Efficient extraction of lignin from moso bamboo by microwave-assisted ternary deep eutectic solvent pretreatment for enhanced enzymatic hydrolysis.

Applications of deep eutectic solvent (DES) systems to separate lignocellulosic components are of interest to develop environmentally friendly processes and achieve efficient utilization of biomass. To enhance the performance of a binary neutral DES (glycerol:guanidine hydrochloride), various Lewis acids (e.g., AlCl3·6H2O, FeCl3·6H2O, etc.) were introduced to synthesize a series of ternary DES systems; these were coupled with microwave heating and applied to moso bamboo. Among the ternary DES systems evaluated, the FeCl3-based DES effectively removed lignin (81.17%) and xylan (85.42%), significantly improving enzymatic digestibility of the residual glucan and xylan (90.15% and 99.51%, respectively). Furthermore, 50.74% of the lignin, with high purity and a well-preserved structure, was recovered. A recyclability experiment showed that the pretreatment performance of the FeCl3-based DES was still basically maintained after five cycles. Overall, the microwave-assisted ternary DES pretreatment approach proposed in this study appears to be a promising option for sustainable biorefinery operations.

Demethylation of Alkali Lignin with Halogen Acids and Its Application to Phenolic Resins.

Lignin, a byproduct from the chemical processing of lignocellulosic biomass, is a polyphenolic compound that has potential as a partial phenol substitute in phenolic adhesive formulations. In this study, HBr and HI were used as reagents to demethylate an alkali lignin (AL) to increase its hydroxyl content and thereby enhance its reactivity for the preparation of phenolic resins. Analyses by FT-IR, 1H-NMR and 2D-NMR(HSQC) demonstrated both a decrease in methoxyl groups and an increase in hydroxyl groups for each demethylated lignin (DL). In addition, the molar amounts of phenolic hydroxyls, determined by 1H-NMR, increased to 0.67 mmol/g for the HI-DL, and 0.64 mmol/g for the HBr-DL, from 0.52 mmol/g for the AL. These results showed that HI, a stronger nucleophilic reagent than HBr, provided a higher degree of AL demethylation. Lignin-containing resins, prepared by copolymerization, met the bonding strength standard for exterior plywood with DL used to replace as much as 50 wt.% of phenol. The increased hydroxyl contents resulting from the lignin demethylations also imparted faster cure times for the lignin-containing resins and lower formaldehyde emissions. Altogether, the stronger nucleophilicity of HI, compared to HBr, impacted the degree of lignin demethylation, and carried through to measurable differences the thermal properties and performance of the lignin-containing PF resins.

Effect of Acaromyces Ingoldii Secondary Metabolites on the Growth of Brown-Rot (Gloeophyllum Trabeum) and White-Rot (Trametes Versicolor) Fungi.

We investigated the antifungal activities of an endophytic fungus identified as Acaromyces ingoldii, found on a loblolly (Pinus taeda L.) pine bolt in Louisiana during routine laboratory microbial isolations. The specific objectives were to determine the inhibitory properties of A. ingoldii secondary metabolites (crude extract) on the mycelial growth of a brown-rot fungus Gloeophyllum trabeum and a white-rot fungus Trametes versicolor, and to determine the effective concentration of A. ingoldii crude preparation against the two decay fungi in vitro. Results show the crude preparation of A. ingoldii from liquid culture possesses significant mycelial growth inhibitory properties that are concentration dependent against the brown-rot and white-rot fungi evaluated. An increase in the concentration of A. ingoldii secondary metabolites significantly decreased the mycelial growth of both wood decay fungi. G. trabeum was more sensitive to the inhibitory effect of the secondary metabolites than T. versicolor. Identification of specific A. ingoldii secondary metabolites, and analysis of their efficacy/specificity warrants further study. Findings from this work may provide the first indication of useful roles for Acaromyces species in a forest environment, and perhaps a future potential in the development of biocontrol-based wood preservation systems.

Effect of biochar amendment on tylosin adsorption-desorption and transport in two different soils.

The role of biochar as a soil amendment on the adsorption-desorption and transport of tylosin, a macrolide class of veterinary antibiotic, is little known. In this study, batch and column experiments were conducted to investigate the adsorption kinetics and transport of tylosin in forest and agricultural corn field soils amended with hardwood and softwood biochars. Tylosin adsorption was rapid at initial stages, followed by slow and continued adsorption. Amounts of adsorption increased as the biochar amendment rate increased from 1 to 10%. For soils with the hardwood biochar, tylosin adsorption was 10 to 18% higher than that when using the softwood biochar. Adsorption kinetics was well described by Elovich equation ( ≥ 0.921). As the percent of biochar was increased, the rates of initial reactions were generally increased, as indicated by increasing α value at low initial tylosin concentration, whereas the rates during extended reaction times were generally increased, as indicated by decreasing ß value at high initial tylosin concentration. A considerably higher amount of tylosin remained after desorption in the corn field soil than in the forest soil regardless of the rate of biochar amendment, which was attributed to the high pH and silt content of the former. The breakthrough curves of tylosin showed that the two soils with biochar amendment had much greater retardation than those of soils without biochar. The CXTFIT model for the miscible displacement column study described well the peak arrival time as well as the maximum concentration of tylosin breakthrough curves but showed some underestimation at advanced stages of tylosin leaching, especially in the corn field soil. Overall, the results indicate that biochar amendments enhance the retention and reduce the transport of tylosin in soils.

