Impact of Ceratocystis wilt on eucalyptus tree growth and cellulose pulp yield

In this study, we determined the effects of Ceratocystis fimbriata wilt on volumetric growth and cellulose pulp yield of eucalyptus. Seven‐year‐old healthy and infected trees were separated into different classes of severity, and the individual volume of each whole tree with bark was determined. Volumetric losses were found regardless of the class of disease severity, resulting in reduction in volumetric growth of the trees from 65% to 87%, depending on the infection level. Two approaches were used for evaluating the effects of the disease on cellulose pulp yield: (i) evaluation of wood basic density and chemical composition, contents of ethanol/toluene extractives and Klason lignin, and the alkaline load and screen yield across Kraft pulping to kappa number 18 ± 0.5 for both healthy and discoloured materials; (ii) determination of the alkaline load and yield across Kraft pulping to kappa number 18 ± 0.5 of woods with different levels of discoloration (0, 25, 50, 75 and 100% of discoloured wood). Discoloured wood presented lower basic density, higher ethanol/toluene extractives and Klason lignin, higher alkaline load and lower pulp screened yield at kappa number 18 ± 0.5 compared with the healthy ones. Increasing the fraction of infected wood in chip furnishes resulted in proportionally increased alkaline load demand and decreased screen yields. Adding 50% of infected wood in the chip furnish resulted in 23.8% increase in the alkali load and 13.7% reduction in the pulp screen yield at kappa number 18 ± 0.5. The results obtained have proved that the disease reduces volumetric growth, increases wood consumption and reduces yield in eucalyptus pulp production.     

Distribution of lignin interunit bonds in the differentiating xylem of compression and normal woods of Pinus thunbergii

The lignification process and lignin distribution at different stages of cell wall differentiation in the secondary xylem of compression and normal woods of Pinus thunbergii were investigated by thioacidolysis and subsequent desulfuration. We prepared 50-µm-thick, contiguous tangential sections of pine shoots, cut from the cambial zone through to mature xylem. In compression wood, uncondensed guaiacyl (G) and p-hydroxyphenyl (H) lignins were deposited simultaneously from early to late stages of lignification. The various types of G-G, G-H, and H-H dimers were detected in compression wood, and the ratio of G-H and H-H dimers to total dimers increased as lignification proceeded. In contrast, uncondensed and condensed H units were detected in trace amounts in normal wood. Significant differences in the relative distributions of lignin interunit linkages were not observed between compression and normal woods or between differentiating and mature xylems in either compression or normal woods.Part of this report was presented at the 10th International Symposium on Wood and Pulping Chemistry, Yokohama, June, 1999     

The mechanism of the Mäule colour reaction introduction of methylated syringyl nuclei into softwood lignin

Summary Ezo spruce (Picea jezoensis) wood meal and milled wood lignin were successively reduced with sodium borohydride, methylated with methanol-HCl, oxidized with Fremy's salt, reduced with sodium dithionite, and methylated with diazomethane. Permanganate oxidation of the treated milled wood lignin showed that 0.08–0.1/C9 units of 3,4,5-trimethoxyphenyl groups were introduced into the softwood lignin. Although hardwood meal (beech, Fagus crenata) methylated with diazomethane gave a purple-red colour with the Mäule test, the treated softwood meal gave only a dark brown colour. The aromatic nuclei of lignin were broken down by the Mäule treatment. The consumption of permanganate by treated softwood lignin was higher than by hardwood lignin, which suggests that the guaiacyl nuclei were broken down severely. It is proposed that the purple-red colour obtained from methylated hardwood lignin with the Mäule colour test is generated by reaction of syringyl groups which were liberated by -ether cleavage under the permanganate oxidation conditions.     

