Insights into hydrothermal treatment of biomass blends: Assessing energy yield and ash content for biofuel enhancement.

This study explores the Hydrothermal Carbonization (HTC) treatment of lignocellulosic biomass blends, delving into the influence of several key parameters: temperature, additive nature and dosage, residence time, and biomass composition. Rapeseeds, Pinus radiata sawdust, oat husks, and pressed olive served as the studied biomasses. One hundred twenty-eight experiments were conducted to assess the effects on mass yield (MY), energy yield (EY), higher heating value (HHV), and final ash content (ASH) by a Factorial Experimental Design. The derived model equations demonstrated a robust fit to the experimental data, averaging an R2 exceeding 0.94, affirming their predictive accuracy. The observed energy yield ranged between 65% and 80%, notably with sawdust and olive blends securing EY levels surpassing 70%, while rapeseed blends exhibited the highest HHV at 25 MJ/kg. Temperature emerged as the most influential factor, resulting in an 11% decrease in MY and a substantial 2.20 MJ/kg increase in HHV. Contrastingly, blend composition and additive presence significantly impacted ASH and EY, with all blends exhibiting increased ASH in the presence of additives. Higher initial hemicellulose and aqueous extractive content in raw biomass correlated proportionally with heightened HHV.

Variation pattern in the macromolecular (cellulose, hemicelluloses, lignin) composition of cell walls in Pinus tabulaeformis tree trunks at different ages as revealed using multiple techniques.

The plant cell wall is a complex, heterogeneous structure primarily composed of cellulose, hemicelluloses, and lignin. Exploring the variations in these three macromolecules over time is crucial for understanding wood formation to enhance chemical processing and utilization. Here, we comprehensively analyzed the chemical composition of cell walls in the trunks of Pinus tabulaeformis using multiple techniques. In situ analysis showed that macromolecules accumulated gradually in the cell wall as the plant aged, and the distribution pattern of lignin was opposite that of polysaccharides, and both showed heterogenous distribution patterns. In addition, gel permeation chromatography (GPC) results revealed that the molecular weights of hemicelluloses decreased while that of lignin increased with age. Two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance (2D-HSQC NMR) analysis indicated that hemicelluloses mainly comprised galactoglucomannan and arabinoglucuronoxylan, and the lignin types were mainly comprised guaiacyl (G) and p-hydroxyphenyl (H) units with three main linkage types: ß-O-4, ß-ß, and ß-5. Furthermore, the C-O bond (ß-O-4) signals of lignin decreased while the C-C bonds (ß-ß and ß-5) signals increased over time. Taken together, these findings shed light on wood formation in P. tabulaeformis and lay the foundation for enhancing the processing and use of wood and timber products.

Distribution of 35 Polycyclic Aromatic Hydrocarbons in Pine Needle Samples from Selected Locations in the Republic of Korea.

Polycyclic aromatic hydrocarbons (PAHs), dust, and wax were measured in pine needles, and PAHs were also measured in surface soil. Pearson correlation analysis was performed between the analytical values. The main compounds responsible for the increase in total PAHs were non-carcinogenic phenanthrene and fluoranthene. Therefore, the % content of carcinogenic PAHs decreased with a slope = -0.037 (r = 0.47, p < 0.01), as the total PAH concentration in pine needles increased. Correlations between individual PAHs in pine needles and surface soil were very high when only low-number ring PAHs (2R- and 3R-PAHs) were statistically analyzed and significant when only high-number ring PAHs were statistically analyzed. Low-number ring PAH mainly moves in the gas phase and diffuses into the wax layer, so it was found to be statistically significant with the wax content of pine needles. High-number ring PAHs showed a high correlation with the amount of dust in pine needles because they mainly attached to dust particles and accumulated on the surface of pine needles. The ratios of fluoranthene/pyrene and methylphenanthrene/phenanthrene for predicting the origin of atmospheric PAHs have also been proven valid for pine needles.

Integrated biorefinery approach for utilization of wood waste into levulinic acid and 2-Phenylethanol production under mild treatment conditions.

In a bid to explore the on-site biorefinery approach for conversion of forestry residues, lignocellulosic biomass into value-added products was studied. The bark white pine wood was subjected to the microwave technique of fast and slow hydrolysis under varying acid and biomass concentrations to produce levulinic acid (LA). The HCl (2% v/v) and plant biomass (1% w/v) were identified as the optimum conditions for fast wood hydrolysis (270 ºC for 12 sec), which led to maximum LA yield of 446.68 g/kgPB. The proposed sustainable approach is mild, quick, and utilized a very low concentration of the HCl for the production of LA. The hydrolysate was used as a medium for Kluyveromyces marxianus growth to produce 2-phenylethanol (2-PE). K. marxianus used 74-95% of furfural from hydrolysate as a co-substrate to grow. The proposed model of the integrated biorefinery is an affordable on-site approach of using forest waste into localized solutions to produce LA and 2-PE.

