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At least 307 records · Page 17

Optical properties and composition of viscous organic particles found in the Southern Great Plains

Abstract. Atmospheric high-viscosity organic particles (HVOPs) were observed in samples of ambient aerosols collected in April and May 2016 in the Southern Great Plains of the United States. These particles were apportioned as either airborne soil organic particles (ASOPs) or tar balls (TBs) from biomass burning based on spetro-microscopic imaging and assessments of meteorological records of smoke and precipitation data. Regardless of their apportionment, the number fractions of HVOPs were positively correlated (R2=0.85) with increased values of absorption Ångström exponent (AAE) measured in situ for ambient aerosol at the site. Extending this correlation to 100 % HVOPs yields an AAE of 2.6, similar to previous literature reports of the class of light-absorbing organic particles known as brown carbon (BrC). One out of the three samples investigated had a significant number of ASOPs, while the other two samples contained TBs. Although there are chemical similarities between ASOPs and TBs, they can be distinguished based on composition inferred from near-edge absorption X-ray fine structure (NEXAFS) spectroscopy. ASOPs were distinguished from TBs based on their average -COOH/C=C and -COOH/COH peak ratios, with ASOPs having lower ratios. NEXAFS spectra of filtered soil organic brine particles nebulized from field samples of standing water deposited after rain were consistent with ASOPs when laboratory particles were generated by bubble bursting at the air–organic brine interface. However, particles generated by nebulizing the bulk volume of soil organic brine had a particle composition different from ASOPs. These observations are consistent with the raindrop generation mechanism responsible for ASOP emissions in the area of study. In contrast, nebulized samples carry with them higher fractions of soil inorganics dissolved in the bulk volume of soil brine, which are not aerosolized by the raindrop mechanism. Our results support the bubble bursting mechanism of particle generation during rainfall resulting in the ejection of soil organics into the atmosphere. In addition, our results show that ASOPs may only be atmospherically relevant during times when suitable emission conditions are met.

54 ENVIRONMENTAL SCIENCES↗

Reducing Coke and Increasing Bio-Oil Yield during Catalytic Fast Pyrolysis of Biomass Using Phosphorus-Modified Zeolite Catalysts

Catalytic fast pyrolysis (CFP) is a promising strategy for producing hydrocarbon transportation fuels from biomass feedstocks. However, catalyst development is needed to increase bio-oil yields and enhance process economics. In this work, we demonstrate how post synthetic modification of formed ZSM-5 with phosphorus shifts CFP selectivity from coke and light gases toward the desired bio-oil product. Microscale experiments demonstrated reduced coke production relative to unmodified ZSM-5 and identified an optimal P loading. Extensive catalyst characterization revealed that P interacted with Al sites to reduce the acid site density, with preferential binding to the strongest acid sites. Insights from the microscale experiments were leveraged to produce kilogram quantities of formed P-ZSM-5 for evaluation in a larger semi-integrated process. These experiments generated liters of bio-oil that was hydrotreated and fractionated into gasoline, diesel, and jet cuts. The phosphorus-modified ZSM-5 improved CFP bio-oil yield, resulting in an 11% relative increase in the carbon yield from biomass to aviation fuel and a 14% decrease in the minimum fuel selling price. These results highlight the impact targeted changes in catalyst acidity, achieved by adding 2.5 wt % P, can have on the carbon efficiency and feasibility of fuel production from biomass feedstocks.

09 BIOMASS FUELS↗

Optical Properties of Boreal Region Biomass Burning Aerosols in Central Alaska and Seasonal Variation of Aerosol Optical Depth at an Arctic Coastal Site

