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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Liquid–Liquid Equilibrium Prediction in Fast Pyrolysis Bio-Oil Systems: A Framework for Incorporating Bio-Oil Complexity

The study of mixtures of bio-oil, water and organic solvents in different proportions can serve as a cost-effective analysis of its content due to the formation of immiscible phases. This manuscript attempts to replicate experimentally determined partition coefficients (K OW ) of relevant species present in fast pyrolysis bio-oil (FPBO). A commercial flowsheeting simulator with surrogate bio-oil model representation is used. Concurrently, pyrolytic lignins in FPBO (‘pyrolignin’) do not have an agreed-upon structural representation, and the literature is ripe with wide variations of said representations. Thus, during the description of FPBO, this pyrolignin fraction was modeled using 20 possible structures (phenolic dimers to tetramers), with the goal of determining the structures for which the experimental data are best described. Two cases were considered: Case 1 normalized the reported experimental mass balance, while Case 2 included the unreported fraction in the mass balance to the total pyroligin. Please, add here a comment on the prediction of the Water oil equilibrium. The best KOW predictions for levoglucosan (LVG) were obtained when the system was modeled with no pyrolignin, presenting an MRE under 10% for both systems WO and BO. Among the possible structures, D2 (dimer), F1 (trimer) and I1, and I3 (tetramers) presented MRE ≤ 13% for both cases.

09 BIOMASS FUELS↗
DOE OSTI2021

Undersizing of aged African biomass burning aerosol by an ultra-high-sensitivity aerosol spectrometer

The ultra-high-sensitivity aerosol spectrometer (UHSAS) differs from most other optical particle spectrometers by using a high-power infrared (IR) laser to detect small particles and reduce the sizing ambiguity due to the non-monotonicity of scattering with particle size. During the NASA ORACLES project (ObseRvations of Aerosols above CLouds and their intEractionS) over the southeast Atlantic Ocean, the UHSAS clearly undersized particles in the biomass burning plume extending from southern Africa. Since the horizontal and vertical extent of the plume was vast, the NASA P-3B research aircraft often flew through a fairly uniform biomass burning plume for periods exceeding 30 min, sufficient time to explore the details of the UHSAS response by selecting single particle sizes with a differential mobility analyzer (DMA) and passing them to the UHSAS. This was essentially an in-flight calibration of the UHSAS using the particles of interest. Two modes of responses appeared. Most particles were undersized by moderate amounts, ranging from not at all for 70 nm aerosols to 15 % for 280 nm particles. Mie scattering calculations show that composition-dependent refractive index of the particles cannot explain the pattern. Heating of brown carbon or tarballs in the beam causing evaporation and shrinking of the particles is the most plausible explanation, though mis-sizing due to non-sphericity cannot be ruled out. A small fraction (10 %–30 %) of the particles were undersized by 25 % to 35 %. Those were apparently the particles containing refractory black carbon. Laboratory calibrations confirm that black carbon is drastically undersized by the UHSAS, because particles heat to their vaporization point and shrink. A simple empirical correction equation was implemented that dramatically improves agreement with DMA distributions between 100 and 500 nm. It raised the median particle diameter by 18 nm, from 163 to 181 nm, during the August 2017 deployment and by smaller amounts during deployments with less intense pollution. Calculated scattering from UHSAS size distributions increased by about 130 %, dramatically improving agreement with scattering measured by nephelometers. The correction is only valid in polluted instances; clean marine boundary layer and free troposphere aerosols behaved more like the calibration spheres. We were unable to directly test the correction between 500 and 1000 nm, though aerodynamic particle sizer (APS) data appear to show that the correction is poor at the largest diameters, which is no surprise as the composition of those particles is likely to be quite different than that of the accumulation mode. This adds to the evidence that UHSAS data must be treated cautiously whenever the aerosol may absorb infrared light. Similar corrections may be required whenever brown carbon aerosol is present.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Influence of Ag metal dispersion on the thermal conversion of ethanol to butadiene over Ag-ZrO 2 /SiO 2 catalysts

