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© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Phosphides and carbides are among the most promising families of materials based on earth-abundant elements for renewable energy conversion and storage technologies such as electrochemical water splitting, batteries, and capacitors. Nickel phosphide and molybdenum carbide in particular have been extensively investigated for electrochemical water splitting. However, a composite of the two compounds has not been explored. Here, we demonstrate preferential deposition of nickel phosphide on molybdenum carbide in the presence of carbon by using a hydrothermal synthesis method. We employ the hydrogen evolution reaction in acid and base to analyze the catalytic activity of phosphide-deposited carbide. The composite material also shows superior electrochemical stability in comparison to unsupported phosphide. We anticipate that the enhanced electrochemical activity and stability of carbide deposited with phosphide will stimulate investigations into the preparation of other carbide–phosphide composite materials.

Development of commercially relevant bioenergy switchgrass cultivars requires reducing recalcitrance for bioprocessing without compromising biomass yield. Low-lignin transgenic switchgrass has been produced via down-regulation of caffeic acid O-methyltransferase (COMT), a lignin biosynthetic enzyme, or by over-expression of the MYB4 transcription factor, a repressor of the lignin biosynthetic pathway. The aim of this study was to evaluate parents and selected hybrids obtained from COMT and MYB4 hybrid families under field conditions for agronomic performance and biomass quality. Plant height, width, number of tillers, dry weight, cell wall composition including lignin content, and sugar release were measured after the establishment year (2014) and the second growing season (2015). For COMT hybrids, biomass yield of the transgenic hybrids was similar to or greater than the wild-type parents selected for high biomass. Lignin content of COMT transgenic hybrids was reduced by 10%, S/G ratio decreased by 27%, and sugar release increased between 20% and 44% compared to their wild-type parents. These results indicate that hybridization of COMT with a high-yielding locally selected genotype resulted in both improved agronomic performance and enhanced biomass quality in the offspring. On the other hand, the MYB transgenic hybrid showed a 10% reduction in biomass yield compared with its wild-type parent in year 1, but not in year 2. The lignin S/G ratio was not reduced in MYB transgenic hybrids, nor was sugar release increased. These data indicate that the MYB transgene may not be suitable for an agronomic setting. More testing is needed of transgenic and wild-type, high-biomass selections for use as breeding parents. These results show that combining low-lignin transgenic switchgrass with a breeding and selection program for biomass yield will allow for the deployment of effective transgenes in high-yielding genetic backgrounds.

© 2019 American Chemical Society. Mixed-metal oxides possess a wide range of tunability and show promise for catalytic stabilization of biomass pyrolysis products. For materials derived from layered double hydroxides, understanding the effect of divalent cation species and divalent/trivalent cation stoichiometric ratio on catalytic behavior is critical to their successful implementation. In this study, four mixed-metal oxide catalysts consisting of Al, Zn, and Mg in different stoichiometric ratios were synthesized and tested for ex-situ catalytic fast pyrolysis (CFP) using pine wood as feedstock. The catalytic activity and deactivation behavior of these catalysts were monitored in real-time using a lab-scale pyrolysis reactor and fixed catalyst bed coupled with a molecular beam mass spectrometer (MBMS), and data were analyzed by multivariate statistical approaches. In the comparison between Mg-Al and Zn-Al catalyst materials, we demonstrated that the Mg-Al materials possessed greater quantities of basic sites, which we attributed to their higher surface areas, and they produced upgraded pyrolysis vapors which contained less acids and more deoxygenated aromatic hydrocarbons such as toluene and xylene. However, detrimental impacts on carbon yields were realized via decarbonylation and decarboxylation reactions and coke formation. Given that the primary goals of catalytic upgrading of bio-oil are deoxygenation, reduction of acidity, and high carbon yield, these results highlight both promising catalytic effects of mixed-metal oxide materials and opportunities for improvement.

Inorganic elements present in lignocellulosic biomass and introduced during harvesting and handling of the feedstock negatively affect biomass conversion to fuels and products. In particular, alkali and alkaline earth metals act as catalysts during thermochemical conversion, contribute to reactor degradation, and decrease the yield and quality of the reaction products. In this study, we investigated an approach to reduce ash content of switchgrass. Several reagents (chelating agents ethylenediaminetetraacetic acid (EDTA) and citric acid, as well as acetic acid, sulfuric acid, and water) under various extraction times (5, 10, 15, and 20 min) were tested using a microwave-assisted extraction method. After the extraction, mass loss, total ash, individual inorganics, and concentration of sugars in the hydrolyzates were measured. EDTA afforded the highest inorganics removal, with near complete extraction of alkali and alkaline earth metals K, Ca, and Mg, and high removal of S and Si. Citric acid and sulfuric acid removed similarly high amounts of K, Ca, and Mg as EDTA, but less Mg, P, S, and Fe. Additionally, extraction with water resulted in near complete removal of K; however, more modest removal of other inorganics was observed compared to other treatments. The mass loss was significantly higher in the sulfuric acid extractions due to hydrolysis of the structural carbohydrates, while EDTA resulted in little carbohydrate degradation due to the more neutral pH conditions. This study illustrated the benefits of extracting with chelating agents, as opposed to mineral acids, to remove inorganics and improve biomass quality.

While previous studies have shown that white-rot fungal pretreatment reduces the severity of chemical pretreatments and improves enzymatic saccharification yields, very few have investigated the synergistic effects of fungal pretreatment combined with organosolv pretreatment on lignin recovery and quality. In this study, loblolly pine chips were incubated with Trametes versicolor for 15, 30 and 45 days, prior to organosolv pretreatment and enzymatic saccharification. Fungal pretreatment for 15 days improved the saccharification yield by 23%, and higher amounts (56%) of lignin-enriched fractions were obtained. Fungal pretreatment for 45 days led to extensive depolymerization, structural modification and enrichment of lignin in the organosolv precipitates (OP). Characterization of the OP fraction showed that samples pretreated for 30 and 45 days contained higher amounts of hydroxyl groups and p-hydroxyphenyl (H) subunits, and showed increases in depolymerization of carbohydrates as well as decreases in G/H lignin ratio. It became apparent that further investigations are needed to explore the benefits of combining fungal and organosolv pretreatments for improving lignin yields from softwoods.

