Spray Coating of Wood with Nanoparticles from Lignin and Polylactic Glycolic Acid Loaded with Thyme Essential Oils.

Ensuring the longevity of wooden constructions depends heavily on the preservation process. However, several traditional preservation methods involving fossil-based compounds have become outdated because they pose a significant risk to the environment and to human health. Therefore, the use of bio-based and bioactive solutions, such as essential oils, has emerged as a more sustainable alternative in protecting wood from biotic attacks. The entrapment of essential oils in polymeric carrier matrices provides protection against oxidation and subsequent degradation or rapid evaporation, which implies the loss of their biocidal effect. In this work, lignin as well as PLGA nanoparticles containing the essential oils from two different thyme species (Thymus capitatus and T. vulgaris) were applied on beech wood samples using spray coating. The prepared coatings were investigated using FTIR imaging, SEM, as well as LSM analysis. Release experiments were conducted to investigate the release behavior of the essential oils from their respective lignin and PLGA carrier materials. The study found that lignin nanoparticles were more effective at trapping and retaining essential oils than PLGA nanoparticles, despite having larger average particle diameters and a more uneven particle size distribution. An analysis of the lignin coatings showed that they formed a uniform layer that covered most of the surface pores. PLGA nanoparticles formed a film-like layer on the cell walls, and after leaching, larger areas of native wood were evident on the wood samples treated with PLGA NPs compared to the ones coated with lignin NPs. The loading capacity and efficiency varied with the type of essential oil, while the release behaviors were similar between the two essential oil types applied in this study.

Electrospun PCL Filtration Membranes Enhanced with an Electrosprayed Lignin Coating to Control Wettability and Anti-Bacterial Properties.

This study reports on the two-step manufacturing process of a filtration media obtained by first electrospinning a layer of polycaprolactone (PCL) non-woven fibers onto a paper filter backing and subsequently coating it by electrospraying with a second layer made of pure acidolysis lignin. The manufacturing of pure lignin coatings by solution electrospraying represents a novel development that requires fine control of the underlying electrodynamic processing. The effect of increasing deposition time on the lignin coating was investigated for electrospray time from 2.5 min to 120 min. Microstructural and physical characterization included SEM, surface roughness analysis, porosity tests, permeability tests by a Gurley densometer, ATR-FTIR analysis, and contact angle measurements vs. both water and oil. The results indicate that, from a functional viewpoint, such a natural coating endowed the membrane with an amphiphilic behavior that enabled modulating the nature of the bare PCL non-woven substrate. Accordingly, the intrinsic hydrophobic behavior of bare PCL electrospun fibers could be reduced, with a marked decrease already for a thin coating of less than 50 nm. Instead, the wettability of PCL vs. apolar liquids was altered in a less predictable manner, i.e., producing an initial increase of the oil contact angles (OCA) for thin lignin coating, followed by a steady decrease in OCA for higher densities of deposited lignin. To highlight the effect of the lignin type on the results, two grades of oak (AL-OA) of the Quercus cerris L. species and eucalyptus (AL-EU) of the Eucalyptus camaldulensis Dehnh species were compared throughout the investigation. All grades of lignin yielded coatings with measurable antibacterial properties, which were investigated against Staphylococcus aureus and Escherichia coli, yielding superior results for AL-EU. Remarkably, the lignin coatings did not change overall porosity but smoothed the surface roughness and allowed modulating air permeability, which is relevant for filtration applications. The findings are relevant for applications of this abundant biopolymer not only for filtration but also in biotechnology, health, packaging, and circular economy applications in general, where the reuse of such natural byproducts also brings a fundamental demanufacturing advantage.

Extraction and Characterization of Acidolysis Lignin from Turkey Oak (Quercus cerris L.) and Eucalypt (Eucalyptus camaldulensis Dehnh.) Wood from Population Stands in Italy.

Acidolysis lignins from the species Quercus cerris L. and Eucalyptus camaldulensis Dehnh. were isolated and characterized using high pressure size exclusion chromatography (HP-SEC), Fourier-transform (FTIR) infrared spectroscopy, analytical pyrolysis-gas chromatography-mass spectrometry (Py-GCMS), and two-dimensional heteronuclear single quantum coherence (2D HSQC) NMR spectroscopy. The acidolysis lignins from the two different species varied in chemical composition and structural characteristics, with Q. cerris L. lignin having a higher S/G ratio and higher molar mass averages with a bimodal molar mass distribution. The different analytical techniques FTIR spectroscopy, Py-GCMS, and 2D NMR spectroscopy provided consistent results regarding the S/G ratio of the lignins from the two wood species. Based on the determined high S/G ratio of both oak and eucalypt lignin, the two wood sources could be promoted as substrates for efficient lignin isolation in modern forest biorefineries in order to develop innovative lignin-based value-added biorefinery products.