Extraction of tannin, colour and aroma compounds in pinot noir wines as affected by clone selection and whole bunch addition.

Our previous study revealed stem inclusion fermentation reduced anthocyanin, and increased tannin and aroma compounds responsible for green notes. This study further investigated the effect of clone selection and whole bunch fermentation on Pinot noir wine composition, with focus on tannin composition. Three treatments were conducted using two clones (AM10/5 and UCD5) in 2021 and 2022: 100% destemmed (DS), 30% whole bunch (WB30), and 60% whole bunch (WB60). WB60 increased stem and skin derived tannins but reduced seed derived tannin proportion in wines. Clone selection had an impact on tannin composition and an even greater impact on tannin concentration, colour, and aroma compounds. AM10/5 produced wines with higher tannin, polymeric pigments and darker colour. AM10/5 wines also had higher concentration of phenylethyl alcohol, but lower concentrations of 3-isobutyl-2-methoxypyrazine and ethyl esters, indicating more floral but less fruity and green notes.

Biomass-Based, Dual Enzyme-Responsive Nanopesticides: Eco-friendly and Efficient Control of Pine Wood Nematode Disease.

Pine wood nematode (PWN) disease is a globally devastating forest disease caused by infestation with PWN, Bursaphelenchus xylophilus, which mainly occurs through the vector insect Japanese pine sawyer (JPS), Monochamus alternatus. PWN disease is notoriously difficult to manage effectively and is known as the "cancer of pine trees." In this study, dual enzyme-responsive nanopesticides (AVM@EC@Pectin) were prepared using nanocoating avermectin (AVM) after modification with natural polymers. The proposed treatment can respond to the cell wall-degrading enzymes secreted by PWNs and vector insects during pine tree infestation to intelligently release pesticides to cut off the transmission and infestation pathways and realize the integrated control of PWN disease. The LC50 value of AVM@EC@Pectin was 11.19 mg/L for PWN and 26.31 mg/L for JPS. The insecticidal activity of AVM@EC@Pectin was higher than that of the commercial emulsifiable concentrate (AVM-EC), and the photostability, adhesion, and target penetration were improved. The half-life (t1/2) of AVM@EC@Pectin was 133.7 min, which is approximately twice that of AVM-EC (68.2 min). Sprayed and injected applications showed that nanopesticides had superior bidirectional transportation, with five-times higher AVM contents detected in the roots relative to those of AVM-EC when sprayed at the top. The safety experiment showed that the proposed treatment had lower toxicity and higher safety for nontarget organisms in the application environment and human cells. This study presents a green, safe, and effective strategy for the integrated management of PWN disease.

Promotion of levoglucosan production from biomass pyrolysis by hydrogen peroxide pre-oxidation.

Due to the complexity of biomass structures, the conversion of raw biomass into value-added chemicals is challenging and often requires efficient pretreatment of the biomass. In this paper, a simple and green pre-oxidation method, which was conducted under the conditions of 2 wt% H2O2, 80 min, and 150 °C, was reported to significantly increase the production of levoglucosan (LG) from biomass pyrolysis. The result showed that the LG yield significantly increased from 2.3 wt% (without pre-oxidation) to 23.1 wt% when pine wood was employed as a sample for pyrolysis at 400 °C, resulting from the removal of hemicellulose fraction and the in-situ acid catalysis of lignin carboxyl groups formed during the pre-oxidation. When the conditions for pre-oxidation became harsher than the above, the LG yield reduced because the decomposition of cellulose fraction in biomass. The study supplies an effective method for utilization of biomass as chemicals.

UV blocking edible films based on corn starch/moringa gum incorporated with pine cone extract for sustainable food packaging.

Corn starch (CS) is a good alternative to synthetic polymers due to its sustainability; nevertheless, because of its weak tensile strength, the matrix requires another polymer. Therefore, 0.5 % (w/v) moringa gum (MG) was added. The purpose of this study was to assess how pine cone extract (PCE) affected the physiochemical and mechanical properties of corn starch and moringa gum (CS/MG) films and their use as UV-blocking composites. The findings suggest that the PCE improved the elongation at break from 3.27 % to 35.2 % while greatly reducing the tensile strength. The hydrogen bonding between CS/MG and PCE was visible in the FTIR spectra. The XRD graph indicated that the films were amorphous. In comparison to CS/MG films, PCE-incorporated edible films demonstrated significant UV-blocking ability indicating their potential as sustainable packaging material for light-sensitive food products.

