杨木预水解过程中化学组分的降解行为及P因子调控作用

预水解具有环境友好性,符合生物炼制的理念。前期关于预水解的研究多集中于半纤维素的降解、分离和利用,而有关预水解过程中木质素降解的系统研究鲜有报道。以杨木为原料,在130~210℃条件下保温30~120 min进行预水解,结合P因子研究得率、葡聚糖、木聚糖、酸不溶木质素和酸溶木质素的降解率,揭示P因子对木质素降解行为的调控作用,探讨各化学组分在预水解过程中的相互作用。研究表明,预水解过程中木质素发生了一定程度的碎片化。随温度升高和时间延长,酸不溶木质素降解率均逐渐升高;当温度为190和210℃时,随时间延长,酸溶木质素降解率先升高后降低。试验证明,P因子对杨木木质素的降解具有调控作用。随着P因子增加,酸不溶木质素降解率呈指数上升,且分为快速降解(P因子<1500)和缓慢降解(P因子>1500)两个阶段;酸溶木质素降解率先上升后下降,在P因子为1926时达到最大值45.9%。此外,预水解过程中碳水化合物和木质素的降解具有相互作用关系。碳水化合物的降解为木质素的溶出打开了物理通道,同时木质素的重新吸附阻碍了其进一步降解。     

γ-戊内酯/水体系下稀酸预处理对玉米秸秆酶解特性的影响

γ-戊内酯预处理可以打破纤维原料的抗降解屏障,改善底物的可降解性能。目前,有关戊内酯预处理对木质纤维原料水解特性和结构变化的研究较少。本试验在戊内酯/水体系下,采用硫酸和硫酸氢钠预处理玉米秸秆,研究了其对底物水解特性和结构的影响。结果表明,戊内酯/水体系能够脱除底物中的半纤维素和木质素。硫酸的催化效果优于硫酸氢钠,硫酸浓度分别为75和150 mmol/L时(120℃下进行预处理1 h),底物中纤维素相对含量从34.82%增至57.41%和72.57%,150 mmol/L硫酸预处理时半纤维素和木质素脱除率为92.0%和77.4%,纤维素酶(10 U/g底物)水解得率分别为52.4%和65.6%。对预处理前后玉米秸秆结构表征结果显示,戊内酯预处理后玉米秸秆纤维表面受到破坏,表面O/C明显增加,木质素和半纤维素被脱除,玉米秸秆结晶度增加。该试验表明戊内酯/水体系下稀硫酸预处理可高效溶出玉米秸秆中的半纤维素和木质素,提高纤维素酶水解效率,具有一定的应用前景。     

木质素改性脲醛树脂对竹层积材甲醛释放量及胶合性能的影响

针对竹层积材中甲醛释放量过高的问题,以碳化竹片为原料,利用木质素作为脲醛树脂胶黏剂的甲醛捕捉改性剂,对脲醛树脂胶黏剂进行共混改性后压制双层竹层积材。采用木质素添加量和组坯方式的双因素分析法,探讨木质素改性脲醛树脂胶黏剂对竹层积材甲醛释放量及胶合性能的影响;采用环境扫描电子显微镜(ESEM)对木质素改性后的竹层积材胶合界面进行微观形貌分析。木质素的加入使竹层积材的甲醛释放量明显降低,各组坯方式下竹层积材的甲醛释放量差异较小,均可达到GB 18580—2001标准规定的E2级;随着木质素添加量的增加,竹层积材的剪切强度逐渐增大,竹黄面与竹黄面无节组坯试件(II)、竹黄面与竹青面无节组坯试件(IO)及竹黄面与竹黄面有节组坯试件(Node)的剪切强度均在木质素添加量为40%时达到最大,分别为7.6,8.0和8.5 MPa,相比空白组分别提高了85%,70%和41%;对于竹黄面与竹黄面组坯试件,带节试件的胶层剪切强度大于无节组;由ESEM可知,碳化竹材胶合界面被压缩甚至压溃,表面细胞不同程度呈扁平碎片状,胶黏剂主要渗透到竹材的表层破坏细胞,多数为薄壁细胞,位于竹材表层的维管束中偶尔也会有胶黏剂存在,极少量胶黏剂可能通过裂隙进入竹材更深部位的细胞。结果表明:在相同木质素添加量条件下,组坯方式对竹层积材甲醛释放量几乎没有影响;黄-黄无节组坯试件、黄-青无节组坯试件及黄-黄有节组坯试件胶层剪切强度随着木质素添加量的增加逐渐增大,黄-青组坯试件的胶层剪切强度普遍优于黄-黄组坯试件,黄-黄有节组坯试件胶层剪切强度均大于无节试件;ESEM分析表明,由于碳化竹片表面易被压缩压溃,木质素含量较大的高黏度胶黏剂缺乏有效渗透,致使胶黏剂集聚在压溃细胞表面,竹片胶合界面有效胶层厚度增大,从而导致胶层剪切强度增加。     