Lignin Nanoparticles with Entrapped Thymus spp. Essential Oils for the Control of Wood-Rot Fungi.

After decades of utilization of fossil-based and environmentally hazardous compounds for wood preservation against fungal attack, there is a strong need to substitute those compounds with bio-based bioactive solutions, such as essential oils. In this work, lignin nanoparticles containing four essential oils from thyme species (Thymus capitatus, Coridothymus capitatus, T. vulgaris, and T. vulgaris Demeter) were applied as biocides in in vitro experiments to test their anti-fungal effect against two white-rot fungi (Trametes versicolor and Pleurotus ostreatus) and two brown-rot fungi (Poria monticola and Gloeophyllum trabeum). Entrapment of essential oils provided a delayed release over a time frame of 7 days from the lignin carrier matrix and resulted in lower minimum inhibitory concentrations of the essential oils against the brown-rot fungi (0.30-0.60 mg/mL), while for the white-rot fungi, identical concentrations were determined compared with free essential oils (0.05-0.30 mg/mL). Fourier Transform infrared (FTIR) spectroscopy was used to assess the fungal cell wall changes in the presence of essential oils in the growth medium. The results regarding brown-rot fungi present a promising approach for a more effective and sustainable utilization of essential oils against this class of wood-rot fungi. In the case of white-rot fungi, lignin nanoparticles, as essential oils delivery vehicles, still need optimization in their efficacy.

Cellulose Nano Crystals (CNC) as Additive for a Bio-Based Waterborne Acrylic Wood Coating: Decay, Artificial Weathering, Physical and Chemical Tests.

Wood coatings prolong the service life of wood-based products, but they are usually of synthetic origin. The aim of the present article is to reduce the fossil-based compounds in a commercial waterborne acrylic coating by CNC addition and to test its performance. The coatings were applied on European beech and Norway spruce wood in order to test durability against Gloeophyllum trabeum (brown wood rot) and Trametes versicolor (white wood rot). Artificial weathering and blue stain, contact angle, physical tests (adhesion, impact and scratch test), chemical (FTIR) and morpho-anatomical analysis (SEM) were carried out. CNC addition increased viscosity, limiting the spreading of the coating into wood pores as visible after SEM observation, which reduced coating adhesion on the substrate. CNC improved fungal resistance as seen by a reduced mass loss and FTIR spectroscopy thanks to crosslinks formation, which reduced water sorption as well. Color change was not significant, and, on the other hand, glossiness was reduced but resulted as more homogeneous than control. CNC addition gave good results also in blue stain protection. CNC improved scratch resistance, but no visible change to impact was registered. CNC has promising results in coatings depending on wood and fungal species and presence of further commercial additives (biocides).

Synthesis and Characterizations of Eco-Friendly Organosolv Lignin-Based Polyurethane Coating Films for the Coating Industry.

Three different formulations of bio-based polyurethane (PU), varying the weight ratio between Organosolv lignin and a commercial isocyanate, were synthesized. The coating formulations were characterized by SEM, pyrolysis-GC/MS, FTIR spectroscopy and FTIR mapping, which confirmed the successful formation of urethane bonds between commercial isocyanate and hydroxyl groups deriving from lignin. The coatings were applied on beech wood samples to measure color and contact angles, and eventually FTIR mapping of the coated wood samples was performed. FTIR mapping is an interesting tool to monitor the distribution of PU chemical bonds on the coating surface and to evaluate the homogeneity of the applied coating films. Increasing the lignin content of the PU coatings results in more red-yellow and darker tones, while the commercial PU coating is transparent. For a higher lignin concentration, the solid content as well as the weight gain of the applied coatings increase. A higher percentage of lignin in the prepared PU formulations leads to superficial cracks and therefore higher coating permeability compared to the commercial PU, but the prepared lignin-based PU coating still makes a raw wood surface significantly more hydrophobic. Apparently, additives such as film-formers with low surface tension to counteract cracks' formation are necessary to improve the performance of lignin-based PU coatings.

Influence of forest stand characteristics on physical, mechanical properties and chemistry of chestnut wood.

Site conditions and forest management affect dendrometric parameters of chestnut (Castanea sativa Mill.) coppices, but there is modest knowledge on the effect of stand dendrometric characters on physical and mechanical wood characteristics. The aim of this study was to verify these relationships in chestnut coppices that were 12-14 years old. Wood density, compression and bending strength, shrinkages were measured on shoots of five different stand in a vulcanic site in Monte Amiata (Central - Italy). Investigated stands differ in number of stools/ha and dominant height, diameter/basal area of the shoots. The main difference in the physical characters among the stands is density. The initial results of the study showed that physical, mechanical wood characters are more dependent by the shoot than by the site. There is a positive relationships between the number of stools/ha and density and a negative one among shoot dominant height and basal area with wood density. Spectroscopic profile by FTIR has not showed relevant differences among the stands. Wood anatomy has showed the breakpoint at cellular level.

