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At least 73 records · Page 4

Resilience of terrestrial and aquatic fauna to historical and future wildfire regimes in western North America

Wildfires in many western North American forests are becoming more frequent, larger, and severe, with changed seasonal patterns. In response, coniferous forest ecosystems will transition toward dominance by fire-adapted hardwoods, shrubs, meadows, and grasslands, which may benefit some faunal communities, but not others. We describe factors that limit and promote faunal resilience to shifting wildfire regimes for terrestrial and aquatic ecosystems. We highlight the potential value of interspersed nonforest patches to terrestrial wildlife. Similarly, we review watershed thresholds and factors that control the resilience of aquatic ecosystems to wildfire, mediated by thermal changes and chemical, debris, and sediment loadings. We present a 2-dimensional life history framework to describe temporal and spatial life history traits that species use to resist wildfire effects or to recover after wildfire disturbance at a metapopulation scale. The role of fire refuge is explored for metapopulations of species. In aquatic systems, recovery of assemblages postfire may be faster for smaller fires where unburned tributary basins or instream structures provide refuge from debris and sediment flows. We envision that more-frequent, lower-severity fires will favor opportunistic species and that less-frequent high-severity fires will favor better competitors. Along the spatial dimension, we hypothesize that fire regimes that are predictable and generate burned patches in close proximity to refuge will favor species that move to refuges and later recolonize, whereas fire regimes that tend to generate less-severely burned patches may favor species that shelter in place. Looking beyond the trees to forest fauna, we consider mitigation options to enhance resilience and buy time for species facing a no-analog future.

54 ENVIRONMENTAL SCIENCES↗

Carbon budget of the Harvard Forest Long-Term Ecological Research site: pattern, process, and response to global change

How, where, and why carbon (C) moves into and out of an ecosystem through time are long-standing questions in biogeochemistry. Here, we bring together hundreds of thousands of C-cycle observations at the Harvard Forest in central Massachusetts, USA, a mid-latitude landscape dominated by 80–120-yr-old closed-canopy forests. These data answered four questions: (1) where and how much C is presently stored in dominant forest types; (2) what are current rates of C accrual and loss; (3) what biotic and abiotic factors contribute to variability in these rates; and (4) how has climate change affected the forest’s C cycle? Harvard Forest is an active C sink resulting from forest regrowth following land abandonment. Soil and tree biomass comprise nearly equal portions of existing C stocks. Net primary production (NPP) averaged 680–750 g C·m –2 ·yr –1 ; belowground NPP contributed 38–47% of the total, but with large uncertainty. Mineral soil C measured in the same inventory plots in 1992 and 2013 was too heterogeneous to detect change in soil-C pools; however, radiocarbon data suggest a small but persistent sink of 10–30 g C·m –2 ·yr –1 . Net ecosystem production (NEP) in hardwood stands averaged ~300 g C·m –2 ·yr –1 . NEP in hemlock-dominated forests averaged ~450 g C·m –2 ·yr –1 until infestation by the hemlock woolly adelgid turned these stands into a net C source. Since 2000, NPP has increased by 26%. For the period 1992–2015, NEP increased 93%. The increase in mean annual temperature and growing season length alone accounted for ~30% of the increase in productivity. Interannual variations in GPP and NEP were also correlated with increases in red oak biomass, forest leaf area, and canopy-scale light-use efficiency. Compared to long-term global change experiments at the Harvard Forest, the C sink in regrowing biomass equaled or exceeded C cycle modifications imposed by soil warming, N saturation, and hemlock removal. Furthermore, the results of this synthesis and comparison to simulation models suggest that forests across the region are likely to accrue C for decades to come but may be disrupted if the frequency or severity of biotic and abiotic disturbances increases.