Atomistic scale models were developed and coupled with experimental investigation to deliver a functional understanding of catalytic activity and selectivity in the conversion of ethanol to 1,3-butadiene over Ag/ZrO 2 /SiO 2 . A detailed evaluation of the structural and electronic properties of the resultant catalyst models led to the identification of critical active sites of the catalyst. More importantly, the extent of Ag dispersion on the SiO 2 support and relative proximity to ZrO 2 were found to vary with the oxidation state of Ag and local coordination environment (Ag-O SiO2 ) allowing for critical control of ethanol conversion towards butadiene or ethylene. Simulations revealed that less dispersed or clustered Ag contain predominantly Ag 0 charge state and promote conversion of ethanol to ethylene. The well-dispersed Ag/ZrO 2 /SiO 2 catalyst instead contain a larger fraction of cationic Ag δ+ , and predominantly promote ethanol dehydrogenation and subsequent production of butadiene. The theoretical insights drawn were validated and confirmed experimentally using TEM, XRD and reactivity measurements demonstrating the effect of Ag dispersion on the selectivity of ethanol conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

One-pot generation of lignin microspheres and digestible substrate with a polyol-DES pretreatment in high solid loading

Previous lignin microspheres (LMS) preparation needs multiple steps with very low yield and high cost. Herein, we developed a high-solid deep eutectic solvent (DES) pretreatment for an effective lignin fractionation and enzymatic saccharification of moso bamboo under mild temperature (110 °C) with high-solid loading. Lignin was significantly removed from the plant cell wall, and cellulose properties (e.g., crystallinity and degree of polymerization) were also altered during the pretreatment. As a result, the enzymatic digestibility of the pretreated bamboo was dramatically increased. Uniform micro-spherical lignin was directly produced from the pretreatment system, and its particle size could be regulated by controlling the solid loadings and pretreatment temperatures. The lignin microspheres formation mechanism was investigated by analyzing the lignin's size distribution, molecular weight distribution, chemical structure, and hydrophobicity. The DES showed excellent recyclability, and the recycled DES could still remove 42.78% lignin even after 7th circulation associated with 100% glucan saccharification. Further, the mass balance based on 1000 g biomass showed that 196.28 g LMS was directly recovered, which exhibited a high RhB adsorption. Besides, 404.91 g glucose and 36.67 g xylose were obtained after the enzymatic saccharification process. Specifically, GAPI analysis exhibited a near total green and yellow portions of the pictogram, indicating our DES process was green enough to make this biorefinery sustainable. Overall, the proposed DES generated synergistic productions of digestible solid and LMS which could contribute to establish a green and sustainable biorefinery sequence with diverse outputs in one pot.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Brown Carbon Fuel and Emission Source Attributions to Global Snow Darkening Effect

Snow and ice albedo reduction due to deposition of absorbing particles (i.e., snow darkening effect (SDE)) warms the Earth system and is largely attributed to black carbon (BC) and dust. Absorbing organic aerosol (BrC) also contributes to SDE but has received less attention due to uncertainty and challenges in model representation. This work incorporates the SDE of absorbing organic aerosol (BrC) from biomass burning and biofuel sources into the Snow Ice and Aerosol Radiative (SNICAR) model within a variant of the Community Earth System Model (CESM). Additionally, 12 different emission regions of BrC and BC from biomass burning and biofuel sources are tagged to quantify the relative contribution to global and regional SDE. BrC global SDE (0.021–0.056 Wm -2 ) is larger than other model estimates, corresponding to 37%–98% of the SDE from BC. When compared to observations, BrC simulations have a range in median bias (-2.5% to +21%), with better agreement in the simulations that include BrC photochemical bleaching. The largest relative contributions to global BrC SDE are traced to Northern Asia (23%–31%), Southeast Asia (16%–21%), and South Africa (13%–17%). Transport from Southeast Asia contributes nearly half of the regional BrC SDE in Antarctica (0.084–0.3 Wm -2 ), which is the largest regional input to global BrC SDE. Lower latitude BrC SDE is correlated with snowmelt, in-snow BrC concentrations, and snow cover fraction, while polar BrC SDE is correlated with surface insolation and snowmelt. This indicates the importance of in-snow processes and snow feedbacks on modeled BrC SDE.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

100+ RON Gasoline Blendstock for High Efficiency, Low Emissions (CRADA 493)

The PNNL/LanzaTech alcohol-to-Jet (ATJ) patented process converts ethanol from LanzaTech’s syngas fermentation process to low aromatic jet-range isoparaffins. Compounds are generated across a wide boiling range by the process. The project goal is to improve the viability of the ATJ process by increasing the RON of the gasoline fraction and determine what types of engines and vehicles can be fueled with this gasoline. PNNL experts’ team will investigate the impact of the process conditions and catalysts formulation on the blendstock composition in relation with the fuel properties. Co-optima capabilities for fuel properties measurements will be leveraged to assess the potential engines/ vehicles applications of the produced blendstock. A techno-economic-analysis will be conducted to assess the commercial viability of the process for generating a high RON gasoline-range fuel.

