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At least 55 records · Page 3

NMR of Fully and Partially 13 C-Enriched Biomass Enhances Pendent Group Structural Characterization

Traditional solution-state NMR experiments may either fail or yield unsatisfactory results when employing fully- 13 C-labeled biomass due to complications arising from 13 C– 13 C coupling. Constant-time analogs of HSQC experiments mitigate such issues and deliver enhanced sensitivity. A rarely reported CT-HSQC-TOCSY experiment allows the proton coupling network to deliver much of the same value as the parent experiment on unlabeled or 10–15%- 13 C-labeled biomass polymers but with enhanced sensitivity. In the absence of a viable HMBC analog for long-range correlations, a relayed C–C experiment, i.e., via directly bonded 13 C-labeled networks, enables the reliable assignment of coupled carbons, with the added advantage of correlating the more elusive quaternaries. A C–C-FLOPSY experiment takes advantage of fully- 13 C-labeled materials for mapping extensive carbon networks in the complex polymer mixtures inherent in biomass. Various pendent groups (tricin units, cis- and trans-p-coumarates, and p -hydroxybenzoates) that adorn lignins, and the cis- and trans-ferulates on arabinoxylan polysaccharides, are exquisitely revealed in spectra from isolated lignins or whole-cell-wall materials from maize, sorghum, and poplar.

biopolymers↗

Microbial Biomass in Soils Receiving Varying Levels of Organic Inputs - A Data Compilation

This dataset contains soil microbial biomass data compiled from published laboratory studies and field manipulations of organic inputs to soils. Each study included at least three levels of a given type of organic input applied to a given type of soil. Studies were selected from the literature that had experimentally manipulated organic input rates to soils using unburned, non-synthetic material (e.g. plant litters, manures, and composts). Fifty-five (55) studies, conducted from 1997 to October 2019, were chosen and compiled into a dataset with 358 observations from 96 combinations of a given organic material applied to a given soil in agricultural systems, laboratory incubations, forests, or grasslands. • Studies were selected when biomass measurements used the chloroform fumigation-extraction procedure followed by carbon analysis, or, in two instances, studies estimated microbial biomass using phospholipid fatty acid analysis. • Studies that used fewer than three input rates or characterized microbial biomass via substrate induced respiration were excluded. • The temporal and spatial aspects of the laboratory and field studies were not essential to the analyses (Craig et al., 2021) and were not included with the measurement data. These data were used to assess the relationship between organic input amounts and microbial biomass. Complete reference citations are provided if additional information is needed. The compiled data are provided in two .csv files: (1) soil treatments and microbial biomass data and (2) literature citations. The “Study” field is the cross reference between files. Also provided is the R code for reproducing the results in the related publication.

54 ENVIRONMENTAL SCIENCES↗

Surface Chemistry and Particle Morphology Changes in Pine Biomass under Indirect Thermal Gradients: Implications for Feed Screw Design

The conversion of biomass feedstocks into fuels and chemicals using fast pyrolysis is a promising approach to renewable energy. Feed screws that convey biomass to pyrolysis reactors, however, often encounter plugging. Indirect heating of the feed screw occurs due to contact with the pyrolysis chamber, resulting in a heating gradient ranging from ambient temperature (22 °C) to reactor temperature (500 °C). Given that major cell wall macromolecules, such as lignin, cellulose, and hemicellulose, begin to produce bio-oils and volatile resin acid compounds within this temperature gradient, we hypothesized that indirect heating during feed screw conveyance is sufficient to cause premature degradation of biomass. We characterized this degradation by observing increases in surface roughness, changes in overall particle morphology, and the production and deposition of bio-oils on biomass particle surfaces. Correlative analysis between optical in situ hot-stage microscopy, confocal Raman spectroscopy, and SEM analysis revealed that heating at temperatures as low as 375 °C caused significant increases in surface roughness, with large fissures forming between and within cell walls. Additionally, droplets of bio-oil were observed on particles, especially in the bark and cambium samples. This work suggests that these phenomena contribute to particle agglomeration, leading to feed screw plugging, and that engineering a solution to cool the feed screw could prevent particle agglomeration and reduce plugging incidents, thereby increasing biomass processing efficiency.