The aim of this work was to evaluate the efficiency of an ionic liquid (IL) 1-butyl-3-methylimidazolium acetate ([C4mim][OAc]) pretreatment (110°C for 30min) in comparison to high severity autohydrolysis pretreatment in terms of delignification, cellulose crystallinity and enzymatic digestibility. The increase in severity of autohydrolysis pretreatment had positive effect on glucan digestibility, but was limited by the crystallinity of cellulose. [C4mim][OAc] pretreated sugarcane bagasse exhibited a substantial decrease in lignin content, reduced cellulose crystallinity, and enhanced glucan and xylan digestibility. Glucan and xylan digestibility was determined as 97.4% and 98.6% from [C4mim][OAc] pretreated bagasse, and 62.1% and 57.5% from the bagasse autohydrolyzed at 205°C for 6min, respectively. The results indicated the improved digestibility and hydrolysis rates after [C4mim][OAc] pretreatment when compared against a comparable autohydrolyzed biomass.

Used creosote-treated wood ties were thermally treated between 250 and 350 °C to recover preservative and upgrade the wood to provide an improved quality biomass for thermochemical processes. With thermal treatments ranging from 250 to 300 °C, the amounts of creosote, mostly consisting of polycyclic aromatic hydrocarbons (PAHs), recovered were from 47 to 79% of total creosote present in the used ties. Thermal treatment at 350 °C recovered 97% of total PAH compounds. Larger amounts of PAHs with higher molecular weights (HMWs) and lower vapor pressures (LVP) were recovered at elevated temperatures. Temperature above 300 °C decomposed the wood matrix, with a mass loss ranging between 50 and 63 wt% and produced large amounts of light organics, anhydrosugars, and phenolic compounds that would contaminate the recovered creosote. Our study concluded that thermal treatment ranging between 275 and 300 °C would be preferred to recover preservative for recycling and improve the wood quality, i.e., high carbon content and caloric value, and low hazardous pollutants (creosote residues) for thermochemical processes such as pyrolysis or gasification. These findings suggest that the proposed approach could be a commercially viable and environmentally beneficial alternative to landfill for used railroad ties.

We present an investigation related to catalytic upgrading of cellulose pyrolysis vapors using mixed-metal oxide catalysts derived from layered double hydroxide precursors. We performed principal component analysis on the pyrolysis-gas chromatography/mass spectrometry data to elucidate changes in the product slate between noncatalytic fast pyrolysis, catalytic pyrolysis using the oxides of magnesium, aluminum, and zinc, and catalytic pyrolysis using our synthesized mixed-metal oxides containing the same cations. Our investigations demonstrate that the mixed-metal species behave differently than even a physical mixture of their monometal counterparts, and that they are capable of producing more furanic compounds by fast pyrolysis of cellulose. We also demonstrate that the metal ratio and identity in these catalysts impart different selectivities to the resulting product slates. Taken together, these data establish the utility of the mixed-metal oxide catalysts in producing a liquid product with low oxygen ...

The purpose of this study was to determine the effects of three particle sizes of feedstock and two types of novel bale wraps on the quality of switchgrass by monitoring the chemical changes in cellulose, hemicellulose, lignin, extractives, and ash over a 225-day period. Using NIR (Near-infrared) modeling to predict the chemical composition of the treated biomass, differences were found in cellulose, lignin, and ash content across switchgrass bales with different particle sizes. Enclosing bales in a net and film impacted the cellulose, lignin, and ash content. Cellulose, hemicellulose, lignin, extractives, and ash were different across the 225-day storage period. A quadratic response function made better prediction about cellulose, lignin, and ash response to storage, and a linear response function best described hemicellulose and extractives response to storage. This study yields valuable information regarding the quality of switchgrass at different intervals between the start and end date of storage, which is important to conversion facilities when determining optimal storage strategies to improve quality of the biomass feedstock, based on potential output yield of a bale over time.

The vapors produced from pine wood using an intermediate auger pyrolysis process under various sweeping gas flow rates were condensed by three temperature-controlled condensers and analyzed. Increasing sweeping gas flow rate from 20 to 40 L/min did not change the yield of the pyrolysis products, however, noticeable changes were found in the bio-oil composition, such as a decrease in water content and an increase of amount of organic compounds. Increasing sweeping gas flow rate influenced the bio-oil fractionation in each temperature-controlled condenser with a reduction in bio-oil yield in the first condenser controlled between 85 and 90 °C and outgoing vapor temperature of 121 °C. There were no changes in the second condenser maintained at 45⿿50 °C and outgoing vapor temperature of 107 °C, and an increase in the third condenser regulated at 10⿿15 °C and outgoing vapor temperature of 25 °C. Higher sweeping gas flow rates also resulted in changing the bio-oil composition in the first and second condensers including a reduction in water content and an increase in viscosity and density, suggesting that refining this fraction as an intermediate source would be a more efficiency way to produce fuels and chemicals than treating the whole bio-oil. The bio-oil from the third condenser contained elevated water content, acidity and light oxygenated compounds with increasing sweeping gas flow rate, suggesting that this fraction would be more suitable as an energy source for hydrogen production via microbial electrolysis processes. In summary, the sweeping gas flow rate used for pyrolysis with an intermediate auger reactor is an important factor to change bio-oil properties in temperature-controlled multistage condensation processes.

As interest in soil organic carbon (SOC) dynamics increases, so do needs for rapid, accurate, and inexpensive methods for quantifying SOC. Objectives were to i) evaluate near infrared reflectance (NIR) spectroscopy potential to determine SOC and soil organic matter (SOM) in soils from across Tennessee, USA; and ii) evaluate potential upper limits of SOC from forest, pasture, no-tillage, and conventional tilled sites. Samples were analyzed via dry-combustion (SOC), Walkley–Black chemical SOM, and NIR. In addition, the sample particle size was classified to give five surface roughness levels to determine effects of particle size on NIR. Partial least squares regression was used to develop a model for predicting SOC as measured by NIR by comparing against SOM and SOC. Both NIR and SOM correlated well (R2 > 0.9) with SOC (combustion). NIR is therefore considered a sufficiently accurate method for quantifying SOC in soils of Tennessee, with pasture and forested systems having the greatest accumulations...