A novel seawater hydrothermal-deep eutectic solvent pretreatment enhances the production of fermentable sugars and tailored lignin nanospheres from Pinus massoniana.

Lignocellulose biorefinery depended on effective pretreatment strategies is of great significance for solving the current global crisis of ecosystem and energy security. This study proposes a novel approach combining seawater hydrothermal pretreatment (SHP) and microwave-assisted deep eutectic solvent (MD) pretreatment to achieve an effective fractionation of Pinus massoniana into high value-added products. The results indicated that complex ions (Mg2+, Ca2+, and Cl-) in natural seawater served as Lewis acids and dramatically promoted the depolymerization of mannose and xylan into oligosaccharides with 40.17 % and 75.43 % yields, respectively. Subsequent MD treatment realized a rapid and effective lignin fractionation (~90 %) while retaining cellulose. As a result, the integrated pretreatment yielded ~85 % of enzymatic glucose, indicating an eightfold increase compared with untreated pine. Because of the increased hydrophobicity induced by the formation of acyl groups during MD treatment, uniform lignin nanospheres were successfully recovered from the DES. It exhibited low dispersibility (PDI = 2.23), small molecular weight (1889 g/mol), and excellent oxidation resistance (RSI = 5.94), demonstrating promising applications in functional materials. The mechanism of lignin depolymerization was comprehensively elucidated via FTIR, 2D-HSQC NMR, and GPC analyses. Overall, this study provides a novel and environmentally friendly strategy for lignocellulose biorefinery and lignin valorization.

Wood dimensional stability enhancement by multivalent metal-cation-induced lignocellulosic microfibrils crosslinking.

Wood is a hygroscopic material that responds to the moisture changes of the surrounding environment through swelling and shrinkage, making it dimensionally unstable. Here, we introduce a facile metal-ion-modification (MIM) approach to enhance the dimensional stability of wood. The MIM process involved swelling the wood samples with aqueous metal ion solutions and drying. The high valent metal cations, such as Fe3+, Al3+, and Zr4+, interacted with the hydrophilic groups (e.g., OH, COOH) present in the wood fibers, limiting their access to water and moisture, thereby enhancing the wood's hydrophobicity and dimensional stability. Evaluation of three wood species, southern yellow pine, poplar, and red oak, revealed water contact angles of 120-130° after MIM, indicative of enhanced surface hydrophobicity. Fe3+ treatment decreased southern yellow pine's swelling ratio from 6 % to 4 %. Fe3+-treated wood exhibited tangential anti-swelling efficiencies ranging from 39.83 % to 57.14 % and radial anti-swelling efficiencies from 34.74 % to 48.33 %, varying across wood species. The enhancement of wood dimensional stability can be attributed to the formation of irreversible coordination bonds between metal cations and lignocellulosic microfibrils in the wood cell wall. These bonds prevent the microfibrils from slipping in response to moisture absorption and desorption.

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.

Effectiveness of cork and pine bark powders as biosorbents for potentially toxic elements present in aqueous solution.

Cork oak and pine bark, two of the most prolific byproducts of the European forestry sector, were assessed as biosorbents for eliminating potentially toxic elements (PTEs) from water-based solutions. Our research suggests that bioadsorption stands out as a viable and environmental eco-friendly technology, presenting a sustainable method for the extraction of PTEs from polluted water sources. This study aimed to evaluate and compare the efficiency of cork powder and pine bark powder as biosorbents. Specifically, the adsorption of Fe, Cu, Zn, Cd, Ni, Pb and Sn at equilibrium were studied through batch experiments by varying PTEs concentrations, pH, and ionic strength. Results from adsorption-desorption experiments demonstrate the remarkable capacity of both materials to retain the studied PTE. Cork powder and pine bark powder exhibited the maximum retention capacity for Fe and Cd, while they performed poorly for Pb and Sn, respectively. Nevertheless, pine bark showed a slightly lower retention capacity than cork. Increasing the pH resulted in cork showing the highest adsorption for Zn and the lowest for Sn, while for pine bark, Cd was the most adsorbed, and Sn was the least adsorbed, respectively. The highest adsorption of both materials occurred at pH 3.5-5, depending on the PTE tested. The ionic strength also influenced the adsorption of the various PTEs for both materials, with decreased adsorption as ionic strength increased. The findings suggest that both materials could be effective for capturing and eliminating the examined PTEs, albeit with different efficiencies. Remarkably, pine bark demonstrated superior adsorption capabilities, which were observed to vary based on the specific element and the experimental conditions. These findings contribute to elucidating the bio-adsorption potential of these natural materials, specifically their suitability in mitigating PTEs pollution, and favoring the recycling and revalorization of byproducts that might otherwise be considered residue.