Lignin characteristics of bast fiber and core in kenaf, bark and wood of paper mulberry and mulberry

The structural features of bast fiber and core lignins in kenaf (Hibiscus cannabinus), bark and wood lignin of paper mulberry (Broussonetia papyrifera (L.) Vent × Broussonetia kazinoki Sieb.) and mulberry (Morus bombycis) were characterized by alkaline nitrobenzene oxidation, ozonation and methoxyl group determination. Bj?rkman lignins were isolated from bast fiber and core, and bark and wood fractions of the plant samples, and structural characteristics were investigated by ¹H NMR and ¹³C NMR spectroscopies. Kenaf bast fiber gave very high molar ratio of syringaldehyde to vanillin (S/V) of alkaline nitrobenzene oxidation products, while methoxyl content was about the same as that of the core fraction. Results of ¹H NMR and ¹³C NMR of Bj?rkman lignin suggested the presence of aliphatic fragments in lignins isolated from paper mulberry and mulberry bark, but not in kenaf bast fiber. The lower yield of alkaline nitrobenzene oxidation products from bast fiber and bark might be due to the higher content of condensed structure of lignin compared to core fraction. Total yield of erythronic (E) and threonic (T) acids of ozonation products and the molar ratio of erythronic acid to threonic acid (E/T) of the bast fibers and bark were lower than the corresponding core and wood fractions, suggesting that the contents of arylglycerol-β-aryl ether intermonomer linkages in the bast fiber and bark lignin were lower than those of the core and wood fractions. Methoxyl content of bark lignin was lower than the corresponding wood lignin. The methoxyl content of the extract-free kenaf bast fiber was similar to that of the core fraction, while the values of paper mulberry and mulberry bark were about one-half of the corresponding wood fractions, respectively. In bark lignins, the methoxyl contents of Klason lignin and Bj?rkman lignin from bark were lower than those of the extract-free barks. This result suggests that the purity of Klason lignin and Bj?rkman lignins of bark may be rather low.     

Cellular UV-microspectrophotometric investigations on pine wood ( Pinus taeda and Pinus elliottii) delignification during biopulping with Ceriporiopsis subvermispora (Pilát) Gilbn. & Ryv. and alkaline sulfite/anthraquinone tr

Scanning UV-microspectrophotometry was used to investigate the topochemistry of lignin removal from pine wood (Pinus taeda and P. elliottii) chips during biopulping involving wood treatment with Ceriporiopsis subvermispora (Pilát) Gilbn. & Ryv. followed by alkaline sulfite/anthraquinone delignification. A delignification front starting from the lumen towards the compound middle lamella was clearly observed in micrographs recorded from individual cell wall layers of wood samples biotreated for 30 days. Lignin was removed without cell wall erosion. UV-micrographs of wood samples cooked for a short time (90 min pulping) showed that the S2 of biotreated samples are more homogeneously delignified compared to the S2 of the undecayed controls. Similarly, the compound middle lamella and cell corners are also more delignified in biotreated samples. On the other hand, UV-micrographs of samples cooked for a long time (150 min pulping at 170°C) showed that there are no significant differences in the contents of residual lignin retained in the S2 of undecayed and biotreated wood samples.     

Variation in properties of Phlebiopsis gigantea related to biocontrol against infection by Heterobasidion spp. in Norway spruce stumps

The properties of 64 heterokaryotic strains of Phlebiopsis gigantea, isolated mostly from Norway spruce stumps, were tested for asexual spore production, growth rate and competitive ability against Heterobasidion spp. on agar medium, and for growth rate in spruce wood. Eighteen isolates were also tested for the efficacy of control against Heterobasidion spp. in stem pieces of spruce. The results revealed high variation in traits between different P. gigantea isolates. The efficacy of control against Heterobasidion spp. and the growth rate in spruce wood were closely related to each other (r = 0.727, p < 0.001). These preliminary tests indicate that the growth rate of a P. gigantea strain in spruce wood is the most important characteristic determining its efficiency in controlling the infection and spread of Heterobasidion spp. in spruce stumps.     