A two-step thermal process, an initial thermal treatment at mild temperature followed by a fast pyrolysis step, was investigated to recover wood preservatives and produce preservatives-free wood for production of high quality bio-oil from used creosote-treated railroad ties. During the initial thermal treatment at temperature of 280 °C for 10–30 min, the treated wood ties underwent a 20–25% weight loss with energy yield (77–83%). Energy yield at 280 °C was lower than that at 200 and 250 °C (92–97%) but higher than that at the 300 °C (64–74%). Recovery level of creosote at 280 °C was comparable to that at 300 °C. Fast pyrolysis at 450 °C of the 280 °C-treated wood ties produced high amount of levoglucosan and phenolic compounds with a traceable amount (1.7–1.9% of the total peak area) of creosote compounds.

Correction for ‘Understanding the in situ state of lignocellulosic biomass during ionic liquids-based engineering of renewable materials and chemicals’ by Kalavathy Rajan et al., Green Chem., 2020, 22, 6748–6766, DOI: 10.1039/D0GC02582H.

The United States (US) uses landfills to dispose paper cups at a rate of 40 percent. Landfill rates on plastic disposable dinnerware are even higher at around 80 percent. This study examines consumer preferences for single-use disposable dinnerware with the attributes: uses no trees; contains no plastic; made from agricultural crop byproduct cellulose; cellulose from dedicated crops, and/or organically sourced cellulose; certified biobased; and compostable or recyclable. A Multiple Indicator Multiple Causes (MIMIC) model is used to estimate the effects of demographics, expenditures, and consumer perceptions of disposable dinnerware made with ‘eco-friendly’ materials or processes. The attributes ‘no plastic’ and ‘recyclable’ appealed to consumers over the widest range of preferences for eco-friendly attributes in disposable dinnerware. However, ‘no trees’ and ‘certified biobased’ appeared to appeal to a narrower segment with the strongest preferences for eco-friendly attributes. Demographic characteristics including gender, residential location, household income, household composition, and environmental attitudes also correlated with preferences for single use products made with the attributes examined.

An abundant, low-cost, and high-quality supply of lignocellulosic feedstock is necessary to realize the large-scale implementation of biomass conversion technologies capable of producing renewable fuels, chemicals, and products. Barriers to this goal include the variability in the chemical and physical properties of available biomass, and the seasonal and geographic availability of biomass. Blending several different types of biomass to produce consistent feedstocks offers a solution to these problems and allows for control over the specifications of the feedstocks. For thermochemical conversion processes, attributes of interest include carbon content, total ash, specific inorganics, density, particle size, and moisture content. In this work, a series of switchgrass and pine residues blends with varying physical and chemical properties were evaluated. Physical and chemical properties of the pure and blended materials were measured, including compositional analysis, elemental analysis, compressibility, flowability, density, and particle size distribution. To screen blends for thermochemical conversion behavior, the analytical technique, pyrolysis gas chromatography mass spectrometry (Py-GC/MS), was used to analyze the vapor-phase pyrolysis products of the various switchgrass/pine residues blends. The py-GC/MS findings were validated by investigating the bio-oils produced from the selected blends using a lab-scale fluidized-bed pyrolysis reactor system. Results indicate that the physical properties of blended materials are proportional to the blend ratio of pure feedstocks. In addition, pyrolysis of pine residues resulted in bio-oils with higher carbon content and lower oxygen content, while switchgrass derived pyrolysis products contained relatively greater amount of anhydrosugars and organic acids. The distribution of the pyrolysis vapors and isolated bio-oils appear to be a simple linear combination of the two feedstocks. The concentration of alkali and alkaline earth metals (Ca, K, Mg, and Na) in the blended feedstocks were confirmed to be a critical parameter due to their negative effects on the bio-oil yield. This work demonstrates that blending different sources of biomass can be an effective strategy to produce a consistent feedstock for thermochemical conversion.

Organosolv fractionation is a promising pathway to separate cellulosic biomass into high purity cellulose, hemicelluloses, and lignin. This work specifically investigates the properties of lignins isolated at specific time points as fractionation progressed, with the intent of correlating fractionation time with lignin purity, yield, thermal and chemical properties. Yellow poplar (Liriodendron tulipifera) was fractionated using a mixture of methyl isobutyl ketone, ethanol, and water with sulfuric acid as catalyst at 140 °C over a two-hour period. Aliquots of the liquor were collected by sampling every 15 min during the fractionation to generate a series of lignins. The results showed that with increased fractionation time, lignin purity improved from 90.3 to 94.6% and the glass transition temperature increased from 117 to 137 °C. The loss of aliphatic OH and increase of phenolic OH with fractionation time led to an increase in condensed structures and increased polydispersity at times greater than 90 min. Principal component analysis of Fourier transform infrared spectroscopic data confirmed the shift to higher purity and more condensed chemical structures with increasing fractionation time. Overall, this study demonstrates that thermal and chemical properties of lignin change with the organosolv fractionation time.

A new approach to hydrogen production using an integrated pyrolysis–microbial electrolysis process is described. The aqueous stream generated during pyrolysis of switchgrass was used as a substrate for hydrogen production in a microbial electrolysis cell, achieving a maximum hydrogen production rate of 4.3 L H2/L anode-day at a loading of 10 g COD/L-anode-day. Hydrogen yields ranged from 50 ± 3.2% to 76 ± 0.5% while anode Coulombic efficiency ranged from 54 ± 6.5% to 96 ± 0.21%, respectively. Significant conversion of furfural, organic acids and phenolic molecules was observed under both batch and continuous conditions. The electrical and overall energy efficiency ranged from 149–175% and 48–63%, respectively. The results demonstrate the potential of the pyrolysis–microbial electrolysis process as a sustainable and efficient route for production of renewable hydrogen with significant implications for hydrocarbon production from biomass.

Ionic liquids (ILs) are benign solvents that are highly effective for biomass pretreatment. However, their applications for scale-up biorefinery are limited due to multiple expensive IL recovery and separation steps that are required. To overcome this limitation, it is very critical to develop a compatible enzymatic and microbial biocatalyst system to carry the simultaneous saccharification and fermentation in IL environments (SSF-IL). While enzymatic biocatalysts have been demonstrated to be compatible with various IL environments, it is challenging to develop microbial biocatalysts that can thrive and perform efficient biotransformation under the same conditions (pH and temperature). In this study, we harnessed the robust metabolism of Yarrowia lipolytica as a microbial platform highly compatible with the IL environments such as 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]). We optimized the enzymatic and microbial biocatalyst system using commercial cellulases and demonstrated the capability of Y. lipolytica to convert cellulose into high-value organics such as α-ketoglutaric acid (KGA) in the SSF-IL process at relatively low temperature 28 °C and high pH 6.3. We showed that SSF-IL not only enhanced the enzymatic saccharification but also produced KGA up to 92 % of the maximum theoretical yield.