09 BIOMASS FUELS↗
DOE OSTI2024

Chemical properties and single-particle mixing state of soot aerosol in Houston during the TRACER campaign

Abstract. A high-resolution soot particle aerosol mass spectrometer (SP-AMS) was used to selectively measure refractory black carbon (rBC) and its associated coating material using both the ensemble size-resolved mass spectral mode and the event trigger single particle (ETSP) mode in Houston, Texas, in summer 2022. This study was conducted as part of the Department of Energy Atmospheric Radiation Measurement (ARM) program's TRacking Aerosol Convection interactions ExpeRiment (TRACER) field campaign. The study revealed an average (±1σ) rBC concentration of 103 ± 176 ng m−3. Additionally, the coatings on the BC particles were primarily composed of organics (59 %; 219 ± 260 ng m−3) and sulfate (26 %; 94 ± 55 ng m−3). Positive matrix factorization (PMF) analysis of the ensemble mass spectra of BC-containing particles resolved four distinct types of soot aerosol, including an oxidized organic aerosol (OOABC,PMF) factor associated with processed primary organic aerosol, an inorganic sulfate factor (SO4,BC,PMF), an oxidized rBC factor (O-BCPMF), and a mixed mineral dust–biomass burning aerosol factor with significant contribution from potassium (K-BBBC,PMF). Additionally, K-means clustering analysis of the single-particle mass spectra identified eight different clusters, including soot particles enriched in hydrocarbon-like organic aerosol (HOABC,ETSP), sulfate (SO4,BC,ETSP), two types of rBC, OOA (OOABC,ETSP), chloride (ClBC,ETSP), and nitrate (NO3,BC,ETSP). The single-particle measurements demonstrate substantial variation in BC coating thickness with coating-to-rBC mass ratios ranging from 0.1 to 100. The mixing state index (χ), which denotes the degree of homogeneity of the soot aerosol, varied from 4 % to 94 % with a median of 40 %, indicating that the aerosol population lies in between internal and external mixing but has large temporal and source type variability. In addition, a significant fraction of BC-containing particles, a majority enriched with oxidized organics and sulfate, exhibit sufficiently high κ values and diameters conducive to activation as cloud nuclei under atmospherically relevant supersaturation conditions. This finding bears significance in comprehending the aging processes of rBC-containing particles and their activation into cloud droplets. Our analysis highlights the complex nature of soot aerosol and underscores the need to comprehend its variability across different environments for accurate assessment of climate change.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Chemical imaging of individual stratospheric particles sampled over North America

The increasing size, severity, and frequency of wildfires have led to dramatic increases in particulate matter concentrations in the troposphere. Severe wildfires can generate intense convective systems capable of transporting large quantities of biomass burning organic aerosols (BBOA) to the upper troposphere and lower stratosphere (UTLS). Chemically complex organic matter and light-absorbing carbonaceous material is introduced into stratospheric regions that were historically isolated from direct surface emissions. In this study, stratospheric particles were sampled over North America during the Dynamics and Chemistry of the Summer Stratosphere (DCOTSS) campaign, an aircraft-based research project designed to characterize convective perturbation in the UTLS. Particle samples collected from six research flights during summer 2022 were analyzed using Computer-Controlled Scanning Electron Microscopy and Scanning Transmission X-ray Microscopy to investigate particle size distributions, morphology, chemical composition, and mixing state of stratospheric particles along transects across the continental United States and adjacent Pacific Ocean airspace. Analysis revealed that all sampled particles contained detectable levels of carbon, with most exhibiting organic volume fractions of 0.37 ± 0.20. Notably, about 5% of the particles also contained soot inclusions, which indicates the presence of refractory black carbon transported to stratospheric altitudes and provides direct evidence of wildfire-derived black carbon reaching the UTLS. Typical particle morphology exhibits organic shells over soot and inorganic cores and suggests secondary processing and aging of BBOA during transport to and within the UTLS. These findings provide compelling evidence that wildfire emissions play a critical role in affecting the long-term composition and radiative properties of stratospheric particles.

