Lignin from bark as a resource for aromatics production by hydrothermal liquefaction

Biorefineries, which are using mostly unused side streams of other existing processes like bark or lignin, have a huge potential to open new resources, for example, chemicals. But with new resources new challenges will be met along the way. These challenges must be addressed and discussed to build a solid and far‐sighted process. This work focuses on the formation of monocyclic compounds like catechol as a valuable product during the hydrothermal liquefaction of beech wood bark as well as Kraft lignin from pine wood like Indulin AT. The focus is to get a better knowledge of the behavior of bark during hydrothermal liquefaction for depolymerization aiming at the production of aromatic building blocks for chemicals. Therefore, the influence, for example, of temperature and reaction time, the chemical reaction pathways, and the therefore necessary analytics need to be understood. Several limitations and challenges of common analytical methods are discussed and compared for bark and Kraft lignin, which is relatively well investigated and can act as a reference material to build a common ground and make it possible to build standards for all bioeconomic processes. Hydrothermal conditions increase the yield and selectivity toward bifunctional molecules like catechol. With rising temperatures and longer retention times, the catechol mass yields get lower. At temperatures above 350°C, nearly no catechol could be found any more. Different types of wood deliver different lignin compositions in terms of the monomeric units. However, it can be observed that different lignins show the same trends in regard to the catechol yield concerning temperatures and reaction time dependence, but overall a different product spectrum.     

Anatomical and chemical defenses of conifer bark against bark beetles and other pests

Conifers are long-lived organisms, and part of their success is due to their potent defense mechanisms. This review focuses on bark defenses, a front line against organisms trying to reach the nutrient-rich phloem. A major breach of the bark can lead to tree death, as evidenced by the millions of trees killed every year by specialized bark-invading insects. Different defense strategies have arisen in conifer lineages, but the general strategy is one of overlapping constitutive mechanical and chemical defenses overlaid with the capacity to up-regulate additional defenses. The defense strategy incorporates a graded response from 'repel', through 'defend' and 'kill', to 'compartmentalize', depending upon the advance of the invading organism. Using a combination of toxic and polymer chemistry, anatomical structures and their placement, and inducible defenses, conifers have evolved bark defense mechanisms that work against a variety of pests. However, these can be overcome by strategies including aggregation pheromones of bark beetles and introduction of virulent phytopathogens. The defense structures and chemicals in conifer bark are reviewed and questions about their coevolution with bark beetles are discussed.     

Can the red mangrove provide food,feed and fertilizer?

The red mangrove is one of the principal features of the coastal vegetation throughout tropical America, Mexico, the West Indies, the Bahamas, Bermuda and southern Florida. It is of primary importance as a land retainer and builder. Secondarily, its bark is a source of tannin and yields resins suitable for plywood adhesive. Mangrove wood is heavy and durable. The bark, leaves and shoots furnish various dyes and the bark is an excellent fuel and is much used locally for medicinal purposes. In southern Florida there has been active interest in the value of mangrove leaf meal as cattle feed, the dried and ground leaves have been sold as “Maritime Tea” and prepared in tablet form as a dietary supplement. The leaf meal and the sawdust have been tested as soil conditioners. Despite their high tannin content, red mangrove leaves may warrant investigation as an abundant source of protein.     

Hydrophilic compounds in liquids of enzymatic hydrolyzed spruce and pine biomass

This study was focused on organic acids and metals in biofluids of wood. Without seasoning, fresh woods from spruce and bark, phloem, and heartwood from pine were used as materials, which were degraded with either microbes of oyster mushroom, baker’s yeast, or lactic acid bacteria. Due to neutral pH of the fluids, ambient temperature, atmospheric pressure, and short reaction time, native wood microbe populations were supposed to be present. The water content of the fresh woods was 4 to 20%. The study showed that process methodology and experimental conditions affected the generation of lactic, citric, succinic, and adipic acids, which are considered as source chemicals in the biopolymer industry. In addition to the organic acids and metals, the process produced monosaccharides, polysaccharides, and phenolic acids such as benzoic, salicylic, cinnamic, vanillic, tannic, and conifer (ferulic) acids. Concentrations of total acids and acetic and succinic acids in pine fluids from bark, phloem, and heartwood were 58.4 g/kg and 3.5 to 6.9 g/kg, respectively. In spruce, the most dominant acids were l-lactic and l-malic acids. As for metals, Ag and Cr were detected at 0.01-g/kg quantities in pine bark. Alkali metals K, Mg, Sr, and Ca were detected at 10, 8, 1.3, and 4 g/kg, respectively.     

