Comparing the Variation of Needle and Wood Terpenoids in Scots Pine Provenances

We determined variation in both the concentration and composition of terpenoids in needles and wood within nine Scots pine (Pinus sylvestris) provenances. Seedlings of different provenances representing a 1200-km N–S transect from Estonia to northern Finland were cultivated in Suonenjoki nursery field, central Finland, for seven years. Growth of seedlings and the number of vertical resin ducts in wood were also determined. -Pinene and 3-carene were the major monoterpenes both in the needles and wood. The total monoterpene concentration was about five times higher in the needles than in the wood. A strong positive correlation was found between proportional quantities of several terpenes of the needles and wood, particularly for 3-carene, sabinene, and terpinolene. The needles contained both labdane-type and tricyclic resin acids, whereas the wood contained only tricyclic ones. The wood had a four times higher tricyclic resin acid concentration than the needles. The highest total monoterpene concentration in the needles and in the wood occurred in the most northern Muonio provenance and in the most southern Saaremaa provenance plants, respectively. The amount of high 3-carene genotype trees decreased among the northern provenances. The wood of the most northern Muonio provenance showed the lowest total resin acid concentration, but provenance did not affect total tricyclic resin acids in the needles. Korpilahti provenance trees from central Finland had the best growth in height. In addition, Korpilahti and Ruokolahti provenance trees showed largest radial growth of stem and smallest number of vertical resin ducts. The results suggest that especially the proportional quantity of 3-carene in the needles could be used in estimating the amount of this compound in the wood and vice versa.     

Cellulose digestion inMonochamus marmorator Kby. (Coleoptera: Cerambycidae): Role of acquired fungal enzymes

Larvae of the balsam fir sawyer,Monochamus marmorator Kby. (Coleoptera, Cerambycidae), contain midgut digestive enzymes active against hemicellulose and cellulose. Cellulases from larvae fed on balsam fir wood infected with the fungus,Trichoderma harzianum Rifai (Deuteromycetes, Moniliales, Moniliaceae), were found to be identical to those of the cellulase complex produced by this fungus when compared using chromatography, electrophoresis, and isofocusing. When larvae are maintained on a fungus-free diet, their midgut fluids lack cellulolytic activity, and they are unable to digest cellulose. Cellulolytic capacity can be restored by feeding the larvae wood permeated by fungi. We conclude that the enzymes which enableM. marmorator larvae to digest cellulose are not produced by the larvae. Instead, the larvae acquire the capacity to digest cellulose by ingesting active fungal cellulases while feeding in fungus-infected wood.     

Novel detection of formylated phloroglucinol compounds (FPCs) in the wound wood of Eucalyptus globulus and E. nitens

This study characterized the chemical responses of Eucalyptus globulus and Eucalyptus nitens to artificial inoculation with a basidiomycete decay fungus. Nine-year-old trees responded to mechanical wounding or inoculation with the decay fungus by producing new wound wood characterized by the presence of dark extractives 17 months after wounding. Analysis of crude wound wood extracts by HPLC coupled to negative ion electrospray mass spectrometry revealed the presence of a complex mixture of many unidentified formylated phloroglucinol compounds (FPCs), in addition to a diverse range of other polyphenolic compounds (hydrolyzable tannins, proanthocyanidins, flavanone glycoside, stilbene glycosides). Prior to this study, FPCs have only been reported from leaves and buds of Eucalyptus spp. Unequivocal evidence for the presence of macrocarpal A and B, and sideroxylonal A and B in the crude extracts was obtained, as well as evidence for a wide range of as yet unreported FPCs. Subsequent preliminary in vitro fungal and bacterial bioassays did not support an antimicrobial role for FPCs in host-pathogen interactions in eucalypts.     

