Termite resistance of DMDHEU-treated wood

Four field trials were conducted with wood modified with dimethyloldihydroxy-ethyleneurea (DMDHEU) in contact with subterranean termites. Trials 1 to 3 were conducted with Coptotermes acinaciformis (Froggatt); 1 and 2 in south-east Queensland, and 3 in northern Queensland, Australia. Trial 4 was conducted in northern Queensland with Mastotermes darwiniensis (Froggatt). Four timber species (Scots pine, beech, Slash pine and Spotted gum) and two levels (1.3 M and 2.3 M) of DMDHEU were used. The tests were validated. DMDHEU successfully prevented damage by C. acinaciformis in south-east Queensland, but not in northern Queensland. It also did not protect the wood against M. darwiniensis. Except for beech in trial 4, DMDHEU led to reduced mass losses caused by termite attack compared to the unmodified feeder stakes. Slash pine (in trials 1 and 3) and Spotted gum (in trial 1) presented low mass losses. Modification of Scots pine was more effective against termite damage than the modification of beech.     

Efficacy of didecyldimethylammonium chloride against subterranean termites (Isoptera) in Australia

A laboratory bioassay was conducted on the ability of didecyldimethylammonium chloride (DDAC) to protectPinus radiata D. Don wood specimens from attack by two of Australia's most economically important species of subterranean termite,Mastotermes darwiniensis Froggatt (Mastotermitidae) andCoptotermes acinaciformis (Froggatt) (Rhinotermitidae). Sapwood specimens ofP. radiata, treated to achieve nominal retentions of 0.5, 1.0, 2.0, 4.0 and 6.0 kg/m³ of active ingredient, were bioassayed against each of these termite species for four and eight weeks, respectively. Mean percentage mass loss data showed that between 2.0 and 4.0 kg/m³ of DDAC was necessary to protect specimens from significant attack by both species of termite. The usefulness of DDAC as a termiticide for timber, particularly in the above-ground situation, is discussed.With one table and one figure     

Resistance of Scots pine (Pinus sylvestris L.) wood modified with functionalized commercial silicone emulsions against subterranean termites

Scots pine (Pinus sylvestris L.) sapwood was treated with quat-silicone micro-emulsion (<40?nm), amino-silicone macro-emulsion (110?nm), alkyl-modified silicone macro-emulsion (740?nm) and solutions of inorganic water glass. Three treatment concentrations of 5, 15 and 30% (w/w) were used for the impregnation of the test specimens. Termite resistance was assessed following a 16-week field trial conducted in northern Queensland, Australia. Two different field sites were chosen for exposure to feeding by Coptotermes acinaciformis (Froggatt) and Mastotermes darwiniensis (Froggatt). Following exposure, the test and feeder specimens were inspected and assessed for termite damage using a visual rating system (from 10 sound to 0 completely destroyed) and individual mass losses. The specimens treated with quat- and amino-silicone emulsions resisted damage by both termite species, even at less than 15% weight percent gains (WPGs). Alkyl-modified silicone macro-emulsion and water glass treatment induced somewhat less resistance to termite damage, but imparted protection at higher WPGs.     

Structural changes in lignin of tropical woods during digestion by termite, <Emphasis Type="Italic">Cryptotermes brevis</Emphasis>

Wood samples of apitong (Dipterocarpus grandiflorua) and ilang-ilang (Ilang-Ilang C. dadloyi) and feces of termites [Cryptotermes brevis (Walker)] fed on these woods were collected from University of the Philippines, Los Baňos. Lignin of each sample was isolated by Björkman’s procedure. There was no significant difference in ¹H nuclear magnetic resonance (NMR) spectra or in the methoxyl content between Björkman lignins from original woods and termite feces. Differences were detected in the contents of aliphatic and unconjugated phenolic hydroxyl groups, suggesting minor structural changes of lignin during digestion by termites. In addition, the ratio of syringyl to guaiacyl nuclei of Björkman lignin from termite feces determined by ¹H NMR spectra was higher than those from the original woods. The molar ratio of syringyl to guaiacyl nuclei of termite feces was higher than those from the original woods as determined by alkaline nitrobenzene oxidation. These results suggest that the structural changes of lignin in the termite gut are due to the insignificant formation of C-C linkages in guaiacyl nuclei. It was concluded that there were minor changes in the structural features of lignin under mostly anaerobic conditions, in contrast to the significant changes that occur through biological modification under aerobic conditions.     