A new integrated strategy for high purity pinolenic acid production from Pinus koraiensis Sieb. et Zucc seed oil and evaluation of its hypolipidemic activity in vivo.

Pinolenic acid is a polyunsaturated fatty acid present only in Pinus koraiensis Sieb. et Zucc seed oil. In order to solve the structural instability problem of polyunsaturated fatty acids, pinolenic acid of P. koraiensis seed oil was effectively isolated and purified by the integrated strategy of ethyl esterification followed by urea inclusion for the first time. Under the optimal conditions after the Box-Benhnken Design experimental, ethyl pinolenate with high purity 94.95% could be obtained, and the average content of PNAEE can still reach 86.18%. Then ethyl pinolenate was characterized by Gas chromatography-mass spectrometry, Fourier transform infrared, and Nuclear magnetic resonance spectra, results showed that ethyl pinolenate was successfully prepared. In addition, the hypolipidemic activity of ethyl pinolenate had been tested in vivo and showed that ethyl pinolenate had obvious hypolipidemic activity. The new strategy for high purity ethyl pinolenate production from P. koraiensis seed oil possesses great potential in food healthy field in the future.

Residues of Deltamethrin in Pine Needles and Pine Nuts of Catalonia (Spain).

In recent years, recurrent droughts have weakened stone pine (Pinus pinea) forests and facilitated the emergence of harmful pests and diseases, including the Leptoglossus occidentalis. The production of stone pine nuts has declined over the past five years. To control this hemipteran pest, a synthetic pyrethroid insecticide called deltamethrin is being tested. However, it is necessary to estimate the residue left by these treatments in forest stands. Therefore, a fast and robust analytical procedure was developed based on QuEChERS clean-up extraction, followed by gas chromatography coupled with an electron capture detector. This optimized method can detect residual concentrations of deltamethrin in pine nuts and pine needles up to 0.1 and 6 µg kg-1, respectively, with a limit of quantification of 0.4 and 20 µg kg-1. Great recoveries (between 84 and 102%) were obtained for both matrices, and no matrix effect was observed. The results showed that two weeks after spraying, the deltamethrin content in the needles of stone pines decreased by up to 75%, and after nine months, its presence was like that of nontreated trees.

Water-extractable polysaccharide fraction PNE-P1 from Pinus koraiensis pine nut: Structural features and immunostimulatory activity.

The polysaccharide fraction PNE-P1 was isolated from hot water extract (PNE) of the defatted meal of pine nuts (Pinus koraiensis) using DEAE-cellulose column chromatography. This fraction had three components of molecular masses 1251, 616, and 303 g/mol consisting mainly of arabinose, xylose, and galacturonic acid at a molar ratio of 2:1.6:1. Structural analysis with FTIR/Raman, methylation and GC-MS, and NMR revealed that PNE-P1 is a cell wall polysaccharide complex including arabinan, heteroxylan, homogalacturonan (HM) and rhamnogalacturonan I (RG-I) parts. Being nontoxic to RAW 264.7 macrophages in the concentration range of 10-200 µg/mL, PNE-P1 promoted proliferation of these cells, significantly induced the secretion of proinflammatory cytokines (TNF-α and IL-6) and chemokines (RANTES and MIP-1α) and enhanced the expression of inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2) and nitric oxide (NO). PNE-P1 also markedly induced macrophage-mediated phagocytosis of apoptotic Jurkat T cells. These results demonstrate that pine nuts Pinus koraiensis contain a complex of water-soluble plant cell wall polysaccharides, which can stimulate innate immunity by potentiating macrophage function.

Anti-Aging Constituents from Pinus morrisonicola Leaves.