54 ENVIRONMENTAL SCIENCES↗

Assessment of habitat‐specific competition for oral rabies vaccine baits between raccoons and opossums

Abstract Throughout the eastern United States, the National Rabies Management Program (NRMP) distributes oral rabies vaccine (ORV) baits to manage rabies virus circulation in raccoon ( Procyon lotor ) populations. The consumption of vaccine baits by non‐target species including Virginia opossums ( Didelphis virginiana ) may reduce the effectiveness of ORV programs, but competition for baits remains poorly quantified in many areas of the southeastern United States. We distributed placebo ORV baits injected with a biomarker across 4 land cover types (bottomland hardwood, upland pine, riparian, isolated wetland) on the Savannah River Site in South Carolina, USA, 2017–2019. We then trapped and collected whiskers from 247 raccoons and 78 opossums to assess biomarker presence using fluorescent microscopy. Our data revealed greater bait uptake probability by raccoons (estimated x̅ = 0.30, 95% CI = 0.19–0.44) compared to opossums (estimated x̅ = 0.11, 95% CI = 0.05–0.23) across all cover types surveyed. Probability of bait consumption was not affected by cover type or the abundance of raccoons or opossums. Among raccoons, males were more likely to consume baits than females (estimated x̅ = 0.28, 95% CI = 0.17–0.44 for males and 0.14, 95% CI = 0.05–0.31 for females) and probability of consumption increased by 0.08 with each additional day trapped during the 10‐day trapping session. Uptake rates for raccoons were relatively low compared to other studies and not influenced by competition with opossums. These low consumption rates indicate that additional research addressing the roles of baiting season, bait density, and resource selection will be important to maximize ORV bait uptake by target species in these southeastern landscapes.

59 BASIC BIOLOGICAL SCIENCES↗

Raccoon density estimation from camera traps for raccoon rabies management

Abstract Density estimation for unmarked animals is particularly challenging, yet density estimates are often necessary for effective wildlife management. Raccoons ( Procyon lotor ) are the primary terrestrial wildlife reservoir for Lyssavirus rabies within the United States. The raccoon rabies variant (RRVV) is actively managed at landscape scales using oral rabies vaccination (ORV) within the eastern United States. To effectively manage RRVV, it is important to know the density of raccoons to appropriately scale the density of ORV baits distributed on the landscape. We compared methods to estimate raccoon densities from camera‐trap data versus more intensive capture‐mark‐recapture (CMR) estimates across 2 land cover types (upland pine and bottomland hardwood) in the southeastern United States during 2019 and 2020. We evaluated the effect of alternative camera configurations and durations of camera trapping on density estimates and used an N‐mixture model to estimate raccoon densities, including covariates on abundance and detection. We further compared different methods of scaling camera‐based counts, with the maximum number of raccoons seen on any given image within a day best explaining density. Camera‐trap density estimates were moderately correlated with CMR estimates ( r = 0.56). However, densities from camera‐trap data were more reliable when classifying category of density as an index used to inform management (83% correct when compared to CMR estimates), although the densities in our study fell into the 2 lowest density classes only. Using more cameras reduced bias and uncertainty around density estimates; however, if ≤6 camera traps were used at a site, a line transect approach proved less biased than a grid design. Camera trapping should be conducted for at least 3 weeks for more accurate estimates of raccoon population density in our study area (<5% bias). We show that camera‐trap data can be used to assign raccoon densities to management‐relevant density index bins, but more studies are needed to ensure reliability across a greater range of environmental conditions and raccoon densities.

Davis, Amy J.↗

Influence of biotic and abiotic factors on home range size and shape of invasive wild pigs ( Sus scrofa )

Determining factors influencing animal movements at a temporal scale that is similar to that at which management actions are conducted (e.g. weekly) is crucial for identifying efficient methods of wildlife conservation and management. Using global positioning system (GPS) data from 49 wild pigs in the southeast United States, we constructed weekly 50% and 95% utilization distributions to quantify the effects of biotic and abiotic factors on weekly core area and home range size, as well as home range shape. Here we found vegetative composition (i.e. proportion of bottomland hardwoods), season (based on forage availability), meteorological conditions (i.e. temperature and pressure), and sex influenced wild pig weekly home range and core area size, while vegetative composition (i.e. proportion of upland pines) and landscape features (i.e. distance to streams) also were important factors influencing home range shape. At close distances to streams, wild pigs had more elongate home ranges when their home ranges comprised less upland pine habitat; however, farther from streams, there was no change in home range shape across fluctuating proportions of upland pines. These results demonstrate that fine-scale wild pig home ranges and movements are pliable from week to week and influenced by several habitat, landscape, and meteorological attributes that can easily be quantified from available land use and meteorological databases. These findings are important for designing monitoring studies, identifying high risk zones for disease transmission, planning response to disease emergence events, and allowing more effective and efficient short-term management planning.