Sharpe, Steven [Purdue Univ., West Lafayette, IN (↗
DOE OSTI2021

Structural Reorganization of Noncellulosic Polymers Observed In Situ during Dilute Acid Pretreatment by Small-Angle Neutron Scattering

Production of second-generation bioethanol from lignocellulosic biomass requires pretreatment to open the plant cell wall structure and improve enzyme access. Many different thermochemical pretreatments have been extensively developed and employed, but the exact nature of plant cell wall recalcitrance and the most efficient and economical approach to alter plant cell wall structure via pretreatment still remain elusive. In order to understand the role of noncellulosic switchgrass polymers on the overall efficiency of pretreatment, the structural evolution of the noncellulosic polymers of the plant cell wall were investigated during dilute acid pretreatment (DAP) by employing in-situ small-angle neutron scattering (in-situ SANS). In this study, we observed real-time structural changes not possible to observe by any other technique. To deconvolute the structural evolution of lignin and hemicellulose polymers during DAP, native switchgrass (NATV), and isolated holocellulose (HOLO) and cellulose (CELL) fractions from NATV were studied. Our results show that aggregate particles first appear around 80 °C for NATV and HOLO samples. Further, due to the low temperature and pretreatment severity condition, these particles are likely derived from hemicellulose. The formations of much larger aggregate particles, only observed in the NATV sample, were attributed to lignin. For the HOLO sample, as the temperature and pretreatment severity condition increased, hemicellulose-derived aggregate particle sizes increased, suggesting this process was the nucleation and early stage formation of pseudolignin particles. Consistent with our interpretation of structural evolutions in NATV and HOLO samples, no formation of aggregate particles was observed in CELL samples for the entire duration of the pretreatment. These results suggest that not only lignin but also hemicellulose can form aggregate particles within plant cell walls during pretreatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

A Coupled Theoretical and Experimental Approach to Elucidating the Mechanisms of Methyl Esters

The goal of this project was to probe fundamental kinetics questions regarding the gas phase reactive behavior of oxygenates. In order to succeed, our program necessitated both the development of new experimental tools and the development of theory based kinetic models to explain the chemistry of oxygenate fuels. By using advanced hybrid additive manufacturing/ traditional manufacturing techniques to create specialized ceramic micro-reactors, the team was able to simulate extreme high-temperature environments with much greater precision and durability than was previously possible. These tiny, high-tech tubes allow researchers to capture and identify "fleeting" chemical species—molecules that exist for only a fraction of a millisecond—using sophisticated light sources and mass spectrometry. Additionally, the team supported the development of a tabletop VUV laser system for isomer detection without a synchrotron. Through this work, we have successfully mapped out the specific chemical pathways of various oxygen-rich fuels, solving long-standing mysteries about how these substances break down kinetically. Ultimately, this research provides the fundamental knowledge needed to design next-generation engines and fuels that are better for the environment.

09 BIOMASS FUELS↗
NASA NTRS2019

3+2+X: What Is the Most Useful Depolarization Input for Inverting Lidar Measurements of Non-Spherical Particles to Microphysical Properties?