Analysis of Biomass Composition Using High-Resolution Thermogravimetric Analysis and Percent Bark Content for the Selection of Shrub Willow Bioenergy Crop Varieties

Rapid determination of biomass composition is critical for the selection of shrub willow varieties with optimized biomass properties for conversion into fuels or chemicals. In order to improve the process for identifying and selecting shrub willow clones with distinct biomass composition, high-resolution thermogravimetric analysis (HR-TGA) was developed as a rapid, low-cost method for analyzing large numbers of willow biomass samples. In order to validate the HR-TGA method, bulk biomass collected from 2-year-old stems of a selected set of 25 shrub willow clones was analyzed using traditional wet chemistry techniques in addition to HR-TGA. The results of the wet chemistry and the HR-TGA method were compared using regression analysis resulting in R-squared values above 0.7 for the three main wood components, cellulose, hemicellulose, and lignin. Bark was removed from duplicate stem samples of the same clones, the proportion of bark was determined, and the debarked wood was used for HR-TGA analysis of composition. While there were significant differences in the proportions of lignin and cellulose in debarked wood compared to bulk biomass, as well as significant differences in bark percentage among clones, there was no correlation between bark percentage and bulk biomass component analysis. This work validates the effectiveness, precision, and accuracy of HR-TGA as a reasonably high-throughput method for biomass composition analysis and selection of shrub willow bioenergy crop varieties.     

A New Laboratory Method Used for Investigating the Uptake, Translocation and Metabolism of Bark Banded Morphactin by Trees

Cut twigs of Monterey pine(Pinus radiata D.Don) were banded with a ¹⁴C labelled morphactin formulation and the lower half of the twig placed in a Scholander type pressure bomb. Water was pumped through the twig from a reservoir inside the bomb and exudate collected from the protruding end of the twig. Using this method it was possible to determine that the slowest step in the translocation of morphactin was the passage across the outer layer of bark. Subsequent passage through the twig was not affected by girdling the bark suggesting that morphactin was translocated upwards via the xylem. The ¹⁴C compound in the exudate from live twigs differed from morphactin and was tentatively identified as the carboxylic acid derivative of the morphactin ester. The cut twig system facilitated studies on the uptake, metabolism and translocation of morphactin and should prove useful for studying the uptake and fate of other chemicals considered for bark application to trees.     

Changes in nitrogen levels and free amino acids in rooting cuttings of mulberry (Moms alba)

Total and protein nitrogen in bark and wood of parent stems of mulberry ( Morns alba L. cv. Ichinose) decreased readily and to the same extent during leafing-out of the buds, but the decrease in wood was less marked than in bark. Simultaneously, soluble nitrogen in both bark and wood also declined but the depletion was less marked than that of total and protein nitrogen. During the same period total nitrogen in the new shoots and adventitious roots increased drastically; however, the increase in total nitrogen in the growing parts during rooting was almost the same as the decrease in total nitrogen in the parent stems. Proline, the prevalent amino acid in wood and bark of the parent stems, decreased drastically during rooting, whereas during the same period asparagine in the developing buds, callus and adventitious roots increased markedly and became the predominant amino acid. The amount of arginine was relatively high in bark of the parent stems but Low in wood and the buds. The level of arginine in bark decreased considerably during the experiments (as did that of proline). The results suggest that the nitrogen required by the growing parts (sinks) in the rooting cuttings comes mainly from protein breakdown in bark of the parent stems (source), although stored protein in wood (source) and soluble nitrogen in bark and wood (sources) also play a part in storage of nitrogen. Asparagine is suggested to be the main nitrogen transport compound in the new growth of the tree and the initiating roots of cuttings.     

