IAWA Journal, Vol.

26 (2), 2005: 211220

EFFECTS OF HEARTWOOD EXTRACTIVES ON MECHANICAL PROPERTIES OF LARCH Michael Grabner1, Ulrich Mller1, Notburga Gierlinger2 & Rupert Wimmer1
SUMMARY

The genus Larix is exceptional for its high content of extractives in the heartwood, with the dominant component arabinogalactan found abundantly in cell lumens of tracheids. On parallel samples prepared from 20 European, Japanese and hybrid larch trees (Larix decidua Mill., L. kaempferi Carr., and L. decidua L. kaempferi, respectively) extractive contents and mechanical parameters were measured. The hot-water extractives in the heartwood had a significant effect on transversal compression strength and Youngs Modulus. In heartwood, increasing extractive content went hand-in-hand with better mechanical properties in the transverse direction. The extraction procedure led to negligible changes in the sapwood. Anatomically the extractive-filled tracheids showed a tendency of being arranged radially, closely to wood rays. The extractive arabinogalactan in larch heartwood has multiple effects on different aspects of wood quality, among which is lateral mechanical enforcement. Key words: Extractive, arabinogalactan, compression strength, stiffness, heartwood, Larix, biomechanics.
INTRODUCTION

Besides the cell wall macromolecules cellulose, polyoses and lignin numerous components are categorized as accessory or extractive material of wood. The term extractive commonly refers to the organic compounds only (Fengel & Wegener 1989), although it can also refer to inorganic materials. An important aspect of extractives is their solubility, and with regard to analysis it is useful to distinguish between substances that are soluble in water or in organic solvents. Wood extractives may darken the heartwood and give species such as those within the genus Larix their characteristic colour. Macro- and micro-distribution of extractives within the tree stem vary greatly, with changes radially and vertically on the one hand (DeBell et al. 1999; Gartner et al. 1999; Gierlinger & Wimmer 2004), and different cell locations (Hillis 1971) and positions within earlywood and latewood (Ct et al. 1966) on the other.
1) BOKU University of Natural Resources and Applied Life Sciences Vienna, Department of Material Sciences and Process Engineering, Peter Jordan Strasse 82, A-1190 Vienna, Austria. Corresponding author: M. Grabner [michael.grabner@boku.ac.at]. 2) Max Planck Institute of Colloids and Interfaces, Department of Biomaterials, D-14424 Potsdam, Germany.
Associate Editor: Barbara Gartner

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While the role of heartwood extractives for natural durability has received considerable study, possible effects of extractives on the mechanical performance of wood have been very little documented (Taylor et al. 2002). Any significant differences in mechanical performance between sapwood and heartwood are usually attributed to the radial changes in wood density or anatomical structure and not to whether the sample is heartwood or sapwood, per se (Panshin & DeZeeuw 1980). Among the rare reports, Arganbright (1971), Kuo and Arganbright (1980) and Grabner (2002) presented evidence for a direct influence of extractives on the modulus of rupture and the modulus of elasticity, in addition to their effect on wood density. The genus Larix is known for its exceptionally high content of extractable components in the heartwood, with the dominating component arabinogalactan, usually within the wide range of 530% (Ct et al. 1966; Fengel & Wegener 1989; Dix & Roffael 1994; Gierlinger et al. 2002a). Besides other smaller components, up to 3.5% of flavonoids can also be found in the larch heartwood (Babkin et al. 2001). Arabinogalactans are water-soluble and heavily branched polysaccharides, they belong chemically to the hemicelluloses, and they are present in all softwood species at levels no more than 1%, excepting Larix (Ct et al. 1966; Karcsonyi et al. 1984; Willfr et al. 2002). Unlike all other hemicelluloses, at least 90% of the arabinogalactans in larch are located outside the cell wall (Ct et al. 1966; Sjstrm & Westermark 1999), primarily filling the lumens of tracheids that are close to ray cells. Extractive contents in larch gradually increase from pith to bark, reaching the highest contents at the heartwood/sapwood boundary, followed by an immediate drop to almost zero in the adjacent sapwood (Ct et al. 1966; Hillis 1971; Gierlinger & Wimmer 2004). Because larch has such a high heartwood extractive content the question of interactions with mechanical performance becomes prominent. This study presents data from axial and transversal compression tests obtained with small, clear samples, located at either side of the heartwood / sapwood boundary, unextracted and extracted. The objective was to explore a possible biomechanical role of extractives in larch heartwood.
MATERIAL AND METHODS