The Wood Preservative Potentials of Valonia,Chestnut, Tara and Sulphited Oak Tannins

This study investigated antifungal properties of four different tannins as potential environmentally friendly wood preservatives. Scots pine wood samples were impregnated with 3, 5, 10, and 15% valonia, chestnut, tara, and sulphited oak tannins, and then were exposed to brown rot fungi Coniophora puteana and Postia placenta, and white rot fungi Trametes versicolor and Pleurotus ostreatus attack to determine the best tannin type and the optimum concentration level for sufficient decay resistance. Leaching test was conducted in order to evaluate any loss in effectiveness in decay resistance due to possibility of tannin leaching. Tannins were found efficacious in suppressing brown rot fungi attacks when no leaching prior the decay test was used, however, they seemed to be ineffective against white rot fungi attacks. The lowest weight losses were obtained with valonia and chestnut tannins both for brown and white rot fungi probable related with their high ellagic tannin content.     

Oviposition and feeding preferences of the southern pine coneworm (Lepidoptera: Pyralidae) for different host-plant materials and observations on monoterpenes as an oviposition stimulant

Bioassays were conducted with first-stage larvae and newly emerged females of the southern pine coneworm,Dioryctria amatella (Hulst), to detect feeding and ovipositional preferences for different host-plant materials collected between April and August. Correlations between measures of insect preferences and estimates of wood parameters indicated that larvae preferred to feed on host-plant materials with high moisture contents, low wood densities, and low monoterpene contents. Female moths, however, did not necessarily select those plant materials preferred by larvae for feeding, but tended to oviposit more frequently on materials with high monoterpene contents. A synthetic mixture of monoterpenes similar in composition to those present in fusiform rust galls of slash pine (Pinus elliottii) Englem. var.elliottii) elicited mating and oviposition behavior.Mention of proprietary products does not necessarily imply endorsement by USDA.     

Antimicrobial Activity of Exocrine Glandular Secretion of Chrysomela Larvae

The exocrine glandular secretions of leaf beetle larvae of the taxon Chrysomela are well-known defensive devices used against some generalist predators. Salicylaldehyde is the major repellent component of secretions emitted by larvae of Chrysomela vigintipunctata and C. lapponica, which feed on salicin-rich Salicaceae. In this study, we examined whether salicylaldehyde is also active against the entomopathogenic fungus Metarhizium anisopliae. The germination and growth of this fungus was strongly inhibited when salicylaldehyde was applied directly onto the blastospores. The salicylaldehyde concentration of the larval secretions of the tested willow feeding Chrysomela larvae was much higher than the one necessary to display this antifungal activity. Additionally, salicylaldehyde was shown to reduce germination and growth of M. anisopliae via the gas phase over a distance of 45 mm. Further studies on the antimicrobial activity of the salicylaldehyde-containing secretions of Chrysomela larvae revealed that they act nonspecifically against prokaryotic (Escherichia coli) and eukaryotic cells (Saccharomyces cerevisiae and Trichoplusia ni). All antimicrobial and cytotoxic effects detected proved to be due to salicylaldehyde. The larval secretions of the birch-feeding allospecies of C. lapponica, that do not contain salicylaldehyde, but mainly carboxylic acids and their esters, showed no detectable effects on bacteria or fungi and no cytotoxic effects against insect cells. The results are discussed with respect to their ecological relevance.     

Variation in Growth, Chemical Defense, and Herbivore Resistance in Scots Pine Provenances

