Accumulation analysis and overall measurement to represent airborne toxic metals with passive tree bark biomonitoring technique in urban areas.

Authorities have long proved the utility of bioindicators in monitoring the state of environmental pollution. Some biological indicators can measure environmental pollutant levels, and many tree species have been tested for suitability for monitoring purposes. The differences in morphological characteristics in the trees have demonstrated the effects of human activities on different materials. Measuring bark and wood biomass from contaminated sites was identified and directly compared with those from a clean site or areas characterized by distinct contamination sources. However, preliminary results demonstrate the approach's potential in the realization of strategies for disease control and promoting health to reduce environmental and health inequalities in at-risk urban areas. Picea orientalis L. and Cedrus atlantica Endl., especially their bark, can be regarded as a more robust storage of Cu (37.95 mg/kg) and Mn (188.25 mg/kg) than Pinus pinaster, Cupressus arizonica, and Pseudotsuga menziesii, which and is therefore a better bioindicator for Cu and Mn pollution. Considering the total concentrations as a result of the study, the pollution is thought to be caused by environmental problems and traffic in the region. The deposition of Cu, Mn, Ni, and Zn elements was found P. menziesii (60, 443, 58, and 258 mg/kg) and P. orientalis (76, 1684, 41, and 378 mg/kg) and seems to reflect atmospheric quite clearly compared to P. pinaster, C. arizonica, and C. atlantica. Ni and Zn concentrations have significantly increased since 1983, and P. menziesii and P. orientalis can be potentially valuable bioindicators for emphasizing polluted fields.

Effects of legacy mining on mercury concentrations in conifer needles and mushrooms in northern Palatinate, Germany.

Due to integrated pollution prevention and control measures and the reduced burning of coal, air concentrations of mercury (Hg0) are currently levelling off. In the future, however, evasion from land surfaces will probably reverse this trend. Reasons are the rising temperatures and the loss of forest cover caused by calamities, droughts, storms and wildfires. Plant leaves constitute an important matrix for the accumulation of gaseous mercury and uptake and re-volatilisation by plants depends on the species, the vitality and the age and morphology of leaf organs. It has been shown that older conifer needles show higher concentrations than young needles and Hg accumulation is increasing throughout the season. In present study, we collected branches from Norway Spruce (Picea abies) in a former cinnabar mining region in Northern Palatinate, where artisanal and small-scale mining left innumerable waste dumps. While mining, smelting and processing of the ores were terminated during WWII, high total mercury concentrations remained in the top soils locally, with presumably only small fractions being plant available. In the lab, up to seven needle age classes were analysed. 1000 needle weights increased with age and as expected, also the Hg concentrations were elevated in the older needles. Needle concentrations were higher than those reported from other national biomonitoring programs confirming the regional imprint from legacy mercury. To complement our biomonitoring study, we collected edible mushrooms in former mining areas. Hg concentrations in most samples exceeded the EU maximum residue levels (MRL), while only a few broke the existing cadmium and lead limits. Tolerable weekly intake (TWI) for inorganic mercury would be surpassed with the consumption of a small portion of mushrooms. Further studies should be performed on the outgassing of Hg from mine wastes and the incorporation of Hg in the local food web, including its methylation and biomagnification.

Multiscale assessment of artificial aging treatment of polysaccharides from tonewood species.

In the acoustics of musical instruments with a resonator body, the aging of the wood leads to the improvement of the acoustic properties due to increasing the crystallinity of wood. This phenomenon could be explained by the fact that wood is a complex product based on three-dimensional polymer chains of carbohydrates, its aging being closely related to covalent cross-linking and scission of polymer chains. The aim of this study was to evaluate at a multiscale the changes produced artificial aging of tone wood by measuring the acoustic, mechanical and chemical parameters. The spruce and maple wood samples were investigated before and after exposure to ultraviolet (UV) radiation, through the tensile test, the time-of-flight method (TOF), the analysis of the wood color and the determination of the chemical fingerprint through Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The obtained results showed that the effects of artificial aging are manifested at the chemical level where the crystallinity increases up to the acoustic level, depending on the wood species and their quality class. These results are relevant for musical instrument manufacturers to find treatments that lead to superior acoustic properties.