60 APPLIED LIFE SCIENCES↗

Feedstock and Catalyst Impact on Bio-Oil Production and FCC Co-Processing to Fuels

NREL's thermochemical biomass conversion research is focused on ex-situ upgrading of biomass fast-pyrolysis (FP) vapors as an efficient route to completely biogenic pyrolysis-based fuel precursors, fuels, and value-added chemicals depending on catalyst and process conditions. A near term pathway being developed uses these liquids for co-processing with petroleum feedstocks to assess biogenic carbon incorporation in hydrocarbon fuel feedstocks for potential refinery use. In this work, the impact of feedstock and catalyst on catalytic fast pyrolysis oil (CFPO) composition was determined with the oils then assessed for biogenic fuel production via FCC (fluidized catalytic cracking) co-processing. Biomass vapors were generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce clean vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled to a custom pyrolyzer system designed to produce consistent-composition pyrolysis vapors as feed to the DCR. Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available modified zeolite-based catalysts to produce CFPOs. These upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and simulated distillation (SIMDIS) to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. These exploratory vapor-phase-upgrading results demonstrated the feasibility of producing refinery-compatible hydrocarbon fuel intermediates entirely from biomass-derived fast-pyrolysis vapors using an industry-accepted DCR system for catalytic upgrading. The FCC co-processing results demonstrated the feasibility of using CFPOs with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.

biogenic carbon↗

Rewiring metabolism of Clostridium thermocellum for consolidated bioprocessing of lignocellulosic biomass poplar to produce short-chain esters

Consolidated bioprocessing (CBP) of lignocellulosic biomass uses cellulolytic microorganisms to enable enzyme production, saccharification, and fermentation to produce biofuels, biochemicals, and biomaterials in a single step. However, understanding and redirecting metabolisms of these microorganisms compatible with CBP are limited. Here, a cellulolytic thermophile Clostridium thermocellum was engineered and demonstrated to be compatible with CBP integrated with a Co-solvent Enhanced Lignocellulosic Fractionation (CELF) pretreatment for conversion of hardwood poplar into short-chain esters with industrial use as solvents, flavors, fragrances, and biofuels. The recombinant C. thermocellum engineered with deletion of carbohydrate esterases and stable overexpression of alcohol acetyltransferases improved ester production without compromised deacetylation activities. These esterases were discovered to exhibit promiscuous thioesterase activities and their deletion enhanced ester production by rerouting the electron and carbon metabolism. Ester production was further improved up to 80-fold and ester composition could be modulated by deleting lactate biosynthesis and using poplar with different pretreatment severity.

59 BASIC BIOLOGICAL SCIENCES↗

The role of catalytic iron in enhancing volumetric sugar productivity during autothermal pyrolysis of woody biomass

