Distribution of heartwood extractives in hybrid larches and in their related European and Japanese larch parents: relationship with wood colour parameters

Heartwood is the most valuable part of larch timber when either natural durability or aesthetic aspects of the wood are required. Both properties are directly linked to chemical extractives and particularly to phenols. Based on a broad sample of trees (583) from European and Japanese larch and their interspecific hybrid, we investigated the variability in phenolic content, and particularly of two major compounds, Taxifolin (Tax) and Dihydrokaempferol (DHK), and their link with wood colour. At the individual wood sample level, phenolic contents ranged from 6.0 to 55.9 mg eq. Tax/g DW. Taxifolin was the most abundant constituent (range: 1.3–41.7 mg/g DW) compared with DHK (0.5–13.7 mg eq. Tax/g DW). A high variability among taxa, genotypes and individual trees within taxa and within trees was observed. Japanese larch had the highest amount of total phenols and of Taxifolin and European larch the lowest. For DHK, Japanese larch was the poorest compared with European larch. Hybrid larch had both a high content of Taxifolin and of DHK. Variability for colour parameters was on average weaker than for phenolic content but still large enough to show significant differences between taxa. Correlations between colour parameters and extractives were moderate to weak. At the mean genotype level, a good link (r > 0.51, p < 0.001) was found between a* (red–green axis in CIELAB) and total phenols and Taxifolin contents and between L* (Lightness) and DHK content (r > 0.54). The broad variability observed in this study at different levels for phenolics offers opportunities for breeders to genetically improve the quality of larch heartwood, in particular in relation to decay resistance.     

Phenolic extractives in the trunk of Toxicodendron vernicifluum: chemical characteristics,contents and radial distribution

Phenolic extractives in the trunk of Toxicodendron vernicifluum (syn. Rhus verniciflua) were investigated. Seventeen compounds, gallic acid, protocatechuic acid, (?)-fisetinidol-4β-ol, (?)-fisetinidol-4α-ol, 2-benzyl-2,6,3′,4′-tetrahydroxycoumaran-3-one, (?)-fustin, 1,2,3,6-Tetra-O-galloyl-β-d-glucose, (?)-epifustin, (+)-taxifolin, 1,2,3,4,6-penta-O-galloyl-β-d-glucose, (?)-garbanzol, (?)-fustin-3-O-gallate, (?)-epifustin-3-O-gallate, fisetin, sulfuretin, quercetin and butein, were identified from the heartwood extractives. It was found that only (+)-taxifolin which had 5,7-dihydroxy A-ring possessed a 3R configuration although other flavonoids which had 7-hydroxy A-ring possessed a 3S configuration. Quantitative analysis revealed that the total phenolic contents were much higher in the heartwood (5–7 wt%) than in the sapwood and bark (1–2 wt%), and (?)-fustin was the most abundant extractive in the heartwood (1.4–2.4 wt%). For the radial distribution of phenolic extractives, it was generally found that their content was lowest in the sapwood, increased to the highest in the outer heartwood, and then decreased in the inner heartwood.     

Effects of heartwood extractive fractions of Thuja plicata and Chamaecyparis nootkatensis on wood degradation by termites or fungi

The effect of selective removal of extractives on termite or decay resistance was assessed with matched samples of Thuja plicata Donn ex D. Don and Chamaecyparis nootkatensis (D.Don) Spach heartwood. Samples were extracted using a variety of solvents and then exposed to the subterranean termite Coptotermes formosanus Shiraki in a no-choice feeding test or to the brown-rot fungus Postia placenta (Fr.) M. Larsen & Lombard in a soil bottle test. At the same time, the effect of naturally occurring variations in heartwood extractives on termite or decay resistance was evaluated by testing samples from the inner and outer heartwood of five trees of each species against C. formosanus and P. placenta and analyzing matched wood samples for their extractive content. The results suggest that the methanol-soluble extractives in T. plicata and C. nootkatensis play an important role in heartwood resistance to attack by C. formosanus and P. placenta. Total methanol-soluble extractive content of the heartwood was positively correlated with both termite and decay resistance; however, there was much unexplained variation and levels of individual extractive components were only weakly correlated with one another. Further studies are under way to develop a better understanding of the relationships between individual extractive levels and performance.     