Tree Species-Dependent Inactivation of Coronaviruses and Enteroviruses on Solid Wood Surfaces.

The ongoing challenge of viral transmission, exemplified by the Covid pandemic and recurrent viral outbreaks, necessitates the exploration of sustainable antiviral solutions. This study investigates the underexplored antiviral potential of wooden surfaces. We evaluated the antiviral efficacy of various wood types, including coniferous and deciduous trees, against enveloped coronaviruses and nonenveloped enteroviruses like coxsackie virus A9. Our findings revealed excellent antiviral activity manifesting already within 10 to 15 min in Scots pine and Norway spruce, particularly against enveloped viruses. In contrast, other hardwoods displayed varied efficacy, with oak showing effectiveness against the enterovirus. This antiviral activity was consistently observed across a spectrum of humidity levels (20 to 90 RH%), while the antiviral efficacy manifested itself more rapidly at 37 °C vs 21 °C. Key to our findings is the chemical composition of these woods. Resin acids and terpenes were prevalent in pine and spruce, correlating with their antiviral performance, while oak's high phenolic content mirrored its efficacy against enterovirus. The pine surface absorbed a higher fraction of the coronavirus in contrast to oak, whereas enteroviruses were not absorbed on those surfaces. Thermal treatment of wood or mixing wood with plastic, such as in wood-plastic composites, strongly compromised the antiviral functionality of wood materials. This study highlights the role of bioactive chemicals in the antiviral action of wood and opens new avenues for employing wood surfaces as a natural and sustainable barrier against viral transmissions.

An Integrated Testing Strategy (ITS) to assess the environmental compatibility of wood protection techniques.

To quantify the possible impact of different wood protection techniques on the aquatic environment, we applied a tiered Integrated Testing Strategy (ITS) on leachates obtained from untreated (UTW) Norway spruce (Picea abies), specimens treated with a copper-ethanolamine-based preservative solution, complying with the Use Class 3 (UC3), and specimens thermally modified (TM). Different maturation times in water were tested to verify whether toxicant leaching is time-dependent. Tier I tests, addressing acute effects on Aliivibrio fischeri, Raphidocelis subcapitata, and Daphnia magna, evidenced that TM toxicity was comparable or even lower than in UTW. Conversely, UC3 significantly affected all species compared to UTW, also after 30 days of maturation in water, and was not considered an environmentally acceptable wood preservation solution. Tier II (effects on early-life stages of Lymnea auricularia) and III (chronic effects on D. magna and L. auricularia) performed on UTW and TM confirmed the latter as an environmentally acceptable treatment, with increasing maturation times resulting in decreased adverse effects. The ITS allowed for rapid and reliable identification of potentially harmful effects due to preservation treatments, addressed the choice for a less impacting solution, and can be effective for manufacturers in identifying more environmentally friendly solutions while developing their products.

Phytochemical Characterization, Antioxidant, and Antimicrobial Activity of the Vegetative Buds from Romanian Spruce, Picea abies (L.) H. Karst.

This study aims to investigate the vegetative buds from Picea abies (spruce), naturally found in a central region of Romania, through a comprehensive analysis of the chemical composition to identify bioactive compounds responsible for pharmacological properties. Using HPLC/derivatization technique of GC-MS and quantitative spectrophotometric assays, the phenolic profile, and main components of an ethanolic extract from the buds were investigated. The essential oil was characterized by GC-MS. Moreover, the antioxidant activity with the DPPH method, and the antimicrobial activity were tested. Heavy metal detection was performed by graphite furnace atomic absorption spectrometry. The main components of the alcoholic extract were astragalin, quercetin, kaempferol, shikimic acid, and quinic acid. A total content of 25.32 ± 2.65 mg gallic acid equivalent per gram of dry plant (mg GAE/g DW) and of 10.54 ± 0.083 mg rutin equivalents/g of dry plant (mg RE/g DW) were found. The essential oil had D-limonene, α-cadinol, δ-cadinene, 13-epimanool, and δ-3-carene as predominant components. The spruce vegetative buds exhibited significant antioxidant activity (IC50 of 53 µg/mL) and antimicrobial effects against Staphylococcus aureus. Furthermore, concentrations of heavy metals Pb and Cd were below detection limits, suggesting that the material was free from potentially harmful contaminants. The results confirmed the potential of this indigenous species to be used as a source of compounds with pharmacological utilities.