The typical multiwavelength aerosol lidar data set for inversion of optical to microphysical parameters is composed of three backscatter coefficients (β ) at 355, 532, and 1064 nm and two extinction coefficients (α ) at 355 and 532 nm. This data combination is referred to as 3β +2α or 3+2 data set. This set of data is sufficient for retrieving some important microphysical particle parameters if the particles have spherical shape. Here, we investigate the effect of including the particle linear depolarization ratio (δ) as a third input parameter to the inversion of lidar data. The inversion algorithm is generally not used if measurements show values of δ that exceed 0.10 at 532 nm, i.e. in the presence of non-spherical particles such as desert dust, volcanic ash, and under special circumstances biomass-burning smoke.We use experimental data collected with instruments that are capable of measuring δ at all three lidar wavelengths with an inversion routine that uses the theory of light scattering by randomly oriented spheroids to replicate scattering properties of non-spherical particles. This is the first systematic test of the effect of using all theoretically possible combinations of δ taken at 355, 532, and 1064 nm as input in the lidar data inversion. We find that depolarization information at least at one wavelength already provides useful information in the in version of optical data that describe light-scattering by nonspherical particles. However, any choice of δ(λ) will give lower values of the single-scattering albedo than the traditional 3+2 data set. We find that input data sets that include 355 give a non-spherical fraction that closely resembles the dust ratio we obtain from using β(532) and δ(532) in a methodology applied in aerosol-type separation. The use of 355 in data sets of two or three reduces the fraction of non-spherical particles that is retrieved when using δ(532) and δ(1064). Use of the latter two without accounting for 355 generally leads to high fractions of non-spherical particles that we consider not trustworthy. The use of three δ(λ) instead of two δ(λ) including the constraint that one of these is measured at 355 nm does not provide any advantage over using 3+2+δ(355). Because of the technical challenges involved with accurately measuring δ(1064) we conclude that — depending on measurement capability — the future standard input for inversion using spheroid kernels might be 3+2+δ(355) or 3+2+δ(355)+δ(532).

Tesche, M.↗
DOE OSTI2023

Evidence for multi-decadal fuel buildup in a large California wildfire from smoke radiocarbon measurements

In recent decades, there has been a significant increase in annual area burned in California's Sierra Nevada mountains. This rise in fire activity has prompted the need to understand how historical forest management practices affect fuel composition and emissions. Here we examined the total carbon (TC) concentration and radiocarbon abundance (Δ 14 C) of particulate matter (PM) emitted by the KNP Complex Fire, which occurred during California's 2021 wildfire season and affected several groves of giant sequoia trees in the southern Sierra Nevada. During a 26 h sampling period, we measured concentrations of fine airborne PM (PM 2.5 ), as well as dry air mole fractions of carbon monoxide (CO) and methane (CH 4 ), using a ground-based mobile laboratory. We also collected filter samples of PM 2.5 for analysis of TC concentration and Δ 14 C. High correlation among PM 2.5 , CO, and CH 4 time series confirmed that our PM 2.5 measurements captured variability in wildfire emissions. Using a Keeling plot approach, we determined that the mean Δ 14 C of PM 2.5 was 111.6 ± 7.7‰ (n = 12), which was considerably enriched relative to atmospheric carbon dioxide in the northern hemisphere in 2021 (-3.2 ± 1.4‰). Combining these Δ 14 C data with a steady-state one-box ecosystem model, we estimated that the mean age of fuels combusted in the KNP Complex Fire was 40 years, with a range of 29–57 years. These results provide evidence for emissions originating from woody biomass, larger-diameter fine fuels, and coarse woody debris that have accumulated over multiple decades. This is consistent with independent field observations that indicate high fire intensity contributed to widespread giant sequoia mortality. With the expanded use of prescribed fires planned over the next decade in California to mitigate wildfire impacts, our measurement approach has the potential to provide regionally-integrated estimates of the effectiveness of fuel treatment programs.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Ultra-clean and smoky marine boundary layers frequently occur in the same season over the southeast Atlantic

We study 41 d with daily median surface accumulation mode aerosol particle concentrations below 50 cm -3 (ultra-clean conditions) observed at Ascension Island (ASI; 7.9° S, 14.4° W) between June 2016 and October 2017 as part of the Layered Atlantic Smoke Interactions with Clouds (LASIC) campaign. Interestingly, these days occur during a period of great relevance for aerosol–cloud–radiation interactions, the southeast Atlantic (SEATL)biomass-burning season (approximately June–October). That means that these critical months can feature both the highest surface aerosol numbers, from smoke intrusion into the marine boundary layer, as well as the lowest. While carbon monoxide and refractory black carbon concentrations on ultra-clean days do not approach those on days with heavy smoke, they also frequently exceed background concentrations calculated in the non-burning season from December 2016 to April 2017. This is evidence that even what become ultra-clean boundary layers can make contact with and entrain from an overlying SEATL smoke layer before undergoing a process of rapid aerosol removal. Because many ultra-clean and polluted boundary layers observed at Ascension Island during the biomass burning season follow similar isobaric back trajectories, the variability in this entrainment is likely more closely tied to the variability in the overlying smoke rather than large-scale horizontal circulation through the boundary layer. Since exceptionally low accumulation mode aerosol numbers at ASI do not necessarily indicate the relative lack of other trace pollutants, this suggests the importance of regional variations in what constitutes an “ultra-clean” marine boundary layer. Finally, surface drizzle rates, frequencies and accumulation – as well as retrievals of liquid water path– all consistently tend toward higher values on ultra-clean days. This implicates enhanced coalescence scavenging in low clouds as the key driver of ultra-clean events in the southeast Atlantic marine boundary layer. These enhancements occur against and are likely mediated by the backdrop of a seasonal increase in daily mean cloud fraction and daily median liquid water path over ASI, peaking in September and October in both LASIC years. Therefore the seasonality in ultra-clean day occurrence seems directly linked to the seasonality in SEATL cloud properties. These results highlight the importance of two-way aerosol–cloud interactions in the region.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Methodology for Determination of Cellulosic Glucans and Hemicellulose Content in a Fuel Ethanol Production Facility (CRADA Final Report)