Pinus morrisonicola Hayata is a unique plant species found in Taiwan. Previous studies have identified its anti-hypertensive, anti-oxidative, and anti-inflammatory effects. In this study, a bioactivity-guided approach was employed to extract 20 compounds from the ethyl acetate fraction of the ethanol extract of Pinus morrisonicola Hayata's pine needles. The anti-aging effects of these compounds were investigated using HT-1080 cells. The structures of the purified compounds were confirmed through NMR and LC-MS analysis, revealing the presence of nine flavonoids, two lignans, one coumarin, one benzofuran, one phenylic acid, and six diterpenoids. Among them, PML18, PML19, and PML20 were identified as novel diterpene. Compounds 3, 4, and 5 exhibited remarkable inhibitory effects against MMP-2 and showed no significant cell toxicity at 25 µM. Although the purified compounds showed lower activity against Pro MMP-2 and Pro MMP-9 compared to the ethyl acetate fraction, we speculate that this is the result of synergistic effects.

Optimized extraction of polysaccharide from Pinus elliottii: Characterization, antioxidant, and moisture-preserving activities.

The study on the extraction conditions, purification, and biological activity of slash pine (Pinus elliottii.) is important for the development of slash pine resources. The optimal process conditions for the extraction of slash pine polysaccharide (SPP) were determined, resulting in a liquid-solid ratio of 66.94 mL/g, extraction temperature of 83.74 °C and extraction time of 2.56 h by using the response surface methodology, and the yield of SPP was 5.99% under the optimized conditions. Following the purification of SPP, the SPP-2 component was obtained and its physicochemical properties, functional group composition, antioxidant capacity, and moisturizing capacity were determined. Structural analysis suggested that SPP-2 has a molecular weight of 118.407 kDa, and was composed of rhamnose, arabinose, fucose, xylose, mannose, glucose, and galactose in a ratio of 5.98: 14.34: 1: 1.75: 13.50: 3.43: 15.79. The antioxidant activity analysis showed that SPP-2 has good free radical scavenging activity, and it was also found to have in vitro moisturizing activity and low irritation. These results suggest that SPP-2 has the potential for applications in the pharmaceutical, food, and cosmetic industries.

Toxicity evaluation of Pinus radiata D.Don bark wax for potential cosmetic application.

Radiata pine bark is a widely available organic waste, requiring alternative uses due to its environmental impact on soil, fauna, and forest fires. Pine bark waxes could be used as cosmetic substitutes, but their toxicity requires evaluation since pine bark may contain toxic substances or xenobiotics, depending on the extraction process. This study evaluates the toxicity of radiata pine bark waxes obtained through various extraction methods on human skin cells grown in vitro. The assessment includes using XTT to evaluate mitochondrial activity, violet crystal dye to assess cell membrane integrity, and ApoTox-Glo triple assay to measure cytotoxicity, viability, and apoptosis signals. Pine bark waxes extracted via T3 (acid hydrolysis and petroleum ether incubation) and T9 (saturated steam cycle, alkaline hydrolysis, and petroleum ether incubation) exhibit non-toxicity up to 2% concentration, making them a potential substitute for petroleum-based cosmetic materials. Integrating the forestry and cosmetic industries through pine bark wax production under circular economy principles could promote development while replacing petroleum-based materials. Extraction methodology affects pine bark wax toxicity in human skin cells due to the retention of xenobiotic compounds including methyl 4-ketohex-5-enoate; 1-naphthalenol; dioctyl adipate; eicosanebioic acid dimethyl ester; among others. Future research will investigate whether the extraction methodology alters the molecular structure of the bark, affecting the release of toxic compounds in the wax mixture.

Toumeyella parvicornis versus endotherapic abamectin: three techniques, 1 year after.

BACKGROUND: Toumeyella parvicornis is an invasive soft scale insect native to North America that is rapidly spreading in Italy and France, provoking severe infestations on Pinus pinea L. To date, the control of this pest is entrusted to three endotherapic techniques whose short-term efficacy is partially known. No information on long-term efficacy is currently available, although fundamental. This work aims to report on the long-term effect that abamectin-based insecticides, injected with the three different techniques, have on adult female populations. RESULTS: The study was carried out in an infested P. pinea forest in the area of Rome, Italy. Results showed that the tested methods had a similar long-term effect, and only in one case there were differences with the untreated control. Multiresidue analysis reported a zero level of abamectin in plant tissues 14 months apart from injection, except for one treatment where pesticide concentration was just above the limit of quantification. CONCLUSIONS: This study represents the first long-term evaluation about endotherapic control strategy against T. parvicornis. In fact, the pest may quickly bring the death and fall of the stone pines, representing a concerning risk for citizens, however, control actions to manage it are still partially known and deserve more in-depth investigations. © 2023 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.