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     

Quantitative analysis of lignin using an UV microscopic image analyser. variation within one growth increment

Summary The variation of the lignin content within one growth increment of Abies sachalinensis was investigated with the aid of an ultraviolet microscopic image analyser. The lignin content was determined continuously in each cell within a growth increment. The direct photometric scanning method of UV image is believed to give accurate results for determination of the lignin content of the cell wall, since it contains fewer assumptions. The lignin content of the earlywood was higher than that of latewood in adult wood as same as the others. It was high, however, in the terminal zone of the latewood. The trends of the juvenile wood were quite different from those of the adult wood. The lignin content increased from earlywood to latewood.This paper was presented at the Wood Anatomy Congress of IAWA, Aug. 27, 1979, Amsterdam. The authors wish to express their gratitude to Prof. Dr. J. Bauch for helpful advice     

Lignin biochemistry: Biosynthesis and biodegradation

Summary Lignin biosynthesis via shikimate-cinnamate pathways in plants, and the biosynthetic differences of guaiacyl-and syringyl lignins between gymnosperms and angiosperms have been elucidated by tracer experiments using ¹⁴C labeled precursors and the following enzyme reactions. The formation of guaiacyl lignin but not syringyl lignin in gymnosperms was attributed to the following factors; absence of ferulate-5-hydroxylase, poor affinity of O-methyltransferase toward 5-hydroxyferulate, and lack of activation and/or reduction of sinapatc. A mechanism of lignin-carbohydrate complexes formation in wood cell walls was elucidated based on the reaction of the quinone methide of guaiacylglycerol--guaiacyl ether with sugars, and the analysis of DHP-polysaccharide complexes.The main cleavage mechanisms of side chains and aromatic rings of lignin model compounds and synthetic lignin (DHP) by white-rot fungi and their enzymes, lignin peroxidase and laccase have been elucidated using ²H, ¹³C and ¹⁸O-labeled lignin substructure dimcrs with ¹⁸O₂ and H₂ ¹⁸O. Side chains and aromatic rings of these substrates were cleaved via aryl cation radical and phenoxy radical intermediates, in reaction mediated only by lignin peroxidase/H₂O₂ and laccase/O₂.Academy Lecture presented at the Cellucon 88 in Japan, International Symposium on New Functionalisation Developments in Cellulosics and Wood, held in Kyoto, Japan, November 28 to December 1, 1988This paper is a conclusion of our investigations on the biosynthesis and microbial degradation of lignin for 30 years in the Research Section of Lignin Chemistry, Wood Research Institute, Kyoto University. The author is greatly indebted to Drs. M. Shimada, F. Nakatsubo, T. Yamasaki, H. Ohashi, M. Tanahashi, Y. Nakamura, H. Kuroda, H. Kutsuki, T. Katayama, Y. Kamaya, T. Umezawa and Messrs. H. Fushiki, M. Ohta, A. Noguchi, H. Namba, T. Habe, S. Kawai, S. Yokota, and T. Hattori for their kind cooperation in these investigations. These invstigations were supported in part by Grant-in-Aid Nos. 548047, 57480058, 59760124, 60760130, 60440015, 61760142, 61560193, 62790250 for Scientific Research, and 1980 Grant-in-Aid for Environmental Science (R-33-8), No. 403064 from the Ministry of Education, Science and Culture of Japan, and a 1980 Weyerhaeuser grant     

Structural changes of residual lignin in softwood kraft pulp treated with manganese peroxidase

