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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Editorial: Microorganisms for Consolidated 2nd Generation Biorefining

In the last few decades, lignocellulosic biomass has attracted substantial interest as a feedstock for fermentative production of fuels and other commodity chemicals due to its wide availability and low cost. However, lignocellulose has innate complexity and recalcitrance to biodegradation. In natural environments, effective plant biomass decay is obtained by synergistic activity of complex microbial communities.

59 BASIC BIOLOGICAL SCIENCES↗

Fermentative conversion of unpretreated plant biomass: A thermophilic threshold for indigenous microbial growth

Here, naturally occurring, microbial contaminants were found in plant biomasses from common bioenergy crops and agricultural wastes. Unexpectedly, indigenous thermophilic microbes were abundant, raising the question of whether they impact thermophilic consolidated bioprocessing fermentations that convert biomass directly into useful bioproducts. Candidate microbial platforms for biomass conversion, Acetivibrio thermocellus (basionym Clostridium thermocellum; T opt 60 °C) and Caldicellulosiruptor bescii (T opt 78 °C), each degraded a wide variety of plant biomasses, but only A. thermocellus was significantly affected by the presence of indigenous microbial populations harbored by the biomass. Indigenous microbial growth was eliminated at ≥75 °C, conditions where C. bescii thrives, but where A. thermocellus cannot survive. Therefore, 75 °C is the thermophilic threshold to avoid sterilizing pre-treatments on the biomass that prevents native microbes from competing with engineered microbes and forming undesirable by-products. Thermophiles that naturally grow at and above 75 °C offer specific advantages as platform microorganisms for biomass conversion into fuels and chemicals.

59 BASIC BIOLOGICAL SCIENCES↗

Biochemical upgrading of high-protein biomass and grain products

The present invention relates to methods of upgrading biomass to provide useful chemical intermediates, fuels, amino acids, nutrients, etc. In particular examples, the biomass is a by-product of ethanol production and is mainly used as high-protein feed. Described herein are methods for upgrading such biomass, such as by implementing pre-treatment conditions and by employing fermentation conditions including modified organisms.

09 BIOMASS FUELS↗

Biochemical upgrading of high-protein biomass and grain products

The present invention relates to methods of upgrading biomass to provide useful chemical intermediates, fuels, amino acids, nutrients, etc. In particular examples, the biomass is a by-product of ethanol production and is mainly used as high-protein feed. Described herein are methods for upgrading such biomass, such as by implementing pre-treatment conditions and by employing fermentation conditions including modified organisms.

Davis, Ryan Wesley↗

Progress and roadmap for electro-privileged transformations of bio-derived molecules

Biomass incorporates carbon captured from the atmosphere and can serve as a renewable feedstock for producing valuable chemicals and fuels. Here we look at how electrochemical approaches can impact biomass valorization, focusing on identifying chemical transformations that leverage renewable electricity and feedstocks to produce valorized products via electro-privileged transformations. First, we recommend that the field should explore widening the spectrum of platform chemicals derived from bio-feedstocks, thus offering pathways to molecules that have historically been derived from petroleum. Second, we identify opportunities in electrocatalytic production of energy-dense fuels from biomass that utilize water as the hydrogen source and renewable electricity as the driving force. Finally, we look at the potential in electrochemical depolymerization to preserve key functional groups in raw feedstocks that would otherwise be lost during harsh pre-treatments in traditional depolymerization routes. Finally, on the basis of these priorities, we suggest a roadmap for the integration of biomass and electrochemistry and offer milestones required to tap further into the potential of electrochemical biomass valorization.

electrocatalysis↗

Decontamination of Mixed Paper and Plastic Municipal Solid Waste Increases Low and High Temperature Conversion Yields