Rapid assessment of physical properties and chemical composition of thermally modified wood by mid-infrared spectroscopy

Characterisation, quality assessment and property prediction are several of the major industrial challenges for widespread acceptance of thermally modified wood (TMW). This study shows the potential of the multivariate analysis of mid-infrared (MIR) spectral data for the prediction of impact strength, five mechanical parameters in bending, moisture content, weight loss, density and chemical composition of small specimens of thermally modified beech, Norway spruce and Scots pine woods. Anti-swelling efficiency was also studied using DRIFT spectroscopy for spruce wood only. Calibrations were successfully accomplished by partial least-squares regression, with R _Y ² and Q _CUM² values >0.96 for 64 out of 67 models. Predictions were also successful, with relative prediction values >0 and RMSEP:SD ratios <1 in most cases. Changes in the MIR spectra of TMW show that bands arising from the lignin environment and new bands appearing due to the degradation of carbohydrates, giving negative loadings, were related to strength loss, while those bands arising from the polysaccharides were associated with property retention. It is concluded that this approach is a powerful tool to characterise a number of properties of TMW with a single after-treatment measurement.     

Heterogeneity in formation of lignin

Summary The formation of lignin in the cell wall of compression wood of Pinus thunbergii was examined by selective radio-labeling of specific structural units in the lignin and visualization of the label in the different morphological regions by microautoradiography. Deposition of lignin in the tracheid cell wall of compression wood occurred in the order: p-hydroxyphenyl, guaiacyl and syringyl lignin, which is the same order as observed in normal wood. However, the period of lignification in the compression wood was quite different from those of normal and opposite woods. The p-hydroxyphenyl units were deposited mainly in the early stage of cell wall formation in compound middle lamella in normal and opposite woods, while in compression wood, they were formed in both the compound middle lamella and the secondary wall. The most intensive lignification was observed during the formation of the S₂ layer, proceeding from the outer to inner S₂ layers for a long period in compression wood. In the normal or opposite woods, in contrast, the lignification became active after formation of S₃ had begun, then proceeded uniformly in the secondary wall and ended after a short period.A part of this report was originally presented at the 1989 International Symposium on Wood and Pulping Chemistry at Raleigh, NC, U.S.A.     

Lignin characterization of triploid clones of Populus tomentosa Carr.

In order to understand the structural characteristics of lignin in triploid clones of Populus tomentosa and its changes in the processes of pulping and bleaching, milled wood lignin (MWL), lignin carbohydrate complex (LCC) and the residual lignin from kraft pulp (KP) and sulfite pulp (SP) were isolated and analyzed by Fourier transform infrared (FTIR) spectrum and ¹³C nuclear magnetic resonance (NMR). The most diagnostic peaks were assigned and the differences were discussed. The spectral patterns reveal that triploid P. tomentosa shows the specific features of hardwood from temperate areas, but in the spectrum of FTIR, the strength ratio of A 1270 cm⁻¹ to A1226 cm⁻¹ is 0.88, higher than the average of hardwood from temperate areas, which will make the lignin delignification more difficult during pulping and bleaching. The LCC from triploid P. tomentosa is mainly composed of xyloglucan and glucuronic acid, and other glucides have much lower ratio. In LCC FTIR, there are three peaks at 1 427, 1 329 and 1 046 cm⁻¹, indicating that both semi-cellulose and cellulose could exist in LCC, and that there might be relationships between cellulose and lignin. Compared with the residual lignin from KP and SP, the condensed structure in KP is more than that in SP.     

13C CP/MAS nuclear magnetic resonance study of the peroxide bleaching of ultra high yield chemimechanical pulp produced from sound and spruce budworm killed balsam fir

Summary The chemimechanical pulping (CMP) of sound balsam fir and the subsequent peroxide bleaching of the CMP pulp were investigated using solid state ¹³C CP/MAS NMR. A parallel study was made of a CMP pulp produced from spruce budworm killed balsam fir. Changes in the lignin and hemicellulose components were readily evident. The residual lignin and carbohydrate macromolecules in dead balsam fir CMP appeared to be the same as those in the sound wood CMP, before and after bleaching.We are indebted to Mr. S. S. Johal and Dr. J. V. Hatton of PAPRICAN, Vancouver, B.C., for generously supplying the wood and pulp samples. We also appreciate the assistance of Dr. N. R. Jagannathan with the ¹³C CP/MAS NMR measurements. Financial support from NSERC, in the form of a Postdoctoral Fellowship (JMW) and operating grants (FGH), is gratefully acknowledged     

Activities of some enzymes of lignin formation in reaction wood of Thuja orientalis and Metasequoia glyptostroboides 2