Detecting changes in industrial pollution by analyzing heavy metal concentrations in tree-ring wood from Romanian conifer forests.

The impact of air pollution on forests, especially in urban areas, has been increasingly discussed recently. Many pollutants, including heavy metals, are released into the atmosphere from various sources, such as mining, non-ferrous metal processing plants, and fossil fuel combustion. These pollutants can adversely affect not only tree growth but also other species, including humans. This study compared the concentrations of several elements in tree-ring wood from two conifer species (Silver fir, Abies alba; Norway spruce, Picea abies) growing in polluted and unpolluted areas. Two regions in northern Romania (Bicaz and Tarnița) that were subjected to historical pollution changes were selected. Two chemical analyses were used: inductively coupled plasma mass spectrometry (ICP-MS) and X-ray fluorescence spectrometry (XRF). The silver fir trees from the intensively polluted area in the Tarnița region were negatively impacted by industrial pollution: the Mn concentrations were, on average, three times higher in polluted areas than in unpolluted areas (ca. 30 vs. 10 mg kg-1). This finding was consistent for both ICP-MS and XRF analyses. However, in Norway spruce, this difference was found only in the XRF data, which detected Mn concentrations seven times higher in trees from polluted areas than those from unpolluted areas (ca. 700 vs. 100 mg kg-1). In the Tarnița region, Norway spruce accumulated more heavy metals than silver fir, but the most pronounced differences between polluted and unpolluted areas were found in silver fir. The two analytical methods are commonly used to determine metal concentrations in wood, and they complement each other, with ICP-MS having a low detection limit for some elements and XRF having higher detection limits and better accuracy. Each method has its advantages and disadvantages, and the optimal method depends on many factors, such as the type of heavy metal analyzed, its concentration in wood, sample type, cost, analysis time, and sample preparation.

Preparation of Activated Biocarbons from Cones and their Potential Application for Adsorption of Antibiotics (Tetracycline).

The pine cones (PC), spruce cones (SC) and fir cones (FC) were used for biocarbons preparation. Chemical activation with sodium hydroxide was applied to prepare activated biocarbons. All the materials under investigation were characterized by the N2 adsorption, scanning electron microscopy (SEM), elemental analysis (CHNS), infrared spectroscopy (ATR FT-IR), and the Boehm's titration method. Moreover, pHpzc (the point of zero charge) was determined. It was shown that cones are a good, cheap precursor from which biocarbons with a developed porous structure, characterized by good adsorption properties, can be obtained. All the obtained adsorbents are characterized mainly by a microporous structure. Moreover, they contain both acidic and basic surface functional groups (acidic ones prevail over basic ones). The tested activated biocarbons have large specific surface area values ranging from 578 to 1182 m2 g-1. The efficacy of selected materials in the adsorption of an essential contaminant of increasing concern, tetracycline (TC), was investigated. The experimental data were described using the Langmuir and Freundlich adsorption isotherm models. The maximum adsorption capacity of the tested biocarbons ranges from 200 to 392 mg g-1. Thermodynamic studies proved that adsorption is a spontaneous and endothermic process. In summary, economical and environmentally friendly adsorbents were obtained.

Know When You Are Too Many: Density-Dependent Release of Pheromones During Host Colonisation by the European Spruce Bark Beetle, Ips typographus (L.).