09 BIOMASS FUELS↗

A Performance Comparison of Low-Cost Near-Infrared (NIR) Spectrometers to a Conventional Laboratory Spectrometer for Rapid Biomass Compositional Analysis

The performance of a conventional laboratory near-infrared (NIR) spectrometer and two NIR spectrometer prototypes (a Texas Instruments NIRSCAN Nano evaluation model (EVM) and an InnoSpectra NIR-M-R2 spectrometer) are compared by collecting reflectance spectra of 270 well-characterized herbaceous biomass samples, building calibration models using the partial least squares (PLS-2) algorithm to predict five constituents of the samples from the reflectance spectra, and comparing the resulting model statistics. The prediction models developed using spectra from the Foss XDS spectrometer were slightly better than the prediction models developed using spectra from either the TI NIRSCAN Nano EVM and the InnoSpectra NIR-M-R2 as measured by the root mean square error (RMSECV) and the correlation coefficient (R 2 _cv) for “leave-one-out” cross-validation (CV). The models built from the two prototype units were not statistically significantly different from each other (p = 0.05). The Foss spectrometer has a larger wavelength range (400–2500 nm) compared with the two prototypes (900–1700 nm). When the spectra from the Foss XDS spectrometer were truncated so their wavelength range matched the wavelength range of the two prototype units, the resulting model was not statistically significantly different from the models from either prototype.

47 OTHER INSTRUMENTATION↗

Corrosion and Chemical Characterization of Bio-Oils from Biomass with Varying Ash and Moisture Contents

As part of the Feedstock Conversion Interface Consortium four samples of pine chips (all combinations of low and high moisture and ash content) were collected and processed for fast pyrolysis. The prepared biomass samples were liquefied at the National Renewable Energy Laboratory (NREL) using the fast pyrolysis process. Following some characterization of the bio-oils at NREL, the bio-oils were shipped to Oak Ridge National Laboratory (ORNL) for corrosion testing and further characterization.The content and composition of ash in each bio-oil was determined. Corrosion testing consisted of exposing selected metallic and elastomer samples for 1000 hr at 50°C and for longer times at room temperature as well as electrochemical impedance spectroscopy measurements to assess relative corrosivity of the bio-oils. Chemical characterization was conducted to identify the corrosive component of the bio-oils as well as to define the chemical differences among the oils. It was hypothesized that there could be a catalytic effect from the higher ash content in two of the biomass sources. Results of these characterization and corrosion studies will be reported.

Keiser, Jim↗

NREL's Capabilities in Algae-Based Chemicals, Polymers, and Fuels

NREL is advancing research and development (R&D) to maximize photosynthetic carbon capture into biomass for conversion to a broad portfolio of valuable products. Areas of focus include: (1) Carbon capture improvement through photosynthesis engineering; (2) Biotechnology and genetic toolbox development for broad species portfolio; (3) Conversion and fractionation of algal biomass to create high-value products and fuels; (4) Biological seaweed conversion to volatile fatty acids as fuel and product feedstocks; (5) Novel polyurethane production synthesis from fully renewable algae-based feedstocks; (6) Advanced analytical characterization of biomass feedstocks; and (7) Process techno-economic and life cycle modeling.

algae↗

Root biomass and traits across four lowland Panamanian forests from 0 - 1.2 m soil depths

Fine roots are key to ecosystem-scale nutrient, carbon (C), and water cycling, yet our understanding of fine root traits variation within and among tropical forests, one of Earth’s most C-rich ecosystems, is limited. We characterized root biomass, morphology, nutrient content, and arbuscular mycorrhizal fungal (AMF) colonization in 10 cm increments to 1.2 m depth across four distinct lowland Panamanian forests. The datasets provided include a .xlsx file for fine root characteristics across 10 cm increment depths to 1.2 m collected from late 2017 to 2018 across four different forests. Root characteristics include live fine root biomass, dead fine root biomass, coarse root biomass, specific root length, root diameter, root tissue density, specific root area, arbuscular mycorrhizal fungi colonization, root chemistry (e.g., organic chemistry), root %N, root %C, root C/N ratio, and root radiocarbon content. This .xlsx file contain four tabs with 1) Dataset; 2) Metadata with information about each column in the dataset; 3) The sampling methods summarized; 4) Sites information. We also provided csv files for each of these tabs. Additionally, a .kml file is provided with coordinates for all 32 plots included in the study across four forests (n = 8 plots per site/forest). This dataset serves as baseline data before a throughfall exclusion experiment, Panama Rainforest Changes with Experimental Drying (PARCHED), was implemented. No special software is needed to open these files.