Dielectric spectroscopy of Scots pine

Dielectric properties of Scots pine (42 trees) were compared with density, moisture content (MC), and resin acid content (RAC) (of heartwood). The samples were measured in frozen, green, conditioned and non-conditioned dry moisture states to evaluate the potential of dielectric spectroscopy in determining the wood characteristics at different stages of wood processing. Heartwood and sapwood parts of each sample were measured separately, and through-transmission measurement was conducted in longitudinal and tangential direction at frequencies from 1 MHz to 1 GHz. The MC and density correlated significantly with the dielectric parameters in both measurement directions but especially in longitudinal direction. The RAC of the heartwood correlated significantly with tanδ and ε″/(ε′ ? 1) of the green samples measured in the tangential direction at frequencies above 200 MHz. The correlation at 1 GHz was ?0.56 for green samples, ?0.66 for conditioned samples and ?0.61 for non-conditioned samples (P < 0.001, for all). The study suggests that the extractives also affect radio-frequency dielectric responses, which might be used for extractive analyses of pine heartwood.     

Wood properties of juvenile and mature heartwood in Robinia pseudoacacia L.

The aim of this study is to characterise the properties of juvenile and mature heartwood of black locust (Robinia pseudoacacia L.). Content, composition and the subcellular distribution of heartwood extractives were studied in 14 old-growth trees from forest sites in Germany and Hungary as well as in 16 younger trees of four clone types. Heartwood extractives (methanol and acetone extraction) were analysed by HPLC-chromatography. UV microspectrophotometry was used to topochemically localise the extractives in the cell walls. The natural durability of the juvenile and mature heartwood was analysed according to the European standard EN 350-1. Growth as well as chemical analyses showed that, based on extractives content, the formation of juvenile wood in black locust is restricted to the first 10–20 years of cambial growth. In mature heartwood, high contents of phenolic compounds and flavonoids were present, localised in high concentrations in the cell walls and cell lumen of axial parenchyma and vessels. In juvenile wood, the content of these extractives is significantly lower. Juvenile wood had a correspondingly lower resistance to decay by Coniophora puteana (brown rot fungus) and Coriolus versicolor (white rot fungus) than mature heartwood.     

The effect of brown-rot decay on water adsorption and chemical composition of Scots pine heartwood

? The effect of brown-rot (Coniophora puteana) decay on the water adsorption capacity and concentration of extractives of Scots pine (Pinus sylvestris L.) heartwood were studied by comparing corresponding properties of decayed and undecayed wood samples.

? The samples derived from 39 felled trees having a large between-tree variation in the extractive concentrations, and subsequently in the mass loss in the decay test. The water adsorption capacity, expressed as equilibrium moisture content (EMC), was measured at a high relative humidity (RH ～100%, 21 °C).

? In contrast to the widely held belief, the water adsorption capacity of brow-rotted heartwood appeared to be significantly higher than that of undecayed heartwood.

? The chemical composition of heartwood was changed radically by the fungus: the concentration of stilbenes, resin acids and free fatty acids decreased, while the concentration of soluble sugars increased as a result of decay. In addition, fungal sugars were found in the decayed samples. The concentration of total phenolics increased, which obviously reflected chemical changes in cell wall constituents other than extractives.

? As a conclusion, the information concerning the hygroscopicity of brown-rotted wood might be valuable e.g. when carrying out repairs on buildings damaged by advanced decay.

     

Effects of heat treatment on water-soluble extractives and color changes of merbau heartwood

Merbau is widely used for indoor finishing, outdoor constructions, and furniture. However, it has a disadvantage in some applications in that part of its extractives is water-soluble and can be readily leached out to stain adjacent materials. This study examined whether heat treatment could overcome the above-mentioned problem. Effects of the treatment temperature and time on water-soluble extractives and color changes of merbau heartwood were studied. CIELAB ΔL ^*, Δa ^*,Δb ^*, and ΔE ^* parameters and absorbance spectra were used to evaluate color change and water-soluble extractive solutions, respectively. The results show that heat treatment is an efficient technique to overcome the problem caused by water-soluble extractives of merbau heartwood. Surface color of the treated samples tends to become darker and color of the extractive solution becomes fading to transparent when the treatment temperature and time increased. The absorbance of UV light decreases in intensity and the dominant absorption peak appears around 350 nm when the treatment temperature and time increase. The optimized parameters of treatment temperature and time are 170 °C and 4 h. Modulus of rupture and modulus of elasticity of the heat treated samples under the optimized parameters decrease by 29.6 and 12.9 %, respectively, compared with those of the untreated samples.     