The anatomical and chemical characteristics of sweetgum were studied after 11 years of elevated CO2 (544 ppm, ambient at 391 ppm) exposure. Anatomically, branch xylem cells were larger for elevated CO2 trees, and the cell wall thickness was thinner. Chemically, elevated CO2 exposure did not impact the structural components of the stem wood, but non-structural components were significantly affected. Principal component analysis (PCA) was employed to detect differences between the CO2 treatments by considering numerous structural and chemical variables, as well as tree size, and data from previously published sources (i.e., root biomass, production and turnover). The PCA results indicated a clear separation between trees exposed to ambient and elevated CO2 conditions. Correlation loadings plots of the PCA revealed that stem structural components, ash, Ca, Mg, total phenolics, root biomass, production and turnover were the major responses that contribute to the separation between the elevated and ambient CO2 treated trees.

The success of the biorefinery will depend on deriving value from the lignin fraction of lignocellulosic feedstocks. Thus, it will be necessary to develop procedures that provide a separate and usable lignin stream for chemical transformation. A wide range of processes have been developed that afford isolated lignin, but very few of these methods are practical for the biorefinery, as they target lignin analysis or lignin removal, and are largely impractical for large scale use or introduce severe structural changes in the lignin that significantly reduces its potential as a chemical feedstock. This chapter will introduce several methods that isolate lignin for analytical purposes, or for its removal from lignocellulose. The majority of the chapter then discusses processes for biomass fractionation – methodology that gives lignin streams in high yield and purity, and which offer potential utility within the biorefinery.

The aim of this study was to determine the impact of incorporating switchgrass samples that have been in long term storage on the development of near-infrared (NIR) multivariate calibration models and their predictive capabilities. Stored material contains more variation in their respective spectral signatures due to chemical changes in the bales with storage time. Partial least squares (PLS) regression models constructed using NIR spectra of stored switchgrass possessed an instability that interfered with the correlation between the spectral data and measured chemical composition. The models were improved using calibration sample sets of equal parts stored and fresh switchgrass to more accurately predict the chemical composition of stored switchgrass. Acceptable correlation values (rcalibration) were obtained using a calibration sample set composed of 25 stored samples and 25 samples of fresh switchgrass for cellulose (0.91), hemicellulose (0.74), total carbohydrates (0.76), lignin (0.98), extractives (0.92), and ash (0.87). Increasing the calibration sample set to 100 samples of equal parts stored to senesced material resulted in statistically increased (p = 0.05) correlations for total carbohydrates (0.89) and ash (0.96). When these models were applied to a separate validation set (equal to 10% of the calibration sample set), high correlation coefficients (r) for predicted versus measured constituent content were observed for cellulose (0.94), total carbohydrates (0.98), lignin (0.91), extractives (0.97), and ash (0.90). For optimization of processing economics, the impact of feedstock storage must be investigated for implementation in conversion processes. While NIR is a well-known high-throughput technique for characterization of senesced switchgrass, the selection of appropriate calibration samples and consequent multivariate models must be taken into careful consideration for NIR application in a biomass storage facility for rapid chemical compositional determination.

Recently, there has been a growing interest in developing value added uses for lignin, including the utilization of lignins as a precursor for carbon materials. Proper understanding of the association behavior of lignins during solution processing provides important structural information that is needed to rationally optimize the use of lignins in industry in a range of value added applications. In these experiments, we follow the assembly of lignin molecules from a variety of sources in dimethyl sulfoxide, a good solvent for lignins, using small angle neutron scattering. In order to mimic industrial processing conditions, concentrations of lignins were kept above the overlap concentration. At small length scales, short lignin segments with ∼4–10 monolignol units associate to form rigid rod-like/cylindrical building blocks, where the number of repeat units in a cylindrical segment decreases with increasing lignin concentration. These cylindrical building blocks associate to form aggregates with low cross-linking densities and a random coil or network like structures from highly branched lignin structures. The degree of branching of the base lignin molecule, which varies with source, plays a crucial role in determining their association behavior. The overall sizes of the aggregates decrease with increasing concentration at low cross-linking densities, whereas the opposite trend is observed for highly branched lignins.

Background Genetically engineered biofuel crops, such as switchgrass (Panicum virgatum L.), that produce their own cell wall-digesting cellulase enzymes would reduce costs of cellulosic biofuel production. To date, non-bioenergy plant models have been used in nearly all studies assessing the synthesis and activity of plant-produced fungal and bacterial cellulases. One potential source for cellulolytic enzyme genes is herbivorous insects adapted to digest plant cell walls. Here we examine the potential of transgenic switchgrass-produced TcEG1 cellulase from Tribolium castaneum (red flour beetle). This enzyme, when overproduced in Escherichia coli and Saccharomyces cerevisiae, efficiently digests cellulose at optima of 50 °C and pH 12.0. Results TcEG1 that was produced in green transgenic switchgrass tissue had a range of endoglucanase activity of 0.16–0.05 units (µM glucose release/min/mg) at 50 °C and pH 12.0. TcEG1 activity from air-dried leaves was unchanged from that from green tissue, but when tissue was dried in a desiccant oven (46 °C), specific enzyme activity decreased by 60%. When transgenic biomass was “dropped-in” into an alkaline buffer (pH 12.0) and allowed to incubate at 50 °C, cellobiose release was increased up to 77% over non-transgenic biomass. Saccharification was increased in one transgenic event by 28%, which had a concurrent decrease in lignin content of 9%. Histological analysis revealed an increase in cell wall thickness with no change to cell area or perimeter. Transgenic plants produced more, albeit narrower, tillers with equivalent dry biomass as the control. Conclusions This work describes the first study in which an insect cellulase has been produced in transgenic plants; in this case, the dedicated bioenergy crop switchgrass. Switchgrass overexpressing the TcEG1 gene appeared to be morphologically similar to its non-transgenic control and produced equivalent dry biomass. Therefore, we propose TcEG1 transgenics could be bred with other transgenic germplasm (e.g., low-lignin lines) to yield new switchgrass with synergistically reduced recalcitrance to biofuel production. In addition, transgenes for other cell wall degrading enzymes may be stacked with TcEG1 in switchgrass to yield complementary cell wall digestion features and complete auto-hydrolysis.