Long-term monitoring of aerosol optical properties at a boreal forest AERONET site in interior Alaska was performed from 1994 through 2008 (excluding winter). Large interannual variability was observed, with some years showing near background aerosol optical depth (AOD) levels (<0.1 at 500 nm) while 2004 and 2005 had August monthly means similar in magnitude to peak months at major tropical biomass burning regions. Single scattering albedo (omega (sub 0); 440 nm) at the boreal forest site ranged from approximately 0.91 to 0.99 with an average of approximately 0.96 for observations in 2004 and 2005. This suggests a significant amount of smoldering combustion of woody fuels and peat/soil layers that would result in relatively low black carbon mass fractions for smoke particles. The fine mode particle volume median radius during the heavy burning years was quite large, averaging approximately 0.17 micron at AOD(440 nm) = 0.1 and increasing to approximately 0.25 micron at AOD(440 nm) = 3.0. This large particle size for biomass burning aerosols results in a greater relative scattering component of extinction and, therefore, also contributes to higher omega (sub 0). Additionally, monitoring at an Arctic Ocean coastal site (Barrow, Alaska) suggested transport of smoke to the Arctic in summer resulting in individual events with much higher AOD than that occurring during typical spring Arctic haze. However, the springtime mean AOD(500 nm) is higher during late March through late May (approximately 0.150) than during summer months (approximately 0.085) at Barrow partly due to very few days with low background AOD levels in spring compared with many days with clean background conditions in summer.

Eck, T. F.↗

Strangelove ocean at era boundaries, terrestrial or extraterrestrial cause

Negative perturbations in carbon-isotope value of calcite in pelagic sediments were found at times of biotic crisis, marking horizons which are, or were proposed as era boundaries: Cretaceous/Tertiary (K/T), Permian/Triassic (P/T), and Precambrian/Cambrian (PreC/C). The anomaly was also found at several other mass-extinction horizons, such as terminal Ordovician, Frasnian-Famenian, etc. Studies of K/T boundary indicate that only the planktic fraction of the sediments has the negative isotope anomaly, whereas the benthic fraction has the same value across the boundary. This geochemical signal is thus considered a record of strangelove ocean, or an ocean where isotope fractionation of dissolved carbonate ions in surface waters (by biotic function of planktic organisms) has been significantly reduced because of the drastic reduction of the biomass in the oceans. The reduction of marine biomass at each of the era boundaries was related to chemical pollution of the oceans as a consequence of a catastrophic event; a pH decrease of 0.5 could inhibit the fertility of planktons. Studies of earthquakes, volcanic eruptions, and meteorite-impact occurrences have indicated a linearly inverse log/log relationship between the magnitude and frequency of events. The frequency of era boundaries in geologic history supports the postulate that the rare events causing those biotic crises were large bolide-impacts.

Hsue, Kenneth J.↗

Characterization of the Water Soluble Component of Inedible Residue from Candidate CELSS Crops

Recycling of inorganic nutrients required for plant growth will be a necessary component of a fully closed, bioregenerative life support system. This research characterized the recovery of plant nutrients from the inedible fraction of three crop types (wheat, potato, and soybean) by soaking, or leaching, in water. A considerable portion of the dry weight of the inedible biomass was readily soluble (29 percent for soybean, 43 percent for wheat, and 52 percent for potato). Greater weight loss from potato was a result of higher tissue concentrations of potassium, nitrate, and phosphate. Approximately 25 percent of the organic content of the biomass was water soluble, while the majority of most inorganic nutrients, except for calcium and iron, were recovered in the leachate. Direct use of the leachates in hydroponic media could provide between 40-90 percent of plant nutrient demands for wheat, and 20-50 percent of demand for soybean and potato. Further evaluation of leaching as a component of resource recovery scheme in a bioregenerative system requires study of (1) utilization of plant leachates in hydroponic plant culture; and (2) conversion of organic material (both soluble and insoluble) into edible, or other useful, products.