The larch wood investigated in this work originated from the European funded project Towards a European Larch Wood Chain (FAIR CT98-3354; Gierlinger et al. 2002b; Grabner 2002). Wood was sampled from sites that were part of the second IUFRO provenance trial established around 1960 (Schober 1985). In total, 20 larch trees (L. decidua Mill., L. kaempferi Carr., L. decidua L. kaempferi) were selected from the project sample collection encompassing 300 trees grown across Europe (see Table 1 for details). The selected trees originated from young plantations as well as old-growth high elevation alpine sites. Trees were harvested in 1999, and 80 samples were obtained from quartersawn boards. From the air-dried boards samples were split off at either side of the heartwood / sapwood boundary (40 in sapwood, 40 in heartwood) using a wedge-shaped blade that guaranteed zero grain deviation. Beams with a cross section of 7 7 mm and an axial length of 120 mm were machined with the wood rays strictly parallel to the edges. From each sample wood particles were collected during trimming and spectra were

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Table 1. Sampling sites with country origins, latitude and altitude (a.s.l. = above sea level), selected provenances and varieties, number of trees (N) and average tree age.
Country Site name GB Clanna France Coat an Noz Belgium Nassogne Germany Elm Austria Langau France Montgenevre Latitude a.s.l (m) 90 200 320 205 1050 2200 Provenance Larch species N Age

51 43'N, 2 35'W 48 31'N, 3 25'W 50 05'N, 5 20'E 52 00'N, 10 03'E 47 49'N, 15 10'E 44 56'N, 6 44'E

Hybrid Ina Langau Blizyn Langau Montgenevre

L. decidua L. kaempferi L. kaempferi Carr L. decidua Mill. L. decidua Mill. L. decidua Mill. L. decidua Mill.

2 2 4 2 4 6

39 38 38 38 160 237

acquired with a NIR fibre-optical probe linked to a Bruker FT-IR spectrometer Equinox 55 to estimate the acetone and water-soluble extractive contents, based on calibration models previously established (Gierlinger et al. 2002a). For the compression tests a pair of samples, side by side in the longitudinal direction, was sawn from each beam. The axial length was 3 mm, ending up in four samples per tree (one pair from heartwood and one pair from sapwood). The low axial length assured that all extractives are removed. One sample of each pair was extracted while the second one was left untreated. Half of the sapwood and half of the heartwood samples were placed in small glass beakers and extracted in acetone for 24 hours at 20 C, followed by seven days water extraction at 60 C, both durations sufficient to remove all relevant extracts (Gierlinger et al. 2002a). Subsequently, all samples were conditioned in a climate chamber at 20 C and 65% relative humidity to reach equilibrium moisture of 12%. Since sapwood and heartwood sample pairs exhibited a more or less identical anatomical structure, which was checked in a pre-study, differences in mechanical properties can be almost exclusively attributed to sample position (heartwood or sapwood) and to whether the samples were extracted. An analysis of variance was employed to test the null hypothesis if the group means of sapwood and heartwood samples extracted or left unextracted are equal in the population, by comparing the sample variance estimated from the group means to that estimated within the groups. This helped to differentiate between changes of mechanical properties due to extractives, from those due to the extraction treatment. For documentation 1.2 mm thick cross sections were prepared from the beams close to the compression test samples prior to extraction with a double-blade circular saw (Lenz et al. 1976). These cross sections were placed onto X-ray sensitive films and exposed at 10 kV, 24 mA, for 25 min. After exposure the slices were acetone and hotwater extracted and acclimatized before another X-ray exposure was performed. The processed radiographs were digitised with a scanning densitometer (Fig. 1).

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Fig. 1. X-ray densitometry images of (A) unextracted and (B) hot-water/acetone extracted larch cross sections.

Special care was taken that samples had no deformation prior to the compression tests. Compression tests (both axial and loaded in the radial direction) were performed at constant displacement rates on the samples using a Zwick/Roell Z100/SW5A universal testing machine. Sample deformation was monitored through the movement of the crosshead, and stress/strain curves were computed during the tests. From these curves we calculated maximum crushing strength (MCS) and Youngs modulus (MOE). To analyse mechanisms during loading perpendicular to grain the crosshead was halted when the force dropped more than 5% from its maximum. This allowed an observation of single earlywood tracheid failures, as shown by Mller et al. (2003). Extracted and unextracted samples showing apparent post-compressive deformation were imaged with scanning electron microscopy (SEM). The SEM samples were gold sputtered at 1 kV and 20 mA before placement in a Philips, XL30 ESEM, at filament voltages between 10 and 15 kV.
RESULTS