© 2017 American Chemical Society. Removal of copper naphthenate (CN) from used wooden railroad ties was investigated to improve the commercial viability of this biomass as a fuel source and avoid alternative disposal methods such as landfilling. Bench-scale thermal desorption of organic preservative components from CN-impregnated ties was followed by extraction of the copper fraction with ethylenediaminetetraacetic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, or 2,6-pyridine dicarboxylic acid (PDA). Naphthenic acid (NA) and carrier oil were recovered at desorption temperatures between 225 and 300 °C and could potentially be recycled to treat new ties. The thermal treatment also mimicked torrefaction, improving the biomass properties for use as a thermochemical conversion feedstock. Chelation with PDA, a biodegradable chelating agent, after desorption had the highest extraction efficiency of copper and other naturally present inorganics, extracting 100% of the copper from both the raw and 225 °C-treated samples. Optimized desorbed material showed a 64% decrease in ash content when extracted with PDA; however, extraction efficiency decreased as desorption temperature increased, indicating that thermal treatment caused the inorganics to be less extractable. We concluded that the optimum desorption conditions were between 250 and 275 °C for 45 min followed by extraction with PDA when considering both NA removal and inorganic extraction efficiency.

Composites of electrocatalytically active transition-metal compounds present an intriguing opportunity toward enhanced activity and stability. To identify potentially scalable pairs of a catalytically active family of compounds, we demonstrate that phosphides of iron, nickel, and cobalt can be deposited on molybdenum carbide to generate nanocrystalline heterostructures. Composites synthesized via solvothermal decomposition of metal acetylacetonate salts in the presence of highly dispersed carbide nanoparticles show hydrogen evolution activities comparable to those of state-of-the-art non-noble metal catalysts. Investigation of the spent catalyst using high resolution microscopy and elemental analysis reveals that formation of carbide−phosphide composite prevents catalyst dissolution in acid electrolyte. Lattice mismatch between the two constituent electrocatalysts can be used to rationally improve electrochemical stability. Among the composites of iron, nickel, and cobalt phosphide, iron phosphide displays the lowest degree of lattice mismatch with molybdenum carbide and shows optimal electrochemical stability. Turnover rates of the composites are higher than that of the carbide substrate and compare favorably to other electrocatalysts based on earth-abundant elements. Our findings will inspire further investigation into composite nanocrystalline electrocatalysts that use molybdenum carbide as a stable catalyst support.

Replacing petroleum by biomass can be economically feasible by generating revenue from the three primary biomass constituents., The production of renewable chemicals and biofuels must be cost- and performance- competitive with petroleum-derived equivalents to be widely accepted by markets and society. We propose a biomass conversion strategy that maximizes the conversion of lignocellulosic biomass (up to 80% of the biomass to useful products) into high-value products that can be commercialized, providing the opportunity for successful translation to an economically viable commercial process. Our fractionation method preserves the value of all three primary components: (i) cellulose, which is converted into dissolving pulp for fibers and chemicals production; (ii) hemicellulose, which is converted into furfural (a building block chemical); and (iii) lignin, which is converted into carbon products (carbon foam, fibers, or battery anodes), together producing revenues of more than $500 per dry metric ton of biomass. Once de-risked, our technology can be extended to produce other renewable chemicals and biofuels.

The pyrolysis vapor produced from pine wood using an intermediate pyrolysis auger reactor (72 s of solid residence time at 500, 525, and 550 °C) was condensed by three different temperature-profiled condensers. The first condenser had a surface temperature of 60–85 °C and a vapor temperature of 126–193 °C, whereas the second condenser had a surface temperature of 40–60 °C and a vapor temperature of 107–126 °C. The surface temperature of the third water-cooled condenser was ≤25 °C, and the vapor temperature was ∼33–99 °C. The water content was very low (11.1–13.9 wt %) in the bio-oil generated by the first condenser; however, it significantly increased in the bio-oil from the second (28.3–39.2 wt %) and third condensers (52.0–64.0 wt %), which led to the bio-oils with lower viscosities and densities. As the pyrolysis temperature increased, the water-insoluble fraction of the bio-oil was the highest (44–47 wt %) in the first condenser and was significantly lower in the second and third condensers (17–27 wt ...

Biochar pellets produced by blending switchgrass biochar, lignin and fertilizers K and P together followed by pelletization were characterized and investigated for their ability to release K and P. Pellets processed at 180 °C with increasing lignin content from 10 to 30 wt.% had higher density, thermal stability and durability, and produced lower pore volume and smaller pore size than pellets processed at 105 °C. Fertilizer-embedded biochar pellets with 10–30 wt.% lignin and processed at 180 °C had a slower K and P release than pellets dried at 105 °C, with release rates (53–62% in K and 49–62% in P) within the first 24 h followed by gradual releases (78–87% in K and 73–78% in P) for the next 18 days. Therefore, by controlling lignin content and processing temperature of the pellets, one can control the release rate of nutrients present in biochar pellets.

Sciadopitys verticillata (Sv) produces a white, sticky, latex-like resin with antimicrobial properties. The aims of this research were to evaluate the effects of this resin (Sv resin) on bacterial populations and to determine the impact of its primary volatile components on bioactivity. The impact of sample treatment on chemical composition of Sv resin was analyzed using Fourier transform infrared spectroscopy (FTIR) coupled with principal component analysis. The presence and concentration of volatiles in lyophilized resin were determined using gas chromatography/mass spectrometry (GC/MS). Changes in bacterial population counts due to treatment with resin or its primary volatile components were monitored. Autoclaving of the samples did not affect the FTIR spectra of Sv resin, however, lyophilization altered spectra, mainly in the CH and C=O regions. Three primary bioactive compounds that constituted &gt, 90% of volatiles (1R-&alpha, pinene, tricyclene, and &beta, pinene) were identified in Sv resin. Autoclaved resin impacted bacterial growth. The resin was stimulatory for some plant and foodborne pathogens (Pseudomonas fluorescens, P. syringae, and Xanthomonas perforans) and antimicrobial for others (Escherichia coli, Bacillus cereus, Agrobacterium tumefaciens, and Erwinia amylovora). Treatment with either 1R-&alpha, pinene or &beta, pinene reduced B. cereus population growth less than did autoclaved resin. The complex resin likely contains additional antimicrobial compounds that act synergistically to inhibit bacterial growth.