Summary To elucidate biochemical features leading to p-hydroxyphenyl-rich lignin in gymnosperm reaction wood the activities of the following five enzymes involved in the biosynthesis of p-hydroxyphenyl lignin were compared in reaction and opposite woods: phenylalanine ammonialyase (EC 4.3.1.5), cinnamate 4-hydroxylase (EC 1.14.13.11), p-hydroxycinnamate: CoA ligase (EC 6.2.1.12), cinnamyl alcohol dehydrogenase (EC 1.1.1.-) and peroxidase (EC 1.11.1.7). The enzyme activities in the reaction woods of Thuja orientalis and Metasequoia glyptostroboides were remarkably higher than those in the opposite woods, reflecting the higher contents of p-hydroxyphenyl lignin in reaction wood.This work was partly supported by the Grant-in-Aid for Scientific Research (548047) from the Ministry of Education, Science and Culture of Japan. We thank the Ministry of Education for the support     

Thioacidolytic analysis of residual lignins isolated from the chemical pulps of spruce (Picea abies) and beech (Fagus sylvatica) wood

Eight different residual lignins isolated from unbleached chemical pulps [sulfite, kraft, alkaline sulfite-anthraquinone-methanol (ASAM), soda/AQ/MeOH] of spruce and beech were characterized using gel permeation chromatography (GPC), thioacidolysis, and desulfurization to determine average molecular weight, amounts of uncondensed β-O-4 linkages, and dimeric linkage patterns, respectively. The total amounts of G-CHSEt-CHSEt-CH₂SEt and S-CHSEt-CHSEt-CH₂SEt were markedly reduced in residual lignins to 40% to 80% of the values for the corresponding milled wood lignins (MWLs). The number of dimeric units determined by thioacidolysis and desulfurization of the residual lignins was decreased by onehalf to one-fifth compared to the MWLs. Among the diverse types of dimeric units, reduction of β-1 and β-5 units was significant in most of the residual lignins, with the exception of beech ASAM residual lignin. Compared to beech MWL, 40% more C6–C3 main monomers were detected, whereas the relative composition of the dimeric units in the beech residual lignin was very similar to that in the beech MWL. The average molecular weights of residual lignins were less than those of the MWLs. However, the average molecular weights of the spruce kraft and soda residual lignins were determined to be higher than those of the corresponding MWLs.     

Growth of Phlebiopsis gigantea in wood of seven conifer species

Heterobasidion parviporum and Heterobasidion annosum are widely distributed root‐rot fungi that infect conifers throughout Europe. Infection of conifer stumps by spores of these pathogens can be controlled by treating fresh stumps with a competing non‐pathogenic fungus, Phlebiopsis gigantea. In this study, growth of three Latvian strains of P. gigantea and the biological control agent ‘Rotstop’ strain was evaluated in stem pieces of Norway spruce, Scots pine, lodgepole pine, Douglas‐fir, Weymouth pine, Siberian larch and Sitka spruce. The growth rates of one H. parviporum and one H. annosum isolate were also measured in the same stem pieces. The growth rate of P. gigantea varied greatly in wood of different conifer species. It was higher in the three pine species, lower in Norway spruce and lowest in Sitka spruce and Siberian larch, and in Douglas‐fir, this fungus did not grow. The largest area of wood occupied by P. gigantea was in lodgepole pine. Growth of Latvian isolates of P. gigantea in the wood of Pinus and Picea species was comparable to that of the Rotstop isolate. Consequently, stump treatment with local P. gigantea isolates should be recommended. However, our results suggest that Douglas‐fir stump treatment against Heterobasidion by P. gigantea may be ineffective and other stump treatment methods should be considered.     