Garland, Jay↗

Proteome specialization of anaerobic fungi during ruminal degradation of recalcitrant plant fiber

The rumen harbors a complex microbial mixture of archaea, bacteria, protozoa, and fungi that efficiently breakdown plant biomass and its complex dietary carbohydrates into soluble sugars that can be fermented and subsequently converted into metabolites and nutrients utilized by the host animal. While rumen bacterial populations have been well documented, only a fraction of the rumen eukarya are taxonomically and functionally characterized, despite the recognition that they contribute to the cellulolytic phenotype of the rumen microbiota. To investigate how anaerobic fungi actively engage in digestion of recalcitrant fiber that is resistant to degradation, we resolved genome-centric metaproteome and metatranscriptome datasets generated from switchgrass samples incubated for 48 h in nylon bags within the rumen of cannulated dairy cows. Across a gene catalog covering anaerobic rumen bacteria, fungi and viruses, a significant portion of the detected proteins originated from fungal populations. Intriguingly, the carbohydrate-active enzyme (CAZyme) profile suggested a domain-specific functional specialization, with bacterial populations primarily engaged in the degradation of hemicelluloses, whereas fungi were inferred to target recalcitrant cellulose structures via the detection of a number of endo- and exo-acting enzymes belonging to the glycoside hydrolase (GH) family 5, 6, 8, and 48. Notably, members of the GH48 family were amongst the highest abundant CAZymes and detected representatives from this family also included dockerin domains that are associated with fungal cellulosomes. A eukaryote-selected metatranscriptome further reinforced the contribution of uncultured fungi in the ruminal degradation of recalcitrant fibers. These findings elucidate the intricate networks of in situ recalcitrant fiber deconstruction, and importantly, suggest that the anaerobic rumen fungi contribute a specific set of CAZymes that complement the enzyme repertoire provided by the specialized plant cell wall degrading rumen bacteria.

Hagen, Live↗

Impacts of Hydrogen Bond Donor Structures in Phenolic Aldehyde Deep Eutectic Solvents on Pretreatment Efficiency

As a green solvent for biomass processing, deep eutectic solvents (DESs) have shown effectiveness in biomass processing. Here, in this study, phenolic aldehydes with different numbers of methoxy groups, including 4-hydroxybenzaldehyde (HBA, no methoxy), vanillin (VA, monomethoxy), and syringaldehyde (SA, dimethoxy) were employed to synthesize DESs with choline chloride (ChCl). The presence of methoxy groups in the hydrogen bond donor structure affected DES properties, as well as biomass pretreatment performance. The high thermal stability of phenolic aldehyde DESs was shown with over 225 °C onset temperature. The hydrogen bond donor with one aldehyde and one hydroxyl group at the para position without a methoxy group (ChCl-HBA) showed the highest xylan removal and delignification, reaching 59.3 and 88.0%, respectively, leading to the highest enzymatic hydrolysis yield. Sonication after pretreatment further enhanced the hydrolysis yields, achieving 83.3% glucan conversion and 50.1% xylan conversion. In the lignin-rich fraction, the recovered lignin showed a low weight–average molecular weight under 2100 g/mol with a relatively uniform molecular weight dispersity below 1.5. This study provides insights into how the chemical structure of hydrogen bond donors in DESs affects biomass processing and paves the way for designing effective lignin-derived DES in future biorefinery processes.

09 BIOMASS FUELS↗

Photosynthetic fractionation of 13C and concentrations of dissolved CO2 in the central equatorial Pacific during the last 255,000 years