Variation in the growth, chemical defense, and susceptibility to monophagous and polyphagous sucking herbivores was assessed for four Scots pine (Pinus sylvestris) provenances in Petri dish and pot experiments. Seed provenances, Muonio (MU), Suomussalmi (SU), Korpilahti (KO), and Saaremaa (SA) represented a 1200-km N–S gradient. Scots pines from SU were least preferred as a host plant by pine-feeding aphids Schizolachnus pineti Fabr. and Eulachnus agilis, and in pot experiments, pines from SA were most preferred. S. pineti also produced the fewest nymphs on pines from SU. Polyphagous Lygus rugulipennis laid significantly fewer eggs on pines from MU provenance, which were smaller than seedlings from other provenances. The total and some individual terpene concentrations increased, while the total resin acid concentration decreased, towards the north. The absolute concentrations of total or individual terpenes and resin acids in the needles of unfavored SU plants did not differ significantly from the other provenances. Only the proportional quantity of dehydroabietic acid was higher in SU plants than in KO plants, and it correlated, together with sandaracopimaric acid, negatively with the number of S. pineti nymphs in the reproduction experiment. Conversely, absolute concentrations of some terpenes correlated negatively and some resin acids positively with the number of S. pineti nymphs. The length and weight of shoots decreased towards the north, adequately explaining the number of Lygus eggs and the final numbers of both aphids. The results suggest that seedling size is a better estimator of susceptibility of pine seedlings to both specialist and generalist sucking insects than relative or absolute concentrations of monoterpenes and resin acids.     

Increased Terpenoid Accumulation in Cotton (<Emphasis Type="Italic">Gossypium hirsutum</Emphasis>) Foliage is a General Wound Response

The subepidermal pigment glands of cotton accumulate a variety of terpenoid products, including monoterpenes, sesquiterpenes, and terpenoid aldehydes that can act as feeding deterrents against a number of insect herbivore species. We compared the effect of herbivory by Spodoptera littoralis caterpillars, mechanical damage by a fabric pattern wheel, and the application of jasmonic acid on levels of the major representatives of the three structural classes of terpenoids in the leaf foliage of 4-week-old Gossypium hirsutum plants. Terpenoid levels increased successively from control to mechanical damage, herbivory, and jasmonic acid treatments, with E-β-ocimene and heliocide H₁ and H₄ showing the highest increases, up to 15-fold. Herbivory or mechanical damage to older leaves led to terpenoid increases in younger leaves. Leaf-by-leaf analysis of terpenes and gland density revealed that higher levels of terpenoids were achieved by two mechanisms: (1) increased filling of existing glands with terpenoids and (2) the production of additional glands, which were found to be dependent on damage intensity. As the relative response of individual terpenoids did not differ substantially among herbivore, mechanical damage, and jasmonic acid treatments, the induction of terpenoids in cotton foliage appears to represent a non-specific wound response mediated by jasmonic acid. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Drying behavior and decay resistance of rubberwood from steamed log and presteamed lumber

The objective of this study was to evaluate the effect of log steaming and steaming prior to drying singly and both treatments together on the drying behavior and decay resistance of Hevea brasiliensis wood (rubberwood). Logs with a diameter of 34.6?±?4.4?cm were used. Half of the logs were kept in their original condition, and the other half were steamed at 90°C for 36?h. Later, the logs were cut into flat sawn boards. Half of the boards were kept in their original condition, and the other half were presteamed at 90°C for 3?h after 1?h of heating-up. These boards were dried in a drying kiln. The drying defects, drying time, drying rate, and decay resistance of wood to the Pycnoporus sanguineus fungus were determined. The results showed that the steaming is not suitable for decreases in the time and the drying rates of this kind of wood, and it neither reduces the drying defects of boards. Furthermore, these treatments adversely affected the decay resistance of rubberwood to P. sanguineus fungi.     

Higher plant terpenoids: A phytocentric overview of their ecological roles

Characteristics of higher plant terpenoids that result in mediation of numerous kinds of ecological interactions are discussed as a framework for this Symposium on Chemical Ecology of Terpenoids. However, the role of terpenoid mixtures, either constitutive or induced, their intraspecific qualitative and quantitative compositional variation, and their dosage-dependent effects are emphasized in subsequent discussions. It is suggested that little previous attention to these characteristics may have contributed to terpenoids having been misrepresented in some chemical defense theories. Selected phytocentric examples of terpenoid interactions are presented: (1) defense against generalist and specialist insect and mammalian herbivores, (2) defense against insect-vectored fungi and potentially pathogenic endophytic fungi, (3) attraction of entomophages and pollinators, (4) allelopathic effects that inhibit seed germination and soil bacteria, and (5) interaction with reactive troposphere gases. The results are integrated by discussing how these terpenoids may be contributing factors in determining some properties of terrestrial plant communities and ecosystems. A terrestrial phytocentric approach is necessitated due to the magnitude and scope of terpenoid interactions. This presentation has a more broadly based ecological perspective than the several excellent recent reviews of the ecological chemistry of terpenoids.     