Individuals across various animal species communicate their presence to conspecifics. Especially phytophagous and parasitoid insects with their brood developing on limited resources rely on chemical cues, such as host-marking pheromones, to reduce intraspecific competition. Bark beetles are phytophagous insects with some species being economically and ecologically relevant forest pests. Several of them use the volatile compound verbenone to inhibit attraction and reduce intraspecific competition. However, in the Eurasian spruce bark beetle, Ips typographus (L.), temporal emission patterns did so far not quite support the putative function of verbenone as an indicator of densely colonised host trees. More importantly, it is currently unclear how well verbenone emission is actually related to colonisation density and thus intraspecific competition. Here, we inoculated Norway spruce logs with I. typographus at two defined colonisation densities in the greenhouse and measured the emission of verbenone and its precursors α-pinene and verbenol over time. Verbenone emission was 3-7 times greater from colonised logs compared to decaying logs without beetles during the major part of larval development. Furthermore, our data supports the quantitative hypothesis, that the termination of attack on a tree is mediated by a cessation of the release of verbenol and continuous emission of verbenone. The latter is most likely a passively produced host-marking cue reflecting the actual density of conspecifics since per-beetle emission was unaffected by colonisation density. These findings shed new light on the regulation of bark beetle mass aggregations, which are currently causing previously unseen economic damages in temperate forests.

Biomonitoring of atmospheric PAHs using fir and spruce needles in forests in the vicinity of mountain villages.

The aim of the study was to use chemical analyses of spruce and fir needles to determine environmental exposure to polycyclic aromatic hydrocarbons (PAHs) in forests surrounding small mountain towns, including popular tourist destinations. The Beskid Mountains in Poland were chosen as the study area because they are very popular with tourists. The 6- and 12 month old needles were collected in two consecutive years from permanent study plots. Two vintages of needles were used to determine the differences between seasons in the profile of deposited pollutants. Some of plots were located away from roads and buildings, while others were located near tourist destinations. The comparison plots were located in the centre of a tourist resort, near a highway, and in a forest localised in the industrial city characterised by a high degree of urbanization. The analyses of 15 PAHs content showed that the amount and type of compounds retained by the needles were influenced not only by the proximity and amount of the surface emitters, but also by the location of the research sites above sea level. The results obtained can be explained, among other things, by the phenomenon of smog, which is not uncommon in the study region in autumn and winter.

Bioactive Molecules from Myrianthus arboreus, Acer rubrum, and Picea mariana Forest Resources.

Forest trees are the world's most important renewable natural resources in terms of their dominance among other biomasses and the diversity of molecules that they produce. Forest tree extractives include terpenes and polyphenols, widely recognized for their biological activity. These molecules are found in forest by-products, such as bark, buds, leaves, and knots, commonly ignored in forestry decisions. The present literature review focuses on in vitro experimental bioactivity from the phytochemicals of Myrianthus arboreus, Acer rubrum, and Picea mariana forest resources and by-products with potential for further nutraceutical, cosmeceutical, and pharmaceutical development. Although these forest extracts function as antioxidants in vitro and may act on signaling pathways involved in diabetes, psoriasis, inflammation, and skin aging, much still remains to be investigated before using them as therapeutic candidates, cosmetics, or functional foods. Traditional forest management systems focused on wood must evolve towards a holistic approach, allowing the use of these extractives for developing new value-added products.

Gymnosperms of Idaho: Chemical Compositions and Enantiomeric Distributions of Essential Oils of Abies lasiocarpa, Picea engelmannii, Pinus contorta, Pseudotsuga menziesii, and Thuja plicata.

Conifers are of great economic value in terms of lumber production, important for construction and other uses such as pulp and paper. They are also important sources of essential oils. Conifer species have been vital to the ethnobotany and traditional herbal medicine of many different Native American groups. The objective of this work was to obtain and analyze the essential oils of several conifer species (Abies lasiocarpa, Picea engelmannii, Pinus contorta, Pseudotsuga menziesii, and Thuja plicata) growing in Idaho. The foliar essential oils were obtained by hydrodistillation and then analyzed by gas chromatographic methods, including GC-MS, GC-FID, and chiral GC-MS. The essential oils were obtained in varying yields from 0.66% up to 4.70%. The essential oil compositions were largely dominated by monoterpene hydrocarbons and oxygenated monoterpenoids. The chiral monoterpenoids were generally rich in the (-)-enantiomers for members of the Pinaceae, but the (+)-enantiomers predominated in the Cupressaceae. The essential oil compositions obtained in this work are qualitatively similar, but quantitatively different, to previously reported compositions and confirm and complement the previous reports. However, this is the first comprehensive analysis of the chiral terpenoid components in these conifer species. Additional research on essential oils of the Pinaceae and Cupressaceae is needed to describe the chemical profiles, chemical compositions, and enantiomeric distributions more reliably in the various species and infraspecific taxa of these two families.