稀硫酸预处理对毛竹竹黄木质素结构的影响

以毛竹竹黄为原料,研究其木质素在稀酸预处理过程中的结构变化。依据Bjrkman的方法分离纯化得到竹黄和稀酸预处理竹黄的磨木木质素,采用红外光谱(FT-IR)和核磁共振定量~(13)C谱对两个木质素样品结构进行分析。FT-IR和定量~(13)C谱图表明:在酸性条件下,竹黄木质素紫丁香基单元中醚化的联接键发生断裂,S/G比值由1.3降低为1.1。木质素在稀硫酸预处理过程中发生缩合反应,主要发生在愈创木基单元上。木质素芳环上C—O键含量由196.1/100C_9降低为187.7/100C_9,C—H键含量由219.4/100C_9降低为205.7/100C_9,C—C键含量由179.6/100C_9提高为190.3/100C_9,缩合度由31.4%提高为35.2%。     

杉木和"三北"一号杨磨木木质素化学官能团特征的研究

本研究使用Bjrkman的提取方法,分离出针叶材杉木和阔叶材"三北"一号杨的磨木木质素(MWL),并采用Lundguist方法对分离出的MWL进行提纯.用红外光谱仪(FTIR)、超导核磁共振波谱仪(1HNMR)、液相色谱(HPLC)及紫外/可见分光光度仪(UV)测定了这两个树种MWL的化学结构和官能团.结果表明:(1)杉木木质素碳的含量较杨树高1.23%,氢和氧的含量分别低0.22%和0.85%,"三北"一号杨木质素中的甲氧基含量比杉木的高6.26%.(2)杉木和"三北"一号杨两种磨木木质素的苯基丙烷结构单元的经验式分别为C9H8.08O2.46(OCH3)0.94和C9H7.86O2.33(OCH3)1.41.(3)杉木磨木木质素中的脂肪族羟基(OHaliph)和酚羟基(OHph)数在每C9单元中分别是0.93和0.25,分别占总羟基的78.8%和21.2%."三北"一号杨磨木木质素中的脂肪族羟基(OHaliph)和酚羟基(OHph)数在每C9单元中分别是1.02和0.49,分别占总羟基的67.5%和32.5%.(4)杉木与"三北"一号杨磨木木质素在210nm附近的吸收波长基本相同.但在280nm附近杨树磨木木质素的吸收波长为280.2nm,而杉木磨木木质素由于愈疮木基丙烷产生了深色化效果,使吸收波长向长波长方向移动至282.2nm.(5)杉木的红外光谱吸收峰强度具有典型的针叶材特征,"三北"一号杨磨木木质素的红外光谱吸收峰强度与温带阔叶材的特征不完全吻合.(6)杉木和"三北"一号杨磨木木质素中每C9单元的β-O-4结构的平均质子数分别为0.33和0.50.β-5结构(苯基豆满香)中的平均H质子数量分别为0.23和0.16.β-β结构中Hα的平均质子数量分别为0.92和0.67.     