Effect of bio‐oil and epoxidized linseed oil on physical,mechanical, and biological properties of treated wood

In this article, the effects of bio‐oil and epoxidized linseed oil (ELO) on water absorption, tangential swelling, decay and insect resistance, thermo‐gravimetric analysis, and mechanical properties of treated wood samples were studied. The bio‐oil used in this article was by‐product of ThermoWood thermal modification process. Linseed oil and hydrogen peroxide were used to prepare ELO. The results indicated that the samples treated with bio‐oil had lower water absorption than that of the control group. The second treatment with ELO significantly reduced further the water absorption. The decay resistance of treated wood samples with 20% of bio‐oil against brown (Coniophora puteana) and white rot (Trametes versicolor) fungi was very high. According to the insect test results, increasing bio‐oil concentration from 10% to 20% significantly decreased surviving rate of Hylotrupes bajulus. Thermo‐gravimetric analysis showed that all treated samples had higher initial deterioration temperature than that of the control group. Regarding the wood strength, the impregnated bio‐oil generally reduced the mechanical properties of wood except modulus of elasticity (MOE). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1562–1569, 2013     

The role of monoterpenes in resistance of Douglas fir to western spruce budworm defoliation

We conducted defoliation experiments with 7- to 8-year-old clones of Douglas fir [Pseudotsuga menziesii (Mirb.) Franco var. glauca] to assess the role of monoterpenes as a resistance mechanism to western spruce budworm (Choristoneura occidentalis Freeman) defoliation. The grafted clones were derived from mature trees that showed resistance or susceptibility to budworm defoliation in the forest. All clones were exposed to either budworm defoliation or nondefoliation treatments in 1998 and 1999 under greenhouse conditions. We found that the total concentration of monoterpenes in current-year foliage varied greatly between two consecutive years in clones in the greenhouse and in their corresponding mature trees in the forest. Fractional composition of different monoterpenes was similar between different years and between clones and mature trees, indicating genetic control of this trait. Two different defoliation experiments were conducted to assess the importance of budburst phenology as a factor determining host plant resistance. In the 1998 experiment, budworm feeding was matched to the budburst of each individual plant. Monoterpene concentration was high in 1998, and budworm potential fitness was greater on clones from the resistant mature trees that had lower concentrations of total monoterpenes. In the 1999 experiment, budworm feeding was matched to budburst of the whole population of plants in order to mimic conditions similar to insects feeding on trees in the field. The concentration of monoterpenes was low in 1999, and budworm fitness was not related to monoterpenes. Total monoterpene concentration was negatively related to foliar nitrogen concentration, suggesting that C/N balance may affect monoterpene synthesis in needles. However, tree growth was not related to total monoterpene concentration. We concluded that expression of differences in budworm resistance among Douglas fir genotypes might be caused by interactions among multiple resistance mechanisms such as needle monoterpenes and tree budburst phenology.     

Terpene variations in maritime pine constitutive oleoresin related to host tree selection byDioryctria sylvestrella RATZ. (Lepidoptera: Pyralidae)

Gas chromatographic analysis of the volatile terpenes of the wood oleoresin of maritime pines showed that the relative proportions of terpenes within the same tree did not vary according to sampling height and date. Pruning and tree vigor did not affect terpene profiles, but oleoresin composition varied widely from tree to tree. The trees attacked byDioryctria sylvestrella contained a significantly higher percentage of limonene, longipinene, and copaene, and a discriminant analysis, using the relative percentage of six terpenes, significantly separated infested and uninfested trees. The olfactory sensitivity of adult moths to a series of 20 volatile chemicals, including maritime pine oleoresin components, was evaluated with the electroantennogram method. Both sexes were sensitive to monoterpenes, oxygenated terpenoid compounds, and oleoresin samples. The use of terpenes as host attractants and biochemical markers for resistance toD. sylvestrella is discussed.     