Essential Oils as Alternative Biocides for the Preservation of Waterlogged Archaeological Wood.

Waterlogged archaeological wood is exposed to a high risk of biological degradation during the post-excavation phases of storage and restoration. For this reason, often biocides must be used to preserve wooden remains. In the present work three essential oils (cinnamon, wild thyme, and common thyme) were tested as possible alternative biocides to use in the preservation of waterlogged archaeological wood. The oils were first tested in vitro to establish the minimum inhibitory concentration (MIC) and to evaluate the biocidal activity on selected fungal strains. Then, the established MIC was applied on waterlogged archaeological wood samples and during an actual restoration treatment. The effectiveness of the oils was evaluated through cultural analyses, ATP quantification, and next-generation sequencing. The results showed that the oils caused a significant decrease in the vitality of fungal mycelia grown in vitro and of the microbiota present in treated wood and storage water. Furthermore, an influence on the composition of the bacterial communities of treated wood samples was observed. Although further tests are needed to evaluate interferences with the materials used during restoration procedures, essential oils could be considered as a possible alternative to the currently used biocide.

Impact of Bio-Based (Tannins) and Nano-Scale (CNC) Additives on Bonding Properties of Synthetic Adhesives (PVAc and MUF) Using Chestnut Wood from Young Coppice Stands.

Sustainability and ecotoxicity issues call for innovations regarding eco-friendly adhesives in the production of biocomposite wood materials, and solutions involving nano-scale and bio-based compounds represent a valid and promising target. One possible approach is to increase the performance of adhesives such as polyvinyl acetate (PVAc) or melamine-urea-formaldehyde (MUF) by means of nanoparticles in order to obtain a material with better mechanical and environmental resistance. When applying cellulose-based nanoparticles or tannin, the concept of a circular economy is successfully implemented into the forest/wood value chain, and chances are created to develop new value chains using byproducts of forestry operations. In this study, assortments coming from young sweet chestnut (Castanea sativa Mill.) coppice stands were utilized for the preparation of single lap joint assemblies using different commercial adhesives (PVAc, MUF) and cellulose nanocrystals (CNC) and tannin as additives. The results showed that addition of CNC and tannin to PVAc glue increased tensile shear strength in lap joint tests presenting a promising base for future tests regarding the addition of CNC and tannin in MUF or PVAc adhesive formulations. Unfortunately, the tested bio-based additives did not reveal the same encouraging results when tested in the wet state.

Cellulose and Lignin Nano-Scale Consolidants for Waterlogged Archaeological Wood.

Waterlogged archaeological wood comes from submerged archaeological sites (in lake, sea, river, or wetland) or from land waterlogged sites. Even if the wooden object seems to have maintained the original size and shape, the wood is more or less severely decayed because of chemical and biological factors which modify the normal ratio of cellulose and lignin in the cell wall. Drying procedures are necessary for the musealization but potentially cause severe shrinkages and collapses. The conservation practices focus not only on removing water from wood but also on substituting it with materials able to consolidate the degraded wood cell walls like polymers (e.g., PEG), sugars (e.g., lactitol), or resins (e.g., Kauramin). In the present work three different nano-scale consolidants were tested: lignin nanoparticles (LNPs) obtained form beech wood via a non-solvent method involving dialysis; bacterial nanocellulose (BC) obtained from cultures fed with agro-alimentary waste; cellulose nanocrystals (CNC) chemically extracted from native cellulose. Waterlogged archaeological wood samples of different species (oak, elm, stone pine, and silver fir) characterized by different levels of degradation were impregnated with the consolidants. The treatments efficiency was evaluated in terms of macroscopic observation of treated samples, anti-shrink efficiency (ASE) and equilibrium moisture content (EMC). The results obtained for the three consolidants showed substantial differences: LNPs and CNCs penetrated only about a millimeter inside the treated wood, while BC formed a compact layer on the surface of the cell walls throughout the thickness of the samples. In spite of successful BC penetration, physical evaluation of treatment efficiency showed that BC nanoparticles did not obtain a satisfying consolidation of the material. Based on the reported results more focused test protocols are optimized for future consolidation experiments.

Preparation of Lignin Nanoparticles with Entrapped Essential Oil as a Bio-Based Biocide Delivery System.