Structural changes of residual lignin in unbleached softwood kraft pulp (SWKP) during manganese peroxidase (MnP) treatment were investigated to obtain some understanding of the biobleaching action of SWKP with MnP treatment. Alkaline-extracted lignin from darkened SWKP by MnP showed more intense color and contained moreo-quinone than that from control SWKP. However, no difference in the conjugated-carbonyl was observed between the lignins from MnP-treated and control SWKP. The nitrobenzene oxidation analysis revealed that oxidative condensation of non-condensed lignin in SWKP occurs during an early stage of MnP treatment. These observations were supported by the model experiment in which the lignin prepared from control SWKP was subjected to MnP treatments three times, and the changes of color and functional groups in the lignin were determined after each treatment. These results suggested that an increase ino-quinone and the condensation reaction of non-condensed lignin in SWKP are responsible for the characteristic darkening of SWKP during MnP treatment. It was also ascertained that darkened lignin was degraded and brightened by repeated MnP treatments.     

Ozonation of a lignin-carbohydrate complex model compound of the benzyl ether type

Evidence for the presence of lignin-carbohydrate bonds of the benzylic ether type in wood and pulps may be obtained by use of ozonation treatment to selectively degrade the lignin. It was found that the benzyl ether bond in 3-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxy-phenoxy)-3-(methyl--d-glucopyranosid-6-O-yl)-1-propanol was rather stable during ozonation in acetic acid-water-methanol 1631 at 0°C. The corresponding acid, 3,4-dihydroxy-2-(methyl--d-glucopyranosid-6-O-yl)-butanoic acid, was found to be the major reaction product. The use of ozonation followed by acid hydrolysis in connection with studies of lignincarbohydrate linkages is briefly discussed.Part of this paper was presented at the 10th ISWPC, Yokohama, 1999     

Wheat growth as influenced by application of agroforestry-tree prunings in Ethiopian highlands

The response of wheat (Triticum aestivum cv. Enkoy) to application of leaf prunings of nine agroforestry-tree species was investigated in a field trial and a six-week pot trial. The tree species were Grevillea robusta, Erythrina abyssinica, Gliricidia sepium, Albizia schimperiana, Acacia nilotica, Acacia polyacantha, Leucaena leucocephala, Leucaena pallida and Entada abyssinica. L. leucocephala, L. pallida, G. sepium and Entada abyssinica proved to be good pruning sources in the pot trial. G. robusta, A. polyacantha, A. nilotica and E. abyssinica had adverse effects on wheat seedlings with increased pruning loads probably due to immobilization processes or allelopathic effects. N and lignin content, C/N ratio, lignin/N ratio, phenolics/N ratio and (phenolics + lignin)/N ratio of the pruning material were all significantly correlated with shoot dry matter production of the wheat seedlings. With the exception of Entada abyssinica, which performed well under field conditions, a similar ranking as in the pot trial was established in the field experiment, but at harvest differences were not as pronounced as in the pot trial. Gliricidia treated wheat produced by far the highest grain yield with 248 g/m².This revised version was published online in November 2005 with corrections to the Cover Date.     

Modification of the latex paint infusion technique for the determination of vessel-length in hardwoods

Summary The problem of vessel length determination in hardwood trees has been approached in many ways by various workers. The paint infusion technique was utilized in a research programme investigating the subject of vessels of New Zealand beech (Nothofagus) stem sapwood. Two different models of stainless steel paint applicator were used: (a) the horizontal T shaped applicator and (b) the new vertical Y joint applicator. Applicator construction is discussed. The techniques are modifications of the Zimmermann and Jeje (1981) latex paint infuction method.The author gratefully acknowledges Dr. B. G. Butterfield, Dr. B. A. Meylan and L. A. Donaldson for advice and Dr. L. M. H. Middleton for field assistance     

Kinetics of acid-catalysed delignification of Eucalyptus globulus wood by acetic acid

Summary The kinetics of HCl-catalysed delignification of Eucalyptus globulus wood by 70% (w/w) acetic acid solution were satisfactorily explained by a model in which 5% of the lignin fraction could not be eliminated and the remaining 95% was eliminated by a single process which, in view of the activation energy calculated from the data was attributed to the hydrolysis of -aryl ether bonds. The selectivity of the process was effectively independent of HCl concentration and operating temperature for pulp yields >50%. At high temperature (160 °C) and catalyst concentration (0.027 MHCl), lignin condensation and precipitation became significant and the data were better fitted by a model comprising two consecutive processes: lignin solubilization followed by lignin condensation.The authors are grateful to the CICYT for financial support of this work (Project AGF93-0605) and also to the DGICYT for a research grant awarded to J. González     

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.     

