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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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Lignin Depolymerization with Nitrate-Intercalated Hydrotalcite Catalysts

Hydrotalcites (HTCs) exhibit multiple adjustable parameters to tune catalytic activity, including interlayer anion composition, metal hydroxide layer composition, and catalyst preparation methods. Here in this paper, we report the influence of several of these parameters on β-O-4 bond scission in a lignin model dimer, 2-phenoxy-1-phenethanol (PE), to yield phenol and acetophenone. We find that the presence of both basic and NO 3 – anions in the interlayer increases the catalyst activity by 2–3-fold. In contrast, other anions or transition metals do not enhance catalytic activity in comparison to blank HTC. The catalyst is not active for C–C bond cleavage on lignin model dimers and has no effect on dimers without an α-OH group. Most importantly, the catalyst is highly active in the depolymerization of two process-relevant lignin substrates, producing a significant amount of low-molecular-weight aromatic species. The catalyst can be recycled until the NO 3 – anions are depleted, after which the activity can be restored by replenishing the NO 3 – reservoir and regenerating the hydrated HTC structure. These results demonstrate a route to selective lignin depolymerization in a heterogeneous system with an inexpensive, earth-abundant, commercially relevant, and easily regenerated catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A nitrate transporter 1/peptide transporter family gene impacts nitrogen homeostasis and phenylpropanoid production in hybrid poplar

In plants, nitrogen and carbon metabolism are tightly interconnected, and nitrogen availability often negatively correlates with phenylpropanoids that are associated with xylem formation and stress responses. A nitrate transporter 1/peptide transporter (NRT1/PTR) family (NPF) gene (PtNPF6.1), which is expressed in the vasculature, was previously found to have a genetic association with the variation in syringyl lignin content in poplar trees (Populus trichocarpa). PtNPF6.1 belongs to an evolutionarily distinct NPF superfamily with limited taxonomic distribution. RNAi-mediated suppression of PtNPF6.1 led to increases in total foliar nitrogen and amino acids related to nitrogen transport and storage in source leaves. There was also a concomitant decrease in soluble phenolics, including attenuated stress-induced production of anthocyanins and condensed tannins. The proportions of syringyl and p-hydroxyphenyl units in lignin were slightly but significantly decreased in down-regulated lines grown under high nitrogen conditions, while there was an increase in the level of ester-linked p-hydroxybenzoate groups. Together, these results suggest that PtNPF6.1 is involved in maintaining internal nitrogen homeostasis in trees, indirectly impacting the production of nitrogen-free phenolics including lignin and soluble secondary metabolites.

amino acids↗

Kerr Reservoir LANDSAT experiment analysis for March 1981

LANDSAT radiance data were used in an experiment conducted on the waters of Kerr Reservoir to determine if reliable algorithms could be developed that relate water quality parameters to remotely sensed data. A mix of different types of algorithms using the LANDSAT bands was generated to provide a thorough understanding of the relationships among the data involved. Except for secchi depth, the study demonstrated that for the ranges measured, the algorithms that satisfactorily represented the data encompass a mix of linear and nonlinear forms using only one LANDSAT band. Ratioing techniques did not improve the results since the initial design of the experiment minimized the errors against which this procedure is effective. Good correlations were found for total suspended solids, iron, turbidity, and secchi depth. Marginal correlations were discovered for nitrate and tannin + lignin. Quantification maps of Kerr Reservoir are presented for many of the water quality parameters using the developed algorithms.

Lecroy, S. R.↗

Patterns of Bacterial and Archaeal Gene Expression through the Lower Amazon River

Analysis of metatranscriptomic and metagenomic datasets from the lower reaches of the Amazon River between Obidos and the river mouth revealed microbial transcript and gene pools dominated by Actinobacteria, Thaumarchaeota, Bacteroidetes, Acidobacteria, Betaproteobacteria, and Planctomycetes. Three mainstem stations spanning a 625 km reach had similar gene expression patterns (transcripts gene copy-1) across a diverse suite of element cycling genes, but two tributary-influenced stations at the mouth of the Tapajos River and near the Tocantins River at Belem had distinct transcriptome composition and expression ratios, particularly for genes encoding light-related energy capture (higher) and iron acquisition and ammonia oxidation (lower). Environmental parameters that were useful predictors of gene expression ratios included concentrations of lignin phenols, suspended sediments, nitrate, phosphate, and particulate organic carbon and nitrogen. Similar to the gene expression data, these chemical properties reflected highly homogeneous mainstem stations punctuated by distinct tributary- influenced stations at Tapajos and Belem. Although heterotrophic processes were expected to dominate in the lower Amazon, transcripts from photosynthetic bacteria were abundant in tributary-influenced regions, and transcripts from Thaumarcheota taxa genetically capable of chemosynthetic ammonia oxidation accounted for up to 21% of the transcriptome at others. Based on regressions of transcript numbers against gene numbers, expression ratios of Thaumarchaeota populations were largely unchanged within the mainstem, suggesting a relatively minor role for gene regulation. These quantitative gene and transcript inventories detail a diverse array of energy acquisition strategies and metabolic capabilities for bacteria and archaea populations of the world’s largest river system.