Weathering,water absorption,and durability of silicon,acetylated, and heat‐treated wood

In this study, two colloidal dispersions of pure amorphous silicon dioxide particles, acetylated, and heat‐treated samples were tested for a possible application as a wood protection agents. The silicon, acetylated, and heat‐treated samples were exposed to an accelerated weathering experiment, and their dimensional stability was assessed. The weathering experiment comprised cycles of 2 h UV‐light irradiation followed by water spray for 18 min. The surface changes of the weathered samples were characterized by FT‐IR spectroscopy and color measurements. According to results, the silicon treatments showed lower color changes than untreated ones. However, acetylated and heat‐treated samples provided the lowest color changes. The resistance of the silicon, acetylated, and heat‐treated wood to decay was studied by means of brown and white rot fungi in laboratory decay tests. Decay test results revealed that acetylated and heat‐treated wood samples showed better decay resistance against P. placenta and C. versicolor than silicon treatments. Samples modified with silicon were exposed in above ground standard lap‐joint test in Ultuna, Sweden. The dispersions of pure amorphous silicon dioxide impregnated in wood did not significantly influence its hygroscopic and dimensional behavior. However, the silicon treatment reduced the color changes caused by weathering. The silicon impregnated samples showed a weak fungal discoloration similar to that of chromated copper arsenate impregnated controls in above ground standard lap‐joint test. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4506–4513, 2006     

Controlled release of biocides in solid wood. III. Preparation and characterization of surfactant‐free nanoparticles

Polymeric nanoparticles containing the fungicides tebuconazole and chlorothalonil were prepared by a simple, surfactant‐free method and found to have significantly smaller median particle diameters and more stable aqueous suspensions than their surfactant‐stabilized counterparts. These more stable suspensions were delivered into southern yellow pine and birch wood with greater efficiency than the equivalent surfactant‐stabilized nanoparticle suspensions. We found that the suspensions protected the treated wood against fungal attack by Gloeophyllum trabeum, a common brown rot wood decay fungus, and Trametes versicolor, a common white rot wood decay fungus, at low tebuconazole and chlorothalonil contents in the wood. Southern pine lost 5% or less of its mass after 55 days of exposure to G. trabeum when the tebuconazole or chlorothalonil content in the wood was only 0.4 kg/m³, while a tebuconazole or chlorothalonil content of 0.8 kg/m³ in birch wood was sufficient to bring its mass loss to less than 5% after 55 days of exposure to T. versicolor. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 615–621, 2002     

Influence of odor from wood-decaying fungi on host selection behavior of deathwatch beetle,Xestobium rufovillosum

Adult females of Xestobium rufovillosum de Geer demonstrated anemotactic orientation when exposed to an odor plume containing volatiles generated by wood-decaying fungi (Coriolus versicolor, Donkioporia expansa) and decayed oak wood (Quercus petraea, Quercus robur). They did not orient towards undecayed oak wood, beech (Fagus sylvatica), or pine wood (Pinus sylvestris). Although all insects tested showed anemotactic orientation, responses were nonlinear with respect to insect age. Adult females more readily oriented upwind when they were between 10 and 16 days old. Oviposition choice bioassays showed that ovipositing females would preferentially oviposit on extract-treated cellulose paper discs that had been treated with various strains of the wood-decaying fungus, Donkioporia expansa. HPLC-fractionated mycelial extracts were attractive to ovipositing deathwatch beetles, whereas HPLC-fractionated fungal broth extracts were repellent to ovipositing females. The implications of these results are discussed in the context of timber pest management in historically important buildings.     