Studies on enzymatically liberated lignin in some Indian hardwoods

Summary Total effect of action of the wood-destroying fungusPolyporus palustris, belonging to the brown rot group, has been studied on mango (Mangifera indica) and chorapine (Hardwickia pinnata) woods, for various periods of attack at definite intervals and the lignin liberated was extracted. It was observed that the production of lignin was found to increase; if the fungus was allowed to attack for considerable periods and approximately 50 to 60% lignin was produced within two years.     

Comparative studies on lignin distribution by UV microscopy and bromination combined with EDXA

Summary In order to elucidate a previously reported discrepancy in the ratio of the lignin concentration in the middle lamella to that in the secondary wall as determined by ultraviolet (UV) microscopy and bromination combined with EDXA, the ultraviolet absorptivity of the lignin and the lignin reactivity towards bromination were compared for black spruce wood (Picea mariana Mill.). In addition, UV microscopy and EDXA techniques were applied to the determination of lignin distribution in the tracheids in order to establish the relationship between the two techniques. The results indicated that, although the ultraviolet absorptivity in different morphological regions is essentially the same, the secondary wall lignin was 1.70 times more reactive towards bromination than the middle lamella lignin. By applying the value of 1.70 as a correction to the EDXA results, the estimated lignin distribution by EDXA was in fairly good agreement with that from UV microscopy.The authors would like to thank Dr. J.-F. Revol and Dr. M. Tsuji for their assistance during this study     

Study on low mass thermal degradation products of milled wood lignins by thermogravimetry-mass-spectrometry

Summary Thermogravimetry-mass-spectrometry (TGMS) as a sophisticated analytical instrument is described for the thermal analysis of milled wood lignins from spruce (Picea abies L.), beech (Fagus sylvatica L.) and bamboo (Bambus sp.). The samples were heated on the thermobalance in an inert gas atmosphere (Ar) with 20°C/min heating rate. The weight loss curves (TG) and their 1st derivatives (DTG) were recorded. The evolution of 10 low mass degradation products with m/z below 44 was monitored as a function of the temperature by means of a quadrupol mass spectrometer. Thus the intensity profiles of H₂, CH₃ , H₂O, CO, CHO, HCHO, CH₃O, CH₃OH, CH₃CO and CO₂ were recorded and interpreted in terms of lignin structure and the course of carbonization. The results are in agreement with the results of differencial scanning calorimetry (DSC) and pyrolysis-gas-chromatography mass-spectrometry (PyGCMS) of the phenolics.     

13C NMR studies on lignins depolymerized with dry hydrogen iodide

Summary Spruce (Picea mariana) and birch (Betula verrucosa) milled wood lignins were depolymerized with dry hydrogen iodide. ¹³C NMR spectra of the initial and treated lignins were recorded. The data on chemical shifts of a set of model compounds treated with dry HI were used in the assignment of changes in the spectra of the lignins. The results obtained show that a cleavage of ether bonds in lignin and a substitution of -hydroxy and -alkoxygroups by iodine take place during the treatment.     