Radial distribution of thujaplicins in old growth and second growth western red cedar (Thuja plicata Donn)

Summary Radial distribution of thujaplicins in western red cedar (Thuja plicata Donn) trees of varying ages was studied in order to assess relative decay resistance of their wood. Samples were extracted with ethanol: benzene (1: 2), and the extractives were analyzed for thujaplicin codtent by a new method utilizing capillary gas chromatography of their methylated derivatives. The combined concentration of thujic acid and methyl thujate was also determined for each sample. Distribution of extractives, thujaplicins and thujic acid, generally increased from pith to outside heartwood, then decreased in the sapwood. Maximum extractive and thujaplicin contents were also related to tree age. This suggests that products made from the wood of younger trees will be less resistant to decay than similar products made from the wood of old trees.     

柚木黑色条纹心材的颜色和化学特性

印尼岛的柚木心材在年轮周围显示了不规则的黑色条纹变化。本研究调查柚木黑色条纹心材的颜色和化学特性。利用色坐标（CIELAB）测定颜色特性（pH值、无机物含量、抽出物含量和特性）。结果表明：黑色条纹的颜色较对照少12-15个亮度单位。因此,黑色条纹的颜色与对照比较,有较多的红色,较少的黄色、色彩和色度。黑色条纹心材部分的pH值灰度含量和钙含量都比对照的高。黑色条纹的心材抽出物含量较对照的高。推测当生物活性物质（杀虫剂）明显增加时,心材显示发黑的过程可能是一种防御机制。     

Variation of extractives content in heartwood and sapwood of Eucalyptus globulus trees

The variation in extractives content in sapwood and heartwood was investigated among 12 trees in each of four commercial plantations of Eucalyptus globulus in central Portugal. The study was carried out at the 15% height level and extractions used successively dichloromethane, ethanol and water. At all sites, heartwood had significantly more extractives than sapwood, on average 3.8 and 2.4%, respectively. Most extractives consisted of ethanol soluble material (on average 52% of total extractives). Among the sites, there was a statistically significant difference in the content of extractives but the most important source of variation was the within-tree variation between sapwood and heartwood. Differences in the content of extractives were also observed among trees. A strong relation between extractives content and heartwood proportion was found. The potential loss of pulp yield and problems associated with accumulation of extractives are directly related to the heartwood proportion in the eucalypt stems. Forest management should take into account heartwood development and selection for minimising heartwood extractives.     

The influence of heartwood on the pulping properties of Acacia melanoxylon wood

The pulping wood quality of Acacia melanoxylon was evaluated in relation to the presence of heartwood. The sapwood and heartwood from 20 trees from four sites in Portugal were evaluated separately at 5% stem height level in terms of chemical composition and kraft pulping aptitude. Heartwood had more extractives than sapwood ranging from 7.4% to 9.5% and from 4.0% to 4.2%, respectively, and with a heartwood-to-sapwood ratio for extractives ranging from 1.9 to 2.3. The major component of heartwood extractives was made up of ethanol-soluble compounds (70% of total extractives). Lignin content was similar in sapwood and heartwood (21.5% and 20.7%, respectively) as well as the sugar composition. Site did not influence the chemical composition. Pulping heartwood differed from sapwood in chemical and optical terms: lower values of pulp yield (53% vs 56% respectively), higher kappa number (11 vs. 7), and lower brightness (28% vs 49%). Acacia melanoxylon wood showed an overall good pulping aptitude, but the presence of heartwood should be taken into account because it decreases the raw-material quality for pulping. Heartwood content should therefore be considered as a quality variable when using A. melanoxylon wood in pulp industries     

Radial patterns of carbon isotopes in the xylem extractives and cellulose of Douglas-fir

Heartwood extractives (nonstructural wood components) are believed to be formed from a combination of compounds present in the adjacent sapwood and materials imported from the phloem. The roles of local compounds and imported material in heartwood formation could have important implications for the wood quality of species having naturally durable wood. Stable isotope composition (delta(13)C) was analyzed to assess radial variation in sapwood extractives, and to estimate the relative importance of adjacent sapwood extractives and imported photosynthate in the formation of heartwood extractives. Cellulose and extractives from the outer 39 annual rings of six Douglas-fir (Pseudotsuga menziesii (Mirb.) Franco) trees were isolated and their delta(13)C composition determined. Although the extractives and the cellulose showed different absolute delta(13)C values, the patterns of change over time (as represented by the annual rings) were similar in most cases. Within an annual ring, carbon isotope ratios of extractives were correlated with the cellulose isotope ratio (R2 = 0.33 in sapwood, R2 = 0.34 in heartwood for aqueous acetone-soluble extractives; R2 = 0.41 in sapwood for hot-water-soluble extractives). These data suggest that some sapwood extractives are formed when the wood ring forms, and remain in place until they are converted to heartwood extractives many years later. Sapwood extractives appear to be important sources of materials for the biosynthesis of heartwood extractives in Douglas-fir.     