The mode of pheromone evolution: evidence from bark beetles

Sex and aggregation pheromones consist of species-specific blends of chemicals. The way in which different species' blends have evolved has been the subject of some debate. Theoretical predictions suggest that differences between species have arisen not through the accruing of small changes, but through major shifts in chemical composition. Using data on the aggregation pheromones of 34 species of bark beetle from two genera, Dendroctonus and Ips, we investigated how the distributions of the chemical components of their pheromone blends mirror their phylogenetic relationships. We tested whether there were consistent patterns that could be used to help elucidate the mode of pheromone evolution. Although there were obvious differences in pheromone blends between the two genera, the differences between species within each genus followed a less clear phylogenetic pattern. In both genera, closely related species are just as different as more distantly related species. Within Dendroctonus, particularly, most chemical components were distributed randomly across the phylogeny. Indeed, for some chemicals, closely related species may actually be more different than would be expected from a random distribution of chemical components. This argues strongly against the idea of minor shifts in pheromone evolution. Instead, we suggest that, within certain phylogenetic constraints, pheromone evolution in bark beetles is characterized by large saltational shifts, resulting in sibling species being substantially phenotypically (i.e. pheromonally) different from one another, thus agreeing with theoretical predictions.     

Chemical constituents and energy content of some latex bearing plants

The latex bearing plants Plumeria alba, Calotropis procera, Euphorbia nerrifolia, Nerium indicum and Mimusops elengi were evaluated as potential renewable sources of energy and chemicals. Plant parts (leaf, stem, bark) and also whole plants were analyzed for elemental composition, oil, polyphenol, hydrocarbons, crude protein, alpha-cellulose, lignin and ash. The dry biomass yields were between 4.47 and 13.74 kg/plant. The carbon contents in whole plants varied from 38.5% to 44.9%, while hydrogen and nitrogen contents varied from 5.86% to 6.72% and 1.26% to 2.34%, respectively. The bark of the plants contained the highest amount of hydrocarbons (1.78-3.93%) and the leaves contained the lowest amounts (0.26-1.82%). The unsaponifiable materials and fatty acids in the oil fractions of whole plants ranged from 22.8% to 56.4% and 24.7% to 58.7%, respectively. The highest gross heat value was exhibited by C. procera (6145 cal/g) and the lowest by N. indicum (4405 cal/g). Hydrocarbon fractions were characterized by IR and (1)H-NMR and by thermogravimetric analyses. The activation energy (E(a)) in the third stage of decomposition was the greatest in the hydrocarbon fraction obtained from M. elengi (16.40 kJ mol(-1)) and the lowest for C. procera (3.96 kJ mol(-1)). The study indicated that the plant species might be suitable as alternative source of hydrocarbons and other phytochemicals.     

Efficacy of Curcuma aeruginosa rhizome and Adhatoda vasica plant extracts, on red spider mite, Tetranychus urticae in Livistona rotundifolia