Specific degradation ofβ-aryl ether linkage in synthetic lignin (dehydrogenative polymerizate) by bacterial enzymes ofSphingomonas paucimobilis SYK-6 produced in recombinantEscherichia coli

Sphingomonas paucimobilis SYK-6 produces unique and specific enzymes, such as-etherases,O-demethylases, and ring fission dioxygenases, for lignin degradation. Cleavage of arylglycerol--aryl ether linkage is the most important process in the lignin metabolic pathway ofS. paucimobilis SYK-6. We reported the genes (ligD, ligE, ligF) for enzymes that cleaved-aryl ether linkage of dimeric compounds in previous studies. In this study we synthesized the fluorescent high-molecular-weight lignin (UBE-DHP) by dehydrogenative polymerization. We investigated the-aryl ether cleavage ability of these enzymes produced in recombinantEscherichia coli. When UBE-DHP was incubated with LigF, 4-methylumbeliferone was released as a result of-aryl ether cleavage of O-methylumbelliferyl--hydroxypropiovanillone (compound III) incorporated in UBE-DHP. Here, we report that-etherase ofS. paucimobilis SYK-6 can be expressed inE. coli and is able to cleave the-aryl ether linkage in synthetic high-molecular-weight lignin.     

Predicting the decomposition patterns of tree biomass in tropical highland microregions of Kenya

Decomposition- and nitrogen-release patterns of biomass from three agroforestry multipurpose trees (Calliandra calothyrsus, Cordia africana and Grevillea robusta) were investigated in four contrasting environments (microregions) in the Kenyan tropical highlands during two cropping seasons. Dried leafy biomass was placed in 2-mm litter bags, buried at 15-cm depth and recovered after 2, 4, 7, 10, 15 and 20 weeks. Decomposition patterns were best described by first-order exponential decline curves. The decomposition rate constants ranged from 2.1 to 8.2 yr^–1, and the rates of decomposition among the species were in the order: calliandra cordia > grevillea. There was a species-by-environment interaction during both seasons, but the nitrogen released did not follow such a pattern. Among the three tree species, calliandra released the highest amount of cumulative N, followed by cordia and grevillea. Using multiple regression techniques, decomposition pattern was described as a function of three groups of factors: biomass quality (N, C, lignin and polyphenol), climate (soil temperature and rainfall), and soil conditions (pH, soil organic C, total N and P). For all the species and factors combined, the adjusted R ² values were 0.88 and 0.91 for seasons 1 and 2, respectively. Among the three groups of factors, climate and biomass quality had the most influence on decomposition rates. Climatic factors accounted for 75% of the total rate of decomposition in season 1 (irregular season with less rainfall and more soil temperature fluctuations), whereas biomass quality factors were more influential in season 2 (regular season), accounting for 65% of the total variability.Florida Agricultural Experiment Station Journal Series No. R.-05555.     

Leaf litter decomposition of dominant tree species of Namdapha National Park,Arunachal Pradesh,northeast India

Rates of weight loss and nutrient (N and P) release patterns were studied in the leaf litter of the dominant tree species (Ailanthus grandis, Altingia excelsa, Castanopsis indica, Duabanga sonneriatioides, Dysoxylum binectariferum, Mesua ferrea, Shorea assamica, Taluma hodgsonii, Terminalia myriocarpa and Vatica lancefolia) of a tropical wet evergreen forest of northeast India. Nitrogen and phosphorus mineralization rate and decay pattern varied significantly from species to species. In general, the decay pattern, characterized by using a composite polynomial regression equation, exhibited three distinct phases of decay during litter decomposition—an initial slow decay phase (0.063% weight loss day⁻¹), followed by a rapid decay phase (0.494% weight loss day⁻¹) and a final slow decay phase (0.136% weight loss day⁻¹). The initial chemical composition of the litter affected decomposition rates and patterns. Species like D. sonneriatoides, D. binectariferum, and T. hodgsonii with higher N and P content, lower carbon and lignin content, and lower C:N ratio and lignin:N ratio exhibited relatively faster decomposition rates than the other species, for example M. ferrea, C. indica and A. grandis. A slow decay rate was recorded for species such as M. ferrea, C. indica, and A. grandis. The initial N and P content of litter showed significant positive correlations with decay rates. Carbon and lignin content, lignin:N, and C:N showed significant negative correlations with decay rates. Soil total N and P, and rainfall, soil temperature, and soil moisture had positive correlations with decay rates. The rapid decomposition rates observed in comparison with other different forest litter decay rates confirm that tropical wet evergreen forest species are characterized by faster decomposition rates, indicating a faster rate of organic matter turnover and rapid nutrient cycling.