Raman spectroscopic study on the behavior of boric acid in wood

 Raman spectra of Japanese cedar (Cryptomeria japonica D. Don) treated by vacuum impregnation with aqueous boric acid solutions (8.1 × 10⁻² to 7.29 × 10⁻¹ mol dm⁻³) were recorded using a near-infrared laser as an excitation source. Raman spectroscopic measurements were carried out on treated wood blocks of two sizes: 20(T) × 20(R) × 5(L) mm (A-type) and 15(T) × 15(R) × 50(L) mm (B-type). Our attention was focused on a prominent band (ν ₁) assigned to a symmetrical stretching vibration of the BO₃ group because no Raman band due to boron species was observed except bands of B(OH)₃. We observed a change in ν ₁ band intensity with increasing boric acid concentration in the aqueous solution used to treat the A-type wood blocks and investigated the correlation between the intensity and the peak-top wavenumber. Raman line maps in the longitudinal direction of the treated B-type wood blocks revealed that B(OH)₃ is concentrated near the cut ends. These results suggested that two groups of B(OH)₃ exist in wood in terms of the chemical species in the nearest neighbor sphere. Received: March 11, 2002 / Accepted: June 26, 2002     

木质纤维成分的乙酸分离方法及表征

研究了一种用含有少量硫酸的乙酸溶液分离杨木成分的方法。考察了反应时间、乙酸浓度、液比和催化剂浓度对木材成分分离的影响。对分离出的木材三种成分进行了表征。结果表明,分离杨木成分的较佳条件为:硫酸浓度0.3%,液比6,反应时间3h和乙酸浓度90%。残渣的主要成分是α-纤维素和半纤维素。水不溶沉淀物(乙酰化木质素)的重均分子量分布在341到253之间,分散性系数分布在1.1到1.2这一窄范围内。糖分析结果表明,可溶性成分主要来源于半纤维素,以单糖形式存在。     

Efficacy of wood preservatives formulated from okara with copper and/or boron salts

As a substitute for high-cost copper azole (CuAz) and alkaline copper quaternary (ACQ) wood preservatives, alternative wood preservatives were formulated with okara, which is an organic waste from the production of tofu, and copper chloride and/or borax. Each preservative was used in treatment of wood blocks in a reduced-pressure method to measure its treatability. The treated wood blocks were placed in hot water for 3 days to examine the stability of the preservatives against hot-water leaching. The preservatives successfully penetrated into wood blocks, probably due to the use of ammonium hydroxide as a dissociating agent. However, the stability of okara-based preservatives dropped as the concentration of acid in the solutions used for hydrolysis of okara increased. The treatability and leachability of the preservatives were not affected by hydrolysis temperature but were negatively affected by the addition of borax. Leached wood blocks treated with okara-based preservatives and exposed to decay fungi Gloeophyllum trabeum and Postia placenta over 12 weeks showed good decay resistance. Okara-based wood preservatives can protect wood against fungal attack as effectively as CuAz, and have potential for use as environmentally friendly wood preservatives.     

Termite resistance of beech wood treated with zinc oxide and zinc borate nanocompounds*

The field of wood protection is currently changing due to the restrictions imposed by the Biocidal Products Regulation. The need for development of new wood protection technologies is therefore growing. In this work, the resistance of European beech (Fagus sylvatica L.) wood impregnated with nano-dispersions of zinc oxide (nano-ZnO) and zinc borate (nano-ZnB) against the termite Reticulitermes grassei Clement was investigated. Three different concentrations (0.5%, 1%, 2%) of the nanocompounds were tested. The effects of water leaching were also investigated. A severe effect in terms of termite workers mortality was induced by both dispersions, even at the lowest concentration. In terms of termite feeding, nano-ZnO dispersions appeared to be more efficient than nano-ZnB as they induced significant improvement at concentrations as low as 0.5%. Nano-ZnB was applied at 1% or higher concentrations in order to impart similar changes. Nano-ZnB dispersions were efficient in terms of termite resistance for a concentration at least 1%. Further increasing concentration to 2% resulted in a respective increase of wood efficacy against termites. For both tested nanocompounds, water leaching did not result in any significant increase of termite feeding.     