Optimum utilization of lignocellulosic bioenergy feedstock, such as switchgrass, via recovery of value-added phytochemicals and reduction of waste streams will increase the economic feasibility as well as the sustainability of integrated biorefineries. Switchgrass contains significant amount of overlooked non-structural components, i.e. extractives, which encompasses phenolic derivatives with potential antimicrobial and antioxidant properties. As a perennial crop, it is essential to assess the natural variability of switchgrass extractives content and composition in order to determine the feasibility of its extraction and utilization. In this study, three switchgrass cultivars were harvested from four commercial farms in their second and third growing seasons. Their respective extractive fractions were characterized for the presence of free sugars, total phenolics (TPC), hydroxycinnamic acid (HCAs) derivatives, total flavonols, and other important phytochemicals. Biomass harvested in the third growing season displayed greater amounts of TPC, HCAs, and total flavonols. Environmental conditions such as total precipitation, and cultural practices including harvest time, played important roles in the accumulation of TPC. The switchgrass extractives also exhibited DPPH (2,2-diphenyl-1-picrylhydrazyl) radical scavenging activity with a positive correlation between inhibiting concentration (IC50) value and total flavonols content.

Switchgrass (Panicum virgatum) is a perennial grass that has emerged as an ideal candidate for production of biofuel and value-added co-products. One of the primary requirements for the successful manufacturing of these switchgrass-derived bioproducts is to produce a consistent feedstock with reliable and adequate amounts of the substrate constituent needed. For example, the biofuels industry requires a fast-growing energy crop with higher cellulose content and lower inhibitors found in secondary constituents. Other industries would profit from higher lignin content for products such as carbon fibers, or higher water and ethanol-soluble extracts containing compounds of interest. Two switchgrass field plots in eastern Tennessee were monitored over a period of six months, including before and after traditional harvesting times for the biorefinery. Characterization of the biomass and its constituents, such as water and ethanol extracts, cellulose, hemicelluloses, lignin, and ash, was performed to examine chemical changes in switchgrass that occurred prior to, during, and after traditional harvesting times used in a biorefinery setting. Total carbohydrate (65.6–66.7 wt%) and lignin (21.7–23.2 wt%) content was found to peak in January. Extractives content was at a maximum in early harvests at 15.9–16.6 wt% and decreased to 5.5–5.8 wt% in February. An inverse relationship exists between the extractives and lignin content (R2 = 0.94). Nonstructural soluble sugars peaked in early October with 5.1 wt% of the switchgrass composition. Remobilization efficiencies of K, Mg, P, and Fe increased with time, indicating conservation of soil nutrients if harvests were completed in late winter.

Surface properties of switchgrass-derived biochars produced at fast pyrolysis temperatures of 450, 600 and 800 °C were characterized at different solution pHs in order to determine the structural and chemical changes of artificially-weathered biochars when incorporated into soil. As biochars were acidified from pH 7 to 3, crystalline minerals dissolved slowly releasing nutrients; however, residual minerals were still detected in biochars produced at higher pyrolysis temperatures after pH treatment. Moreover, the amount of exchangeable bases and other inorganic compounds released from the biochars increased when pH decreased. As minerals dissolved from the biochars, total surface area and pore volume were found to increase. Surface functional groups and water vapor adsorption capacity at 0.8 P/Po also increased, whereas the potential CEC of biochars decreased due to the replacement of exchangeable sites by hydrogen ion. Therefore, during the aging process, it is predicted that soil-incorporated biochars will slowly release nutrients with changes in surface functionality and porosity, which are expected to enhance water holding capacity of soil and provide a beneficial habitat for microbial colonization.

Switchgrass- and pine wood-derived biochars produced by fast pyrolysis were characterized to estimate the degree of thermochemical transformation and to assess their potential use as a soil amendment and to sequester carbon. The feedstocks were pyrolyzed to biochars in an auger reactor at 450, 600, and 800 °C with a residence time of 30 s. Ash contents of switchgrass and pine wood biochars varied from 13 to 22% and from 1.3 to 5.2%, respectively. Nutrients, such as N, P, K, S, Mg, and Ca, in switchgrass biochars ranged from 0.16 to 1.77%. Under combustion conditions, switchgrass chars were decomposed at lower temperatures than pine wood biochars because of the structural differences between the two feedstocks. Principal component analysis of the Fourier transform infrared (FTIR) spectra allowed for the discrimination of all biochars by significant contributions of cellulose-derived functionality at low pyrolysis temperatures, while the same analysis of the Raman spectra presented apparent separation of al...

High-resolution analysis of stable carbon and oxygen isotopic composition (δ13C and δ18O) of tree-ring α-cellulose has been increasingly in demand for the study of climate seasonality, droughts, and tropical cyclone (hurricane) activity. The peeling–grinding method commonly used for tree-ring α-cellulose preparation is both time-consuming and labor-intensive, and often results in cross-tracheid sampling that masks high-frequency intra-annual climate signals and short-term climate events. Here, we present a new method by extracting tree-ring α-cellulose directly from wholewood spline that omits the peeling–grinding step, and allows for micro-scale δ13C and δ18O analysis that facilitates high-resolution seasonal climate study. This ultrasound-assisted non-destructive extraction method has significantly increased the output of tree-ring α-cellulose preparation while retaining the wood cell fabric. Wood cell-wall fibers collected from the α-cellulose spline were directly loaded into pre-weighed silver (or tin) capsules and packed, after oven drying, for stable oxygen (or carbon) isotope analysis. A 3.045-mm annual ring subdivided over 26 sections for δ13C and δ18O analysis revealed remarkable intra-annual isotopic variations (1.62‰ for δ13C, and 5.85‰ for δ18O). The intra-annual δ13C values inversely covary with the seasonal precipitation pattern, suggesting moisture regulation on tree-ring δ13C variations. The high-resolution δ18O analysis unravels tropical cyclone activities (Hurricanes Frances and Ivan in 2004) that are characterized by an abrupt decline in δ18O values by 2.6‰ with a “V-shape” pattern in tree-ring latewood. An algorithm is developed for establishing regional patterns of tree-ring seasonal δ13C and δ18O for the study of the mean state of climate seasonality and its anomalies.