Partial dissolution of ACQ-treated wood in lithium chloride/N-methyl-2-pyrrolidinone: separation of copper from potential lignocellulosic feedstocks.

A cellulose solvent system based on lithium chloride (LiCl) in N-methyl-2-pyrrolidinone (NMP) was used to assess the merits of partial dissolutions of coarsely ground wood samples. Alkaline Copper Quaternary (ACQ)-treated pine wood was of particular interest for treatment given the potential to generate a copper-rich stream apart from solid and/or liquid lignocellulosic feedstocks. Treatment with NMP alone gave yields of soluble materials that were higher than typical extractives contents thereby suggesting a limited degree of wood dissolution. Inclusion of LiCl, which disrupts hydrogen bonding, gave lower wood residue recoveries (i.e., higher dissolution) with higher LiCl concentration. Lower wood residue recoveries coincided with lower Klason lignin and hemicellulose-derived sugar contents in the wood residues. After treatment with 8% LiCl in NMP, subsequent filtration afforded 34% of the ACQ-treated sapwood as a wood residue retaining only 2% of the original copper. Pouring the filtrate over an excess of water resulted in the recovery of 30% of the solids and 50% of the copper together as a copper-enriched lignocellulosic precipitate. Results demonstrate a solvent system showing potential as a means to separate heavy metals from preservative-treated wood and to recover lignocellulosic feedstocks that may be suitable for use in a biorefinery.

Hydrothermal transformation of Chinese privet seed biomass to gas-phase and semi-volatile products.

Hydrothermal (HT) treatment of seeds from Chinese privet (Ligustrum sinense), a non-native and invasive species in the southeastern United States, was examined with respect to the generation of gas-phase and semi-volatile organic chemicals of industrial importance from a lipid-rich biomass resource. Aqueous seed slurries were transformed into biphasic liquid systems comprised of a milky aqueous phase overlain by a black organic layer. Present in the headspace were elevated levels of CO(2) and acetic acid. Analysis of the semi-volatiles by GC-MS showed the formation of alkyl substituted benzenes, oxygenated cyclic alkenes, phenol, substituted phenolics, and alkyl substituted pyridines. Compared to immature seeds, mature seeds gave high relative amounts of oxygenated cyclic alkenes (cyclopentenones) and alkyl pyridines. The presence of fatty acids in the HT products likely resulted from both lipid hydrolysis reactions and the inherent stability of fatty acids under HT treatment conditions. Estimates of lignin and protein contents showed no definite trend that could be linked to the HT data. The proportion of aromatic HT products appeared to derive primarily from the proportion of extractives. Thus, variations in extractives yields impact HT product yields and thereby demonstrate the importance of timing in feedstock collection to favor targeted HT products.

Biosorbents prepared from wood particles treated with anionic polymer and iron salt: effect of particle size on phosphate adsorption.

Biomass-based adsorbents have been widely studied as a cost-effective and environmentally-benign means to remove pollutants and nutrients from water. A two-stage treatment of aspen wood particles with solutions of carboxymethyl cellulose (CMC) and ferrous chloride afforded a biosorbent that was effective in removing phosphate from test solutions. FTIR spectroscopy of the biosorbent samples showed a decrease in the intensity of the carboxylate signal coinciding with a decrease in particle size. Elemental analysis results showed the iron content of both the biosorbent samples, and wood particles treated with ferrous chloride alone, to also decrease with particle size. The relationship between iron content and particle size for the biosorbent samples appeared to be a function of both the amount of CMC-Fe complex and the efficiency of removing free iron ions after treating. Sorption testing results showed a strong linear correlation between the phosphorous uptake capacities and the iron contents of the samples adjusted for losses of iron during testing. As anticipated, pretreating with the anionic polymer provided additional sites to complex iron and thereby imparted a greater phosphorous uptake capacity. Although the larger wood particles provided a greater amount of iron for phosphate removal, smaller wood particles may be preferred since they afforded the lowest release of iron relative to the amount of phosphate removed.

Phosphate removal by refined aspen wood fiber treated with carboxymethyl cellulose and ferrous chloride.

Biomass-based filtration media are of interest as an economical means to remove pollutants and nutrients found in stormwater runoff. Refined aspen wood fiber samples treated with iron salt solutions demonstrated limited capacities to remove (ortho)phosphate from test solutions. To provide additional sites for iron complex formation, and thereby impart a greater capacity for phosphate removal, a fiber pretreatment with an aqueous solution of a non-toxic anionic polymer, carboxymethyl cellulose (CMC), was evaluated. Problems with excessive viscosities during the screening of commercially available CMC products led to the selection of an ultra low viscosity CMC product that was still usable at a 4% concentration in water. Soxhlet extractions of chipped aspen wood and refined aspen wood fiber samples showed a higher extractives content for the refined material. Analysis of these extracts by FTIR spectroscopy suggested that the higher extractives content for the refined material resulted from the fragmentation of cell wall polymers (e.g., lignin, hemicelluloses) normally insoluble in their native states. Spectroscopic analysis of CMC and ferrous chloride treated fibers showed that the complex formed was sufficiently stable to resist removal during subsequent water washes. Equilibrium sorption data, which fit better with a Freundlich isotherm model than a Langmuir isotherm model, showed that phosphate removal could be enhanced by the CMC pretreatment. Results suggest that the process outlined may provide a facile means to improve the phosphate removal capacity of biomass-based stormwater filtration media.