Carbon isotopically based estimates of CO2 levels have been generated from a record of the photosynthetic fractionation of 13C [is equivalent to epsilon(p)] in a central equatorial Pacific sediment core that spans the last approximately 255 ka. Contents of 13C in phytoplanktonic biomass were determined by analysis of C37 alkadienones. These compounds are exclusive products of Prymnesiophyte algae which at present grow most abundantly at depths of 70-90 m in the central equatorial Pacific. A record of the isotopic composition of dissolved CO2 was constructed from isotopic analyses of the planktonic foraminifera Neogloboquadrina dutertrei, which calcifies at 70-90 m in the same region. Values of epsilon(p), derived by comparison of the organic and inorganic delta values, were transformed to yield concentrations of dissolved CO2 [is equivalent to c(e)] based on a new, site-specific calibration of the relationship between epsilon(p) and c(e). The calibration was based on reassessment of existing epsilon(p) versus c(e) data, which support a physiologically based model in which epsilon(p) is inversely related to c(e). Values of PCO2, the partial pressure of CO2 that would be in equilibrium with the estimated concentrations of dissolved CO2, were calculated using Henry's law and the temperature determined from the alkenone-unsaturation index U(K/37). Uncertainties in these values arise mainly from uncertainties about the appropriateness (particularly over time) of the site-specific relationship between epsilon(p) and 1/c(e). These are discussed in detail and it is concluded that the observed record of epsilon(p) most probably reflects significant variations in delta pCO2, the ocean-atmosphere disequilibrium, which appears to have ranged from approximately 110 microatmospheres during glacial intervals (ocean > atmosphere) to approximately 60 microatmospheres during interglacials. Fluxes of CO2 to the atmosphere would thus have been significantly larger during glacial intervals. If this were characteristic of large areas of the equatorial Pacific, then greater glacial sinks for the equatorially evaded CO2 must have existed elsewhere. Statistical analysis of air-sea pCO2 differences and other parameters revealed significant (p<0.01) inverse correlations of delta pCO2 with sea surface temperature and with the mass accumulation rate of opal. The former suggests response to the strength of upwelling, the latter may indicate either drawdown of CO2 by siliceous phytoplankton or variation of [CO2]/[Si(OH)4] ratios in upwelling waters.

NASA Discipline Exobiology↗

Model of Fluidized Bed Containing Reacting Solids and Gases

A mathematical model has been developed for describing the thermofluid dynamics of a dense, chemically reacting mixture of solid particles and gases. As used here, "dense" signifies having a large volume fraction of particles, as for example in a bubbling fluidized bed. The model is intended especially for application to fluidized beds that contain mixtures of carrier gases, biomass undergoing pyrolysis, and sand. So far, the design of fluidized beds and other gas/solid industrial processing equipment has been based on empirical correlations derived from laboratory- and pilot-scale units. The present mathematical model is a product of continuing efforts to develop a computational capability for optimizing the designs of fluidized beds and related equipment on the basis of first principles. Such a capability could eliminate the need for expensive, time-consuming predesign testing.

Bellan, Josette↗

Effect of Moisture and Feedstock Variability on the Rheological Behavior of Corn Stover Particles

Continuous feeding, processing, and handling of biomass powders is pivotal to the economic viability of integrated biorefineries. However, current challenges associated with the operational reliability of bulk solids handling and transport greatly impact the process economics and ultimately the widespread commercialization of integrated biorefineries. In this work, we examine the effect of moisture and feedstock variability on the flow behavior of corn stover biomass particles. The total flow energy, compressibility, shear properties, and wall friction angles were measured for corn stover samples A and B containing 0%, 15%, 25%, 50%, and 75% (mass fraction) moisture contents using a FT4 powder rheometer. In general, the flowability of both A and B was reduced when moisture was present as indicated by the stability and variable flow rate, compressibility, and shear tests. The 15% moisture sample had the highest flow energy, revealing the interplay between the increased surface tension and looser packing both of which were caused by liquid bridging. The 75% moisture sample had the highest compressibility and the lowest flowability factor (ff c ). The trend in wall friction angle was found to be dependent upon the surface hydrophobicity of the wall material. The wall friction angle on the hydrophilic, stainless-steel surface increased with moisture and therefore poses additional handling challenges. On the other hand, the wall friction angle on the hydrophobic polymer surfaces were the lowest for samples with intermediate moisture contents. Sample B had greater bulk density, smaller compressibility, and greater flowability than the sample A , as suggested by the compressibility and shear tests. The wall friction angle of sample B was higher than or equal to that of sample A depending on both the type and the surface roughness of the wall material.