Queen palm, Livistona rotundifolia foliage contributes greatly in export industry. Red spider mite (RSM) (Tetranychus urticae) infests on the foliage and reduces its affordable market quality. T. urticae is found in dry environment and is one of the phytophagous mite belongs to family Tetranychidae. Different chemicals such as 80% sulphur + Diazinon @ (50g+12ml/10L) are recommended against red spider mite, but these have lesser effect on this tiny mite. Since these chemicals are not environment friendly, Green Farms Ltd., in Sri Lanka prefers to use biological agents for mite management. Extracts of Curcuma aeruginosa rhizome and Adhatoda vasica plant parts were studied separately causing mortality on T. urticae. Field experiments were conducted to study the efficacy of C. aruginosa extract for controlling RSM on L. rotundifolia leaves. Curcuma aruginosa was tested at concentrations of 2, 5, 10, 15, 20 and 25 g/L and a control with equal amount of water. C aruginosa extracts of different concentrations were treated six times at five days interval on the palms separately. Living spider mites and eggs were pre-counted in marked leaves before applying C. aruginosa extracts. Next count was taken a day prior to next spraying. The result revealed that all the concentrations except 2 g/L were found to be effective compared to control. However there was no difference between the concentrations from 5 to 25 g/L. Hence C. aruginosa rhizome extract at its lowest concentration of 5 g/L is equally effective for the control of RSM on L. rotundifolia leaves. In another experiment extracts of Adhatoda vasica bark, leaves, and flower and water as control were applied thrice with three days interval. Pre treatment counting of living spider mites and eggs were taken in marked leaves. Post count was taken a day prior to next spraying. Third and forth counting were done after three days and four weeks from final spraying respectively. The results revealed that bark, flowers were found to be more effective compared to control. Flowers and bark were the best and hence there is no need of third sprayings as almost all the spider mites population were eradicated after second spraying. Flower extraction showed best performance until three months since final spraying. Flower and bark extracts showed higher acaricidal property and leaf showed moderate acaricidal property.     

Silvichemicals from the forest

Tree species vary in properties because of the chemical nature of their respective extractive components. Extractives play an important role in ever increasing silvichemical industries. Numerous industrial extractive chemicals derived from wood and bark are discussed here.     

Mexican Bark Paper: Evidence of History of Tree Species Used and Their Fiber Characteristics

Mexican Bark Paper: Evidence of History of Tree Species Used and Their Fiber Characteristics. The use of bark fibers (secondary phloem) for the manufacture of the Mexican bark paper called amate can be traced back to the pre–Hispanic period. This paper was used extensively during this period, and for the last four decades has been produced as a handicraft by the Ñahñus of San Pablito village in the Sierra Norte de Puebla region of México. Due to the high demand for this product, new species are now used as a source of bark and specific phases of the traditional production technique have been modified. The focus of this study was to register all the species that have been used for bark paper manufacturing, both traditionally and more recently, and to analyze their fiber characteristics, mainly fiber length and lignin content. The main questions addressed by this study were: a) Which species have been used for bark paper production, both prior to and following its commercialization as a handicraft? b) Which anatomical and histochemical fiber characteristics of these species enable their use for bark paper production, regardless of taxa? And c) is there a relationship between the adoption and use of new species and recent changes in traditional paper making techniques? Based on an ethnobotanical study, a list of 13 species used for bark paper production was compiled and bark samples from each species were collected for phloem anatomical and histochemical analysis. Artisans and local healers were also asked to determine the main characteristics of each fiber and paper type. The results demonstrate that bark from currently used species differs anatomically and histochemically from species used during the pre–Hispanic period and until a few decades ago, and in terms of the quality assessed by local healers and artisans. Among other characteristics, the fibers of the new species have higher lignin content than the traditional ones, and this constitutes the main reason behind the modification of certain phases of the traditional paper making process.     

The mode of evolution of aggregation pheromones in Drosophila species

Aggregation pheromones are used by fruit flies of the genus Drosophila to assemble on breeding substrates, where they feed, mate and oviposit communally. These pheromones consist of species-specific blends of chemicals. Here, using a phylogenetic framework, we examine how differences among species in these pheromone blends have evolved. Theoretical predictions, genetic evidence, and previous empirical analysis of bark beetle species, suggest that aggregation pheromones do not evolve gradually, but via major, saltational shifts in chemical composition. Using pheromone data for 28 species of Drosophila we show that, unlike with bark beetles, the distribution of chemical components among species is highly congruent with their phylogeny, with closely related species being more similar in their pheromone blends than are distantly related species. This pattern is also strong within the melanogaster species group, but less so within the virilis species group. Our analysis strongly suggests that the aggregation pheromones of Drosophila exhibit a gradual, not saltational, mode of evolution. We propose that these findings reflect the function of the pheromones in the ecology of Drosophila, which does not hinge on species specificity of aggregation pheromones as signals.     