Develop a single methodology for determination of the total cellulosic glucan, including both cellulose and beta-glucans, along with hemicellulose content in corn kernel fiber which could be utilized by the dry grind corn ethanol production industry to determine the cellulosic converted fraction of the corn kernel fiber. The work will build upon a methodology already described in literature but will specifically focus on a more complete determination of the structural polysaccharides in corn kernel fiber to make it more applicable to the corn ethanol industry.

09 BIOMASS FUELS↗
DOE OSTI2020

A phytophotonic approach to enhanced photosynthesis

Photosynthesis is the dominant biotic carbon sink on earth and hence presents an opportunity for enhanced sequestration of CO 2 . If the average net carbon fixation efficiency of terrestrial plants could be increased by 3.3%, all anthropogenic CO 2 accumulating in the atmosphere could instead be reduced and incorporated into terrestrial biomass. Plants make inefficient use of the overly abundant sunlight available to them, a result of having evolved to be competitive and survive highly dynamic environmental conditions rather than maximize photosynthetic productivity. We explore herein a phytophotonic approach to enhanced photosynthesis, whereby sunlight is redistributed by means of luminescent or persistent luminescent (PersL) materials. Phytophotonics has potential at varied scales, ranging from photobioreactors to greenhouses all the way to crops in the field, the latter having the potential to impact planetary CO 2 levels. The approach is three-fold: a spectral redistribution to relieve high-light-stress at the top surface of leaves and increasingly drive photosynthesis deeper in leaves and canopies; a minute-scale temporal redistribution to bridge periods of intermittent shade and reduce shock associated with variable light conditions; and a multiple-hour temporal redistribution to shift a fraction of high-intensity midday lighting to evening hours. Based on simulations of photoluminescent materials and light quality experiments with a model algal system, it is shown that while lengthening daylight hours will require significant improvements in PersL materials, the other two approaches show more immediate promise. We demonstrate a means of concentrating PersL light from SrAl 2 O 4 :Eu,Dy, approaching levels needed to effectively bridge periods of natural shade, and outline the scientific questions and technical hurdles remaining to realize the benefits of the proposed spectral shift.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Application of Time-Domain 1 H NMR for Investigating Dynamics of Vegetative Lipids in Bioenergy Crops at Different Developmental Stages

Sweet sorghum is typically cultivated for the food and fodder market. Recently, sweet sorghum varieties are being metabolically transitioned to enhance energy density by accumulating oil droplets in their vegetative tissues for bioenergy applications. Owing to the high biomass yield of sorghum, the transgenic lines can compete with oil-seed crops for biodiesel yield per unit area. In the initial phase of transgenic development, a high-throughput phenotyping method can bridge the gap between the production pipeline and analysis to improve the efficiency of the process. To meet the requirement, the present study extends the application of time-domain 1 H-NMR spectroscopy for rapid quantification and characterization of the total in-situ lipids of sweet sorghum ‘ramada’ to lay the groundwork for analyzing the upcoming large quantity of transgenic samples. NMR technology has been successfully established for analyzing lipid contents of vegetative tissues of non-transgenic variety. The multiexponential analysis of spin-lattice (T 1 ) relaxation spectra obtained from TD-NMR aided the investigation of the dynamics of the free and bound lipid fraction with plant development. The total lipid concentration of bagasse and leaves of non-transgenic sweet sorghum remained unchanged throughout the plant development. Leaves displayed a higher percentage of bound lipids as compared to bagasse. Here, a significant variation in the lipid concentration of juice was observed at the different growth stages with a maximum lipid accumulation of 1.21 ± 0.04% w/w at the boot stage that decreased with further maturity of the plant.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2016