54 ENVIRONMENTAL SCIENCES↗

Comparing Calibration Algorithms for the Rapid Characterization of Pretreated Corn Stover Using Near-Infrared Spectroscopy

Rapid characterization of biomass composition is a key enabling technology for biorefineries—the ability to measure the chemical composition of biomass materials entering the biorefinery as well as the composition of key process intermediate streams would allow real-time process control and the development of robust models to predict process performance. The utility of near-infrared (NIR) spectroscopy for rapid characterization requires multivariate algorithms for building calibration models. The most prevalent algorithm used for building calibration models using NIR spectra is the linear modeling algorithm Partial Least Squares Regression (PLS). Nonlinear regression algorithms (which are typically more computationally intensive than linear modeling approaches) have gained popularity in recent years due to their ability to solve a wide variety of classification and regression problems and the dramatic increase in available computational resources. In this work, we demonstrate that a calibration model can predict the composition of corn stover process intermediate samples pretreated with three different treatments—hot water (HW), dilute acid (DA), and deacetylation followed by dilute acid (DDA). We quantitatively compare three different algorithms for building prediction models based on near-infrared spectroscopy—partial least squares (PLS), support vector machines (SVM), and random forests (RF). We demonstrate the utility of improving model performance by accounting for instrument performance variability using repeated measurements of standard materials (e.g., the “repeatability file” strategy) and investigate its performance with nonlinear regression techniques, and we discuss methods for quantifying the uncertainties of specific predictions among the three methods.

09 BIOMASS FUELS↗

Chapter 4: "Waste"-to-Energy for Decarbonization - Transforming Nut Shells Into Carbon-Negative Electricity

This chapter presents a study demonstrating waste pistachio nut shells as a renewable feedstock for climate-friendly electricity generation via industrial gasification technology. The study includes biomass feedstock characterization (i.e., pistachio waste critical material attributes), process variability (i.e., bulk material handling), and overall operational reliability and conversion performance through extended testing. Additionally, techno-economic analysis (TEA) and life cycle assessment (LCA) were performed to assess the economic feasibility and environmental impact of the technology to transform agricultural waste to biopower. For processing pistachio waste material, among critical material attributes, fines content in the biomass (<1/4") had the largest potential to reduce the operating time of the gasifiers due to plugging. Pelletizing fines and co-feeding them with the mixed pistachio waste increased the average feed density, feed rate, and biochar production. Compared to pine wood chips, mixed pistachio waste yielded higher biochar quantity but slightly reduced quality. In general, a systematic Quality by Design methodology is the preferred approach for designing preprocessing and material conveyance systems, where a downstream technology (end user) for the produced intermediate is specified at the outset. TEA results show that the biochar production rate and selling price had an overwhelming impact on the modeled Minimum Electricity Selling Price (MESP), which ranged from 35.5 to 39.9 cents/kWh for the cases studied (16 h/day operational basis). Moreover, LCA results show that the valorization of pistachio shells for biopower generation is a "carbon negative" process that can help decarbonize the U.S. electricity grid. The specific carbon intensity was -0.29 to -0.71 kg CO2e/kWh, compared to 0.45 kg CO2e/kWh for the average U.S. electricity mix. Biochar production from pistachio waste as a potential means for carbon sequestration was a significant driver for the LCA. The highly stable biochar permanently sequesters a considerable fraction of biochar carbon in the ground, more than enough to offset the life cycle emissions, and can be a complementary climate change mitigation strategy.

bio-char↗

Demonstrating a butylamine-based deconstruction method for poplar biomass and conversion by diverse microbial strains

