Volatile organic compounds from wood and their influences on museum artifact materials II: Inference of causal substances of deterioration based on intercomparison of laser Raman spectra of deteriorated products

Volatile organic compounds (VOCs) from wood and their effects on artifacts are of intense interest to museum staff who must strictly manage the preservation environment. In this study, the causal substances of deterioration were inferred by comparison with laser Raman (LR) spectra of deterioration products. The artifact samples were deteriorated using VOCs from woods (WV test), and using specific substances that occur in wood VOCs (SV test). The deteriorated samples were analyzed by LR spectroscopy and the results of the WV and SV tests were compared. Hinokitiol and acetic acid were found to be two of the main causal substances of deterioration in western red cedar. Deterioration of iron and copper by spruce did not appear to be caused by acetic acid, as is generally assumed, but by some other unknown compound(s). Sensitivity to wood-based VOC components depended on the type of artifact. In western red cedar, mitsudasou (litharge) was very sensitive to acetic acid, while other artifacts were sensitive to hinokitiol. The LR method used in this study is very useful for the inference of causal substances of deterioration based on the detection of small amounts of deteriorated products such as those generated by deterioration due to wood VOCs. Part of this article was presented at the 25th Annual Meeting of the Japan Society for the Conservation of Cultural Property, Kyoto, June 2003     

Supercritical fluid impregnation of selected wood species with tebuconazole

The effects of pressure and temperature on supercritical fluid impregnation of tebuconazole were evaluated on Douglas-fir, western red cedar, red alder, white spruce, and white oak. Higher pressure markedly enhanced both the retention and distribution of tebuconazole in these species. When the rate of pressure release was altered at the ends of treatments of Douglas-fir, results varied. Generally, a higher rate of venting increased the steepness of the preservative gradient inward from the surface. Elevated pressures also affected some wood properties. Western red cedar and white spruce showed collapse, while the other three species were free of such defects. Modulus of Elasticity (MOE) and Modulus of Rupture (MOR) tended to decline with higher pressure in western red cedar and white spruce, but the differences were rarely significant. No significant changes in MOE/MOR occurred with the other 3 species. Received 9 November 1998     

Effects of moisture content and specific gravity on static bending properties and hardness of six wood species

This study was designed to investigate the effects of moisture content (MC) and specific gravity (SG) on the bending strength and hardness of six wood species including Japanese cedar (Cryptomeria japonica D. Don), China fir (Cunninghamia lanceolata), western hemlock (Tsuga heterophylla), red meranti (Shorea spp.), Selangan batu (Shorea spp.), and red oak (Quercus spp.). The experimental results are summarized as follows: Effects of MC and SG on the strength (MOR), stiffness (MOE), and hardness (H _B) could be represented by a multiregression formulas. A negative correlation existed between these properties and MC, whereas a postive correlation showed between them and the SG. The changing rate of these properties induced by 1% MC changes varied with the wood species: 2.6% change in MOR was observed in Japanese cedar, China fir, western hemlock, red meranti, and Selangan batu; and 3.9% was found in red oak. For MOE, a 0.58% change was observed in Japanese cedar, China fir, and red meranti; western hemlock and Selangan batu exhibited 1.2% and red oak 2.5%. For hardness, a 1.1% change was observed in Japanese cedar, western hemlock, and red oak; red meranti and China fir exhibited 3.3%; and Selangan batu 1.8%.A part of this report was presented at the 48th annual meeting of the Japan Wood Research Society in Shizuoka, Japan, April 3-5, 1998     