Conifer-killing bark beetles locate fungal symbionts by detecting volatile fungal metabolites of host tree resin monoterpenes.

Outbreaks of the Eurasian spruce bark beetle (Ips typographus) have decimated millions of hectares of conifer forests in Europe in recent years. The ability of these 4.0 to 5.5 mm long insects to kill mature trees over a short period has been sometimes ascribed to two main factors: (1) mass attacks on the host tree to overcome tree defenses and (2) the presence of fungal symbionts that support successful beetle development in the tree. While the role of pheromones in coordinating mass attacks has been well studied, the role of chemical communication in maintaining the fungal symbiosis is poorly understood. Previous evidence indicates that I. typographus can distinguish fungal symbionts of the genera Grosmannia, Endoconidiophora, and Ophiostoma by their de novo synthesized volatile compounds. Here, we hypothesize that the fungal symbionts of this bark beetle species metabolize spruce resin monoterpenes of the beetle's host tree, Norway spruce (Picea abies), and that the volatile products are used as cues by beetles for locating breeding sites with beneficial symbionts. We show that Grosmannia penicillata and other fungal symbionts alter the profile of spruce bark volatiles by converting the major monoterpenes into an attractive blend of oxygenated derivatives. Bornyl acetate was metabolized to camphor, and α- and ß-pinene to trans-4-thujanol and other oxygenated products. Electrophysiological measurements showed that I. typographus possesses dedicated olfactory sensory neurons for oxygenated metabolites. Both camphor and trans-4-thujanol attracted beetles at specific doses in walking olfactometer experiments, and the presence of symbiotic fungi enhanced attraction of females to pheromones. Another co-occurring nonbeneficial fungus (Trichoderma sp.) also produced oxygenated monoterpenes, but these were not attractive to I. typographus. Finally, we show that colonization of fungal symbionts on spruce bark diet stimulated beetles to make tunnels into the diet. Collectively, our study suggests that the blends of oxygenated metabolites of conifer monoterpenes produced by fungal symbionts are used by walking bark beetles as attractive or repellent cues to locate breeding or feeding sites containing beneficial microbial symbionts. The oxygenated metabolites may aid beetles in assessing the presence of the fungus, the defense status of the host tree and the density of conspecifics at potential feeding and breeding sites.

Odors Attracting the Long-Legged Predator Medetera signaticornis Loew to Ips typographus L. Infested Norway Spruce Trees.

Predatory long-legged flies of the genus Medetera are important, but currently understudied, natural enemies of Scolytinae bark beetles such as Ips typographus. Medetera flies lay eggs on beetle-infested trees, where the developing larvae find their prey, but the chemical cues used by Medetera to locate infested trees are currently unknown. To identify odors attracting Medetera signaticornis, a species in Europe, headspace samples were collected at several time-points through different stages of I. typographus attacks on logs of Norway spruce (Picea abies). The headspace samples were analyzed using combined gas chromatography and mass spectrometry (GC-MS), and gas chromatography coupled with electroantennographic detection (GC-EAD) to determine compounds that stimulate M. signaticornis antennae. Antennae of M. signaticornis males and females were found to detect (-)-cis-verbenol, ( +)-trans-verbenol and myrtenol, which are known to be produced by bark beetles. Antennal responses were also observed for verbenene, isoterpinolene, α-pinene oxide, camphor, pinocamphone, terpinene-4-ol, myrtenal, borneol, α-terpineol, geranyl acetone, and verbenone, which are primarily produced by microorganisms, and α-pinene, α-fenchene, ß-pinene, camphene, 3-carene, limonene, γ-terpinene, and terpinolene, known spruce tree compounds. In field experiments testing two synthetic blends containing 18 antennal active and two additional compounds 2-methyl-3-buten-2-ol and ipsdienol we observed significant attraction of M. signaticornis within 24 h. These attractive blends can form the basis for development of Medetera monitoring lures for use in future forest and pest management.

Fundamental Insights on the Physical and Chemical Properties of Organosolv Lignin from Norway Spruce Bark.