59 BASIC BIOLOGICAL SCIENCES↗

Broadband optical properties of biomass-burning aerosol and identification of brown carbon chromophores

The radiative effects of biomass burning aerosols on regional and global scale is substantial. Accurate modeling of the radiative effects of smoke aerosols require wavelength-dependent measurements and parameterizations of their optical properties in the UV and visible spectral ranges along with improved description of their chemical composition. To address this issue, we used a recently developed approach to retrieve the time- and spectral-dependent optical properties of ambient biomass burning aerosols between 300 and 650 nm wavelength during a regional bonfire festival in Israel. We report that during the biomass burning event, the overall absorption at 400 nm increased by about two orders of magnitude, changing the size-weighted single scattering albedo from a background level of 0.95 to 0.7. Based on the new retrieval method, we provide parameterizations of the wavelength-dependent effective complex refractive index from 350 to 650 nm for freshly emitted and aged biomass burning aerosols. In addition, PM 2.5 filter samples were collected for detailed off-line chemical analysis of the water soluble organics that contribute to light absorption. Nitrophenols were identified as the main organic species responsible for the increased absorption at 400-500 nm. These include species such as 4- nitrocatechol, 4-nitrophenol, nitro-syringol and nitro-guaiacol; oxidation-nitration products of methoxyphenols, known products of lignin pyrolysis. Our findings emphasize the importance of both primary and secondary organic aerosol from biomass burning in absorption of solar radiation and in effective radiative forcing.

54 ENVIRONMENTAL SCIENCES↗

Antarctic Soils Select Copiotroph-Dominated Bacteria

The life strategies of bacterial communities determine their structure and function and are an important driver of biogeochemical cycling. However, the variations in these strategies under different soil resource conditions remain largely unknown. We explored the bacterial life strategies and changes in structure and functions between Antarctic soils and forest (temperate, subtropical, and tropical) soils. The results showed that the weighted mean rRNA operon copy number in temperate soils was 19.5% lower than that in Antarctic soils, whereas no significant differences were observed among Antarctic, subtropical, and tropical soils. An unexpected result was that bacterial communities in Antarctic soils tended to be copiotrophs, such as Actinobacteriota and Bacteroidota, whereas those in temperate soils tended to be oligotrophs, such as Acidobacteriota and Chloroflexi. Functional predictions showed that in comparison to copiotrophs in Antarctic soils, temperate-inhabiting oligotrophic bacteria exhibited an 84.2–91.1% lower abundance of labile C decomposition genes (hemicellulose, cellulose, monosaccharides, and disaccharides), whereas a 74.4% higher abundance of stable C decomposition (lignin). Genes involved in N cycling (nitrogen fixation, assimilatory nitrate reduction, and denitrification) were 24.3–64.4% lower in temperate soils than in Antarctic soils. Collectively, our study provides a framework for describing the life strategies of soil bacteria, which are crucial to global biogeochemical cycles.

Microbiology↗

Identification of Critical Material Attributes in Lignin Streams Based on Pseudomonas putida Performance