柚木石油醚抽提物成分及其对心边材颜色的影响

为探究国产柚木抽提物对心材和边材颜色差异的影响,采用3种沸程的石油醚溶液分别对国产柚木的心材与边材进行抽提处理,利用气相色谱-质谱法分析抽提液的成分和含量,并以差异较大的抽提物溶液处理柚木边材,通过色度学参数表征柚木边材的变色情况,从而验证影响柚木心材和边材颜色的主要抽提物成分。结果表明:在3种沸程的石油醚抽提液中,柚木心材抽提物在成分种类数量和含量上均显著高于边材;不同沸程的石油醚对柚木心、边材中抽提物成分有一定的影响,其中30~60℃(低沸程)和60~90℃(中沸程)石油醚抽提物成分和含量的差异较小,而90~120℃(高沸程)石油醚抽提物的含量较高,约为中、低沸程抽提物含量的2倍;柚木心材抽提液中酚类、醌类、烯烃类物质的含量较多,但这些物质在边材中含量极低;4-叔丁基-2-苯基苯酚、2-甲基蒽醌(柚木醌)、全反式三十碳六烯(角鲨烯)是柚木心、边材抽提物含量差异最明显的物质。经角鲨烯溶液处理后的柚木边材表面颜色变黄,更接近心材颜色,因此,角鲨烯是导致柚木心边材颜色差异的重要抽提物成分。     

Radial variations of vibrational properties of three tropical woods

The radial trends of vibrational properties, represented by the specific dynamic modulus (E′/ρ) and damping coefficient (tan δ), were investigated for three tropical rainforest hardwood species (Simarouba amara, Carapa procera, and Symphonia globulifera) using free-free flexural vibration tests. The microfibril angle (MFA) was estimated using X-ray diffraction. Consistent patterns of radial variations were observed for all studied properties. E′/ρ was found to decrease from pith to bark, which was strongly related to the increasing pith-bark trend of MFA. The variation of tan δ along the radius could be partly explained by MFA and partly by the gradient of extractives due to heartwood formation. The coupling effect of MFA and extractives could be separated through analysis of the log(tan δ) versus log(E′/ρ) diagram. For the species studied, the extractive content putatively associated with heartwood formation generally tends to decrease the wood damping coefficient. However, this weakening effect of extractives was not observed for the inner part of the heartwood, suggesting that the mechanical action of extractives was reduced during their chemical ageing.     

Chemical characterization of Pinus halepensis sapwood and heartwood

ABSTRACT

This paper describes the chemical composition of sapwood (SW) and heartwood (HW) of Pinus halepensis Mill stem. Extractives were first isolated by accelerated solvent extraction and then analysed by gas chromatography-mass spectrometry (GC-MS). The cellulosic polysaccharide content present in the pre-extracted wood samples was determined with acid hydrolysis and GC. The hemicelluloses content was determined with acid methanolysis and GC. Free monomers were additionally analysed by GC. The amount of lignin was determined gravimetrically by the Klason lignin method and the acid-soluble lignin was determined by a UV method. Formic and acetic acids in wood were determined after alkaline hydrolysis and analysed by HP-SEC. It was found that lipophilic and hydrophilic extractives were more abundant in heartwood (1.6% and 2.5%) than in sapwood (1.1% and 1.8%). Celluloses content was higher in sapwood (42.5%) than in heartwood (39.7%), whereas lignin, hemicelluloses and sugar monomer contents were more abundant in heartwood (28.9%, 26.8% and 0.3%) than in sapwood (28.0%, 24.5% and 0.2%). The variation in acetic and formic acids and ash contents between sapwood (0.7%, 0.2% and 0.5%) and heartwood (0.6%, 0.1% and 0.4%) was small. The acetylation degrees were found to be slightly similar in sapwood (0.4) and heartwood (0.3).     

