Determination of lignin,holocellulose, and organic solvent extractives in fresh leaf,litterfall, and organic material on forest floor using near-infrared reflectance spectroscopy

We report the results of a study regarding the near-infrared reflectance spectra of various leaf stages from fresh to senescing, and to decomposing leaf. A broad absorbance feature increased in the region of 1100–1400nm with the advance of the leaf senescence and leaf decomposition. A decrease was seen in the region over 1440nm during the senescence and decomposition process. These differences of spectra showed the changes in constituents of leaf in terms of the degree of the senescence and decomposition. A comparison of multiple linear regression between the near-infrared reflectance spectra and proximate chemical analyses showed that near-infrared reflectance spectroscopy achieved a certain level of useful accuracy. We consider that near-infrared reflectance spectroscopy has the potential to predict the contents of carbon fractions in plant materials, and that this method can replace previous methods due to faster determination of carbon fractions, and its ability to significantly increase the number of samples that can be collected and measured.     

Studies on holocellulose and alpha-cellulose from spruce wood using cryo-ultramicrotomy

Summary Cryo-ultramicrotomy was applied to holocellulose and alpha-cellulose from spruce wood (Picea abies Karst.) for a light and electron microscopical study of the removal of lignin during chlorite delignification and the changes in swelling during delignification and alkali extraction. The swelling state of the fibre walls during each stage of treatment was well preserved, and distinct differences could be observed. Staining with uranyl acetate brought out the fine structure of the fibre walls down to the range of elementary fibrils.Submitted by Deutsche Forschungsgemeinschaft. The assistance of Dr. D. Grosser at the light microscope and of Miss U. Schwarz with the chemical analysis is greatly appreciated.     

Application of near-infrared spectroscopy to wood discrimination

 This study deals with a new nondestructive discriminant analysis by which wood can be classified on the basis of a combination of near-infrared (NIR) spectroscopy and Mahalanobis' generalized distance. Its accuracy and reasonability were examined for wood samples with various moisture contents ranging from oven-dried to a fully saturated free water state. In a discriminant analysis employing second derivative spectra, each wood group was well distinguished. Mahalanobis' generalized distances between softwoods are relatively independent of analytical pattern, whereas the distances between hardwoods are large for easy classification. There may be two reasons for selecting a wavelength: (1) when the chemical component of wood substance relates to the discriminant analysis; and (2) when the difference in moisture content with wood species relates to them. When we correctly construct the database of NIR spectra, confirming the purpose of the analysis, suitable wood discrimination should be possible. Received: January 23, 2002 / Accepted: March 15, 2002 Acknowledgment The authors sincerely thank the Tanabe Southeast Asia Nations Friendship Foundation for financial support. Part of this report was presented at the 51nd Annual Meeting of the Japan Wood Research Society, 2001 Correspondence to:S. Tsuchikawa     

Nondestructive evaluation of drying stress level on wood surface using near-infrared spectroscopy

A nondestructive technique for swiftly measuring the stress level of the surface of wood is proposed, which is important for process control in timber drying. Partial least squares (PLS) regression models for predicting surface-released strain (ε) were developed using NIR spectra obtained from Sugi (Cryptomeria japonica D. Don) samples during drying. The predictive ability of the models was evaluated by PLS analysis and by comparing NIR-predicted ε with laboratory-measured values. The PLS regression model using the NIR spectra pre-processed by MSC and second derivatives with a wavelength range of 2,000–2,220 nm showed good agreement with the measurement (R ² = 0.72). PLS analysis identified the wavelengths around 2,035 nm as making significant contributions to the prediction of ε. Orthogonal signal correction (OSC) was an effective pre-processing technique to reduce the number of factors required for the model using the wavelength range 1,300–2,500 nm. However, the predictive ability of the OSC-corrected model was not improved. Elapsed times to reach the maximum tensile stress (T _max) and the stress reversal point (T _rev) at the wood surface during drying were detected correctly for 75 % of the samples. The results show that NIR spectroscopy has potential to predict the drying stress level of the timber surface and to detect critical periods in drying, such as T _max and T _rev.     