烘焙提升生物质燃料品质的研究

以稻壳(RH)和木屑(PS)为原料，使用小型烘焙装置，研究了烘焙对生物质燃料品质的提升作用。相比原料，烘焙稻壳(TRH)和烘焙木屑(TPS)固定碳质量分数的最大上升量分别为7.18%和11.76%;C元素质量分数的最大上升量分别3.50%和5.80%,挥发分和O元素质量分数明显下降，H元素质量分数小幅降低；热值有所提升，最大提升幅度分别为11.1%(RH)和15.9%(PS);半纤维素大量分解，至300℃后烘焙的稻壳和木屑中半纤维素质量分数仅为2.41%和1.06%,降幅均超过90%,木质素质量分数显著增加，最大增幅分别为119%(RH)和208%(PS)。生物质烘焙后，内部纤维结构被破坏，可磨性提高，随着烘焙程度的加深，烘焙稻壳研磨后粒径在0.15 mm以下的颗粒显著提升；—OH和C—O等含氧官能团减少，疏水性提升，250℃烘焙30 min的稻壳和木屑的疏水性提升幅度分别为28.08%和25.66%。     

组合预处理对橡实壳组成及酶解转化的影响

为脱除果壳类原料中的半纤维素和木质素,减少其对纤维素酶的无效吸附,提高酶解转化率。采用蒸汽爆破、Na OH、碱性H2O2及其组合预处理方法,研究不同方法对橡实(蒙古栎种子)壳组成及酶解转化的影响。结果表明,经过2.25 MPa蒸汽爆破预处理后,橡实壳半纤维素由26.81%降低至5.79%,半纤维素脱除率达87.28%,酶水解120 h后葡萄糖得率由10.32%提高至38.36%。橡实壳蒸汽爆破组合氢氧化钠处理后,木质素脱除率可达54.29%。而蒸汽爆破组合碱性H2O2处理后,酶解120 h葡萄糖得率可达76.65%,是未处理橡实壳的7.4倍。     

β-5型木质素模型化合物热解机理研究

木质素作为三维网状无定形高聚物,其化学结构非常复杂。为探究热解过程中产物的分布及形成路径,利用PyGC/MS联用仪在不同的热解温度下对软木木质素中最典型的C—C键(β-5型)模型化合物的热解产物进行详细研究。结果表明:β-5型化合物在低温下主要发生C—O键的开环断裂,热解产物仍以二聚体的酚类和酮类化合物为主。随着热解温度的升高,二聚体继续发生二次裂解反应,形成大量的小分子芳香族化合物,相对含量约占15%～30%;当热解温度为900℃时,热裂解生成的化合物之间能够通过缩聚反应形成萘和茚,其相对含量约占产物含量的9%。同时,反应路径也进一步揭示了热解过程中的转化机理。     

蒸煮爆破处理过程中毛竹材加工剩余物主要化学成分的变化研究

采用硫酸水解法(aldito-acetate procedure)、X射线粉末衍射(XRD)、傅里叶变换红外光谱(FTIR)分析了蒸爆过程中毛竹材加工剩余物纤维聚集态结构及主要化学成分的变化.研究结果表明,(1)毛竹材加工剩余物经蒸爆处理,60%左右的半纤维素水解,木质素低分子化且裸露到纤维表面,易被80%乙醇及木质素溶剂提取,从而实现毛竹材加工剩余物主要组分的有效分离.(2)毛竹材加工剩余物经蒸爆处理,80%乙醇抽提物得率提高,综纤维素得率减少,木质素含量减少:葡萄糖相对含量增加,半纤维素降解明显.(3)210℃处理10 min和220℃处理10 min的蒸爆浆的化学组成变化几乎没有区别,但两者与200℃处理10 min差别较大,210℃处理10 min是毛竹材加工剩余物适宜的处理温度.(4)FTIR结果显示蒸爆处理后在1040～1060 cm-1区的吸收峰分裂为明显的2个峰表明半纤维素降解,1166 cm-1处的吸收强度明显减弱,表明C-O-C键有不同程度的断裂.X-身寸线衍射分析结果显示毛竹材加工剩余物蒸爆处理后纤维素相对结晶度增加.     