Passivation of naturally occurring AAEM in biomass enhances sugar yields from the fast pyrolysis of biomass by preventing these metals from catalyzing the fragmentation of pyranose rings in cellulose and hemicellulose. However, because AAEM also catalyzes lignin depolymerization, its passivation can be accompanied by undesirable char agglomeration. Pretreatment of biomass with ferrous sulfate both passivates AAEM and substitutes ferrous ions as lignin depolymerization catalysts. This pretreatment has been particularly successful for high ash biomass like corn stover, but of limited value for low ash biomass like wood. This study explores the reasons for this discrepancy and offers a combined pretreatment of ferrous sulfate and ferrous acetate pretreatment to overcome char agglomeration in wood. Furthermore, this new pretreatment increased sugar yields from 4.4 wt% to 15.5 wt% and 5.4 wt% to 19.0 wt% for hardwood and softwood biomasses, respectively. This pretreatment produces an iron-rich biochar that catalyzes oxidation of the biochar under the oxygen-rich conditions of autothermal pyrolysis, which is preferentially consumed to provide the enthalpy for pyrolysis, preserving bio-oil as a more desirable energy product. Instead of producing carbon monoxide, which dominates oxidation of biochar from untreated biomass, the iron catalyzes oxidation to carbon dioxide, producing more energy per mole of oxygen consumed. In fact, oxygen demand to support autothermal pyrolysis of red oak and southern yellow pine was reduced 15% by the presence of iron in the biochar.

42 ENGINEERING↗

3D printed lignin/polymer composite with enhanced mechanical and anti-thermal-aging performance

Lignin is the most abundant natural aromatic polymer globally but is still underutilized as a renewable material, even with its versatile properties. One approach to using lignin is to incorporate it in polymer composites, but this application is often limited by the poor mechanical performance of the resultant composite due to the poor interfacial adhesion. Following the structure–property relationship, stronger interactions were designed to be enhanced by alternating the functional groups of lignin. Here, this study applied a demethylation method to hardwood lignin (Ori-Lig) to introduce more phenolic hydroxyl groups. Research studies with rheology behavior and molecular simulations demonstrated that an increased phenolic hydroxyl content could improve the adhesion between the modified lignin (OH-Lig) and the polymer matrix at the interface. The tensile performance of the samples from the fused depositional modeling (FDM) 3D printing technique was also improved due to the improved interfacial adhesion. Specifically, by adding 10 wt% of the modified lignin, the tensile strength of the 3D printed samples could reach 46.1 MPa (40.2 MPa of Polyamide 12, PA12), and Young’s Modulus could be improved to 1.73 GPa (1.48 GPa of PA12). OH-Lig also improved anti-aging performance so that the tensile strength of the OH-Lig composite after thermo-aging (100 h at 140 °C) remained ~48MPa. The enhanced mechanical performance with anti-aging properties indicated that the OH-Lig composite may replace PA12 to reduce the use of petrol-based materials. This work showed the method of purposefully designing and modifying lignin structures to fulfill the interaction requirements between lignin and polymer matrix. The as-prepared lignin could be used to prepare functional composites to achieve improved mechanical performance and targeted functions at the same time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Properties and performance of lignin-based polyurethane foams from lignin and castor oil as synergistic bio-polyols

Lignin and castor oil with intrinsic hydroxyl groups are attractive green resources for polyurethane (PU) applications. However, lignin's heterogeneous and highly crosslinked structure, poor processability, as well as the feedstock variability, lead to inconsistent and poor performance of the final foam products. Castor oil-based polyurethane foam (PUF) has a relatively high price and density, which are big hurdles to its practical applications. Here, in this study, we hypothesized that synergistic bio-polyol mixtures composed of lignin and castor oil could balance the drawbacks from individual component. Castor oil could improve the dispersity of lignin, while lignin simultaneously addressed the issues caused by PUF prepared with castor oil, such as its high density and low thermal stability. For a comprehensive understanding of the effects of structural properties of lignin on its PUF processing and applications, various lignin fractions were isolated by co-solvent enhanced lignocellulosic fractionation (CELF) from different species, including hardwood, softwood, and herbaceous plants, and the processed lignins with different molecular weights were applied with castor oil. The lignin fractions with lower molecular weight showed good dispersity in castor oil with a high lignin content (up to 50 wt%) and completely replaced petroleum-based polyols. The produced foam with 50 wt% low-molecular-weight lignin fractions from woody biomass showed comparable/higher compressive strength (up to 20 psi) and thermal insulation performance (up to 5.69 R-value in −1 for 50 % L-Pine foam). In addition, this study revealed the relationship between lignin's structural properties and foam performance, providing insights for practical applications of lignin-based PUF.