Rapid estimation of kraft pulp yield and lignin in Eucalyptus camaldulensis and Leucaena leucocephala by diffuse reflectance near-infrared spectroscopy (NIRS)

Near-infrared spectroscopy has been used to develop calibration models for the rapid determination of kraft pulp yield (KPY) and lignin in Eucalyptus camaldulensis and Leucaena leucocephala. The correlation coefficient for cross-validation is 0.90 for KPY and 0.95 for lignin prediction, while the root mean square error for cross-validation for KPY and lignin prediction are 1.46 and 0.77, respectively. The method has been validated with 37 samples of E. camaldulensis and 18 samples of L. leucocephala. The root mean square error of prediction for KPY (1.53) is higher than for lignin (0.77). The method is rapid and can be used for screening a large number of samples.     

Mechanical properties of wood materials using near-infrared spectroscopy based on correlation local embedding and partial least-squares

This study used near-infrared(NIR)spectroscopy to predict mechanical properties of wood.NIR spectra were collected in wavelengths 900–1700 nm,and spectra averaged by radial and tangential surface spectra were used to establish a partial least square(PLS)model based on correlation local embedding(CLE).Mongolian oak(Quercus mongolica Fisch.ex Ledeb.)was used to test the eff ectiveness of the model.The cross-validation method was used to verify the robustness of the CLE–PLS model.Ninety samples were tested as the calibration set and forty-fi ve as the validation set.The results show that the prediction coeffi cient of determination(R2 p)is 0.80 for MOR,and 0.78 for MOE.The ratio of performance to deviation is 2.23 for MOR and 2.15 for MOE.     

Electron-dense particles in wood decayed by Ganoderma applanatum

Summary Hemlock sawdust samples degraded by Ganoderma applanatum showed no electron-dense particles either in hyphae or in wood cell walls after aldehyde/OsO₄ fixation. After KMnO₄ fixation at early stage of attack, particles were in hyphae, hyphal sheath and wood cell walls. In samples prepared by a cytochemical technique which localizes cellulase activity at the ultrastructural level, particles were in hyphae, hyphal sheath and wood cell walls. The smallest diameter range of the particles lay between 3 and 7 nm which corresponds to the size of cellulases. Larger diameter particles were peresent which are probably aggregates of the smaller units. We believe that particles present in hyphal cytoplasm and hyphal sheath are cellulolytic enzymes. Whether particles present in attacked wood cell walls are enzymes or degradation products cannot be determined by this study. Nevertheles, the particles reveal the decay pattern in wood by the white-rot fungus G. applanatum.     

Cytochemical localization of cellulases in decayed and nondecayed wood

Summary Enzyme assay showed that the commercial cellulase from Trichoderma reesei degraded several polysaccharide substrates; highest activity was on xylan. Transmission electron micrographs showed that the T. reesei cellulase degraded nondecayed wood extensively; the attack always progressed from the point of contact into the cell wall. Cytochemically prepared wood that had been decayed by Poria placenta showed uniform distribution of electron-dense particles throughout the walls; the same results were observed with added T. reesei cellulase. In wood decayed by Ganoderma applanatum without or with added T. reesei cellulase, the progress of degradation was similar to that in nondecayed wood. Negatively stained T. reesei cellulase had 3–7 nm diameter for the smallest particles; the smallest diamaters of electron-dense particles in wood ranged from 3–7 nm. This suggests that the electron-dense particles probably are cellulase molecules.     

Determination of melamine content in amino resins by near-infrared spectroscopy

Melamine-urea-formaldehyde resin production has increased in the last years due to low formaldehyde emissions and improved moisture resistance when applied on wood-based panels. Melamine is a relatively high-cost raw material in the resin formulation and has a significant effect on wood-based panel properties. It is important for industry to implement efficient quality control methods to determine melamine content in resins. The main objective of this work was to develop chemometric techniques for off-line monitoring of melamine content using near-infrared spectroscopy. The use of interval partial least squares regression allowed identifying the most interesting spectral ranges for analysis (4,400–4,800 and 5,200–5,600 cm^?1) and the best preprocessing methods to use in the determination of this property. When the appropriate spectral range and preprocessing methods are selected, it is possible to obtain calibration models with high correlation coefficients.     