漆酶-超声波协同处理碱木质素的表面化学结构特征

分别采用超声波、漆酶及超声波协同漆酶的方法处理麦草碱木质素,通过化学分析法结合红外光谱、X射线光电子能谱和电子自旋共振等仪器分析手段,对比各处理过程木质素酚羟基含量、表面官能团、表面元素及表面自由基的变化,探讨3种处理方式对碱木质素结构的影响机理。结果表明,超声波处理后的木质素,总酚羟基含量比未处理的有所增加,漆酶处理后酚羟基含量减少。与未经处理的纯碱木质素相比,木质素经超声波处理后自由基浓度减少了38%,而漆酶处理后自由基浓度显著增加,其中单一漆酶处理增加了112%,超声波后再进行酶处理增加了193%。超声波空化作用可使木质素发生脱甲氧基反应及连接键断裂;漆酶处理过程中有解聚反应,同时酚羟基氧化变成苯氧自由基,进而发生自由基反应;超声波后生成的木质素小分子更易与漆酶反应,C—O单键被氧化。     

Growth of Phlebiopsis gigantea in wood of seven conifer species

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

Growth of Mixed Birch-Coniferous Stands in Relation to Pure Coniferous Stands at Similar Sites in South-eastern Norway

Mean age, mean and top heights and yield were studied in 20 mixed stands of birch ( Betula pubescens Ehrh. and B. pendula Roth) and Picea abies (L.) Karst. and nine mixed stands of birch and Pinus sylvestris L. in south-eastern Norway. Each mixed stand and the adjacent pure coniferous stand (control) were growing under the same site conditions and had not been commercially thinned. There were no significant differences in mean age at breast height or in top heights between birch and conifers in the mixed stands, while mean height was significantly higher for birch than for spruce. A growth index was calculated based on total volume and age at breast height. For the spruce sites the growth in young mixed stands (birch < 17 m) was superior to that of pure spruce, while the difference was insignificant in older stands. The growth index correlated positively with the ratio between generatively and vegetatively regenerated birch trees, and negatively with the age of the oldest species in the mixture and with site quality. For the pine sites there was no significant difference in the growth index between mixed birch-pine and pure pine stands. A mixture effect of birch on the volume yield of spruce or pine could not be demonstrated.     

Defoliation by the Needle-shortening Pine Gall Midge,Thecodiplosis brachyntera,on Pines in Central Sweden

An outbreak of the needle-shortening pine gall midge, Thecodiplosis brachyntera , occurred on Scots pine, Pinus sylvestris (L.) and lodgepole pine, P. contorta (Dougl.) in central Sweden during 1995-1998. The larval feeding of T. brachyntera kills current-year needles and heavy infestation causes severe defoliation. A pattern of fluctuating defoliation among years and sites was found on both pine species. Defoliation was evenly distributed in the crown of P. sylvestris during years of high as well as low infestation; apical whorls had as much defoliation as basal whorls. In P. contorta , however, there was a tendency for defoliation to be concentrated on branches in the most apical whorls. Growth ring increments on P. sylvestris with high levels of defoliation (71%) did not differ from trees with moderate levels (26%) of defoliation. Shoot lengths were significantly shorter, however, on heavily infested trees the year after defoliation.     

Decomposition and nutrient loss from prunings of different contour hedgerow species in tea plantations in the sloping highlands of Sri Lanka