Aerosol Optical Properties at the Lulin Atmospheric Background Station in Taiwan and the Influences of Long-Range Transport of Air Pollutants

The Lulin Atmospheric Background Station (LABS, 23.47 deg. N 120.87 deg. E, 2862 m ASL) in Central Taiwan was constructed in 2006 and is the only high-altitude background station in the western Pacific region for studying the influence of continental outflow. In this study, extensive optical properties of aerosols, including the aerosol light scattering coefficient [Sigma(sub s)] and light absorption coefficient [Sigma(sub a)], were collected from 2013 to 2014. The intensive optical properties, including mass scattering efficiency [Sigma(sub s)], mass absorption efficiency [Sigma(sub a)] single scattering albedo (Omega), scattering Angstrom exponent (A), and backscattering fraction (b), were determined and investigated, and the distinct seasonal cycle was observed. The value of [Alpha(sub a)] began to increase in January and reached a maximum in April; the mean in spring was 5.89 m(exp. 2) g(exp. -1) with a standard deviation (SD) of 4.54 m(exp. 2) g(exp. -1) and a 4.48 m(exp. 2) g(exp. -1) interquartile range (IQR: 2.95-7.43 m(exp. 2) g(exp. -1). The trend was similar in [Sigma(sub a)], with a maximum in March and a monthly mean of 0.84 m(exp. 2) g(exp. -1). The peak values of Omega (Mean = 0.92, SD = 0.03, IQR: 0.90 - 0.93) and A (Mean = 2.22, SD = 0.61, IQR: 2.12 = 2.47) occurred in autumn. These annual patterns of optical properties were associated with different long-range transport patterns of air pollutants such as biomass burning (BB) aerosol in spring and potential anthropogenic emissions in autumn. The optical measurements performed at LABS during spring in 2013 were compared with those simultaneously performed at the Doi Ang Kang Meteorology Station, Chiang Mai Province, Thailand (DAK, 19.93 deg. N, 99.05 deg. E, 1536 m a.s.l.), which is located in the Southeast Asia BB source region. Furthermore, the relationships among [Sigma(sub s)], [Sigma(sub a)], and (b) were used to characterize the potential aerosol types transported to LABS during different seasons, and the data were inspected according to the HYSPLIT 5-day backward trajectories, which differentiate between different regions of air mass origin.

aerosol optical properties↗
DOE OSTI2023

Integrated hydropyrolysis and vapor-phase hydrodeoxygenation process with Pd/Al 2 O 3 for production of advanced oxygen-containing biofuels from cellulosic wastes

This study focuses on developing advanced oxygen-containing biofuels with high furan, cyclic ketone, and ethanol content from holocellulose and cellulosic wastes. To achieve this, we employed an integrated process that combined hydropyrolysis and vapor-phase hydrodeoxygenation using Pd/Al 2 O 3 as a catalyst. In the first stage, the non-catalytic hydropyrolysis of hemicellulose resulted in furfural and acetic acid fractions that were effectively converted into furans, cyclic ketones, and ethanol in the second-stage reactor over Pd/Al 2 O 3 under 0.3 MPa H 2 . We found that a hydropyrolysis temperature of 440 °C in the first stage reactor resulted in the highest yield of oxygen-containing biofuels (171.1 mg/g) with 89.2% hemicellulose conversion. However, increasing the hydrodeoxygenation temperature in the second stage reactor reduced the yield of oxygen-containing biofuels, and at 400 °C, excess deoxygenation led to hydrocarbon production. The Pd/Al 2 O 3 catalyst demonstrated high stability during the vapor-phase hydrodeoxygenation of primary furfural and acetic acid intermediates, with only 2.1% coke formation after three reaction cycles. This scalable process enables the conversion of various cellulosic wastes into advanced oxygen-containing biofuels, with considerable total yields. Our findings suggest that this integrated process holds great promise for converting biomass waste into advanced oxygen-containing biofuels.

09 BIOMASS FUELS↗