Ionic liquids (ILs) have been increasingly recognized as novel solvents for dissolution and pretreatment of cellulose. However, cellulases are inactivated in the presence of ILs, even when present at low concentrations. To more fully exploit the benefits of ILs it is critical to develop a compatible IL-cellulases system in which the IL is able to effectively solubilize and activate the lignocellulosic biomass, and the cellulases possess high stability and activity. In this study, we investigated the stability and activity of a commercially available cellulases mixture in the presence of different concentrations of 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]). A mixture of cellulases and β-glucosidase (Celluclast1.5L, from Trichoderma reesei, and Novozyme188, from Aspergillus niger, respectively) retained 77% and 65% of its original activity after being pre-incubated in 15% and 20% (w/v) IL solutions, respectively, at 50°C for 3 h. The cellulases mixture also retained high activity in 15% [Emim][OAc] to hydrolyze Avicel, a model substrate for cellulose analysis, with conversion efficiency of approximately 91%. Notably, the presence of different amounts of yellow poplar lignin did not interfere significantly with the enzymatic hydrolysis of Avicel. Using this IL-cellulase system (15% [Emim][OAc]), the saccharification of yellow poplar biomass was also significantly improved (33%) compared to the untreated control (3%) during the first hour of enzymatic hydrolysis. Together, these findings provide compelling evidence that [Emim][OAc] was compatible with the cellulase mixture, and this compatible IL-cellulases system is promising for efficient activation and hydrolysis of native biomass to produce biofuels and co-products from the individual biomass components.

Laser-induced breakdown spectroscopy (LIBS), a rapid and potentially field-deployable technology for estimating total carbon in soil, represents a novel approach to address important issues in soil science and carbon management. Our study has shown that models relating LIBS signal intensity at 247.85 nm to percent total carbon determined by dry combustion vary as a function of elemental and textural characteristics of the soil, and, to a lesser extent, wavelength and excitation energy of the laser. To better quantify these sources of variation, two wavelengths and three excitation energies were used to analyze soils from various locations. The emission line of carbon at 247.85 nm was pronounced at an excitation wavelength of 532 nm and energy of 45 mJ, but it was largely obscured by the 248.9 nm Fe line at 1064 nm and excitation energies of 90 and 135 mJ. Univariate analysis revealed linear, but soil-specific correlations between signal intensity at 247.85 nm and total carbon concentration. A single calibration model correlating LIBS spectra to carbon concentration in all samples was obtained using a multivariate approach. Several emission lines in addition to the strong carbon line contributed significantly to the multivariate model. These results show that multivariate analysis can bemore » used to construct a robust calibration model for LIBS spectra and therein provide a reliable estimate of total soil carbon. Such results must be confirmed for a broader range of soils, yet crop and soil scientists, carbon managers, and instrument developers should find these results encouraging.« less

The application of near infrared (NIR) spectroscopy for the prediction of the thermal decomposition behavior of lignocellulosic biomass (three types of woody biomass and three types of herbaceous biomass) was successfully performed along with statistical analysis. The thermal degradation behaviors of the woody and herbaceous biomass were different because of their different chemical compositions. Herbaceous biomass was degraded at lower temperature than woody biomass. The weight-loss profiles as a function of temperature were obtained by thermogravimetric analysis (TGA) at a heating rate of 25°C/min under nitrogen gas. The weight-loss percentage at 10 temperatures in the range 150–600°C was predicted by a wavelet partial least squares (PLS) model, which showed significantly better predictive performance than the ordinary PLS model. The results show that the data predicted by the wavelet PLS model was well fitted to the original data by TGA, in which the root-mean-square error in prediction values less than 5.5 suggested that NIR spectroscopy was applicable for rapid analysis to characterize the thermal decomposition behavior of lignocellulosic biomass for energy production. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Switchgrass (Panicum virgatum L.) is a candidate feedstock in bioenergy, and plant breeding and molecular genetic strategies are being used to improve germplasm. In order to assess these subsequent modifications, baseline biomass compositional data are needed in a relevant variety of environments. In this study, switchgrass cv. Alamo was grown in the field, greenhouse, and growth chamber and harvested into individual leaf and stem tissue components. These components were analyzed with pyrolysis vapor analysis using molecular beam mass spectrometry, Fourier transform infrared, and standard wet chemistry methods to characterize and compare the composition among the different growth environments. The details of lignin content, S/G ratios, and degree of cross-linked lignin are discussed. Multivariate approaches such as projection to latent structures regression found a very strong correlation between the lignin content obtained by standard wet chemistry methods and the two high throughput techniques employed to rapidly assess lignin in potential switchgrass candidates. The models were tested on unknown samples and verified by wet chemistry. The similar lignin content found by the two methods shows that both approaches are capable of determining lignin content in biomass in a matter of minutes.

Yellow poplar (Liriodendron tulipifera L.) wood flour was chemically modified with acetic anhydride at varying times and initial moisture contents at a constant temperature. All samples exhibited increasing weight gains in the range of 5–16% with increasing reaction or treatment time. The acetylated poplar wood flour was characterized by means of Fourier transform infrared spectroscopy and near infrared (NIR) spectroscopy. Principal component analysis performed on the spectral data revealed clusters according to the esterification level. Partial least squares regression models developed from NIR data were able to predict the weight gain and the percentage of reacted OH groups. The correlations show that there is a direct and linear relationship between the spectra and the weight percentage gain and, therefore, the degree of acetylation.

In this work, near infrared (NIR) and pyrolysis-molecular beam mass spectra (MBMS) of loblolly pine (Pinus taeda) were studied by means of generalized two-dimensional correlation spectroscopy in order to assign specific contributions of cellulose in the two spectral domains. Homo- and hetero-correlation techniques were employed to analyze the concentration-dependent spectral variations of cellulose. Specific bands of cellulose were assigned in the NIR and MBMS spectra, and moreover two masses m/z at 114 and 173, commonly assigned to cellulose fragments, were found to not originate from the pyrolysis of cellulose.