Characterization of the lignin-derived products from wood as treated in supercritical water

Sugi (Cryptomeria japonica D. Don) and buna (Fugus crenata Blume) woods were treated with supercritical water (>374°C, >22.1 MPa) and fractionated into a water-soluble portion and a water-insoluble residue. The latter was washed with methanol to be fractionated further into a methanol-soluble portion and a methanol-insoluble residue. Whereas the carbohydrate-derived products were in the water-soluble portion, most of the lignin-derived products were found in the methanol-soluble portion and methanol-insoluble residue. The lignin-derived products in the methanol-soluble portion were shown to have more phenolic hydroxyl groups than lignin in original wood. The alkaline nitrobenzene oxidation analyses, however, exhibited much less oxidation product in the methanol-soluble portion and methanol-insoluble residue. These lines of evidence suggest that the ether linkages of lignin are preferentially cleaved during supercritical water treatment. To simulate the reaction of lignin, a study with lignin model compounds was performed;-O-4-type lignin model compounds were found to be cleaved, whereas biphenyl-type compounds were highly stable during supercritical water treatment. These results clearly indicated that the lignin-derived products, mainly consisting of condensed-type linkages of lignin due to the preferential degradation of the ether linkages of lignin, occurred during supercritical water treatment.This study was presented in part at the 45th lignin symposium, Ehime, Japan, October, 2000; and the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1988     

Determination of the distribution and reaction of polysaccharides in wood cell walls by the isotope tracer technique VII: Double radiolabeling of xylan and pectin in magnolia (Magnolia kobus DC) and comparison of their behaviors during kraft pulping by radiotracer technique

myo-Inositol-[2-³H] and d-glucuronic acid-[6-¹⁴C] were administered simultaneously to a growing stem of magnolia (Magnolia kobus DC) to label xylan and pectin, respectively, in the cell wall. Determination of the radioactivity of nitrobenzene oxidation products and sulfuric acid hydrolysates of the newly formed xylem indicated that xylan and pectin were labeled with ³H and ¹⁴C, respectively. The doubly labeled wood tissue was treated to kraft pulping, and the radioactivity of the pulping black liquor and treated wood tissue were determined at various stages of the pulping to compare the dissolving behavior between pectin and xylan during the pulping. The results showed that pectin was not dissolved as easily as xylan and was not redeposited on pulp fiber at the late stage of the pulping.Part of this report was presented at the 40th Lignin Symposium at Tsukuba, October 1995     

The influence of acetosolv pulping conditions on the enzymatic hydrolysis of Eucalyptus pulps

Eucalyptus globulus wood was subjected first to HCl–catalysed delignification with 70% acetic acid under conditions realizing an incomplete 3 × 3 × 3 factorial design (HCl concentration 0, 0.025 or 0.05%; temperature 120, 140 or 160 °C; reaction time 1, 2.5 or 4 h), and then to enzymatic hydrolysis. The hydrolysis kinetics conformed to both Ghose's empirical model and a biexponential equation. The biexponential fit implies the presence of both readily and reluctantly hydrolysed cellulose fractions, and the fitted coefficients show hydrolysis yield to depend largely on the digestibility of the latter. Multiple regression of performance variables on pulping conditions showed that neither the rate nor the extent of hydrolysis is greatest for pulps with minimum lignin or xylose contents; we attribute this circumstance to the condensation and precipitation of lignin under severe pulping conditions, which protects the cellulose of the pulp from enzymatic attack. Received 20 June 1998     

Mineralization of the methoxyl carbon of isolated lignin by brown-rot fungi under solid substrate conditions

