARC. In conclusion, our analysis finds that ARC will have a viable power and particle exhaust solution which is compatible with high-power operations, and this solution will be validated in experiments on SPARC.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Halide Vapor Phase Epitaxy of Ge from an Elemental Source

Halide vapor phase epitaxy shows promise for low-cost photovoltaic device manufacturing because of its high growth rates and lower cost elemental precursors but previously has not been used to deposit epitaxial Ge. Here, we demonstrate Ge deposition by generating GeCl 2 in situ from solid Ge and HCl in a N 2 ambient. To achieve Ge growth, we inject AsH 3 and PH 3 as sources of active hydrogen to the growth surface to create a driving force for growth. We do not observe Ge growth unless a supply of hydrogen is added, consistent with thermodynamic calculations. Furthermore, we show the hydrogen source must crack readily on the substrate surface to enable growth; relatively stable sources such as H 2 do not cause growth. Unintentional group V doping is one drawback of using AsH 3 and PH 3 to drive the Ge reaction. We observed As or P concentrations in the Ge films ranging from 4 x 10 17 to 1 x 10 18 atoms/cm 3 , concentrations that can drastically influence device characteristics. However, we note there are numerous other "helper molecule" options that can provide active hydrogen without doping or etching the material. This work provides a path forward for Ge deposition for optoelectronic devices from an elemental source.

14 SOLAR ENERGY↗

Fast Pyrolysis of Opuntia ficus-indica (Prickly Pear) and Grindelia squarrosa (Gumweed)

Opuntia ficus-indica (prickly pear) and Grindelia squarrosa (gumweed) are two exceptionally drought tolerant plant species capable of growing in arid and semiarid environments. Additionally, they have unique cell wall structures. Prickly pear contains pectin and high levels of ash (16.1%) that is predominantly Ca and K. Gumweed has high levels of extractives that contain grindelic acid and monoterpenoids. The objective of this paper was to evaluate how these unique cell wall components alter the pyrolysis performance of prickly pear and gumweed. Using a tandem micropyrolyzer with GC-MS/FID/TCD, a detailed account of the product slate is given for products generated between 450 and 650 degrees C. Pyrolysis of prickly pear showed that the high levels of ash increase the amount of organics volatilized and shifted product pools, making it possible to generate up to 7.3% carbonyls vs 3.8% for Pinus taeda (loblolly pine) and 10.5% hydrocarbons vs 1.8% for pine depending on reaction conditions. Pyrolysis of gumweed showed that the extractives were volatilized at low temperatures and led to 17.7% grindelic acid and monoterpenoids derivatives in the condensed vapor phase. In conclusion, at high temperatures, the extractives and other biomass components are converted to aromatics and C 5 -C 10 hydrocarbons, giving a total yield of 16.6%, and also generate large amounts of C 2 -C 4 hydrocarbons, 11.3%.

09 BIOMASS FUELS↗

Reformulated Red mud: a robust catalyst for in situ catalytic pyrolysis of biomass

Biomass feedstocks contain inorganic compounds generally classified as ash. The ash consists of compounds of potassium, calcium, magnesium, silicon, phosphorous and other elements. These elements have been reported to influence both the pyrolysis reactions as well as destabilizing the pyrolysis oils during storage. The inorganic elements have also been reported to deposit on catalyst surfaces during in situ catalytic pyrolysis leading to the eventual deactivation of acidic catalysts such as zeolites. The deposition of inorganic elements and their effect on formulated red mud (FRM) catalyst during in situ catalytic pyrolysis of pinyon juniper wood was investigated. The inorganic elements were measured for the fresh, coked, and regenerated catalysts. The BET specific surface area of the FRM catalyst decreased from 76 m2/g for the fresh catalyst to 53 m2/g for the stable regenerated catalyst. After three regenerations, the BET specific surface area stabilized at 53 m2/g and remained constant after all other regenerations. Potassium, calcium, magnesium, and phosphorous were deposited on the catalyst. Potassium deposition was linear with the number of regenerations while magnesium and calcium depositions were initially rapid but leveled off after three regenerations of the catalyst. Phosphorous deposition was almost linear, but the data were more scattered compared to potassium. The potassium deposition was attributed to physical phenomenon whereas calcium and magnesium depositions were more akin to chemical reactions related to the loss of BET surface area of the catalyst. The deposition of these elements on the surface of the catalyst did not deactivate it. After each catalyst regeneration, the oil yield was not significantly affected and the oil oxygen content and viscosity decreased slightly. This clearly showed that formulated red mud is a robust catalyst suitable for in situ catalytic fast pyrolysis of biomass.

Agblevor, Foster↗

Molecular Transformation of Dissolved Organic Matter during the Processes of Wildfire, Alum Coagulation, and Disinfection Using ESI(-) and ESI(+) FT-ICR MS

Forest fires alter the quality of terrestrial dissolved organic matter (DOM) flushed into source water, which could be further changed during alum coagulation and serve as potential disinfection byproduct (DBP) precursors in water facilities. To unveil this molecular transformation, we applied 12T Fourier transform ion cyclotron resonance mass spectrometry on a controlled study which used the leachates of black and white ashes (collected immediately after the 2013 Rim Fire, CA) along with unburned white fir (Abies concolor) and ponderosa pine (Pinus ponderosa). Here, results showed that the assigned features in DOM from burned ashes had a smaller molecular weight (MW), contained more unsaturated, aromatic, and oxidized and less fraction of labile compounds, and were enriched with nitrogen, relative to unburned litters. After alum coagulation, we observed the disappeared features with higher MW and S/C and N/C atom ratios than the resistant features. During the following disinfections, the disappeared features serving as the potential DBP precursors had higher MW and unsaturation degree, contained more S- and N-containing functionalities, and were more aromatic, compared to the resistant features. Our study suggested organic compounds with small MW and high aromaticity as the targets for water facilities to improve post-fire drinking water quality.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