09 BIOMASS FUELS↗

Interactions among soil texture, pore structure, and labile carbon influence soil carbon gains

Perennial vegetation with high plant diversity, e.g., restored prairie, is known for stimulation of soil carbon (C) gains, due in part to enhanced formation of pore structure beneficial for long-term C storage. However, the prevalence of this phenomenon across soils of different types remains poorly understood. The aim of the study was to assess the associations between pore structure, soil C, and their differences in monoculture switchgrass and polyculture restored prairie vegetation across a wide range of soils dominating the Upper Midwest of the USA. Six experimental sites were sampled, representing three soil types with texture ranging from sandy to silt loams. The two vegetation systems studied at each site were (i) monoculture switchgrass (Panicum virgatum L.), and (ii) polyculture restored prairie, also containing switchgrass as one of its species. X-ray computed micro-tomography (µCT) was employed to analyze soil pore structure. Structural equation modeling and multiple path analyses were used to assess direct and indirect effects of soil texture and pore characteristics on microbial biomass C (MBC), particulate organic matter (POM), dissolved organic C (DOC), short-term respiration (CO 2 ), and, ultimately, soil organic C (SOC). Across studied sites, prairie increased fractions of medium (50–150 µm Ø) pores by 11–45 %, SOC by 3–69 %, and MBC by 18–59 % (except for one site). The greater were the prairie-induced increases in the medium pore volumes, the greater were the prairie-induced SOC gains. Greater C losses via CO 2 and DOC contributed to slower C accumulation in the prairie soil. We surmise that the interactive feedback loop relating medium pores and soil C acts across a wide range of soil textures and is an important mechanism through which perennial vegetation with high plant diversity, such as restored prairie, promotes rapid SOC gains.

54 ENVIRONMENTAL SCIENCES↗

Polyurethanes Based on Unmodified and Refined Technical Lignins: Correlation between Molecular Structure and Material Properties

The structural complexity and robust intermolecular interactions have challenged the incorporation of technical lignin into value-added polymeric materials for decades. To study the correlation between lignin molecular structure and material properties of lignin-based polyurethanes, we applied co-solvent enhanced lignocellulosic fractionation pretreatment followed by sequential precipitation to produce three distinct lignin preparations with narrowly distributed (molecular weight dispersity <2) and comparatively low molecular weight (<1500 g/mol) from poplar biomass. Structural characterization indicated that these lignin preparations differed in average molecular chain length and stiffness as well as hydroxyl group distribution. Secondary hydroxyl group providers such as aliphatic diols and polyethers were incorporated as building blocks into the lignin-based polyurethanes to provide additional hydrogen capacity to improve the dispersion of lignin in the polyurethane network. The selected aliphatic diols and polyethers interacted with lignin molecules at different levels of strength depending on their molecular structure, and their impacts were ultimately reflected in the mechanical and thermal properties of the resulting lignin-based polyurethanes. The copolymerization of technical lignin with tailored structure and secondary hydroxyl providers could provide new strategies in formulating lignin-based/containing polyurethanes for various functional applications.

36 MATERIALS SCIENCE↗

Technology Case Study: Techno-Economic and Life Cycle Analysis for Microalgae Conversion Pathways to Fuels and Products

This technology case study report details the cost and sustainability prospects for an emerging feedstock - microalgae - converted to fuels and products via a fractionation and upgrading approach termed combined algae processing (CAP). Detailed techno-economic analysis (TEA) and life cycle analysis (LCA) are conducted for the conversion of farmed algae biomass, with two primary scenarios considering the conversion of either high-compositional-quality biomass enriched in lipids (high-lipid [HL]) or lower-quality biomass enriched in protein (high-protein [HP]). Each scenario employs a different biorefinery configuration tailored towards extracting the maximum value from the given biomass composition. The HL scenario produces fuels and non-isocyanate polyurethane (NIPU) as the primary products, while the HP scenario products fuels and a residual solid coproduct which can be used as a co-feed for producing thermoplastics. The results for the HL scenario were particularly promising, with a minimum fuel selling price (MFSP) of $\$$3.68 per gasoline gallon equivalent (GGE) and fuel GHG emissions translating to 54%-76% reduction compared to petroleum fuels depending on the coproduct handling method used. In contrast, the HP scenario faced more challenges in producing biofuels economically, projecting an MFSP of $\$$7.92/GGE despite significant revenues from the residual algae solids. LCA results for the HP case reflected a 24% reduction potential in biorefinery-level GHG emissions. However, these GHG reductions were primarily associated with the thermoplastic coproduct, which accounted for 93% of all biorefinery outputs by mass. Using a process-level allocation method, carbon intensity results were less promising, indicating a net increase in fuel GHG emissions versus petroleum fuels and highlighting the reliance of this scenario on the thermoplastic coproduct.