Terpene Chemistry of Eastern Hemlocks Resistant to Hemlock Woolly Adelgid

Recent studies have identified a small number of individual eastern hemlock trees that demonstrate relative resistance to the introduced sap-feeding insect, the hemlock woolly adelgid. Using gas chromatography, we compared concentrations of twenty-two terpenoids in susceptible and relatively resistant trees, both in the forest and in propagated cuttings in a common-garden setting. Terpenoid concentrations were higher in twig tissue of resistant versus susceptible trees, across six sampling dates and at both sites. These changes may be particularly important because the hemlock woolly adelgid feeds on twig tissue. Because the common-garden cuttings were free of herbivores, the higher terpenoid concentrations are interpreted as a constitutive defense. Increased levels of monoterpenes and sesquiterpenes imply an overall increase in the input of carbon precursors to both terpenoid synthesis pathways.     

Antipredator Defense of Biological Control Agent Oxyops vitiosa Is Mediated by Plant Volatiles Sequestered from the Host Plant Melaleuca quinquenervia

The weevil Oxyops vitiosa is an Australian species imported to Florida, USA, for the biological control of the invasive weed species Melaleuca quinquenervia. Larvae of this species feed on leaves of their host and produce a shiny orange secretion that covers the integument. When this secretion is applied at physiological concentrations to dog food bait, fire ant consumption and visitation are significantly reduced. Gas chromatographic analysis indicates that the larval secretion qualitatively and quantitatively resembles the terpenoid composition of the host foliage. When the combination of 10 major terpenoids from the O. vitiosa secretion was applied to dog food bait, fire ant consumption and visitation were reduced. When these 10 terpenoids were tested individually, the sesquiterpene viridiflorol was the most active component in decreasing fire ant consumption. Fire ant visitation was initially (15 min after initiation of the study) decreased for dog food bait treated with viridiflorol and the monoterpenes 1,8-cineole and -terpineol. Fire ants continued to avoid the bait treated with viridiflorol at 18 g/mg dog food for up to 6 hr after the initiation of the experiment. Moreover, ants avoided bait treated with 1.8 g/mg for up to 3 hr. The concentrations of viridiflorol, 1,8-cineole, and -terpineol in larval washes were about twice that of the host foliage, suggesting that the larvae sequester these plant-derived compounds for defense against generalist predators.     

Temporal and Spatial Variation of Terpenoids in Eastern Hemlock (Tsuga canadensis) in Relation to Feeding by Adelges tsugae

The terpenoid content of eastern hemlock (Tsuga canadensis) foliage was measured over an annual cycle of development from bud opening, shoot elongation, shoot maturation, to bud-break at the start of the next growing season. The objective was to determine if variation in terpenoid composition is linked with spatial and temporal feeding preferences of the hemlock woolly adelgid (HWA; Adelges tsugae). The HWA has two periods of feeding over the course of 1 yr spanning two complete generations. There are two periods of feeding separated by a nonfeeding period where the adelgid estivates. HWA prefers to feed on mature, rather than young, expanding tissue. Feeding occurs in the leaf cushion at the base of the needle. The needle is the only tissue in hemlock with resin canals that store terpenoids. The needle and leaf cushion of both the current and previous years’ growth were analyzed separately over a 1-yr period to examine the variation of terpenoid composition in space and time. Terpenoids were quantified by using headspace solid-phase microextraction/gas chromatography/mass spectrometry (SPME/GC/MS). New growth needles and leaf cushions do not resemble the previous year’s growth either visually or in chemical composition until October/November, when the adelgid breaks estivation and begins feeding. Nearly all of the 23 terpenoids present exceeding 0.1% varied significantly either temporally or spatially, usually with complex interactions. Ordination and factor analysis revealed that terpenoids are less variable in mature leaf cushions than in young tissue. By entering a nonfeeding diapause during the late spring and summer, HWA avoids the unstable, variable levels of terpenoids in the immature leaf cushion and needles.