Ectomycorrhizal colonisation of roots and ash granules in a spruce forest treated with granulated wood ash

Granulated wood ash has been proposed as a slow release fertiliser suitable for forest soils. In this study ectomycorrhizal colonisation of roots and ash granules was studied in a 40-year-old spruce forest treated with 0, 3 or 6 t ha⁻¹ granulated wood ash. We used PCR-RFLP methods for ITS-typing and identification of ectomycorrhizal fungi. In total 20 different ITS-types were recognised on roots in the organic soil horizon. Five of these were identified to species and two to genus. Six species, Tylospora fibrillosa Donk, Cortinarius sp. 3, Piloderma sp. 1, and three unidentified ITS-types (Ve-95-1, Tö-95-3 and Ve-95-9) each occurred on over 5% of the total root tips analysed. Together these comprised 55% of the ectomycorrhizal community on the screened roots.

Ash granules collected from the fertilised plots were normally colonised by fungal mycelia. PCR-RFLP analysis of these mycelia revealed the presence of four ITS-types. Three of these (Piloderma sp. 1, Ha-96-3 and Tor-97-1) were also present on the mycorrhizal roots. Piloderma sp. 1 was the most abundant species colonising roots. A possible role of ectomycorrhizal mycelia in the direct mobilisation of nutrients from ash granules is discussed.     

Durability of isocyanate resin adhesives for wood I: Thermal properties of isocyanate resin cured with water

The thermal properties of isocyanate (IC) resin cured with water were studied using dynamic mechanical analysis (DMA) and Fourier transform infrared spectroscopy. The thermal properties of cured phenol formaldehyde (PF) resin were also studied for comparison purposes. The DMA specimens were prepared using a unique technique. The relation between the mechanical and chemical changes of the resin during DMA was clarified. The cured PF resin had better thermal stability than the IC resin cured with water. The improvement of thermal stability in cured IC resin by heat treatment was considered to be less effective. The effect of the heating rate on the mechanical properties was also investigated. The apparent activation energy in the thermal degradation of cured IC resin was calculated based on the results obtained.Part of this paper was presented at the 47th Annual Meeting of the Japan Wood Research Society, Kochi, April 1997     

Relationship between production of hydroxyl radicals and degradation of wood, crystalline cellulose, and a lignin-related compound or accumulation of oxalic acid in cultures of brown-rot fungi

The degradation of wood, filter paper cellulose, and a lignin-substructure model, was measured in cultures of seven fungi usually regarded as brown-rot fungi. Hydroxyl radical production and the accumulation of oxalic acid in the cultures were also measured. Four of the fungi, Gloeophyllum trabeum, Tyromyces palustris, Laetiporus sulphureus, and Postia placenta, were typical brown-rot fungi, in that they preferentially degraded and eliminated the polysaccharides in wood and produced large amounts of hydroxyl radical. The rates of hydroxyl radical generation in cultures of the four fungi were directly proportional to the degradation rates of wood, cellulose, and the lignin-related compound, and inversely proportional to the amount of oxalic acid in the cultures. Two of the fungi, Daedalea dickinsii and Lentinus lepideus, did not degrade any of the substrates significantly and produced very little hydroxyl radical. Coniophora puteana had the highest rate of cellulose degradation, but did not degrade wood or the lignin model significantly and produced only negligible amounts of hydroxyl radical. These results indicate that brown-rot fungi produce large amounts of hydroxyl radical for the degradation of wood and crystalline cellulose.     

Sorption of Cr(VI) on the wood of Japanese larch treated with concentrated sulfuric acid

A carbonaceous sorbent was prepared from the wood of Japanese larch (Larix leptolepis) by dehydration with concentrated sulfuric acid in a 69% yield. The abilities of the sorbent to remove Cr(VI) from aqueous solutions were investigated. Research parameters included the initial solution pH, temperature, and initial concentration of Cr(VI) in solution. The removal of Cr(VI) was highly solution pH dependent and was mainly governed by physicochemical sorption under weak acidic conditions. The equilibrium data fit well in the Langmuir isotherm model. The Langmuir constants were calculated at different temperatures, and the sorption capacity increased with rising temperature, indicating the endothermic nature of the Cr(VI) sorption onto the sorbent. The desorption experiments suggest that the Cr(VI) sorption is generally irreversible, owing to strong interaction of HCrO ₄ ⁻ with the active sites of the sorbent.     