Ophiostomatoid fungi can emit the bark beetle pheromone verbenone and other semiochemicals in media amended with various pine chemicals and beetle-released compounds

Fungal volatile compounds can mediate fungal-insect interactions. Whether fungi can emit insect pheromones and how volatile chemicals change in response to chemicals the fungi naturally encounter is poorly understood. We analyzed volatiles emitted by Grosmannia clavigera (symbiont of the mountain pine beetle) and Ophiostoma ips (symbiont of the pine engraver beetle) growing in liquid media amended with compounds that the fungi naturally encounter: (−)-α-pinene, (+)-α-pinene, (−)-trans-verbenol, verbenone, or ipsdienol. Nine volatile compounds were identified among the fungal and amendment treatments. Volatiles qualitatively and quantitatively differed between fungal species and among amendment treatments. The bark beetle anti-aggregation pheromone (−)-verbenone was detected from both fungi growing in (−)-trans-verbenol-amended media. G. clavigera and O. ips can emit beetle pheromones and other beetle semiochemicals, suggesting that ophiostomatoid fungi could contribute to the chemical ecology of bark beetles. However, such contributions could be modulated by the presence of other environmental chemicals.     

Exploring Indian Rosewood as a promising biogenic tool for the synthesis of metal nanoparticles with tailor-made morphologies

Stem bark extracts of Indian Rosewood, a traditionally used Indian medicinal plant, were used as highly efficient multifunctional green chemicals/biogenic agents in the rapid synthesis of stable, monometallic Ag and Au nanoparticles and their corresponding bimetallic alloy nanoparticles with interesting shapes and morphological characteristics. We determined that the high efficiency of these extracts is due to the presence of complex multifunctional molecules, such as polyphenolics and hydroxyflavonoids, which are involved in the reduction of Au^III and Ag^I ions to zerovalent metallic nanoparticles and the stabilization of their corresponding nanoparticles.     

Risk Assessment Using EUSES; Refinement Options to Estimate Atmospheric Transportation by its Operational Priority Substances Model (OPS)

The Operational Priority Substances (OPS) model is part of the European Union System for the Evaluation of Substances (EUSES) and is used to estimate air concentrations and atmospheric depositions for risk assessment of chemicals. Traditionally, EUSES assesses environmental exposure using a standardized scenario based on explicit assumptions and default parameter settings. Under the new European Union REACH legislation—which stands for Registration, Evaluation, Authorisation, and restriction of Chemicals—industry is responsible for the risk assessment of chemicals. The current work investigates the potential impact and importance of source parameter refinement on the emission distribution and environmental fate of chemicals as modelled by OPS. In total, 60 scenarios with different combinations of (non) default values for emission heat content, emission source height, and emission source radius, were run for a typical particle-bound substance. Increasing heat content and emission source height reduced the modelled air concentrations and depositions and caused maximum air concentrations to occur further away from the emission source. Results show that estimated air concentrations and total depositions used for risk assessment can become more realistic by using more site-specific emission source parameters. This article proposes risk assessment refinement options and provides recommendations on future updates of EUSES.     

Compositional Characterization and Pyrolysis of Loblolly Pine and Douglas-fir Bark