With the implementation of China’s Green Fence Policy and the following National Sword Policy, there is a need to divert previously accepted waste materials away from the landfill. Mixed plastic and paper wastes that are too contaminated to be economically recycled can be used for conversion into fuels and products. The effect of common contaminants present in waste streams must be determined to make municipal solid waste (MSW) a viable alternative to agricultural feedstocks for conversion. In this study, MSW was sourced from a dual stream materials recovery facility (MRF) in Emmet County, Michigan and characterized via mass balance. The most common contaminants in mixed paper and plastic were quantified and targeted for decontamination when mixed paper was explored for low temperature conversion pathways and plastics for high temperature conversion pathways. Ink, stickies, and plastic contamination were sorted out of the mixed paper stream and did not have an impact on sugar yields during enzymatic hydrolysis (EH). Although no improvement in yield was found, it was noted that copy paper within the mixed paper stream had an elevated pH and higher concentration of fermentation inhibitors, suggesting that intrinsic properties of some paper types may not be ideal for EH and fermentation conversion. Dilute alkaline pretreatment and mechanical refining of mixed paper increased the EH yield of mixed paper, suggesting this previously established process could be used as a decontamination method. “Dirt” and particulates were washed from mixed plastic using either an aqueous detergent or a non-aqueous chemical washing method. Liquid oil yields were increased during microwave assisted fast pyrolysis. All decontamination techniques met the cost target of less than $30/dry ton with plastic decontamination ranging from $18.16 to $24.81/dry ton. Because dilute alkaline pre-treatment and mechanical refining is considered part of the conversion process, the decontamination cost during feedstock preprocessing was considered $0/dry ton.

09 BIOMASS FUELS↗

Rapid and high-throughput determination of sorghum ( Sorghum bicolor ) biomass composition using near infrared spectroscopy and chemometrics

Compositional characterization of biomass is vital for the biofuel industry. Traditional wet chemistry-based methods for analyzing biomass composition are laborious, time-consuming, and require extensive use of chemical reagents as well as highly skilled personnel. In this study, near-infrared (NIR) spectroscopy was used to quickly assess the composition of above-ground vegetative biomass from 113 diverse, photoperiod-sensitive, biomass-type sorghum (Sorghum bicolor) accessions cultivated under field conditions in Central Illinois. Biomass samples were analyzed using NIR spectra collected in the spectral range of 867–2536 nm, with their chemical compositions determined following the National Renewable Energy Laboratory (NREL) protocol. Advanced spectral pre-treatment and band selection techniques were utilized to develop calibration models using partial least squares regression (PLSR). The models’ effectiveness was assessed through cross-validation and independent data tests. The predictions for moisture, ash, extractives, glucan, xylan, acid-soluble lignin (ASL), acid-insoluble lignin (AIL), and total lignin were accurate and reliable, demonstrating the capability of NIR spectroscopy to provide rapid and precise characterization of sorghum biomass. The results demonstrated that NIR spectroscopy is an efficient tool for rapidly characterizing sorghum biomass, making it a sustainable option for screening desirable feedstock for biofuel or bioproduct production.

09 BIOMASS FUELS↗

Data for Rapid and High-Throughput Determination of Sorghum ( Sorghum bicolor ) Biomass Composition using Near Infrared Spectroscopy and Chemometrics

Compositional characterization of biomass is vital for the biofuel industry. Traditional wet chemistry-based methods for analyzing biomass composition are laborious, time-consuming, and require extensive use of chemical reagents as well as highly skilled personnel. In this study, near-infrared (NIR) spectroscopy was used to quickly assess the composition of above-ground vegetative biomass from 113 diverse, photoperiod-sensitive, biomass-type sorghum ( Sorghum bicolor ) accessions cultivated under field conditions in Central Illinois. Biomass samples were analyzed using NIR spectra collected in the spectral range of 867–2536 nm, with their chemical compositions determined following the National Renewable Energy Laboratory (NREL) protocol. Advanced spectral pre-treatment and band selection techniques were utilized to develop calibration models using partial least squares regression (PLSR). The models’ effectiveness was assessed through cross-validation and independent data tests. The predictions for moisture, ash, extractives, glucan, xylan, acid-soluble lignin (ASL), acid-insoluble lignin (AIL), and total lignin were accurate and reliable, demonstrating the capability of NIR spectroscopy to provide rapid and precise characterization of sorghum biomass. The results demonstrated that NIR spectroscopy is an efficient tool for rapidly characterizing sorghum biomass, making it a sustainable option for screening desirable feedstock for biofuel or bioproduct production.