Overall, contents of total extractable substances in heartwood ranged between 4.0 and 28.5% dry weight, and in sapwood between 0.6 and 4.4%. By far the highest contribution was given by the hot-water extractives, which varied between 3.3 and 25.1%. Figure 1 shows X-ray graphs of a sample prior and post extraction. In Figure 1A extractive-filled tracheids are clearly seen. It is also seen that the filled tracheids have the tendency to be radially arranged along the wood rays, beside of being randomly distributed across the annual ring (Fig. 1 & 4). After hot-water extraction all substances located in the tracheid lumens have disappeared (Fig. 1B). Two-way ANOVAs were performed with position (sapwood or heartwood) and the extraction treatment (unextracted or extracted) as the main effects (Table 2, Fig. 2) for transverse and axial MCS and MOE. Most variance was explained for transverse MCS (R2 = 0.55), followed by transverse MOE (R2 = 0.33) in a second ANOVA. The ANOVAs for MCS in the axial direction had a considerably lower degree of explanation (R2 = 0.18), and no variance was explained for axial MOE (Table 1).

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Table 2. Two-way ANOVA for transversal and axial MCS and MOE as dependent variables, with position (heartwood or sapwood) and treatment (unextracted or extracted) as main effects (df = degree of freedom).
Dependent Variable: transversal MCS (maximum crushing strength) Source Corrected Model Intercept Position Treatment Position x Treatment Error Total Corrected Total Adjusted R2 = 0.54 Dependent Variable: transversal MOE (modulus of elasticity) Source Corrected Model Intercept Position Treatment Position x Treatment Error Total Corrected Total Adjusted R2 = 0.33 Dependent Variable: axial MCS (maximum crushing strength) Source Corrected Model Intercept Position Treatment Position x Treatment Error Total Corrected Total Adjusted R2 = 0.18 Dependent Variable: axial MOE (modulus of elasticity) Source Corrected Model Intercept Position Treatment Position x Treatment Error Total Corrected Total Adjusted R2 = 0.01 Type III Sum of Squares 48234.2 91733053.9 0.0 30591.1 23184.3 5374109.4 98412759.9 5422343.5 df 3 1 1 1 1 82 86 85 Mean Square 16078.1 91733053.9 0.0 30591.1 23184.3 65537.9 F 0.25 1399.70 0.00 0.47 0.35 Sig. 0.86 0.00 0.99 0.50 0.55 Type III Sum of Squares 2733.5 260319.7 889.6 1132.3 510.0 10348.4 280569.3 13081.9 df 3 1 1 1 1 82 86 85 Mean Square 911.2 260319.7 889.6 1132.3 510.0 126.2 F 7.22 2062.75 7.04 8.97 4.04 Sig. 0.00 0.00 0.10 0.04 0.48 Type III Sum of Squares 871484.3 7876201.1 286440.6 460703.5 101276.9 1612188.7 10530910.2 2483673.0 df 3 1 1 1 1 76 80 79 Mean Square 290494.8 7876201.1 286440.6 460703.5 101276.9 21213.0 F 13.7 371.3 13.5 21.7 4.8 Sig. 0.00 0.00 0.00 0.00 0.03 Type III Sum of Squares 702.7 3620.1 295.6 248.7 138.7 566.3 5002.7 1269.0 df 3 1 1 1 1 76 80 79 Mean Square 234.2 3620.1 295.6 248.7 138.7 7.6 F 31.4 485.8 39.7 33.4 18.6 Sig. 0.00 0.00 0.00 0.00 0.00

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14 Transversal MCS (N / mm2 )

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600 -

12 10 86420-

Transversal MOE (N / mm2 )

500 400 300 200 100 0-

unextracted

extracted

unextracted

extracted

unextracted

extracted

unextracted

extracted

Sapwood

Heartwood

Sapwood

Heartwood

Fig. 2. Estimated marginal means for transverse maximum crushing strength (MCS) (A) and Youngs modulus (MOE) (B) of adjacent larch sapwood and heartwood samples, unextracted and extracted (n = 80).

Fig. 3. SEM micrographs of earlywood tracheids containing arabinogalactan before the transverse compression load was applied (A). Differences in plastic deformation of the wood cell wall versus the more ductile arabinogalactan (B) are visible.

Fig. 4. Cross-sectional SEM image of a high extractive sample (unextracted) after transversal (radial) load. (A) Continuous rows of filled tracheids (arrow) that served as mechanical reinforcement. (B) Buckling of the empty tracheids initiated transverse compression failure (arrows), which limited transverse compression strength.