The interest in the bark and the attempt to add value to its utilization have increased over the last decade. By applying an integrated bark biorefinery approach, it is possible to investigate the recovery of compounds that can be used to develop green and sustainable alternatives to fossil-based materials. In this work, the focus is on extracting Norway spruce (Picea abies) bark lignin via organosolv extraction. Following the removal of the extractives and the subcritical water extraction to remove the polysaccharides, a novel cyclic organosolv extraction procedure was applied, which enabled the recovery of lignin with high quality and preserved structure. Main indicators for low degradation and preservation of the lignin structure were a high ß-O-4' content and low amounts of condensed structures. Furthermore, high purity and low polydispersity of the lignin were observed. Thus, the obtained lignin exhibits high potential for use in the direct development of polymer precursors and other bio-based materials. During the extraction sequence, around 70% of the bark was extracted. Besides the lignin, the extractives as well as pectic polysaccharides and hemicelluloses were recovered with only minor degradation, which could potentially be used for the production of biofuel or other high-value products such as emulsifiers or adhesives.

O2 as initiator of autocatalytic degradation of hemicelluloses and monosaccharides in hydrothermal treatment of spruce.

The influence of oxygen (0-50 bar) on the molar mass and composition of hemicelluloses after hydrothermal treatment of spruce chips was studied in a batch reactor setup at 130 °C-160 °C. Purified galactoglucomannan was studied as a reference. The dissolved oxygen enhanced significantly the depolymerization of hemicelluloses from over 15,000 g/mol to 180 g/mol (monomers) as well as promoted acids formation from the monosaccharides. About 2-3 times faster depolymerization was observed already with rather low amounts of oxygen (2-8 bar), while the kinetics of depolymerization was significantly slower in inert atmosphere. The decrease in pH from neutral to as low as 2.5 lead to an autocatalytic effect on the polysaccharide hydrolysis and the consecutive reactions of monosaccharides. The results emphasize the importance of performing hydrothermal treatment under inert atmosphere if large polymeric hemicellulsoses are desired or if monosaccharides are targeted in hydrolysis of hemicelluloses. If autocatalysis begins, it is difficult to stop.

Behaviour of Extractives in Norway Spruce (Picea abies) Bark during Pile Storage.

The current practices regarding the procurement chain of forest industry sidestreams, such as conifer bark, do not always lead to optimal conditions for preserving individual chemical compounds. This study investigates the standard way of storing bark in large piles in an open area. We mainly focus on the degradation of the most essential hydrophilic and hydrophobic extractives and carbohydrates. First, two large 450 m3 piles of bark from Norway spruce (Picea abies) were formed, one of which was covered with snow. The degradation of the bark extractives was monitored for 24 weeks. Samples were taken from the middle, side and top of the pile. Each sample was extracted at 120 °C with both n-hexane and water, and the extracts produced were then analysed chromatographically using gas chromatography with flame ionisation or mass selective detection and high-performance liquid chromatography. The carbohydrates were next analysed using acidic hydrolysis and acidic methanolysis, followed by chromatographic separation of the monosaccharides formed and their derivatives. The results showed that the most intensive degradation occurred during the first 4 weeks of storage. The levels of hydrophilic extractives were also found to decrease drastically (69% in normal pile and 73% in snow-covered pile) during storage, whereas the decrease in hydrophobic extractives was relatively stable (15% in normal pile and 8% in snow-covered pile). The top of the piles exhibited the most significant decrease in the total level of extractives (73% in normal and snow-covered pile), whereas the bark in the middle of the pile retained the highest amount of extractives (decreased by 51% in normal pile and 47% in snow-covered pile) after 24-week storage.

Molecular Characteristics and Antioxidant Activity of Spruce (Picea abies) Hemicelluloses Isolated by Catalytic Oxidative Delignification.