Jeong, Soyeon [State Univ. of New York (SUNY), Syr↗

Transient simulation of biomass combustion in a circulating fluidized bed riser

Interest in circulating fluidized bed (CFB) boilers as a power generation technology has sky-rocketed in recent years because of several advantages this technology offers over conventional boilers, such as increased gas-solid mixing, which results in higher combustion efficiency and the ability to use lower rank fuels. CFB combustors are operated at lower temperatures than conventional thermal power generation combustors, thus reducing NO x emissions, while SO 2 emissions can be conveniently controlled through the addition of Ca-based sulfur sorbents within the combustor. Herin this paper summarizes the modeling effort on a 50 kW th CFB combustor designed, built, and operated at CanmetENERGY in Ottawa, Canada. The numerical model employs the multiphase particle-in-cell (PIC) approach in the open-source Multiphase Flow with Interphase eXchanges (MFiX) Software Suite. The MFiX-PIC model parameters for the simulation are tuned against cold-flow experiments from CanmetENERGY using olivine sand as the inert bed material. It is shown that for the relatively coarse fluid meshes and large parcel sizes necessitated by the scale of the simulation, filter size dependent corrections to the drag law must be incorporated to ensure accuracy of the simulation results. The validated cold flow model is extended to simulate reacting flow with torrefied hardwood as the feedstock and to validate the combustion reaction scheme. The species concentrations at the riser outlet are compared against CanmetENERGY’s experiments and show satisfactory agreement. The simulations demonstrate the ability of MFiX-PIC to accurately capture both the physics and chemistry of a CFB combustor at bench scales, which can be further extended to pilot- and industrial-scale systems.

09 BIOMASS FUELS↗

A renewable lignin-based thermoplastic adhesive for steel joining

Adhesive bonding of metals has become increasingly relevant in recent years due to the demand for reducing weight and improving performance in structural applications such as automobiles and aerospace. We developed renewable thermoplastic adhesives from technical organosolv lignin isolated from hardwood biomass and acrylonitrile butadiene co-polymer rubber (NBR) for joining steel substrates. NBR33, NBR41 and NBR51 with acrylonitrile molar ratios of 33, 41 and 51%, respectively, were blended with lignin to form two-phase thermoplastic adhesives, and their adhesion, viscoelastic and surface properties were measured. Lignin content in the compositions were varied, ranging from 40% to 80% (w/w), to alter toughness, stiffness, and surface energy characteristics of the material. Better interaction or reactivity between the lignin and NBR phases was observed with greater nitrile content in NBR, leading to greater modulus and stiffness of the adhesive. Simultaneously, increasing the proportion of lignin reduced toughness and improved stiffness, with the highest adhesive strength of 13.1 MPa measured in a 60% lignin loading ratio with NBR51. Surface energy measurements revealed that total surface energy (sum of polar and dispersive surface energy) raised with lignin loading, suggesting that both surface energy and matrix strength play a critical role in the adhesive properties of the synthesized materials. A finite element-based cohesive zone model (CZM) was developed and implemented to study the failure strength of the adhesively bonded joint. Here, this study demonstrates the viability of lignin as a valuable building block for adhesives, not only due to its inherent chemical structure and rigidity, but also for its surface energy characteristics.

36 MATERIALS SCIENCE↗

Carbon starvation is absent regardless of season of burn in Liquidambar styraciflua L.

In the Southeastern United States, the function and stability of pine ecosystems depends on frequent low intensity fires. One of the critical effects of frequent fire is the inhibition of hardwood competition by removing above-ground stems (top-kill). Previous long-term studies have correlated early growing season burns with higher understory mortality when compared to dormant season burns. Seasonal differences in mortality from insufficient carbon reserves in roots after leaf flush were posited as the mechanism but this was never explicitly tested. In this experiment, we burned two-year-old pot-grown sweetgums (Liquidambar styraciflua L.) in the dormant season (February), growing season (May), and compared their physiological responses to plants that were unburned. By the end of the first post-burn growing season, mortality was higher after the dormant season burn than the growing season burn and unburned trees had nearly twice the mass of either the burned treatments. Tissue starch concentrations were similar across all treatments highlighting the resiliency of sweetgum carbon stocks to recover from above-ground stem removal regardless of season. We showed the critical importance of top-killing stems regardless of season of burn. Our findings further suggest that dormant season fires can be more lethal to young sweetgum, possibly due to susceptibility of tender new shoots to freezing damage.