A multi-species comparison of delta13C from whole wood, extractive-free wood and holocellulose

The stable carbon (C) isotope composition (delta13C) of tree rings is a powerful metric for reconstructing past physiological responses to climate variation. However, accurate measurement and interpretation are complicated by diagenesis and the translocation of compounds with distinct isotopic signatures. Isolation and analysis of cellulose minimizes these complications by eliminating variation due to biosynthetic pathways; however, isolation of cellulose is time-consuming and has no clear endpoint. A faster and better-defined analytical method is desirable. Our objectives were to determine if there is a direct relationship between the isotopic compositions of whole wood (WW), whole wood treated with solvents to remove mobile extractives (extractive-free wood; EF) and holocellulose (HC) isolated by extractive removal and subsequent bleaching. We also determined if total C concentration could explain the isotopic composition and variation among these three wood components of each sample. A set of wood samples of diverse phylogeny, anatomy and chemical composition, was examined. The mean offset or difference between HC and EF delta13C was 1.07 +/- 0.09 per thousand and the offset between HC and WW was 1.32 +/- 0.10 per thousand. Equivalence tests (with alpha = 0.05) indicated that the relationship between EF delta13C and HC delta13C had a slope significantly similar to 1 +/- 5.5%, whereas for the WW delta13C: HC delta13C relationship, the slope was significantly similar to 1 +/- 10.08%. A regression model using EF delta13C to predict HC delta13C had a slope of 0.97, which was not significantly different from unity (P = 0.264), whereas the regression for WW had a slope of 0.92 which was significantly different from unity (P = 0.0098). Carbon concentration was correlated with HC:WW offset and cellulose:EF offset (P = 0.0501 and 0.007, respectively), but neither relationship explained much of the variation (r2 = 0.12 and 0.14, respectively). We suggest that HC extraction is unnecessary for most analyses of tree-ring delta13C; a simple solvent extraction is a suitable alternative for many applications.     

Classification of the hot air heat treatment degree of larch wood using a multivariate analysis of near-infrared spectroscopy

In this study, hot air heat treatments of larch (Larix kaempferi) wood specimens were conducted at various temperatures (160–220 °C) and times (1–12 h) to classify the degree of hot air heat treatment using near-infrared (NIR) spectroscopy. NIR reflectance spectra were acquired from specimen cross-sections and were then preprocessed using the standard normal variate. Hierarchical clustering analysis (HCA) using the complete linkage and squared Euclidean distance was conducted to classify the three degrees of heat treatment. A principal component score plot of the NIR spectra was well grouped by the HCA grouping result, and the first component reflected the cluster analysis grouping well. A partial least squares discriminant analysis was performed to develop the discriminant regression model of the three heat treatment degrees. The R² and root mean square error of validation were 0.959 and 0.191, respectively. NIR is considered to be a good candidate to routinely measure the degree of hot air treatment for larch wood.     

Determination of physical and chemical properties and degradation of archeological Japanese cypress wood from the Tohyamago area using near-infrared spectroscopy

Here, we evaluated the application of near-infrared (NIR) spectroscopy for estimating the degradation level of archeological wood samples from the Tohyamago area, the dendrochronological ages of which were also determined. The wood samples were radially cut from three logs obtained from the Tohyamago area. NIR reflectance spectra were measured from the tangential faces of air- and oven-dried wood samples using a Fourier transform NIR spectrophotometer. The second derivative spectra within the wavenumber range of 6400–5200 cm^?1, in which the effect of moisture content in wood is suspected to be insignificant, showed a characteristic behavior with age. By comparing the second derivative spectral change in our wood samples with that in wood degraded by aging, thermal treatment, fungal attack, and lightning reported in the literature, we found that the second derivative spectra of wood samples from one log was similar to those of wood degraded by hygro-thermal treatment, whereas those of wood samples from another log was similar to those of wood degraded by brown-rot fungi. The physical and chemical properties of archeological wood were well predicted using a combination of partial least square regression analysis and NIR spectroscopy.     