A review of heartwood properties of Tectona grandis trees from fast-growth plantations

Teak (Tectona grandis L. f) has been introduced to reforestation programs in many tropical countries for timber production. The use of teak plantations has changed the supply from large-diameter logs to small-diameter logs featuring a higher proportion of juvenile wood and more knots. Generally, the teak from fast-growth plantation is harvested after 15–30 years of growth, with logs ranging from 12 to 30 cm in diameter. The goal of this work was to review the factors that influence the heartwood formation, variation, quality, color, and durability in teak and to understand which factors should be controlled in fast-growth plantations. Important factors in the heartwood properties of teak trees from fast-growth plantations are as follows: the tree age, longitudinal variation, geographic location, environmental conditions, and silvicultural activities. These factors influence heartwood extractive content, color variation, and durability.     

A mid-IR multivariate analysis study on the gross calorific value in longleaf pine: impact on correlations with lignin and extractive contents

Twenty 70-year-old longleaf pine trees from a spacing, thinning, and pruning study were harvested, from which samples were analyzed for gross calorific value (GCV). A strong correlation was found between GCV and extractive contents for the unextracted wood samples. Although lignin content should impact GCV, no correlation was found between the variation in GCV with lignin content for the extractive-free wood samples. Mid-IR spectroscopy coupled with multivariate analysis provided strong correlations between the mid-IR-predicted and calorimetry-determined values for the unextracted wood samples. Plotting the regression coefficients for GCV and extractive contents showed that the same mid-IR bands were responsible for the strength of these models. Spectral differences were observed between the different extract samples, and relative peak intensities appeared to be dependent upon the extractive contents from the wood samples. Thus, models were also built based on the corresponding wood extractive contents using the actual extracts. These provided good correlations, suggesting a proportional change in extractive compositions coinciding with the total amount of extractives present in the unextracted wood samples.     

Influence of heat treatment on antioxidant properties and colour stability of beech and spruce wood and their extractives

Heat treatment of wood in absence of oxygen and under mild conditions allows for obtaining a material with many interesting properties, such as enhanced dimensional stability and increased biological durability. The aim of this work was to study the influence of a thermal treatment on the antioxidant activity of the extractives of two wood species – beech and spruce – by using the DPPH method and quantifying the formation of phenoxyl radicals using ESR as wood and extractives are exposed to light irradiation. The relationship between the kinetics of formation of free radicals in the extracts of heat-treated wood and the antioxidant properties is discussed. Links with colour modification are discussed.     

The characterization of wetwood in western hemlock

Summary One of the problem areas in the kiln drying of western hemlock lumber is the wide variation in final moisture content of the wood. This variation in moisture content is due to the presence of sinker or wetwood in the heartwood. The features of wetwood which differentiate it from the normal heartwood include higher specific gravity, higher extractives content, and lower permeability. The apparent higher specific gravity can be fully accounted for by the higher extractives content. The principial extractive is α-conidendrin. The wetwood in western hemlock often occurs together with ring shake and under these circumstances the white deposit on the shake surfaces is also α-conidendrin and not matairesinol, the substance usually associated with ring shake in western hemlock. A viewpoint is presented on the origin of wetwood as the endproduct of a reaction by the tree to injury, i.e., ring shake, in which additional extractives are deposited. The extractives result in a greatly lowered permeability, which prevents loss of moisture during heartwood formation and thereby resulting in wetwood. Bacteria usually found in wetwood and responsible for many of the symptoms associated with wetwood are a result of the high moisture content which favors bacterial growth in wood. Presumably, the two primary sources of loss in kiln drying of western hemlock, shake and wetwood, are often intimately associated. The authors appreciate the assistance of Allen H. Doerksen and Louis W. Hamlin of the Forest Research Laboratory. All samples collected for this study were donated by Willamette Industries, Inc., Dallas, Oregon, and a portion of the research was supported by the Forest Research Laboratory, Oregon State University.     

人工林米老排木材化学成分及其在树干高度上的变异

采用我国木材化学成分分析国家标准,对人工林米老排木材化学成分进行了测定和研究分析.结果表明:人工林米老排木材冷水抽提物含量和热水抽提物含量分别为2.67%和3.12%,1%NaOH抽提物含量为17.08%,纤维素含量为47.49%,综纤维素含量为80.42%,木素含量为28.80%,pH值为5.44;木材冷水抽提物和综纤维素含量在树干的不同高度上略有差异,但方差分析检验,差异不显著,热水抽提物、1%NaOH抽提物、纤维素和木素含量在树干的不同高度上差异显著,达到1%显著性水平;由树基往上,热水抽提物含量略呈两端高、中间低的趋势,冷水抽提物、1%NaOH抽提物和木素的含量逐渐降低,综纤维素含量和木材pH值逐渐升高;纤维素含量在树干上的分布规律为中间高、两端低,而且从树干中部往上的降低幅度较大.