54 ENVIRONMENTAL SCIENCES↗

Drivers and ecological impacts of a wildfire outbreak in the southern Appalachian Mountains after decades of fire exclusion

During one of the warmest and driest droughts of the last century, the southern Appalachian Mountains experienced a regional outbreak of over a dozen large wildfires in late fall of 2016. We provide a synthesis of long-term forest changes leading up to the 2016 wildfires, examine the climatic setting and patterns of burn severity in relationship to topography, and discuss the ecological and management implications of these and future fires. During the pre- and post-European settlement periods, frequent low- and mixed-severity wildfires interacted with complex topographic gradients and maintained heterogenous landscapes dominated by several species of oak (Quercus spp.), pine (Pinus spp.), and the American chestnut (Castanea dentata). Land-use changes associated with European settlement, loss of the American chestnut, and 20th century fire exclusion resulted in large scale shifts towards mesic, fire-intolerant species (i.e. mesophication). Wildfire activity began increasing in the early 1980s, but most fires in the region are small (<1,000 ha). In Fall of 2016, deciduous tree leaf fall occurred concurrently with a period of anomalously dry and warm weather, creating ideal conditions for fire ignition and spread. Thousands of ignitions across the region strained suppression resources and eight fires grew to greater than 5,000 ha. The 2016 fires were larger and burned more area than in the previous three decades combined. In one unique landscape setting, the Chimney Tops 2 Fire, a synoptic wind event drove extreme fire behavior and burned large, high-severity patches resulting in devastating effects in the wildland urban interface. However, immediate post-fire burn severity mosaics for other fires were composed primarily of low- (73 %) and moderate-severity (21 %) fire effects. High-severity fire comprised only 6 % of the area burned, and occurred mostly on steep upper slopes and ridges on south-facing aspects, reflecting the importance of bottom-up topographic drivers in this region. Although the fires will likely enhance biodiversity by restoring fire-dependent species and creating early seral habitat, invasions of non-native plant species, delayed mortality of mature pines and oaks, and rapid re-sprouting of pyrophyllic shrubs pose significant management challenges. Although similar large fire outbreaks may become more common under future climatic conditions, they are unlikely to reverse the effects of mesophication and significantly alter forest dynamics at broad spatial scales. Furthermore, the 2016 fires exposed the vulnerability of the region to wildfire during acute fall drought and demonstrate the potential ecological effects of future wildfires in mixed pine-hardwood landscapes of the southern Appalachians.

54 ENVIRONMENTAL SCIENCES↗

Whole-tree dormant season nitrogen pools for different species receiving combinations of fertilization and irrigation after one short rotation

Our understanding of the accretion and distribution of tree tissue nitrogen (N) pools across a variety of species and genotypes suitable for short-rotation woody crop (SRWC) production in response to water and N availability remains limited. We measured dormant-season, rotation-length, whole-tree N pools for five tree genotypes from four species (two eastern cottonwood, Populus deltoides Bartr., genotypes; American sycamore, Platanus occidentalis L.; American sweetgum, Liquidambar styraciflua L.; and loblolly pine, Pinus taeda L.) receiving irrigation (I), fertilization (F), their combination (IF), or no resources manipulation (C). Our results demonstrate that foliar nitrogen concentration [N] responded to fertilization but was constrained within genotype-specific ranges and varied temporally. Tree genotypes differed in their composite and component tissue N content (N C ), and these differences mostly reflected tissue mass (i.e., larger components and trees resulted in higher N C ). Resource amendments (I, F, IF) resulted in up to 3.8-fold increases in N C compared with C, which were most pronounced for sycamore and sweetgum with F and IF treatments, respectively. By the end of the rotation, forest stands accumulated 73 to 452 kg N ha –1 in tree tissues with 40 – 78 % distributed aboveground and 22 – 60 % distributed belowground. A critical difference between genotypes was that all hardwoods exhibited larger belowground N distributions than the evergreen conifer. Our results stress the importance of belowground N pools and highlight differences among genotypes. Furthermore, our study underscores valuable information about N pools across genotypes suitable for SRWC production, which can be leveraged to inform fertilization plans and devise sustainable nutrient management as production expands across marginal lands.