Summary The objectives of this work were to begin developing an experimental system for studying the demethylation of lignin by brown-rot fungi and to examine the influence of selected culture parameters. As substrate for demethylation, we used partially 3-O-demethylated lignin that had been isolated earlier from brown-rotted spruce wood; we remethylated with¹⁴CH₃I, giving a lignin with both [3-¹⁴C]methoxyl and [4-¹⁴C]methoxyl groups. This lignin was added to pine wood flakes, which were incubated with selected brown-rot fungi, and the evolved¹⁴CO₂ was trapped and measured. Of eight fungi examined,Gloeophyllum trabeum andWolfiporia cocos gave the highest rates of mineralization of the¹⁴C-methoxyl carbons. With the former but not the latter fungus, methoxyl mineralization was over twice as fast in an atmosphere of O₂ than in air. Amending the cultures with ammonium tartrate suppressed mineralization to some extent. Further studies withG. trabeum showed that glutamate lowered the rate of mineralization and that glucose and glycerol sharply suppressed it. Addition of Fe²⁺ and Mn²⁺ slightly increased the rate of mineralization. Our results suggest that in unsupplemented cultures the rate-limiting step in methoxyl mineralization is the initial demethylation. Thus the two likely initial C₁ products, methanol and formaldehyde (as¹⁴C compounds), were mineralized much more rapidly than the methoxyl carbon of the lignin (as was formic acid), and no low molecular weight labeled intermediates from the [¹⁴C]-methoxyl lignin accumulated in the cultures. Our results also provide evidence that the spruce lignin was partially polymerized byG. trabeum. Mineralization of the methoxyl carbon of a synthetic [3-¹⁴C]-methoxyl lignin was slower than that of the spruce lignin, suggesting either that the synthetic lignin was more recalcitrant or that the [4-¹⁴C]methoxyl group in the [3,4-¹⁴C]-methoxyl spruce lignin was attacked more readily.We thank Karen L. Martinson and Michael D. Mozuch for excellent technical help, and Tor P. Schultz for valuable suggestions. This research was supported in part by the U.S. Department of Agriculture, Wood Utilization Research Program, Project No. 350-0612, to Mississippi State University.The Forest Products Laboratory is maintained in cooperation with the University of Wisconsin. This article was written and prepared by U.S. Government employees on official time, and it is therefore in the public domain and not subject to copyright in the United States.     

Effects of UV light irradiation on colour stability of thermally modified, copper ethanolamine treated and non-modified wood: EPR and DRIFT spectroscopic studies

A series of experiments were carried out to investigate the colour stability of chemically treated and thermally modified wood compared to non-modified wood during long term artificial UV light irradiation. One set of wood samples was vacuum-pressure impregnated with alkaline (pH 9.8) copper (II) ethanolamine aqueous solution, while another set of samples from the same wood block was thermally modified at 210°C and −0.90 bar for 2 h. The treated and modified wood samples along with the non-modified ones were exposed to artificial UV light with the wave length in the region of UVA (315–400 nm) and UVB (280–315 nm) intermittently for 500 h. Colour measurements were carried out throughout the irradiation period at an interval of 100 h according to CIEL*a*b* system, where the results are presented in terms of ΔE, ΔL*, Δa* and Δb* values. Better photo-stability in terms of colour changes was recorded for both treated and modified woods compared to the non-modified one. By means of EPR and DRIFT spectroscopic study it was shown that some degree of colour stability of treated and modified woods, achieved during artificial UV light irradiation, resulted from lignin modifications and monomers of phenolic compounds.     

Impact of thermal modification on color and chemical changes of spruce and oak wood

Thermal modification of wood is an environment-friendly alternative method for improving several properties of wood without the use of chemicals. This paper deals with the examination of color and chemical changes in spruce (Picea abies L.) and oak wood (Quercus robur F.) that occur due to thermal treatment. The thermal modification was performed at 160, 180, and 210 °C according to thermowood process. The color changes were measured by the spectrophotometer and described in the L*a*b* color system. Chemical changes were examined by wet chemistry methods, infrared spectroscopy and liquid chromatography. During the experiment, oak samples showed smaller color changes than spruce samples at all temperature values. During thermal modification, the content of cellulose, lignin, and extractives increases; however, the hemicellulose content drops by 58.85% (oak) and by 37.40% (spruce). In addition to deacetylation, new carbonyl and carboxyl groups are formed as a result of oxidation. Bonds in lignin (mainly β-O-4) and methoxyl groups are cleaved, and lignin is condensed at higher temperatures.     

Moisture diffusion coefficient of reaction woods: compression wood of Picea abies L. and tension wood of Fagus sylvatica L.

The moisture diffusion coefficient of compression wood in spruce (P. abies) and tension wood in beech (F. sylvatica) was examined. The results indicated that the diffusion coefficient measured under steady-state condition (cup method) could well characterize the drying kinetics of the reaction woods. The compression wood offered more resistance to the moisture diffusivity when compared with the corresponding normal wood. The thick cell wall rich in lignin explains the small mass diffusivity in compression wood. In contrast, the mass diffusivity in beech is almost always higher in tension wood than in normal wood, in spite of similar density values. The high moisture diffusion in tension wood can be explained by the ease of bound water diffusion in the gelatinous layers (G-layers).