Freezing tolerance of conifer seeds and germinants

Survival after freezing was measured for seeds and germinants of four seedlots each of interior spruce (Picea glauca x engelmannii complex), lodgepole pine (Pinus contorta Dougl. ex Loud.), Douglas-fir (Pseudotsuga menziesii (Mirb.) Franco) and western red cedar (Thuja plicata Donn ex D. Donn). Effects of eight seed treatments on post-freezing survival of seeds and germinants were tested: dry, imbibed and stratified seed, and seed placed in a growth chamber for 2, 5, 10, 15, 20 or 30 days in a 16-h photoperiod and a 22/17 degrees C thermoperiod. Survival was related to the water content of seeds and germinants, germination rate and seedlot origin. After freezing for 3 h at -196 degrees C, dry seed of most seedlots of interior spruce, Douglas-fir and western red cedar had 84-96% germination, whereas lodgepole pine seedlots had 53-82% germination. Freezing tolerance declined significantly after imbibition in lodgepole pine, Douglas-fir and interior spruce seed (western red cedar was not tested), and mean LT50 of imbibed seed of these species was -30, -24.5 and -20 degrees C, respectively. Freezing tolerance continued to decline to a minimum LT50 of -4 to -7 degrees C after 10 days in a growth chamber for interior spruce, Douglas-fir and lodgepole pine, or after 15 days for western red cedar. Minimum freezing tolerance was reached at the stage of rapid hypocotyl elongation. In all species, a slight increase in freezing tolerance of germinants was observed once cotyledons emerged from the seed coat. The decrease in freezing tolerance during the transition from dry to germinating seed correlated with increases in seed water content. Changes in freezing tolerance between 10 and 30 days in the growth chamber were not correlated with seedling water content. Within a species, seedlots differed significantly in freezing tolerance after 2 or 5 days in the growth chamber. Because all seedlots of interior spruce and lodgepole pine germinated quickly, there was no correlation between seedlot hardiness and rate of germination. Germination rate and freezing tolerance of Douglas-fir and western red cedar seedlots was negatively correlated. There was a significant correlation between LT50 after 10 days in the growth chamber and minimum spring temperature at the location of seedlot origin for interior spruce and three seedlots of western red cedar, but no relationship was apparent for lodgepole pine and Douglas-fir.     

Effect of adding steam-exploded wood flour to thermoplastic polymer/wood composite

The effect of steam-exploded wood flour (SE) added to wood flour/plastic composite was examined using SE from beech, Japanese cedar, and red meranti and three kinds of thermoplastic polymer: polymethylmethacrylate, polyvinyl chloride, and polystyrene. Addition of SE increased the fracture strength and water resistance of the composite board to an extent dependent on the polymer species and the composition of wood/SE/polymer. However, water resistance decreased with the increasing proportion of SE when SE meranti was added. Effects of the wood species of SE on the properties of resulting board were small. An increased moisture content of wood flour or SE (or both) increased the variation of board performance.     

Assessing VOC emission by different wood cores using the PTR-ToF-MS technology

To date, the chemical composition and the amount and diversity of volatile organic compounds (VOCs) released by different woody plants samples have been measured and characterized through one of the most common techniques, the gas chromatography–mass spectrometry. However, this technique is very time-consuming and requires sample preparation. By contrast, the Proton-Transfer-Reaction Time-of-Flight Mass spectrometry (PTR-ToF-MS) represents an innovative tool able to provide the whole mass spectra of VOCs with short response time, high mass resolution and without sample preparation. This technique is fast, non-invasive, highly sensitive with a rapid detection system and a very low mass fragmentation of the volatile molecules. The goal of this study was to characterize the VOCs profile of different wood sample cores using a PTR-ToF-MS tool and thereafter to assess whether VOC emissions were specific for some groups of trees. VOCs released from core wood samples belonging to 14 different species were analyzed and subsequently, using an advanced multivariate class-modeling approach, the groups (softwood and hardwood) and the different tree species were discriminated. PTR-ToF-MS was able to detect VOCs from wood and to discriminate between hardwood and softwood and among different species. The great potential and the rapidity of this analysis method allow the PTR-ToF-MS to become a commercial standard tool for monitoring VOCs emitted by wood.     

Anatomical explanations for the changes in properties of western red cedar (<Emphasis Type="Italic">Thuja plicata</Emphasis>) wood during heat treatment

Thermal treatment is an alternative to the chemical treatment in wood preservation, which has been used to some extent in improving timber quality. Despite the enormous works done so far on the effects of heat treatment on wood properties, very little is known about the anatomical changes in the various wood species during the process. Wood samples from western red cedar (Thuja plicata) were heat-treated at a temperature of 220°C for 1 and 2 h. The anatomical structures were examined before and after the heat treatment process by using scanning electron microscope (SEM) and related to density, water uptake, thickness swelling and modulus of rupture of wood samples obtained from the same board. Heat treatment of red cedar wood resulted in the destruction of tracheid walls, ray tissues and pit deaspiration. The destroyed tracheid walls and ray tissues appeared to blow up, thus increasing the size of the specimen. The process of pit deaspiration also resulted in increasing size of the pits, thus creating more openings in the wood. These changes in wood anatomy indicate that the well-established chemical degradation is not the only reason for changes in wood properties during heat treatment. However, it is believed that the effects of the chemical changes still outweigh those of the anatomical changes based on the modification observed during the process of heat treatment.     