Contour hedgerows of multipurpose tree species in the sloping tea lands of Sri Lanka are expected to reduce soil erosion and also add significant amounts of plant nutrients to the soil via periodic prunings. The objective of this experiment was to characterize the biomass decomposition pattern and quantify the amount of nutrients added through prunings of six tree species (Calliandra calothyrsus, Senna spectabilis, Euphatorium innulifolium, Flemingia congesta, Gliricidia sepium and Tithonia diversifolia) currently being used in hedgerows associated with tea. Withered leaf and stem prunings (50 g) were enclosed in 2-mm litter bags, placed at 5-cm depth and retrieved after one, three, six, nine and 12 weeks. Loss of initial dry weight, N, P and K was measured. Single exponential decay function adequately described both dry weight and nutrient loss. Tree species differed significantly in their rate of breakdown with decomposition constants (k) varying from 0.0299 to 0.2006 week⁻¹ for leaves and from 0.0225 to 0.0633 week⁻¹ for stems. Gliricidia showed the highest k for leaves with the rest in the following descending order: Senna > Tithonia ≥ Euphatorium > Calliandra > Flemingia. A similar pattern was observed for loss of all nutrients with Calliandra and Flemingia always having lower k values than the rest. Although N immobilization was not observed, immobilization of P and K was observed during the first week of incubation in some species, particularly in stem prunings. Annual biomass of prunings differed significantly between tree species in the following descending order: Calliandra > Senna > Flemingia > Tithonia > Gliricidia > Euphatorium. Calliandra added the greatest amount of nutrients annually to the soil with Euphatorium adding the least. Calliandra prunings provided the annual total K requirement and 49% of the N requirement of mature tea. However, none of the species provided more than 5% of the P requirement. It is concluded that among the tree species tested, Calliandra and Flemingia are the most suitable for contour hedgerows in tea plantations of this agroclimatic region because of their higher soil nutrient enrichment capacity and slower decomposition rates which would minimize leaching losses. This revised version was published online in June 2006 with corrections to the Cover Date.     

Effects of Seed Weight and Seed Type on Early Seedling Growth of Pinus sylvestris under Harsh and Optimal Conditions

The effects of seed weight and seed type on seedling growth of Pinus sylvestris (L.) were studied by seeding individually weighed orchard and stand seed in different mixtures under harsh (direct seeding in field) and optimal (seeding in nursery) conditions. In the nursery experiment an increase in the seed weight from 3 to 7 mg increased the seedling height by 10-27% and total weight by 27-113%, and decreased the height/diameter ratio by 5-6% after 2 yrs. With elimination of seed weight effects, orchard seedlings were 2% taller than stand seedlings in year 2. Without elimination of seed weight effects, orchard seedlings were 7-13% taller. In the field experiment an increase in the seed weight from 3 to 7 mg increased seedling height by 18-65%, stem volume by 81-274% and the number of top-buds by 23-34% in year 5. After elimination of seed weight effects, orchard seedlings were 7-13% taller than stand seedlings and without elimination of seed weight effects 20-21% taller after 5 yrs. Even after elimination of both seed weight and genetic effects orchard seedlings were 3-9% larger than stand seedlings in the field experiment. In conclusion, the influence of seed weight and seed type on growth traits and slenderness is highly significant and the influence seems to be greater in harsh conditions.     

Modelling of adequate pretwist for obtaining straight timber

Abstract

Wood in general and wooden studs in particular are often distorted owing to uneven shrinkage during the drying process in the sawmill. Twist is often the most detrimental of all types of distortion, and it is caused by spiral grain in combination with variations in moisture content. For sawmills, the objective is to produce dried, straight boards, and one method of dealing with boards with excessive spiral grain is to sort them out and then dry them in a pretwisted position to obtain straight boards after drying. A model using the finite element (FE) method for the simulation of drying twist distortions was first calibrated against laboratory experiments in which boards were dried with and without restraints and pretwists. After the calibration, the FE results were compared with industrial test results for boards that were dried without restraints or with restraints with zero pretwist, i.e. straight restraints. The FE model used an elastic–ideally plastic material model to obtain permanent deformations. The calibration was to set the yield stresses so that there was a good match between FE results and results from the laboratory experiments. The comparison between the industrial test results and the FE results showed that the FE model is capable of realistic simulations of drying boards with and without restraints and presumably also pretwists.     