Biomass Analytics↗

Engineering Synthetic Anaerobic Consortia Inspired by the Rumen for Biomass Breakdown and Conversion

Lignocellulosic plant biomass is a widely-abundant renewable resource that can be harnessed for value-added production of fuels & chemicals. While microbes have been engineered to breakdown lignocellulose and turn released sugars into products, this remains an energy-intensive process that requires expensive pre-treatment and separation steps. Furthermore, it is difficult to engineer all desirable traits for breakdown and conversion into one organism. This project developed a new strategy that relies on microbial partnerships formed in the herbivore rumen to liberate sugars from crude plant biomass and convert that sugar to value-added chemicals. Microbial consortia consisting of fungi, bacteria, and archaea form tight associations in the herbivore rumen, which divide-and-conquer the difficult tasks of biomass breakdown. This project leveraged a “synthetic rumen” consortium composed of anaerobic fungi and chain-elongating bacteria to study which metabolites are shared and exchanged between microbes and identify strategies to bolster lignocellulose conversion to value-added products. Our approach developed high-throughput systems and synthetic biology approaches to realize stable synthetic consortia that route lignocellulosic carbon into short and medium chain fatty acids (SCFAs/MCFAs) rather than methane. Key research objectives were to (1) design and predict anaerobic fungal and bacterial consortia that efficiently convert lignocellulosic biomass into medium-chain fatty acids (MCFAs), (2) understand how fermentation parameters and microbe-microbe interactions regulate and drive microbiome metabolic fluxes, and (3) use genomic editing to alter the fermentation byproducts of anaerobic fungi and bolster MCFA titers and yields.

09 BIOMASS FUELS↗

Low-Temperature Processing of Pyrolysis Bio-Oil for Sustainable Biographite Production

Catalytic graphitization of pyrolysis bio-oil with iron (Fe) can produce an anode material for lithium-ion batteries (LIBs) at a moderate temperature. The key challenge to scaling up the process is foaming, which occurs due to the oxidation of Fe by the organic acids present in bio-oil. This study explored five different pathways to control foaming in bio-oil upon Fe addition, including (i) defoamers use, (ii) use of iron oxide (Fe2O3) as graphitization catalyst, (iii) pH adjustment of bio-oil, (iv) bio-oil coking (300-500 degrees C), and (v) low-temperature pretreatment of bio-oil (150-200 degrees C). The low-temperature pretreatment successfully avoided foaming by removing the volatile acids in bio-oil. The bio-oil was solidified and powdered for even mixing with the Fe catalyst. The biographite catalytically prepared at 1500 degrees C following this pathway demonstrated nearly theoretical specific gravimetric capacity (~370 mAh/g), high initial Coulombic efficiency (90.03%), and minimal capacity fading after 50 cycles in LIB half-cells. The low-temperature pretreatment pathway also addressed the viscosity, swelling, and aging issues associated with bio-oil processing and will make scale-up endeavors more attainable.

09 BIOMASS FUELS↗

Enrichment of amino acids from biomass residuum

The present invention relates to methods of providing a biomass residuum and compositions thereof. In particular examples, the biomass residuum includes one or more high value amino acids, even after removal of mixed alcohol components. In particular, the methods include implementing pre-treatment conditions and employing fermentation conditions including modified organisms.

Davis, Ryan Wesley↗

Ultraviolet radiation pre-treatment of wastewater, improving its utility for algal cultivation

The present invention relates to a process of remediating wastewaters, preferably agricultural wastewaters resulting from animal production or contained animal feeding operation sites. The water is treated to promote assimilation of nutrients into algal biomass, which can be harvested and sold, and the resultant wastewater is then purified. According to the invention, short wavelength UV radiation (less than 280 nm wavelength) is used to pretreat wastewater, with the dose determined by absorbance of the water, not by bacterial load. Pretreated water exhibits changes in chromophoric dissolved organic matter that allows for improved and increased algae production by as much as 88%.