On the loss factor of wood during radio frequency heating

 The radial direction loss factor of full-size western hemlock sapwood and heartwood, as well as western red cedar heartwood timbers was measured using the direct calorimetric method with a laboratory-scale radio frequency/vacuum dryer at the frequency of 13.56 MHz, moisture content range between 10 and 80%, temperature range between 25 and 55 °C, and root mean square (rms) electrode voltages of 0.8 and 1.1 kV, respectively. The results indicated that the moisture content, temperature, electric field strength and wood type significantly affected the loss factor. Empirical regression equations were derived based on the experimental data that made possible the calculation of the loss factor and power density within wood during RF heating. Received 18 January 1997     

Effect of fungal exposure on the strength of thermally modified Norway spruce and Scots pine

Abstract

Thermal modification at elevated temperatures changes the chemical, biological and physical properties of wood. In this study, the effects of the level of thermal modification and the decay exposure (natural durability against soft-rot microfungi) on the modulus of elasticity (MOE) and modulus of rupture (MOR) of the sapwood and heartwood of Scots pine and Norway spruce were investigated with a static bending test using a central loading method in accordance with EN 408 (1995). The results were compared with four reference wood species: Siberian larch, bangkirai, merbau and western red cedar. In general, both the thermal modification and the decay exposure decreased the strength properties. On average, the higher the thermal modification temperature, the more MOE and MOR decreased with unexposed samples and increased with decayed samples, compared with the unmodified reference samples. The strength of bangkirai was least reduced in the group of the reference wood species. On average, untreated wood material will be stronger than thermally modified wood material until wood is exposed to decaying fungi. Thermal modification at high temperatures over 210°C very effectively prevents wood from decay; however, strength properties are then affected by thermal modification itself.     

木质复合材有机挥发气体采样舱

人造板释放的有害挥发气体有500多种,其中,重要气体包括萜烯、乙醛、酮, 苯和甲苯等.东北林业大学在国内率先研制出这种有机挥发气体采样舱,通过一个小的不锈钢环境舱,对复合材料如地板、墙板、涂料和家具制作材料释放的有机挥发气体浓度采样,并制定出相应的取样规程,初步研究实验表明:该采样仓各项性能稳定,采集的样品能够真实反映代表性气体的品种和数量,取样效果明显,该装置具有较高实用价值.     

Physiological effects in humans induced by the visual stimulation of room interiors with different wood quantities

To clarify the visual effects of room interior with wooden materials on humans, pulse rate, blood pressure, and brain activity were measured while the subjects were exposed to visual stimuli using actual-size model rooms. The wood ratios (the ratio of the area covered with wooden material to the whole area of the ceiling, walls, and floor) of the rooms were 0%, 45%, and 90%. Subjective evaluation was also conducted. In the 0% room, diastolic blood pressure decreased significantly, but the observed change in the autonomic nervous activity was relatively small. In the 45% room, a significant decrease in the diastolic blood pressure and a significant increase in pulse rate were observed. This room tended to have the highest scores in subjective “comfortable” feeling. The 90% room caused significant and large decreases in systolic blood pressure and diastolic blood pressure at the beginning of the test, but the large coverage of wood appeared to cause a rapid decrease in brain activity and an increase in pulse rate. The present study demonstrated that a difference in wood ratio in the interior caused different physiological responses, especially in the autonomic nervous activity, by using actual-size rooms for the first time.     

Acetaldehyde emission from wood induced by the addition of ethanol

A mechanism of acetaldehyde emission from wood induced by the addition of ethanol was proposed. It is known that acetaldehyde generation is due to the oxidation of ethanol via a metabolic process involving alcohol dehydrogenase (ADH) in living bodies. However, it remains unclear whether the enzymatic alcohol oxidation is applicable to wood. We investigated possible factors of wood parts, conditioning, storage sites, and heating and sterilization treatments on acetaldehyde emission using the syringe method and HPLC analysis. We reconfirmed that acetaldehyde emission was observed only when ethanol was added to wood. Greater acetaldehyde emissions were obtained in heartwood compared to sapwood in both Japanese cedar (Cryptomeria japonica D. Don) and Japanese cypress (Chamaecyparis obtusa Endl.) specimens. In addition, an acetaldehyde conversion rate of 1–2 mol% was determined in green cedar heartwood samples, while, conversely, air-dried cedar heartwood samples showed 4–5 mol%. Ethylene oxide gas sterilization had the effect of decreasing acetaldehyde emission on air-dried wood, but not on green wood. Autoclave sterilization could completely prevent acetaldehyde emissions from both green and air-dried wood. These results suggested that an original ADH in wood and an attached ADH from the outside via microorganisms onto wood were assumed to be the primary causes of acetaldehyde emissions from wood induced by the addition of ethanol.     