Discriminant analysis of wood-based materials using near-infrared spectroscopy

 This study deals with the suitable discriminant techniques of wood-based materials by means of near-infrared spectroscopy (NIRS) and several chemometric analyses. The concept of Mahalanobis' generalized distance, K nearest neighbors (KNN), and soft independent modeling of class analogy (SIMCA) were evaluated to determine the best analytical procedure. The difference in the accuracy of classification with the spectrophotometer, the wavelength range as the explanatory variables, and the light-exposure condition of the sample were examined in detail. It was difficult to apply Mahalanobis' generalized distances to the classification of wood-based materials where NIR spectra varied widely within the sample category. The performance of KNN in the NIR region (800–2500 nm), for which the device used in the laboratory was employed, exhibited a high rate of correct answers of validation (>98%) independent of the light-exposure conditions of the sample. When employing the device used in the field, both KNN and SIMCA revealed correct answers of validation (>88%) at wavelengths of 550–1010 nm. These results suggest the applicability of NIRS to a reasonable classification of used wood at the factory and at job sites. Received: March 13, 2002 / Accepted: July 19, 2002 Acknowledgments The authors thank Gifu Prefectural Human Life Technology Research Institute and Kubota Co. for their support. We also thank Professor Dr. Shiro Kimura and Dr. Hideyuki Yokochi for their constructive discussions about the research.     

Nondestructive estimation of wood chemical composition of sections of radial wood strips by diffuse reflectance near infrared spectroscopy

The use of calibrated near infrared (NIR) spectroscopy for predicting the chemical composition of Pinus taeda L. (loblolly pine) wood samples is investigated. Seventeen P. taeda radial strips, representing seven different sites were selected and NIR spectra were obtained from the radial longitudinal face of each strip. The spectra were obtained in 12.5 mm sections from pre-determined positions that represented juvenile wood (close to pith), transition wood (zone between juvenile and mature wood), and mature wood (close to bark). For these sections, cellulose, hemicellulose, lignin (acid soluble and insoluble), arabinan, galactan, glucan, mannan, and xylan contents were determined by standard analytical chemistry methods. Calibrations were developed for each chemical constituent using the NIR spectra, wood chemistry data and partial least squares (PLS) regression. Relationships were variable with the best results being obtained for cellulose, glucan, xylan, mannan, and lignin. Prediction errors were high and may be a consequence of the diverse origins of the samples in the test set. Further research with a larger number of samples is required to determine if prediction errors can be reduced.     

Characterization of acetylated wood decayed by brown-rot and white-rot fungi

The objective of this study was to characterize the decay of acetylated wood due to brown-rot and white-rot fungi by analysis of chemical composition, X-ray measurements, and¹³C-NMR spectroscopy. The decay by brown-rot fungus became inhibited at a weight percent gain (WPG) due to acetylation of more than 10%, and the mass loss (LOSS) due to decay became zero at a WPG of about 20%. The LOSS due to white-rot fungus decreased slowly with the increase in WPG, reaching zero at a WPG of about 12%. The losses of lignin by brown-rot decay increased initially with the decrease in LOSS owing to the progressing acetylation and then decreased at a LOSS of less than 60%. Polysaccharides were more easily decomposed than lignin during the decay of acetylated wood due to brown-rot fungus. The losses of both components due to white-rot decay decreased as the LOSS decreased with progressing acetylation. The white-rot fungus tended to preferentially decompose the lignin during the decay of acetylated wood. The brown-rot fungus decomposed the cellulose in the crystalline region to a large degree when the LOSS was more than 40%, whereas the white-rot fungus decomposed the crystalline region and the noncrystalline region in acetylated wood to the same degree. The brown-rot fungus preferentially decomposed unsubstituted xylose units in acetylated wood and partly decomposed the mono-substituted xylose units. It was suggested that the mono- and disubstituted cellulose were partly decomposed by brown-rot fungus.This paper was presented at the 46th and 47th annual meetings of the Japan Wood Research Society at Kumamoto and Kochi in April 1996 and April 1997, respectively     

Stiffening phenomena in annual rings of coniferous wood

Summary The structure of coniferous wood is characterized by pronounced differences in density between earlywood and latewood. This could result in disadvantages in wood strength especially against bending. A summary of the observations in this paper leads to the following hypothesis: Coniferous trees meet this danger by forming numerous stiffenings especially in broad annual rings with a high percentage of earlywood. Such stiffenings may be produced by more or less slight fluctuations of density or chemistry within annual rings in radial as well as in tangential directions. The question remains open which anatomical or chemical reasons, upon sandblasting, locally cause radial or radially branched ribs and craters in cross sections, waviness in radial sections and cloudy structures in tangential sections.Paper presented to the IUFRO-Division 5. Conference in Madison, Wisc. 1983.     

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.