Characterization of sp<Superscript>2</Superscript>- and sp<Superscript>3</Superscript>-bonded carbon in wood charcoal

Japanese cedar (Cryptomeria japonica) preheated at 700°C was subsequently heated to 1800°C and characterized by electron microscopy, X-ray diffraction, and micro-Raman spectroscopy. The degree of disorder of carbon crystallites and the amount of amorphous phase decreased considerably with an increase in heat treatment temperature to 1400°C, while carbon crystallites clearly developed above this temperature, showing that the microstructure of carbonized wood undergoes drastic changes around 1400°C. Besides showing the bands for sp²-bonded carbon, the Raman spectra showed a shoulder near 1100 cm⁻¹ assigned to sp³-bonded carbon. With an increase of heat treatment temperature, the peak position of the Raman sp³ band shifted to a lower frequency from 1190 to 1120 cm⁻¹, which is due to the transformation of sp³-bonded carbon from an amorphous phase to a nanocrystalline phase. These data showed that the microstructure of carbonized wood from 700° to 1800°C consisted of the combination of sp²- and sp³-bonded carbon, which is probably due to the disordered microstructure of carbonized wood. It is suggested that the sp³-bonded carbon is transformed from an amorphous structure to a nanocrystalline structure with the growth of polyaromatic stacks at temperatures above 1400°C.     

Distribution of stem decay in the beech trees of the Azerbaijan and its impact on the output of commercial wood

To determine the distribution of stem decay in the beech stands of Azerbaijan, we sought to identify the species, number, and height of attachment of fruiting bodies;the extent of decay in tree trunks growing under different conditions;and its influence on the trees’ commercial wood. The research was conducted on three farms representing the most common forest types of the Greater Caucasus within Azerbaijan. Examination of the presence of fruiting bodies in the tree trunk revealed that stem decay is the most common infection in beech (Fagus orientalis) stands, especially in fresh, moist areas, with less infection under dry growing conditions. In this work, the length, diameter, and volume of decay were studied by infecting the trunks of 93 model trees affected with mushrooms in 1–4 m cuttings. Our results showed that as the age of the stand increased, extent, diameter, and volume of decay increased significantly: the extent of decay from 1.47 to 6.43 m;the diameter of the decay from 8.15 to 32.7 cm;and the volume of decay from 2.5 to 13.2%. The relationship between age and the specified indicators is presented graphically. Using data obtained from the same sample of trees, we determined the expected and actual yield of commercial wood by age class. We determined that stem decay in beech stands leads to a decrease in the yield of commercial wood on average from 25.1% in the middle-aged to 14.8% in overmature plantations, respectively, with an estimated yield of 40.8–62.7%. Here we present mathematical models of the output of commercial wood from the infected part of the stands by age classes with the use of average data on the extent of decay in model trees.     

Decay development in living sapwood of coniferous and deciduous trees inoculated with six wood decay fungi

Development of decay and/or discoloration was assessed in the functional sapwood of one coniferous and three deciduous trees after wounding and artificial inoculation with six wood decay fungi. Living stems of mature Douglas fir, beech, oak, and sycamore trees were wounded in spring 2002 and immediately inoculated with brown, white, and soft rot fungi. Extent of discoloration and decay, wood weight loss, and total phenols in the reaction zone (zone of active response at a dynamic interface between living sapwood and wood colonized by decay fungi) were assessed 16 and 28 months after inoculation.     