Feris, Kevin↗

Understanding Biomass and Polymer Feedstock Variability Through Analytical Pyrolysis and Two Dimensional Gas Chromatography and Mass Spectrometry

Moving toward a circular carbon economy requires enabling reuse of carbon-based macromolecules like those in biomass and polymers. Meeting this goal requires increased upcycling of waste products into higher value products. For biomass waste such as corn stover, pine needles, or bark, one approach is using pyrolysis to convert these feedstocks into bio-oil that can be used for liquid fuel or transformed into other hydrocarbon based products, like bio-polymers. Waste plastics can be upcycled or recycled into new products, or alternatively converted into bio-oil by pyrolysis. Macromolecules from biomass and polymers are challenging to convert into liquid fuel or chemical feedstocks, due to large and sometimes heterogeneous networks of polymeric bonds. We work with the Idaho National Laboratory’s Biomass Feedstock National User Facility and Department of Energy’s Feedstock Conversion Interface Consortium to develop a molecular understanding of biomass variability that occurs naturally and as a result of storage or preprocessing techniques applied to feedstocks, to understand chemical reactions occurring during pyrolysis and other biomass or polymer conversion techniques. Using two dimensional gas chromatography mass spectrometry coupled to analytical pyrolysis provides insight into the molecular changes that occur during the pyrolysis event, and these insights can extend to bench or pilot scale pyrolysis conversions. Understanding pyrolysis of biomass and polymers at a molecular level contributes to development of new tools to predict and manipulate the optimum conditions and identify the best storage, preprocessing, and conversion techniques to maximize output of specific high-value chemical species in the conversion to fuels, or to characterize feedstocks for blending before pyrolysis. Identification and understanding of the molecular level changes resulting from novel preprocessing techniques that can be used to control and manipulate the chemical output of bench or pilot scale pyrolysis is another focus of investigation, including the use of gamma irradiation, acid, or enzyme pre-treatments. We also focus on the impacts of storage conditions and techniques, which can affect moisture levels, degradation, and impacts from naturally occurring microbes in the environment.

09 BIOMASS FUELS↗

Reduced accrual of mineral-associated organic matter after two years of enhanced rock weathering in cropland soils, though no net losses of soil organic carbon

Abstract Enhanced rock weathering (ERW), the application of crushed silicate rock to soil, can remove atmospheric carbon dioxide by converting it to (bi) carbonate ions or solid carbonate minerals. However, few studies have empirically evaluated ERW in field settings. A critical question remains as to whether additions of crushed rock might positively or negatively affect soil organic matter (SOM)—Earth’s largest terrestrial organic carbon (C) pool and a massive reservoir of organic nitrogen (N). Here, in three irrigated cropland field trials in California, USA, we investigated the effect of crushed meta-basalt rock additions on different pools of soil organic carbon and nitrogen (i.e., mineral-associated organic matter, MAOM, and particulate organic matter, POM), active microbial biomass, and microbial community composition. After 2 years of crushed rock additions, MAOM stocks were lower in the upper surface soil (0–10 cm) of plots with crushed rock compared to unamended control plots. At the 2 sites where baseline pre-treatment data were available, neither total SOC nor SON decreased over the 2 years of study in plots with crushed rock or unamended control plots. However, the accrual rate of MAOM-C and MAOM-N at 0–10 cm was lower in plots with crushed rock vs. unamended controls. Before ERW is deployed at large scales, our results suggest that field trials should assess the effects of crushed rock on SOM pools, especially over multi-year time scales and in different environmental contexts, to accurately assess changes in net C and understand the mechanisms driving interactions between ERW and SOM cycling.