Compressive deformation of wood impregnated with low molecular weight phenol formaldehyde (PF) resin IV: Species dependency

Flat-sawn specimens of eight wood species, albizia (Paraserianthes falkata, 0.23 g/cm³), Japanese cedar (Cryptomeria japonica, 0.31 g/cm³), red lauan (Shorea sp., 0.36 g/cm³), European spruce (Picea abies, 0.44 g/cm³), Douglas fir (Pseudotsuga douglasii, 0.50 g/cm³), elm (Ulmus sp., 0.51 g/cm³), Japanese beech (Fagus crenata, 0.64 g/cm³), and Japanese birch (Betula maximowicziana, 0.71 g/cm³), were impregnated with low molecular weight phenol-formaldehyde (PF) resin and their compressive deformations were compared. The volume gain (VG) and weight gain due to 20% resin solution impregnation were different among species. Furthermore, the specific volume gain (VG/specific gravity), indicating the degree of swelling of the cell wall, also varied from 17.7% for European spruce to 26.4% for elm. Oven-dried specimens of each species were compressed using hot plates fixed to an Instron testing machine. The deformation behavior of resin-impregnated wood up to 10MPa was significantly different among the species. Stress development during cell wall collapse for low density wood was minimal. As a consequence, a significant increment of density occurred up to 2MPa for low density wood such as albizia and Japanese cedar. When PF resin-impregnated wood was compressed up to 2MPa and the pressure was kept constant for 30min, the density of Japanese cedar reached 1.18g/cm³, about 30% higher than the density of compressed Japanese birch, which possesses an original density that is 2.5 times higher than that of Japanese cedar. The mechanical properties of resin-impregnated wood, especially low density wood, increased with density. Hence, it is manifested that low density wood species have an advantage as raw materials for obtaining high-strength wood at low pressing pressure.     

Electromagnetic shielding efficiency of the electric field of charcoal from six wood species

Six wood species were carbonized under various carbonization temperatures and nonoxygen conditions to obtained charcoal. The effects of wood species, rate of temperature rise, and carbonization temperature on the electromagnetic shielding efficiency (ESE) of the electric field were investigated. The wood species used in this study were Japanese cedar, China fir, western hemlock, red oak, fortune paulownia, and Taiwan acacia. Tested materials were carbonized in a high-temperature oven under the following conditions: rate of temperature rise 1°–5°C/min; carbonization temperature 500°–1100°C, with temperature intervals of 100°C; maximum temperature maintained for 1h; and flow rate of nitrogen 300ml/min. The electromagnetic insulation strength system was used to detect the ESE of the electric field of charcoal. It was found that western hemlock and fortune paulownia charcoal showed maximum ESE values of of 36 and 61dB generated at a carbonization temperature of 1000°C. The charcoals derived from four other wood species showed maximum ESE values of 28dB for Japanese cedar, 23dB for China fir, 32dB for red oak, and 38dB for Taiwan acacia, respectively, at a carbonization temperature of 1100°C. The ESE value for fortune paulownia charcoal was similar to those of metal nets. The relations between ESE and logarithmic values of resistivity (log) could be represented by a negatively exponential formula.Part of this report was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, April 2000     

Influence of inorganic matter on wood pyrolysis at gasification temperature

The influence of inorganic matter on the pyrolysis of Japanese cedar (Cryptomeria japonica) wood was studied at a gasification temperature of 800°C with demineralization through acid washing. Some influences on the formation of char, tar, and low molecular weight products coincided with results reported at temperatures lower than the gasification temperature. However, the carbonization behavior of the volatile products and the yield of polysaccharide fraction were not able to be explained as a sum of the pyrolysis of cellulose, hemicellulose, and lignin even after demineralization. These results suggest some interactions between wood constituent polymers other than the influence of inorganic matter.     

Effects of moisture in wood materials on the SNR of GPS signals

This study was performed to investigate the factors responsible for the reduction in the signal-to-noise ratio (SNR) of a global positioning system (GPS) when used in a forest. We investigated the relationship between the SNR values of GPS signals and the moisture in wood materials and clarified this relationship through experimentation and simulation. Although the wood material itself had a minimal effect on SNR reduction, moisture in the wood had an obvious effect. It is noteworthy that wood material with a moisture resistance quantity (Mw) of 2 g/cm² caused a reduction of more than ~10 dB in the SNR. This Mw value corresponds to Japanese cedar with a green stem thickness of ~7 cm. Under unobstructed sky conditions, SNR is less than ~20 dB, so a reduction of 10 dB has a marked effect on GPS reception. The reduced SNR under canopies resulted from moisture in stems and the canopy. Furthermore, a simulation performed in a Japanese cedar forest revealed that 77.8% of the SNR reduction was caused by stems, 8.1% by branches, and 14.1% by needles.     