Variability in chemical composition of corn stover feedstocks has been suggested to play a role in biocatalyst performance during the conversion of lignocellulosic biomass to value-added compounds. In previous studies, we investigated the performance of Pseudomonas putida CJ781 - an engineered bacterium that converts aromatic compounds to muconate - on various lignin streams produced from the deacetylation of corn stover, and we found significant differences on muconate production. To better understand the origin of these differences, we down selected twenty-two compounds from literature - that had previously been detected as extractives in lignin streams - and we analyzed their concentrations in 12 lignin streams generated from different feedstocks. P. putida CJ781 was then cultivated in mock lignin streams supplemented with various concentrations of these compounds. Bacterial growth was tracked in microtiter plates and the performance was measured by comparing maximum growth rates among conditions. At maximum concentrations that may be found in lignin streams, sodium was the material attribute that limited growth rate in a greater extent, with a reduction in growth rate by 8 to 37%, depending on the counter ion, with sodium nitrate being the most inhibitory, followed by sodium acetate, sodium chloride, and sodium sulfate. Ammonium acetate was also found to be inhibitory at average concentrations of ammonium in lignin streams, reducing maximum growth rate by 18%. Overall, the data from this study has allowed to down select critical material attributes in lignin streams and process parameters that significantly affect the performance of P. putida and will be used as input to predictive models that aim to reduce risks attributed to feedstock variability in lignocellulosic biorefineries.

biocatalyst↗

Dissecting the Genetic Architecture of Carbon Partitioning in Sorghum Using Multiscale Phenotypes

Carbon partitioning in plants may be viewed as a dynamic process composed of the many interactions between sources and sinks. The accumulation and distribution of fixed carbon is not dictated simply by the sink strength and number but is dependent upon the source, pathways, and interactions of the system. As such, the study of carbon partitioning through perturbations to the system or through focus on individual traits may fail to produce actionable developments or a comprehensive understanding of the mechanisms underlying this complex process. Using the recently published sorghum carbon-partitioning panel, we collected both macroscale phenotypic characteristics such as plant height, above-ground biomass, and dry weight along with microscale compositional traits to deconvolute the carbon-partitioning pathways in this multipurpose crop. Multivariate analyses of traits resulted in the identification of numerous loci associated with several distinct carbon-partitioning traits, which putatively regulate sugar content, manganese homeostasis, and nitrate transportation. Using a multivariate adaptive shrinkage approach, we identified several loci associated with multiple traits suggesting that pleiotropic and/or interactive effects may positively influence multiple carbon-partitioning traits, or these overlaps may represent molecular switches mediating basal carbon allocating or partitioning networks. Conversely, we also identify a carbon tradeoff where reduced lignin content is associated with increased sugar content. The results presented here support previous studies demonstrating the convoluted nature of carbon partitioning in sorghum and emphasize the importance of taking a holistic approach to the study of carbon partitioning by utilizing multiscale phenotypes.

59 BASIC BIOLOGICAL SCIENCES↗

The practice and economics of hybrid poplar biomass production for biofuels and bioproducts in the Pacific Northwest

Hybrid poplar demonstration-scale farms were managed in Oregon, Washington, Idaho, and California to establish management practices, yields, harvesting methods, and the economics of biomass production. Yield during the 2-year establishment cycle averaged 3.5 dry Mg ha –1 year –1 increasing to 11.6 Mg ha –1 year –1 in the ensuing 3-year coppice cycle. Populus deltoides (Bartram ex Marsh.) × P. maximowiczii (Henry) varieties preformed best in Oregon during the coppice cycle with the best variety producing 18.1 Mg ha –1 year –1 , while P. ×generosa (Henry) varieties maximized yields in Washington at 22.1 Mg ha –1 year –1 . P. ×canadensis (Moench) varieties excelled in Idaho and California with upper yields of 13.6 Mg ha –1 year –1 and 12.9 Mg ha –1 year –1 , respectively. Stands were cut with a single-pass harvester 2 years after planting and a second time after 3 years of coppice growth; material capacity, limited by poor ground conditions, varied between 21.7 to 31.3 green Mg h –1 . Chemical composition averaged 1.87% inorganics, 7.74% extractives, 26.90% lignin, 38.07% glucan, 13.66% xylan, 1.61% galactan, 1.14% arabinan, and 2.76% mannan. Production costs (USD) projected over a 20-year rotation of six coppice cycles were $71.81 Mg –1 in Washington, $89.91 Mg –1 in Oregon, $98.76 Mg–1 in Idaho, and 179.07 Mg–1 in California. Here, land rental, establishment, crop care, harvest, transportation, and land restoration, respectively, accounted for 23%, 5%, 19%, 30%, 17%, and 6% of total feedstock cost. Farms were successfully restored to conditions existing before poplar conversion. In the absence of fertilization, increases in soil pH and decreases in nitrate-nitrogen, zinc, iron, and organic matter were consistently noted but could not be associated with poplar production alone.

09 BIOMASS FUELS↗