Laser-induced breakdown spectroscopy (LIBS) has been used in the elemental analysis for a variety of environmental samples and as a proof of concept for a host of forensic applications. In the first application, LIBS was used for the rapid detection of carbon from a number of different soil types. In this application, a major breakthrough was achieved by using a multivariate analytical approach that has brought us closer towards a “universal calibration curve”. In a second application, it has been demonstrated that LIBS in combination with multivariate analysis can be employed to analyze the chemical composition of annual tree growth rings and correlate them to external parameters such as changes in climate, forest fires, and disturbances involving human activity. The objectives of using this technology in fire scar determinations are: 1) To determine the characteristic spectra of wood exposed to forest fires and 2) To examine the viability of this technique for detecting fire occurrences in stems that did not develop fire scars. These examples demonstrate that LIBS-based techniques are inherently well suited for diverse environmental applications. LIBS was also applied to a variety of proof of concept forensic applications such as the analysis of cremains (human cremation remains) and elemental composition analysis of prosthetic implants.

Low‐field proton NMR was evaluated as a nondestructive and rapid technique for measuring ethanol‐soluble extractives in southern pine wood. Matchstick‐sized wood specimens were steeped in extractive‐containing solutions to generate extractive‐enriched samples for analysis. Decay curves obtained by the Carr‐Purcell‐Meiboom‐Gill (CPMG) pulse sequence were analyzed with Contin, a constrained regularization program used to generate continuous distributions of transverse (spin‐spin) relaxation times. Air‐dry wood samples gave maximum signal amplitudes that did not clearly reflect differences in extractives content. Oven drying removed signals for bound water that were superposed with those for the extractives. Relaxation times and the corresponding amplitudes were then positively correlated with the added extractives. Treatment of air‐dry samples with dichloromethane‐d 2 prior to analysis increased the mobility of the extractives, thereby resulting in a shift of the corresponding signals to longer rel...

Long-term exposure of sweetgum trees to elevated atmospheric CO 2 concentrations significantly shifted inner bark (phloem) and outer bark (rhytidome) chemical compositions, having implications for both defense and nutrient cycling. Changes in plant tissue chemistry due to increasing atmospheric carbon dioxide (CO2) concentrations have direct implications for tissue resistance to abiotic and biotic stress while living, and soil nutrient cycling when senesced as litter. Although the effects of elevated CO2 concentrations on tree foliar chemistry are well documented, the effects on tree bark chemistry are largely unknown. The objective of this study was to determine the effects of a long-term elevated CO2 treatment on the contents of individual elements, extractives, ash, lignin, and polysaccharide sugars of sweetgum (Liquidambar styraciflua L.) bark. Trees were harvested from sweetgum plots equipped with the Free-Air CO2 Enrichment (FACE) apparatus, receiving either elevated or ambient CO2 treatments over a 12-year period. Whole bark sections were partitioned into inner bark (phloem) and outer bark (rhytidome) samples before analysis. Principal component analysis, coupled with either Fourier transform infrared spectroscopy or pyrolysis–gas chromatography–mass spectrometry data, was also used to screen for differences. Elevated CO2 reduced the N content (0.42 vs. 0.35 %) and increased the C:N ratio (109 vs. 136 %) of the outer bark. For the inner bark, elevated CO2 increased the Mn content (470 vs. 815 mg kg−1), total extractives (13.0 vs. 15.6 %), and residual ash content (8.1 vs. 10.8 %) as compared to ambient CO2; differences were also observed for some hemicellulosic sugars, but not lignin. Shifts in bark chemistry can affect the success of herbivores and pathogens in living trees, and as litter, bark can affect the biogeochemical cycling of nutrients within the forest floor. Results demonstrate that increasing atmospheric CO2 concentrations have the potential to impact the chemistry of temperate, deciduous tree bark such as sweetgum.

Chars from the thermal degradation of silver maple (Acer saccharinum), red maple (Acer rubrum), sugar maple (Acer saccharum), and white oak (Quercus spp.), performed at temperatures from 250 to 350 °C, were examined using time domain-nuclear magnetic resonance spectroscopy. Prior to analysis, the chars were equilibrated under conditions insuring the presence of bound water only and both bound water and free water. Transverse relaxation times were found to be related to the moisture content of the chars, which varied with temperature. At elevated temperatures the number of signals assigned to free water decreased, indicative of an increase in pore size within the chars.

The time domain of 1H NMR spectroscopy allows straightforward editing of the T 2 relaxation profiles in maritime pine wood. A new method from the Carr-Purcell-Meiboom-Gill sequence is proposed to measure the amount and distribution of water in wood, as well as the location of major dissolved organic materials. A general calibration model giving reliable and precise identification of these parameters is described. The method presented for editing T 2 relaxation profiles (obtained by the Contin program) may be helpful in solving practical drying and gluing problems in the wood industry. It can be used for monitoring chemical modifications of wood fibers involved in the design of wood composite materials.

In this work, the effect of temperature on charcoal structure and chemical composition is investigated for four tree species. Wood charcoal carbonized at various temperatures is analyzed by mid infrared spectroscopy coupled with multivariate analysis and by thermogravimetric analysis to characterize the chemical composition during the carbonization process. The multivariate models of charcoal were able to distinguish between species and wood thermal treatments, revealing that the characteristics of the wood charcoal depend not only on the wood species, but also on the carbonization temperature. This work demonstrates the potential of mid infrared spectroscopy in the whiskey industry, from the identification and classification of the wood species for the mellowing process to the chemical characterization of the barrels after the toasting and charring process.

The assessment of the mechanical properties of wood using non-destructive evaluation (NDE) tools has been widely developed and refined. These NDE tools mainly rely on vibrational, ultrasonic or stress-wave approaches. Vibrational techniques generally show higher correlations between the estimated modulus of elasticity (MOE), or modulus of rupture (MOR), and the measured MOE, or MOR, than stress-wave techniques. They are, however, relatively difficult to apply in the field due to boundary conditions common in many timber structures. Thus, improved tools for assessing timber structures are still needed. Recently, near infrared (NIR) spectroscopy (500–2400 nm) has shown promise for predicting the MOE and MOR of wood. This work focuses on extending the use of NIR for measuring the load applied to small wood beams. The reflectance NIR spectrum was measured as the applied load was increased. Good correlations (r > 0.96) between the measured load and the predicted load were obtained using spectra taken from both the tension and compression surfaces of the small wood beams.