Low-boiling alkylamines such as butylamine offer promise as effective biomass pretreatment solvents that can be readily recovered and recycled; however, their capability to support microbial conversion of nutrients present in hydrolysates represents an important area for investigation. Here we employed butylamine to pretreat poplar biomass and characterize its effects on the release of fermentable sugars after solvent removal and enzymatic hydrolysis, as well as the biocompatibility of the produced hydrolysates with three organisms commonly used as bioconversion hosts. We observed that residual butylamine and the derivative butylacetamide were present in high enough concentrations to exert toxicity to strains of Aspergillus niger, Pseudomonas putida, and Rhodosporidium toruloides that produce malic acid, isoprenol and bisabolene, respectively. Removal of the toxic compounds by charcoal filtration and nutrient supplementation resulted in a hydrolysate containing >100 g L −1 of sugars that enabled strong growth, substrate consumption and bioproduct accumulation, outperforming defined cultivation media. This is the first demonstration of a butylamine-based deconstruction process for poplar biomass at a pilot-scale to achieve conversion of high sugar concentrations to valuable bioproducts with engineered microbes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Root Characteristics Vary with Depth Across Four Lowland Seasonal Tropical Forests

Fine roots are key to ecosystem-scale nutrient, carbon (C), and water cycling, yet our understanding of fine root trait variation within and among tropical forests, one of Earth’s most C-rich ecosystems, is limited. We characterized root biomass, morphology, nutrient content, and arbuscular mycorrhizal fungal (AMF) colonization to 1.2 m depths across four distinct lowland Panamanian forests, and related root characteristics to soil C stocks. We hypothesized that: (H1) Fine root characteristics vary consistently with depth across seasonal tropical forests, with deeper roots exhibiting more exploratory traits, such as for deep water acquisition; (H2) fine root characteristics vary among tropical forests mainly in surface soils, where resource availability also varies. Here we found consistent variation with depth across the four forests, including decreased root biomass, root tissue density, and AMF, and increased specific root length. Among the forests, there was variation in some fine root characteristics, including greater surface root biomass and lower SRL in the wettest forest, and smaller fine root diameter in the driest forest. We also found that root characteristics were related to total soil C stocks, which were positively related to root biomass and negatively related to specific root length. These results indicate emergent properties of root variation with depth across tropical forests, and show site-scale variation in surface root characteristics. Future work could explore the flexibility in root characteristics under changing conditions such as drought.

13C NMR↗

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↗

At-Line Sampling and Characterization of Pyrolytic Vapors from Biomass Feedstock Blends Using SPME-GC/MS-PCA: Influence of Char on Fast Pyrolysis

Solid-phase microextraction (SPME) coupled with GC-MS analysis was used for at-line sampling of pyrolytic vapors produced during fast pyrolysis of biomass. The pure and binary blends of switchgrass (SWG) and pine harvest residues (PT6) were used as feedstock. Sequential SPME sampling allowed for monitoring of changes in the pyrolysis vapors as char accumulated in the fluid bed. The concentration and composition of the vapors desorbed from the SPME fibers were investigated using GC-MS, and the data sets were then analyzed using principal component analysis (PCA) to compare the composition of the pyrolysis vapors over the course of the pyrolysis run. The chemical composition of both carbohydrate and lignin fragments varied as the char builds up in the reactor bed. Fragments derived from cellulose and xylan included anhydrosugars, furans and light oxygenated compounds. Lignin fragments included methoxyphenols, phenolic ketones and aldehydes, low molecular weight aromatics. The composition of the carbohydrate fragments changed more than the lignin fragments as the char build-up in the fluid bed. This combination of SPME-GC/MS-PCA were a novel, easy and effective method for measuring the composition and changes in the composition of pyrolysis vapors during the fast pyrolysis process. Here, this work also highlighted the effect of char build-up on the composition of the overall pyrolysis vapors.

09 BIOMASS FUELS↗

Go with the Flow: Additives to Improve the Flowability of Crumbled Corn Stover

For this work, magnesium stearate (MgSt), a common flow additive and anticaking agent, was applied to corn stover feedstocks with three particle sizes. The material handling properties of dry, 15%, and 30% moisture content corn stover were measured with a Freeman FT-4 powder rheometer and mass flow hopper calculations. While hydrated biomass typically exhibits poor flowability, introducing MgSt led to a significant increase in flowability for dry and 15% moisture content feedstocks, with less impact at 30% moisture content. Inverse gas chromatography showed a decrease, up to 40%, in the surface energy of MgSt-coated corn stover. While MgSt may not be ideal for biofuel or chemical production, this study highlights the potential of flow additives to reduce adhesive and cohesive forces, improving biomass feedstock handling.