Decay resistance of sapwood and heartwood of untreated and thermally modified Scots pine and Norway spruce compared with some other wood species

Abstract

Thermal modification has been developed for an industrial method to increase the biological durability and dimensional stability of wood. In this study the effects of thermal modification on resistance against soft- and brown-rot fungi of sapwood and heartwood of Scots pine and Norway spruce were investigated using laboratory test methods. Natural durability against soft-rot microfungi was determined according to CEN/TS 15083-2 (2005) by measuring the mass loss and modulus of elasticity (MOE) loss after an incubation period of 32 weeks. An agar block test was used to determine the resistance to two brown-rot fungi using two exposure periods. In particular, the effect of the temperature of the thermal modification was studied, and the results were compared with results from untreated pine and spruce samples. The decay resistance of reference untreated wood species (Siberian larch, bangkirai, merbau and western red cedar) was also studied in the soft-rot test. On average, the soft-rot and brown-rot tests gave quite similar results. In general, the untreated heartwood of pine was more resistant to decay than the sapwood of pine and the sapwood and heartwood of spruce. Thermal modification increased the biological durability of all samples. The effect of thermal modification seemed to be most effective within pine heartwood. However, very high thermal modification temperature over 230°C was needed to reach resistance against decay comparable with the durability classes of “durable” or “very durable” in the soft-rot test. The brown-rot test gave slightly better durability classes than the soft-rot test. The most durable untreated wood species was merbau, the durability of which could be evaluated as equal to the durability class “moderately durable”.     

徐州出土汉代棺木用材树种鉴定及其化学性质

木材是人类日常生活的常见材料,也是从古至今人类文明与民族文化的重要载体。伴随着考古发掘工作的进行,来自不同地区、不同朝代的大量木质文物出土并需要持续保护,因此掌握出土木质文物所用的木材树种情况,并研究其化学组分的降解状态,可为制定合理的木质文物修复和保护方案提供科学依据。通过对徐州万达汉墓墓群中1号与4号墓出土棺木进行取样和对标准三切面的切片进行观察,根据三切面显微构造特征对棺木所用木材树种进行鉴定,经与标准切片比对,结果表明M1c、M1oc、M4c、M4oc棺木树种分别为楠木(Phoebe sp.)、硬木松(Pinus sp.)、梓木(Catalpa sp.)、榉木(Zelkova sp.)。进一步采用荧光显微镜与傅里叶变换红外光谱、X射线衍射相结合的方法,分析棺木的主要化学组分降解情况。结果表明:与现代健康材相比,古木在长期埋藏过程中,木材的主要多糖类化学组分纤维素和半纤维素降解严重,纤维素结晶度降低;古木各类型细胞中木质素的自发荧光效应均减弱,且红外光谱分析表明木质素化学结构发生改变;古木在埋藏过程中木材的整体构造保存较好,但主要化学组分发生了降解,这与其地下饱水低氧的埋藏环境有很大关系。     

Headspace solid‐phase microextraction gas chromatography–mass spectrometry for the detection of volatile organic compounds released from Ganoderma boninense and oil palm wood

Basal stem rot disease caused by the white‐rot fungus Ganoderma boninense is a major threat to the oil palm industry, and hence, the ability to detect infections at an early stage of development is desired. In this study, a headspace solid‐phase microextraction (HS‐SPME) method coupled with gas chromatography–mass spectrometry (GC‐MS) was employed to analyse the volatile organic compounds (VOCs) released from G. boninense cultures and infected oil palm wood. We examined VOCs released from three types of samples: G. boninense mycelium, oil palm wood and oil palm wood colonized by G. boninense. This preliminary study led to the tentative identification of 57 VOCs, including alcohols, alkanes, volatile acids, ketones, aldehydes, esters, sesquiterpenes and polycyclic aromatic hydrocarbon groups. Aliphatic compounds with eight‐carbon atoms, such as 1‐octen‐3‐ol, 3‐octanone, 1‐octanol and (E)‐2‐octenal, were the most abundant constituents of the Ganoderma samples, whereas furfural and hexanal were the major compounds detected in the oil palm wood samples. Chemometric analyses using cluster heat maps and principal component analyses were used to discriminate between the VOC profiles. The results indicated that the novel method described here could be used to detect Ganoderma disease and, more generally, for chemoecological studies of plant–pathogen interactions.     

人造板VOCs检测方法与限量规定

VOCs为熔点低于室温而沸点在50～ 260℃的挥发性有机化合物的总称.本文介绍了人造板VOCs对人体及环境的危害,人造板VOCs的来源主要是胶粘剂、表面加工过程、染色过程以及木材本身含有,并综述了国内外人造板VOCs的检测方法和限量规定.