54 ENVIRONMENTAL SCIENCES↗

Preparation and characterization of aminated co-solvent enhanced lignocellulosic fractionation lignin as a renewable building block for the synthesis of non-isocyanate polyurethanes

Lignin is a major bioresource from 2nd generation biorefinery process streams and from pulp and paper production that is still severely underutilized nowadays. Its natural polymeric and aromatic structures make it suitable as a potential building block for biopolymer production. Due to the growing environmental and health concerns over conventional polyurethane (PU) manufacturing processes that utilize toxic isocyanates, there is a great interest to develop a non-isocyanate PU (NIPU) route. Herein, we demonstrate a novel strategy that uses highly pure lignin isolated from co-solvent enhanced lignocellulosic fractionation (CELF) pretreatment of poplar wood to produce biobased NIPUs. In this strategy, hardwood poplar is firstly fractionated via a CELF pretreatment to produce a clean lignin stream that is rich in phenolics. The CELF lignin was then aminated by a Mannich reaction, and the aminated CELF lignin was finally reacted with bicyclic carbonates to yield an advanced NIPU. In this work, the structure, mechanical, and thermal properties of these novel NIPUs were elucidated by FTIR, NMR, tensile test, dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). The mechanical properties of these lignin based NIPUs could be tuned from highly rigid to elastic polymers by simply modifying the lignin constituents of the polymer. The thermal stabilities of NIPUs were improved because of the addition of aminated lignin, and NIPU containing 55 and 23 wt% lignin showed the highest tensile strength (~1.2 MPa) and elongation at break (~140%), respectively. The results obtained in this study demonstrate that the reaction of cyclic carbonate with aminated lignin represents an interesting pathway for the synthesizing of lignin based NIPU with a relative high lignin content.

54 ENVIRONMENTAL SCIENCES↗

Structure-performance relationships in lignin-based transesterification vitrimers: The role of lignin structural features

Lignin has been hailed as an ideal renewable alternative for petrochemical-based prepolymers in material synthesis for a sustainable and circular economy, due to its abundant aromatic network and high carbon content. However, the properties and performance of lignin-derived macromolecules are strongly influenced by the lignin itself. While numerous studies have explored the impact of lignin content on the thermomechanical performance of lignin-based vitrimers, literature on how the inherent structural features of lignin affect these properties is scanty. In this study, hardwood organosolv lignin was fractionated in ethyl acetate, ethanol, and acetone to obtain lignin fractions with varying structural characteristics. These fractions were then modified through carboxylation and crosslinked with epoxidized soybean oil (ESO) at a hydroxyl to epoxy group ratio of 1:1 to produce lignin-based transesterification vitrimers (LVs). The thermal properties (i.e. glass transition temperature and thermal stability), tensile strength, storage modulus, and stress relaxation behavior of the LVs were studied and carefully related to the structural features of lignin. The results revealed a positive relationship between strong hydroxyl content in modified lignin and the tensile strength (5.10–9.71 MPa), storage modulus (1099.4 – 1372.8 MPa), crosslinking density, and stress relaxation of the LVs. Additionally, both the storage modulus and tensile strength exhibited a positive relationship with the ratio of rigid linkages in modified lignin, while lignin molecular weight was found to significantly impact the thermal properties of LVs (i.e Tg and thermal stability). This study not only highlights the valorization of lignin in vitrimer synthesis but also provide insights for designing lignin-based materials with tailored properties for specific applications.

Bio-based polymer↗