Lignin isolated from beech sawdust was used for the preparation of lignin nanoparticles (LNPs) with entrapped essential oil (EO) from cinnamon bark (Cinnamomum zeylanicum Blume), common thyme (Thymus vulgaris L.), and wild thyme (Thymus serpyllum L.) using a fast antisolvent method. Analysis of EO-loaded LNPs by pyrolysis-gas chromatography-mass spectrometry and Fourier transform infrared spectroscopy confirmed molecular interaction between EOs and LNPs. Quantification of EO incorporation into the LNPs and their in vitro release profiles were assessed by reversed phase high-performance liquid chromatography. Utilized EOs were, to different extents, successfully entrapped inside LNPs, which were attributed to extensive π-stacking between aromatic compounds in EOs like cinnamaldehyde, thymol, and carvacrol on one side and aromatic lignin units on the other side. In vitro release of common thyme and wild thyme EOs from EO-loaded LNPs was strongly delayed compared to the use of pure oil, giving a promising outlook for the development of new bio-based biocide delivery systems for wood preservation.

Characterization of black patina from the Tiber River embankments using Next-Generation Sequencing.

Black patinas are very common biological deterioration phenomena on lapideous artworks in outdoor environments. These substrates, exposed to sunlight, and atmospheric and environmental agents (i.e. wind and temperature changes), represent extreme environments that can only be colonized by highly versatile and adaptable microorganisms. Black patinas comprise a wide variety of microorganisms, but the morphological plasticity of most of these microorganisms hinders their identification by optical microscopy. This study used Next-Generation Sequencing (NGS) (including shotgun and amplicon sequencing) to characterize the black patina of the travertine embankments (muraglioni) of the Tiber River in Rome (Italy). Overall, the sequencing highlighted the rich diversity of bacterial and fungal communities and allowed the identification of more than one hundred taxa. NGS confirmed the relevance of coccoid and filamentous cyanobacteria observed by optical microscopy and revealed an informative landscape of the fungal community underlining the presence of microcolonial fungi and phylloplane yeasts. For the first time high-throughput sequencing allowed the exploration of the expansive diversity of bacteria in black patina, which has so far been overlooked in routine analyses. Furthermore, the identification of euendolithic microorganisms and weathering agents underlines the biodegradative role of black patina, which has often been underestimated. Therefore, the use of NGS to characterize black patinas could be useful in choosing appropriate conservation treatments and in the monitoring of stone colonization after the restoration interventions.

Assessment of environmental impact of biomass power plants to increase the social acceptance of renewable energy technologies.

OBJECTIVE: The objectives of the European Union (EU) policy agenda are to reduce the greenhouse gas emissions and to decrease the dependence of EU member countries from fossil fuel sources. In order to achieve these policy objectives, in the last decades the number of biomass power plants has increased throughout the EU. This study analyzed the environmental impacts of the bioenergy systems at global and local level to support communication and information strategies to increase social acceptance and to reduce conflicts between stakeholders. The environmental impacts were estimated to a sample of biomass power plants in North Italy selected based on the size, feedstock and type (cogeneration or heating). The study aims to identify and evaluate the environmental impacts associated with the thermal energy production in biomass power plants using a Life Cycle Assessment (LCA) approach. MATERIALS AND METHODS: For each biomass district plant an LCA analysis was performed to: compare the environmental impacts associated with the production of the same functional unit, quantifying and valuating the environmental performance deriving from the production process life cycle, and highlighting the production phases with greater impact. RESULTS: The results show an average climate change impact by biomass energy plant of 45.84 gCO2eq MJ-1 and a range between 14.93 gCO2eq MJ-1 and 90.70 gCO2eq MJ-1. The results show that the size of the biomass energy plant (less than 1 MW or more than 1 MW) and the feedstock used (forest or sawmill woodchip) are two main variables that influence many categories of environmental impact.

Preparation of Lignin Nanoparticles from Wood Waste for Wood Surface Treatment.

Lignin was isolated from wood wastes comprising Iroko sawdust (IR) and mixed sawdust from Iroko and Norway spruce (IRNS), furnished by a local wood houses producer. The respective acidolysis lignin fractions were structurally characterized using pyrolysis (Py)-GCMS, two-dimensional heteronuclear single quantum correlation nuclear magnetic resonance (2D HSQC NMR), Fourier-transform infrared FTIR and ultraviolet-visible (UV-VIS) spectroscopies, size exclusion chromatography, and standard wet-chemistry methods for Klason lignin and polysaccharides determination. The isolated lignin fractions were subsequently used for the preparation of lignin nanoparticles (LNPs) using a non-solvent method. LNPs were then used for wood surface treatment using a dip-coating technique. The coated wood samples were analyzed by colorimetry and scanning electron microscopy (SEM) before and after artificial weathering experiments in a UV chamber to investigate the UV protection potential of the LNPs coatings. Wood samples dip-coated with LNPs showed promising surface modifications resembling a sort of film of fused LNPs. Coatings made from IR-LNPs and IRNS-LNPs performed significantly better in artificial weathering experiments than uncoated reference samples.