Potential to harness superior nutritional qualities of exotic baobabs if local adaptation can be conferred through grafting

Baobab leaves form an important part of the local diet in Sahel countries and elsewhere in Africa. Existing leaf nutritional data and agroforestry performance information are based solely on Adansonia digitata L., the baobab of continental Africa. The introduction potential of Adansonia species from the center of diversity in Madagascar and from Australia remains untapped. To assess this potential, the mineral contents and B₁ and B₂ vitamin levels of dried baobab leaves were determined for five-year old trees of A. digitata, A. gibbosa (A. Cunn.) Guymer ex D. Baum, A. rubrostipa Jum. & H. Perrier (syn. A. fony Baill.), A. perrieri Capuron and A. za Baill. grown in an introduction trial in Mali. Nutritional data were evaluated against survival and vigor to identify promising germplasm. Leaf vitamin and crude protein contents were highest in the Madagascar species, especially A. rubrostipa (B₁ 88 mg 100 g⁻¹, B₂ 187 mg 100 g⁻¹, protein 20.7% dry weight). However, the local species far outperformed the introductions in survival, tree height, basal diameter and resistance to termites. We suggest grafting as a way of harnessing the vigor of well-adapted local baobab varieties to the superior nutritional profiles of A. rubrostipa and others. Cross-species grafting tests in Adansonia were successful, thus creating new agroforestry possibilities with different scion/rootstock combinations.     

Boron in forest trees and forest ecosystems

This review critically examines the role of boron (B) in forests in view of recent findings on B nutrition and the continuing occurrence of B deficiency. Many perceptions about the role of B in plants and its uptake and mobility have been altered since the last review on B in forest trees in 1990. Now there is evidence for a fundamental role of B in the formation of the pectic structure in primary cell walls in plants, and further roles in membrane function are being explored. In plants, channel-mediated B uptake, active B uptake and B uptake by mycorrhizas have been shown, B transporters have been identified, and B retranslocation has been shown. We explore these findings and their consequences on forest trees and on ecosystems that they dominate. Particular emphasis is placed on B retranslocation and B in mycorrhizal symbiosis, given their importance in trees.     

Survival and Growth of Picea abies Regeneration after Shelterwood Removal with Single- and Double-grip Harvester Systems

Three stands in Sweden were followed for 7 yrs to study the survival and growth of Norway spruce [Picea abies (L.) Karst.] regeneration after shelterwood removal with single- and double-grip harvester systems. The height of all seedlings within circular plots was recorded before and after final cutting. The tallest seedling and one randomly selected seedling on each circular plot were permanently marked and their annual height growth was measured each year during the period 1993-1999. No significant differences between single- and double-grip harvester systems were found with respect to their effects on regeneration density, survival or annual height growth. The annual height growth of the individual seedlings after shelterwood removal was significantly correlated with seedling height before shelterwood removal. Significant differences were found in annual height growth between seedlings with high and low vitality. Logging damage did not affect the annual height growth. Several practical conclusions were drawn. First, the choice of harvester system does not affect seedling height growth or survival after shelterwood removal. Secondly, the removal of a 200 m³ shelterwood with 200 stems ha^-1 does not seem to constitute a serious problem for seedling survival and growth. Finally, estimated vitality and seedling height both seem to be fairly good predictors of postrelease survival and growth.     

Development of Pinus sylvestris Main Stems Following Three Different Precommercial Thinning Methods in a Mixed Stand

Reducing competition by point cleaning may be an attractive alternative to conventional precommercial thinning in forestry. In this study, survival and development of main stems of Scots pine (Pinus sylvestris L.) following point cleaning were examined in a mixed stand of mainly Scots pine and birch (Betula pendula Roth and Betula pubescens Ehrh.) in northern Sweden. Treatments studied were: no precommercial thinning, conventional precommercial thinning, point cleaning of all secondary stems, and point cleaning of only the secondary stems that were higher than the main stem, within a radius of 0.8 m from the main stem, respectively. A randomised complete block design with three replicates was used. Measurements taken 13 growing seasons after these treatments showed that conventional precommercial thinning was the best treatment for retaining Scots pines as main stems. However, conventional precommercial thinning resulted in the poorest timber quality of the remaining Scots pines in terms of stem taper, thickest branch diameter and relative live crown height. In conclusion, point cleaning has to be followed by a complementary cleaning operation if the objective is to retain Scots pines as main stems in such mixed stands.