An interaction effect is a change in the main effect of one variable over levels of the second. Position treatment interaction was significant for transverse MCS and MOE. This means that the position treatment interaction is a change in the main effect of treat-

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ment over levels of position, or vice versa. Sapwood extraction had a minor effect on mechanical properties, while in heartwood the effect was great (Fig. 2). This affirms that removal of high extractive contents ceteris paribus had a significant consequence on transversal MCS and MOE, while the extraction procedure itself had little impact. We also looked at anatomical evidence of this finding. Figure 3 shows an SEM of extractive-filled earlywood tracheids. Prior to transverse compression loading (Fig. 3A) the interfaces between cell walls and extractive substances were barely visible and appeared more or less as a continuum. As transverse forces deformed the samples (halted as force dropped 5% from its maximum), the ductile hot-water extractives filling the lumens separated from the more visco-elastic cell walls (Fig. 3B). Heartwood samples were arranged by their original extractive contents and plotted along with the corresponding transversal MCS and MOE data (Fig. 5). Although trends are clearly seen, the mechanical data showed considerable scatter with increasing extractive content.
25 20

trans. (MPa)

15 10 5 0

10 15 20 25 Total extractive content (%)

30

1000 Youngs Modulus (MPa) 800 600 400 200 0 0

10 15 20 25 Total extractive content (%)

30

Fig. 5. Compression strength (A) and Youngs modulus (B) of heartwood samples and initial total extractive content. $ = unextracted and O = extracted values; : = differences between unextracted and extracted samples (n = 20).

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DISCUSSION

The hot-water extractives in the larch heartwood have a significant effect on transverse maximum crushing strength (MCS) and Youngs modulus (MOE). Increasing extractive content goes hand-in-hand with better mechanical properties in the transverse direction, while the same extraction procedure had minor changes in the sapwood. These results were seen primarily in the transverse direction, the mechanical properties in axial direction did not show changes of the same magnitude. Larch heartwood contains high amounts of extractives (Dix & Roffael 1997) and the major part is attributed to arabinogalactan, a water-soluble and heavily branched polysaccharide, usually found within similar ranges as those reported here (530% dry weight, Ct et al. 1966). The high amounts of arabinogalactan are specific to larch, mainly located in the cell lumen, and their direct role is still unclear (Ct et al. 1966). In brown-rot decay it may enhance fungal growth by being a nutrient resource (Srinivasan 1999). On the other hand it could also serve as a mechanical barrier for fungal hyphae penetrating the wood structure laterally. The current work has shown that watersoluble extractives, i.e. arabinogalactans, act as a mechanical enforcement in the wood structure laterally. This might go hand-in-hand with a mechanical barrier function for fungi penetrating wood laterally. Besides arabinogalactan, up to 3.5% flavonoids are found in larch heartwood (Hegnauer 1962; Giwa & Swan 1975; Babkin et al. 2001), which plays a direct role in decay resistance. Anatomically the extractive-filled tracheids showed the tendency to be arranged radially with wood rays. Similar results were reported by Kuo and Arganbright (1980), who related presence and degree of extractive deposits in tracheids with respect to alignment and distance to ray parenchyma. Ct et al. (1966) suggested that arabinogalactans are formed in the living ray cells at the sapwoodheartwood boundary, similar to other extractives. From the ray cells arabinogalactan penetrates into the tracheids, which explains the higher likelihood of filled tracheids being close to wood rays. In the lateral direction high spread of MCS and MOE values were observed with increasing extractive content, which is associated with the radially oriented, extractivefilled tracheids rows: the rows of extractive-filled tracheids are frequently interrupted by single empty tracheids, which limit compression strength by the critical buckling load of their cell walls (Fig. 4). As a consequence, MCS of softwoods perpendicular to grain is determined by the critical stress of these empty cell walls (Kollmann 1959, 1982; Mller et al. 2003), a fact that seems to be more prone in smaller samples due to the stochastic occurrence of uninterrupted radial, extractive-filled tracheids rows. Buckling of the weakest cell walls initiates transversal compression failure (Mller et al. 2003), while samples with uninterrupted filled-tracheid rows may have significantly higher compression strength in the transverse direction. Because arabinogalactan is more deposited in earlywood than latewood (Ct et al. 1966), the reinforcement effect of the wood ray accompanying filled tracheid rows is assumed to be higher in the initial tree-ring portion. Mechanical loading perpendicular to grain in the radial direction and elastic deformation of the tissue (bumping out, start of buckling) are relevant for Youngs modulus. Because of the filled tracheids, mechani-

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cal stresses and the likelihood of buckling are reduced, resulting in higher values of Youngs modulus. The available samples represented a range of hot-water extractive contents in larch heartwood. In practical saw-milling, larch is known to be cumbersome, as the resin (i.e. arabinogalacatan) tends to built up on saw-blades causing loss of straightness of the sawn boards. As a common strategy the blades are water-sprinkled during sawing, reducing the negative effects. This serves as more evidence that arabinogalactan in larch has multiple effects on wood quality, including workability, glueability, drying behaviour, and warping.
ACKNOWLEDGEMENTS This study is in part funded by the European Union, Fair project CT98- 3354 Towards a European Larch Wood Chain, coordinated by Dr. Luc Paques, INRA.

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