Spruce (Piceaabies) wood hemicelluloses have been obtained by the noncatalytic and catalytic oxidative delignification in the acetic acid-water-hydrogen peroxide medium in a processing time of 3-4 h and temperatures of 90-100 °C. In the catalytic process, the H2SO4, MnSO4, TiO2, and (NH4)6Mo7O24 catalysts have been used. A polysaccharide yield of up to 11.7 wt% has been found. The hemicellulose composition and structure have been studied by a complex of physicochemical methods, including gas and gel permeation chromatography, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. The galactose:mannose:glucose:arabinose:xylose monomeric units in a ratio of 5:3:2:1:1 have been identified in the hemicelluloses by gas chromatography. Using gel permeation chromatography, the weight average molar mass Mw of hemicelluloses has been found to attain 47,654 g/mol in noncatalytic delignification and up to 42,793 g/mol in catalytic delignification. Based on the same technique, a method for determining the α and k parameters of the Mark-Kuhn-Houwink equation for hemicelluloses has been developed; it has been established that these parameters change between 0.33-1.01 and 1.57-472.17, respectively, depending on the catalyst concentration and process temperature and time. Moreover, the FTIR spectra of the hemicellulose samples contain all the bands characteristic of heteropolysaccharides, specifically, 1069 cm-1 (C-O-C and C-O-H), 1738 cm-1 (ester C=O), 1375 cm-1 (-C-CH3), 1243 cm-1 (-C-O-), etc. It has been determined by the thermogravimetric analysis that the hemicelluloses isolated from spruce wood are resistant to heating to temperatures of up to ~100 °C and, upon further heating, start destructing at an increasing rate. The antioxidant activity of the hemicelluloses has been examined using the compounds simulating the 2,2-diphenyl-2-picrylhydrazyl free radicals.

Compositional analysis of essential oil and solvent extracts of Norway spruce sprouts by ultrahigh-resolution mass spectrometry.

INTRODUCTION: Coniferous trees, especially their needles and bark, are a rich source of bioactive compounds. The developing needles of Norway spruce (Picea abies), also known as spruce sprouts, are enriched with vitamin C and other antioxidants, and thus they are used as a dietary supplement and have been traditionally used to treat various inflammatory disorders such as rheumatism and gout. Their chemical composition is only limitedly known, however. OBJECTIVES: The main objective of this work was to have a deeper understanding on the chemical composition of spruce sprouts to assess their full potential in different pharmaceutical, nutraceutical, or technochemical applications. MATERIALS AND METHODS: Ultrahigh-resolution Fourier-transform ion cyclotron (FT-ICR) mass spectrometry, coupled to direct-infusion electrospray ionisation (ESI) or atmospheric pressure photoionisation (APPI) techniques, was used for in-depth compositional analysis of solvent extracts and essential oil of spruce sprouts. RESULTS: A combined use of ESI and APPI techniques offered a great complementary insight into the rich chemistry of different spruce sprout extracts, allowing detection of thousands of chemical constituents with over 200 secondary metabolites tentatively identified. These compounds belonged to different classes such as organic acids, terpenes, flavonoids, stilbenes, sterols, and nitrogen alkaloids. CONCLUSION: Spruce sprouts have a complex metabolite profile that differs considerably from that of the old, developed needles.

Correlation between rheological measurements and morphological features of lignocellulosic micro/nanofibers from different softwood sources.

The transition of nanocellulose production from laboratory to industrial scale requires robust monitoring systems that keeps a quality control along the production chain. The present work aims at providing a deeper insight on the main factors affecting the rheological behavior of (ligno)cellulose micro/nanofibers (LCMNFs) and cellulose micro/nanofibers (CMNFs) and how they could correlate with their characteristics. To this end, 20 types of LCMNFs and CMNFs were produced combining mechanical refining and high-pressure homogenization from different raw materials. Aspect ratio and bending capacity of the fibrils played a key role on increasing the viscosity of the suspensions by instigating the formation of entangled structures. Surface charge, reflected by the cationic demand, played opposing effects on the viscosity by reducing the fibrils' contact due to repulsive forces. The suspensions also showed increasing shear-thinning behavior with fibrillation degree, which was attributed to increased surface charge and higher water retention capacity, enabling the fibrils to slide past each other more easily when subjected to flow conditions. The present work elucidates the existing relationships between LCMNF/CMNF properties and their rheological behavior, considering fibrillation intensity and the initial raw material characteristics, in view of the potential of rheological measurements as an industrial scalable characterization technology.