09 BIOMASS FUELS↗

Heterodoxy in Fast Pyrolysis of Biomass

As the field of fast pyrolysis has matured, it has been accompanied by a kind of orthodoxy in its practice. Among these orthodoxies are the following: (1) oxygen should be excluded from the pyrolysis process; (2) little sugar is produced during pyrolysis; and (3) the major product of pyrolysis is a low-value emulsion in water. Adherence to these tenets is an impediment to the commercial development of fast pyrolysis. Over the past 15 years, research at Iowa State University’s Bioeconomy Institute has challenged these tenets with what might be called heterodoxy in the science and engineering of fast pyrolysis: adding oxygen producing sugars, and fractionating bio-oil into valorized products. This paper reviews these new approaches to pyrolysis and concludes with an outlook for further developing them.

42 ENGINEERING↗

Design Study for Bio-Oil Production from Biomass Using a Dual Fluidized-Bed Reactor

To evaluate the re-design and reconfiguration of a dual-fluidized bed (DFB) gasification system into a recirculating pyrolysis reactor, Computation Fluid Dynamic (CFD) simulations of the system were conducted. The Barracuda Virtual Reactor® computational particle fluid dynamic code was used to perform simulations of the pyrolysis process. Modeling of the chemical reaction kinetics for both gas phase and solid particle phase were included. The recirculating pyrolysis reactor shown in Fig. 1a is based on a bubbling-bed biomass pyrolyzer and a riser combustor to convert the remaining char. The operational differences in the re-configuration of the DFB gasification system into a recirculating pyrolysis system for the production of bio-oil are (1) replacement of a low-surface area inert bed material with a high-surface-area bed material that has acidic properties to provide catalytic activity for the production of bio-oil with reduced oxygen content, (2) lower temperature and residence time for bio-oil production from pyrolysis, (3) replacement of the fluidization gas in the bubbling bed pyrolyzer from steam to nitrogen, and (4) the reduction of pyrolyzer freeboard volume. The bed material used for catalytic pyrolysis is Sasol 300 (300-micron dia., bulk density 0.94 kg/l, and surface area 130 m2/g) and is a theta-alumina with mild acidity. This is in comparison with previous standard bed material Carbo HSP (430-micron dia., bulk density 2.01 kg/l, and surface area 0.03 m2/g) used for gasification. For bio-oil production, pyrolysis in the bubbling bed requires temperatures in the range of 550 C in comparison with gasification temperatures near 850 C. To attain this lower temperature requires management of the energy mass balances, with control of the bed material recirculation rate between bubbling bed pyrolyzer and riser combustor, the introduction of a nitrogen purge in the pyrolyzer, and adjusting the pressure balance between the two vessels. To extract bio-oil from the pyrolysis reactor with a snorkel, two different freeboard configurations were evaluated. In Fig. 1 b the existing high freeboard configuration is shown and in Fig. 1 c the reduced freeboard design is presented. The introduction of a nitrogen purge for the high free board configuration provided the highest bio-oil production from the CFD simulations. To decrease the bed-material circulation rate, primary and secondary air on the combustor side were reduced, and the pressure on the combustor was slightly increased. A portion of the biomass and bio-oil was observed to be transported to the combustor, leading to a smaller pyrolysis yield. The control of the pyrolyzer temperature is performed by controlling the circulation rate. Good fluidization of the bubbling bed and cascade PID control are required to keep the temperature from oscillating due to large time delay experienced when changing primary and secondary air. (a) (b) (c) Figure 1. (a) Dual Fluidized Bed pyrolysis system configuration, (b) mole fraction of nonpolar biooil in high freeboard configuration, and (c) mole fraction of nonpolar bio-oil in low freeboard configuration with nitrogen purge introduced in both configurations.

BASIC BIOLOGICAL SCIENCES,BIOMASS FUELS↗