Two potential biofuel resources, Douglas-fir and Loblolly pine bark, were subjected to extensive chemical and compositional analysis. The barks were initially extracted with dichloromethane, and the resulting extracted compounds were characterized by gas chromatography coupled with mass spectrometric analysis. Characterization of the major bark biocomponents indicated that Douglas-fir and Loblolly pine bark contained 22.5 and 13.2 % tannins, 44.2 and 43.5 % lignin, 16.5 and 23.1 % cellulose, and 7.6 and 14.1 % hemicellulose, respectively. Of particular interest is the high content of tannins and lignin, which make these barks excellent potential precursors for bio-oils and/or other value-added chemicals. ¹³C nuclear magnetic resonance (NMR) was used to characterize the chemical structure of the lignin and tannins. These samples were also analyzed by ³¹P NMR after phosphitylation of the hydroxyl groups in lignin and tannins. The NMR spectral data indicated that the lignin in both barks contained p-hydroxyphenyl (h) and guaiacyl (g) of lignin monomers with an h/g ratio of 10:90 and 22:78 for Douglas-fir and Loblolly pine bark, respectively. Gel permeation chromatography was used to analyze the molecular weight distributions of extracted tannins, isolated cellulose, and ball-milled lignin. The pyrolysis of Douglas-fir and pine bark at 500°C in a tubular reactor generated 48.2 and 45.2 % of total oil, of which the light oil contents are 14.1 and 20.7 % and heavy oil are 34.1 and 24.4 %. Similarly, fast pyrolysis at 375°C yielded 56.1 and 49.8 % of total oil for Douglas-fir and pine bark, respectively.     

Control of resin production in Araucaria angustifolia,an ancient South American conifer

Araucaria angustifolia is an ancient slow‐growing conifer that characterises parts of the Southern Atlantic Forest biome, currently listed as a critically endangered species. The species also produces bark resin, although the factors controlling its resinosis are largely unknown. To better understand this defence‐related process, we examined the resin exudation response of A. angustifolia upon treatment with well‐known chemical stimulators used in fast‐growing conifers producing both bark and wood resin, such as Pinus elliottii. The initial hypothesis was that A. angustifolia would display significant differences in the regulation of resinosis. The effect of Ethrel^® (ET – ethylene precursor), salicylic acid (SA), jasmonic acid (JA), sulphuric acid (SuA) and sodium nitroprusside (SNP – nitric oxide donor) on resin yield and composition in young plants of A. angustifolia was examined. In at least one of the concentrations tested, and frequently in more than one, an aqueous glycerol solution applied on fresh wound sites of the stem with one or more of the adjuvants examined promoted an increase in resin yield, as well as monoterpene concentration (α‐pinene, β‐pinene, camphene and limonene). Higher yields and longer exudation periods were observed with JA and ET, another feature shared with Pinus resinosis. The results suggest that resinosis control is similar in Araucaria and Pinus. In addition, A. angustifolia resin may be a relevant source of valuable terpene chemicals, whose production may be increased by using stimulating pastes containing the identified adjuvants.     

Variation of stilbene glucosides in bark extracts obtained from roots and stumps of Norway spruce (Picea abies [L.] Karst.)

Acetone-soluble compounds found in different root zones and stumps of Norway spruce (Picea abies [L.] Karst), which were grown on either peatland or a mineral soil site, were studied. Samples from stumps and roots of different sizes and ages were collected a day after the trees were felled. The wood and bark of stumps and three zones of the roots were separated and extracted with acetone in an ultrasonic bath. Extracts were silylated and analysed by gas chromatography–mass spectrometry. The stilbene glucosides astringin and isorhapontin were major compounds in the spruce bark samples. The resveratrol glucoside piceid and the flavonoid catechin were also extracted from spruce bark. We also found the lignan hydroxymatairesinol in some wood extracts. Total concentrations of stilbene glucosides in bark of stumps and different root zones varied between 0.53 and 8.29 % (w/w, dry weight) with isorhapontin being the major compound. Isorhapontin concentrations were highest in the spruce samples grown on mineral soil. The bark of the roots close to the stem is a rich source of stilbenes for commercial utilisation.     

Low-temperature induction of starch degradation in roots of a biennial weed

Decreasing temperatures were observed to induce starch degradation in roots of mullein, a biennial weedy species. Virtually no starch remains in the roots when the acclimation period of decreasing temperatures is followed by an extended period of exposure to 4 °C. The breakdown of starch which is presumed to occur in late autumn under field conditions may provide cryoprotective chemicals for the overwintering rosette. Such chemicals might also serve as an energy source for the bolting process which occurs during the following spring or early summer.