09 BIOMASS FUELS↗

Climate and air pollution impacts of generating biopower from forest management residues in California

California faces crisis conditions on its forested landscapes. A century of aggressive logging and fire suppression in combination with conditions exacerbated by climate change have created an ongoing ecological, economic, and public health emergency. Between commercial harvests on California’s working forestlands and the increasing number of acres the state treats each year for fire risk reduction and carbon sequestration, California forests generate millions of tons of woody residues annually—residues that are typically left or burned in the field. State policymakers have turned to biomass electricity generation as a key market for woody biomass in the hope that it can support sustainable forest management activities while also providing low-carbon renewable electricity. However, open questions surrounding the climate and air pollution performance of electricity generation from woody biomass have made it difficult to determine how best to manage the risks and opportunities posed by forest residues. The California Biomass Residue Emissions Characterization (C-BREC) model offers a spatially-explicit life cycle assessment framework to rigorously and transparently establish the climate and air pollution impacts of biopower from forest residues in California under current conditions. The C-BREC model characterizes the variable emissions from different biomass supply chains as well as the counterfactual emissions from prescribed burn, wildfire, and decay avoided by residue mobilization. We find that the life cycle ‘carbon footprint’ of biopower from woody residues generated by recent forest treatments in California ranges widely—from comparable with solar photovoltaic on the low end to comparable with natural gas on the high end. This variation stems largely from the heterogeneity in the fire and decay conditions these residues would encounter if left in the field, with utilization of residue that would otherwise have been burned in place offering the best climate and air quality performance. California’s energy and forest management policies should account for this variation to ensure desired climate benefits are achieved.

54 ENVIRONMENTAL SCIENCES↗

Yield, chemistry, and TEA/LCA data for 84 switchgrass (Panicum virgatum L.) variants

Switchgrass yield, chemistry, technoeconomic assessment (TEA), and life cycle assessment (LCA) data referenced in the manuscript "Economics and Sustainability impacts of yield and composition variation in bioenergy crops: Panicum virgatum L.", Happs, et. al. (manuscript in revision at ACS Sustainable Chemistry & Engineering). These results are based on analysis of yield data generated from a set of switchgrass common garden experiments established by the Center for Bioenergy Innovation (CBI; https://cbi.ornl.gov/). These data include estimates of commercial-scale yields and characterization of biomass chemistry (fermentable carbohydrate fraction) for 84 different switchgrass variants from a genome-wide association study population, as well as estimates of minimum fuel selling price and various life-cycle footprint metrics for cellulosic ethanol produced from that switchgrass biomass.

switchgrass, biofuels↗

Dataset_for_Conserved_macromolecular_architecture_of_Poplar_secondary_cell_walls_revealed_by_ssNMR_and_atomistic_modeling

This dataset contains solid-state 13C NMR data and atomistic molecular dynamics simulation files supporting the study of nanoscale secondary cell wall architecture across 13 genetically diverse Populus trichocarpa genotypes grown under uniform greenhouse conditions in 13C-enriched CO2 atmospheres (~89% 13C enrichment).The dataset contains two collections of solid-state 13C NMR data. (1) 200 MHz data (Bruker Avance III HD, 4 mm HX probe, 10 kHz MAS): raw Bruker TopSpin experiment folders and DMFIT-exported ascii spectra for selective and non-selective 1D 13C-13C spin diffusion experiments (3000 ms mixing) used to quantify inter-polymer spatial proximities, and short-mixing (1 ms) reference spectra used for polymeric abundance quantification by spectral deconvolution. (2) 600 MHz data (Bruker Avance III, 1.6 mm PhoenixNMR HXY probe, 30 kHz MAS): raw Bruker TopSpin experiment folders containing 2D CORD, 2D CP-INADEQUATE, and 13C/1H relaxation (T1, T1rho) experiments for all 13 genotypes, with processed Excel workbooks per experiment type. Molecular dynamics simulation code, coordinate files, and analysis scripts (NAMD/CHARMM/Python) for six atomistic cell wall models are included. Summarized ssNMR data are compiled into a single excel file and subjected to statistical analysis. Multivariate analysis code (PCA, Pearson correlation) and summary data are provided as excel worksheets and Jupyter notebooks (Python 3).

09 BIOMASS FUELS↗