Distribution of sulphur fractions in lysimeters previously treated with sulphuric acid,NPK fertilizer and a combination of acid and fertilizer

The retention of applied ³⁵S was studied in a lysimeter experiment, in which the lysimeters, consisting of soil columns with intact field and groundlayer vegetation, had previously been treated with either sulphuric acid, NPK or a combination of sulphuric acid and NPK.³⁵S was applied as Na₂³⁵SO₄ to all lysimeters in an amount corresponding to 2 kg S ha^?1, 3 months before the termination of the experiment. Of the applied ³⁵S, 4.7 ± 1.6% (the error term showing the standard error of the mean) was leached from the lysimeters; ³⁵SO₄^2?, was preferentially sorbed in the upper part of the B horizon, >61% being sorbed in the B horizon as a whole. The influence of previous treatments was seen in SO₄^2? content in the B horizon and also in the SO₄^2? concentrations in the leachates from the lysimeters. Sorption of ³⁵SO₄^2? was enhanced by the acid treatment in the A₀ and A₁/A₂ horizons. Ratios between water-extractable SO₄^2? and KCl-extractable SO₄^2? varied from 0.88 in the A₁/A₂ horizon to 0.46 in the lower part of the B horizon, indicating a preferential sorption of less available SO₄^2? fractions in that part of the soil.Significant positive correlations between soil organic carbon and various sulphur fractions, both labelled and unlabelled, indicated the importance of biological S transformations in the A₀ and A₁/A₂ horizons.Positive correlations between KCl-extractable Al and KCl-extractable SO₄^2? were found in the B horizon. Equilibrium calculations suggested that the SO₄^2? activity and Al³⁺ activity in leachates from control and acidified lysimeters were within the stability fields of basaluminite (Al₄(OH)₁₀SO₄), activities in leachates from the latter group of lysimeters, also being close to jurbanite (Al(OH)SO₄).     

Anatomical characterization of decayed wood in standing light red meranti and identification of the fungi isolated from the decayed area

To further our understanding of wood decay in living light red meranti (Shorea smithiana) trees, microscopic characteristics of the cell and cell wall degradations of S. smithiana wood in the presence of the decay fungi, the identity of the causal fungi, and the decay potential and pattern by an isolated fungus were investigated. Cell wall degradations, including cell wall thinning, bore holes formation, rounded pit erosion, and eroded channel opening were clearly observed under light and scanning electron microscopy. In transverse view, many large voids resulting from a coalition of degraded wood tissue appeared in the decayed canker zone. All these observations suggest the well-known simultaneous decay pattern caused by white-rot fungi. By phylogenetic analysis based on the sequences of internal transcribed spacer region of ribosomal DNA, a basidiomycete fungus isolated from the decayed wood was identified as Schizophyllum commune. The degradation caused by this fungus on sound S. smithiana wood in an in situ laboratory decay test was classified as the early stage of simultaneous decay, and showed a similar pattern to that observed in the wood samples naturally decayed.     

Genetic variation in wood color and its correlations with tree growth and wood density of <Emphasis Type="Italic">Calycophyllum spruceanum</Emphasis> at an early age in the Peruvian Amazon

Calycophyllum spruceanum (Benth.) Hook. f. ex K. Shum. is an important timber-tree species in the Peruvian Amazon Basin. Markets currently prefer wood with a uniform, light yellow color, but these preferences may change in the future. As farmers and industry commonly use wood from young trees, it is important to investigate genetic and environmental variation in juvenile-wood properties to assess whether tree improvement programs could make adjustments to changing preferences. A provenance/progeny test was established to evaluate genetic variation in growth and wood properties of young trees, the strength of their genetic control as well as their interrelationships both at the genetic and the phenotypic level in different planting zones. This paper presents analyses of variation in wood color at 39 months, and their correlations with tree growth and wood basic density. CIELab means for lightness ranging from black to white (L), green to red hues (a*) and blue to yellow hues (b*) were 67.63, 5.34 and 22.12, respectively; means for chroma (C) and hue angle (h)* were 22.76 and 76.43, respectively (C and h* were estimated from a* and b*). Significant variation due to provenances and especially due to families within provenances was found in some wood color characteristics, and some color characteristics also differed significantly among planting zones. Genetic correlations indicate that, in general, selection of faster growing trees and/or trees with denser wood would have little effect on wood color and its uniformity. In general, wood color had relatively low heritability (h _i ²): among all trees, h _i ² = 0.31 for L; and variance due to families was not significant for a* and b*. Genetic control of color was highest in the planting zone where trees grew most rapidly: h _i ² = 0.48 and 0.52 for a* and b*, respectively; but variance due to families was not significant for L. Results suggest that selection based on wood color would be more effective in zones with more fertile soils and higher rainfall.      