58 GEOSCIENCES↗

Systems Engineering of Rhodococcus opacus to Enable Production of Drop-in Fuels from Lignocellulose

Production of drop-in fuels from lignocellulose using Rhodococcus opacus PD630 (hereafter R. opacus) is a challenging goal. During the grant period we have pushed the field forward significantly in several areas of research. Towards the end goal of accelerating the adoption of R. opacus in biofuel production, during the grant period we have expanded the phenotypic characterization of R. opacus grown in single aromatic (model lignocellulosic) compounds or their mixtures, modeling the growth conditions in lignocellulosic biomass. Harnessing the power of adaptive evolution, we produced evolved R. opacus isolates with superior lignin valorization capabilities and identified differentially expressed genes and pathways after adaptation. We used next generation multi-omic techniques such as genomic, transcriptomic, and metabolomic analyses, to identify the catabolic pathways used by R. opacus to degrade aromatic compounds and funnel these degradation products into central metabolism, as well as the aromatic transport genes required for increased tolerance and utilization. Taking this information one step further, we identified endogenous transcription factors and regulatory mechanisms important for degradation of five model aromatic compounds. To accurately estimate R. opacus growth and consumption on model lignin compounds we pioneered the use of novel extraction procedures prior to GC-MS analysis. Alongside 13 C-metabolic flux analysis, we have elucidated the metabolic routes preferred by Rhodococcus opacus during aromatic compound degradation. Finally, we used in tandem lipidomics and high-resolution mass spectrometry to identify the modulation of mycolic acids and phospholipid membrane composition modification as a strategy for aromatic tolerance in R. opacus. Being a non-model organism, R. opacus lacks the breadth of tools and technical foundation which drive biofuel research in more well-understood microbes such as Escherichia coli. To reduce this burden for use, we designed and produced new tools for genomic manipulation and engineering in R. opacus. These engineering breakthroughs support efficient genomic editing, enabling gene overexpression, repression, and genetic alteration. Using these tools, we have generated synthetically engineered strains with increased lipogenesis and growth, both positive traits required for increased lignin valorization. Optimizing engineered strains for biofuel production from lignocellulose requires extremely sophisticated synthetic rewiring of metabolism. To facilitate systems-level reorganization of metabolism in R. opacus, we created a genome-scale model that accurately predicts metabolic flux and growth rates on the aromatic compound phenol. Lignin requires extensive pre-treatment before biological degradation by R. opacus. Towards an eventual goal of degrading real-world lignin, we developed new depolymerization processes to generate lignin breakdown products (LBP). We optimized LBP storage and composition analysis techniques, enabling accurate prediction of specific LBP compound integration into cell wall components. Overall, through the work funded by this grant we generated 20 manuscripts (17 published, 3 in review/preparation), methods for increased accuracy in metabolomics of aromatic compounds, multiple genetic tools for altering the R. opacus genome, genome scale models for predicting flux through metabolic pathways, as well as multi-omic data for community use. The work funded by this grant has increased the knowledge of aromatic degradation in bacteria and advanced our efforts to optimize R. opacus for lignin valorization.

09 BIOMASS FUELS↗

Scale-Up of a Two-Stage Cu-Catalyzed Alkaline-Oxidative Pretreatment of Hybrid Poplar

A two-stage alkaline-oxidative pretreatment of hybrid poplar was investigated at scale (20 L reactor volume) with the goals of understanding how reaction conditions as well as interstage mechanical refining impact downstream process responses. The pretreatment comprises a first stage of alkaline delignification (alkaline pre-extraction) followed by a second delignification stage employing Cu-catalyzed alkaline hydrogen peroxide with supplemental O 2 (O 2 -enhanced Cu-AHP). Increasing pre-extraction severity (i.e., temperature and alkali loading) and pre-treatment oxidation (increasing H 2 O 2 loading) were found to increase mass and lignin solubilization in each stage. Lignin recovered from the first stage was subjected to oxidative depolymerization and led to aromatic monomer yields as high as 23.0% by mass. As a result, lignins recovered from the second stage Cu-AHP pretreatment liquors were shown to exhibit aliphatic hydroxyl contents more than six-fold higher than for a typical hardwood kraft lignin, indicating these lignins could serve as a biobased polyol for a range of polyurethane applications.

09 BIOMASS FUELS↗