Acetosolv delignification of marabou (<Emphasis Type="Italic">Dichrostachys cinerea</Emphasis>) wood with and without acid prehydrolysis

The chemical composition of marabou(Dichrostachys cinerea) wood and its treatment with acetic acid were investigated.Two different treatment approaches,direct acetosolv and combined acid prehydrolysis/acetosolv,were evaluated.The effects of acetic acid concentration(50%,70% and 90%) and temperature(normal boiling temperature and 121°C) on yield of solids,solubilization of lignin and hemicelluloses and recovery of cellulose were evaluated for both treatments.High solubilization of marabou components was observed in the direct acetosolv treatment at 121°C,especially at the highest acetic acid concentration,where around 84.8% of lignin and 78% of hemicelluloses were removed.When the material was subjected to acid prehydrolysis prior to acetosolv treatment,lignin solubilization was improved,especially at low acetic acid concentrations.Above 80% of the solubilized lignin was recovered from the liquors in the direct acetosolv treatment,but the recovery was lower in the combined treatment.Cellulose was well preserved in all the treatment schemes.     

Age trends in the genetic parameters of wood density and the relationship with growth rates in hybrid larch (Larix gmelinii var. japonica × L. kaempferi) F1

Age trends in variance components and heritability of overall wood density, earlywood and latewood density, and latewood proportion were investigated in 29-year-old trees of 19 full-sib families of hybrid larch (Larix gmelinii var. japonica × Larix kaempferi) F₁. The age–age correlation and optimum selection age for these traits were also estimated and genetic and phenotypic correlations between wood density and radial growth rate were calculated for each growth ring. Intraring wood density data were obtained using X-ray densitometry. The coefficient of additive genetic variance was stable over all ages, whereas the coefficient of environmental variances gradually decreased with increasing age, resulting in increases in heritability estimates with age for overall density. The latewood proportion had the highest heritability estimates at all ages, ranging from 0.44 to 0.66. Overall density and its various components at 28 years of age showed strong genetic correlations with their respective traits at all younger ages. Optimum selection ages for the wood density traits ranged from 8 to 14 years, at which point maximum gain efficiencies per year were obtained. There were negative correlations between wood density and radial growth rate at early ages, although these relationships tended to be weaker with increasing age. These results suggest that selection at a young age is effective for wood density, but particular care must be taken in selecting trees with an improved radial growth rate because rapid growth will result in a low-density wood product, especially in the early growth period.     

Characterizing the setting of cement when mixed with cork, blue gum, or maritime pine, grown in Portugal II: X-ray diffraction and differential thermal analyzes

It is already known by the scientific and industrial communities that lignocellulosic substrates are, to a certain extent, inhibitors of the hydration reaction of cement. The extent to which and how they influence such reactions is still a matter of debate. Several techniques, such as calorimetry, i.e., the measurement of the heat evolved or obtaining temperature profiles during the hydration, the determination of extractive contents of lignocellulosic substrates and their relation with the characteristics of the hydration curves, or even testing of the mechanical properties of the wood-cement composites, have been used in previous research. This study complements past research using two techniques that have been used in the analysis of cement hydration but are not usually applied to lignocellulose-cement mixes, namely X-ray diffraction (XRD) and differential thermal analysis (DTA). The raw materials for this study were three lignocellulosic materials of Portuguese origin: cork (the bark of Quercus suber L.), blue gum (Eucalyptus globulus Labill.), and maritime pine (Pinus pinaster Ait); and Portland cement. The two techniques allowed tracking of the evolution of the main cement constituents during hydration. It was found that all the lignocellulosic substrates had detrimental effects on cement hydration. The blue gum exhibited the fastest hydration kinetics in the initial stage of reaction, but was then overtaken by cork, which at the end gave the highest hydration conversion amongst the three lignocellulosic substrates. Although pine caused the slowest initial hydration kinetics, with the passage of time its effect approached that of blue gum. At the end of the hydration period, specimens containing either species had similar quantities of hydration reaction products. The DTA and XRD results were consistent and are in good agreement with the temperature profiles and compatibility indexes reported in a previous work.