Acid fraction evolution in wood extractives ofPinus pinaster ait

The changes in the acid fraction of wood extracts fromPinus pinaster Ait. have been studied. Qualitative and quantitative compositions have been determined in samples that were just extracted and then seven and twelve months after extraction. Samples were prepared according to Technical Association of Pulp and Paper Industry Standards, extracted with petroleum ether (b.p. 40–60°C) in a Soxhlet apparatus and saponified with ethanolic 0.4N potassium hydroxide. The acid fraction was methylated with diazomethane, and its qualitative composition was determined by combined gas chromatography/mass spectrometry. The quantitative composition was determined by gas chromatography with a DEGS packed column. An increase was observed in the percentage of palmitic, oleic, pimaric and dehydroabietic acids, and there was a decrease in the percentage of linoleic and abietic acids. No variation was observed in extract composition after seven and twelve months.     

Removal of anionic dye Congo red from aqueous solution by raw pine and acid-treated pine cone powder as adsorbent: equilibrium, thermodynamic, kinetics, mechanism and process design

Pine cone a natural, low-cost agricultural by-product in Australia has been studied for its potential application as an adsorbent in its raw and hydrochloric acid modified form. Surface study of pine cone and treated pine cone was investigated using Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). The modification process leads to increases in the specific surface area and decreases mean particle sizes of acid-treated pine cone when compared to raw pine cone biomass. Batch adsorption experiments were performed to remove anionic dye Congo red from aqueous solution. It was found that the extent of Congo red adsorption by both raw pine cone biomass and acid-treated biomass increased with initial dye concentration, contact time, temperature but decreased with increasing solution pH and amount of adsorbent of the system. Overall, kinetic studies showed that the dye adsorption process followed pseudo-second-order kinetics based on pseudo-first-order and intra-particle diffusion models. The different kinetic parameters including rate constant, half-adsorption time, and diffusion coefficient were determined at different physico-chemical conditions. Equilibrium data were best represented by Freundlich isotherm model among Langmuir and Freundlich adsorption isotherm models. It was observed that the adsorption was pH dependent and the maximum adsorption of 32.65 mg/g occurred at pH of 3.55 for an initial dye concentration of 20 ppm by raw pine cone, whereas for acid-treated pine cone the maximum adsorption of 40.19 mg/g for the same experimental conditions. Freundlich constant 'n' also indicated favourable adsorption. Thermodynamic parameters such as ?G(0), ?H(0), and ?S(0) were calculated. A single-stage batch absorber design for the Congo red adsorption onto pine cone biomass also presented based on the Freundlich isotherm model equation.     

红松松仁膜衣提取物体外抗氧化活性研究

本文旨在探明长白山红松松仁膜衣提取物的体外抗氧化活性。分别采用60%乙醇和50%丙酮为提取剂,提取物冻干后,用分光光度法测其总多酚和总黄酮纯度,研究其自由基清除能力和还原铁离子的能力。结果表明,松仁膜衣乙醇提取物总多酚纯度为39.02%,总黄酮纯度为10.19%;丙酮提取物总多酚纯度为44.09%,总黄酮纯度为14.59%。红松松仁膜衣提取物清除ABTS⁺·、DPPH·、羟自由基（·OH）的能力和还原铁离子能力都呈现一定的剂量效应关系,且对DPPH·的清除作用和还原铁离子能力强于BHT;丙酮提取物对ABTS⁺·和·OH的清除能力显著高于乙醇提取物,表明丙酮提取物的抗氧化能力强于乙醇提取物。同时,在实验范围内,红松松仁膜衣提取物的抗氧化能力与其总多酚、总黄酮的纯度存在正相关性。      

Enhancing exterior performance of clear coatings through photostabilization of wood. Part 2: coating and weathering performance

Clear-coated boards have not been recommended for use in exterior conditions since irradiation with visible and UV radiation darkens them and photodegrades the lignin in the wooden surface beneath the coating, leading to delamination and subsequent catastrophic coating failure due to the continued action of sun, rain, and biological factors. Many approaches to rectify this problem have been explored. Chemical modification of the surface with hexavalent chromium, reaction with various anhydrides, grafting of UV absorbers, and esterification are among the methods attempted. A second approach has been via the clear coating itself where UV absorbers, antioxidants, and ultrafine titanium and iron oxides have been added. However, these have had limited or no success in stopping photodegradation processes. Since the main cause of photodegradation is photooxidation of lignin in the wooden surface as a consequence of free radical reactions initiated by UV irradiation, the approach taken in the present study, in an attempt to enhance the weathering performance of clear-coated boards outdoors, was to delignify the surfaces of wooden boards and then apply clear coatings to try and retard possible photodegradation. Two different pretreatments were used. Firstly, chemical surface delignification with a peracetic acid treatment created a partial delignification to a depth of 2–3 mm while still retaining the structural integrity of the surface. Secondly, a preweathering treatment, which resulted in a 100-μm-deep delignification zone, was compared. The coatings applied to the exposure surface of the pretreated boards were either polyurethane or an acrylic varnish. The clear-coated boards were exposed to exterior and accelerated weathering regimes for 3 years or 3000 h, respectively. Pretreated coated boards did not darken and yellow on exposure but untreated coated boards did. However, despite apparently arresting photodegradative processes on board surfaces, there were no significant gains in the performance ratings of coated pretreated boards over those of coated untreated control boards. Explanations for this involve the effectiveness of design factors incorporated into boards for exposure trials. These factors were the fungicidal dipping of boards before coating, precoating the exposure surface with a reactive primer, and applying a full polyurethane system to the back side and edges of boards. Both pretreatments resulted in clear-coated board surfaces that performed very similarly on exposure outperforming systems reported previously. It was surprising to observe that the preweathering treatment, which resulted in a 100-μm-deep delignification zone, performed as effectively as the chemically pretreated boards with 2- to 3-mm treatment zone. However, preweathered surfaces had lost all lignin in the middle lamella and there was cell separation, whereas in peracetic acid-treated boards, there was more or less complete lignin removal from the cell corner middle lamella only and partial lignin removal from other cell wall regions. Furthermore, it is anticipated that refinements in treatment methods and coating formulations will bring desired benefits and future work should focus in this area.     

长白松热解特性及热解动力学研究

为获取长白松的热解特性,预防森林火灾发生,以长白松的树枝、球果、树皮和松针作为研究对象进行热解过程分析,并采用Coats-Redfern法进行热解动力学分析,以球果为研究对象探究各种因素对长白松热解的影响。实验结果表明：4种材料的热解过程均可分为4个阶段,其中主要失重阶段的质量损失率为60%左右。升温速率越大,热解越不充分,并且存在热滞后现象,25℃/min时质量损失率最小(80.34%);粒径大小对TG、DTG曲线影响较小,粒径越小,内外部受热更均匀,因此0.20 mm粒径的材料质量损失率最大(91.18%);氮气气氛下主要失重阶段有一个失重峰,而在高纯空气气氛下有两个失重峰,且长白松球果在高纯空气中热解时间更长,热解更充分,促进作用更强,质量损失率为98.14%。热解动力学分析结果显示：4种材料的最佳机理函数为“三维扩散”,活化能最大的是树枝(157.04 kJ/mol),最小的是松针(98.19 kJ/mol),球果的活化能为148.08 kJ/mol,树皮的活化能为115.04 kJ/mol,因此,要格外注意对松针和树皮的防火工作。     

不同提取工艺的马尾松松针提取物抗氧化性能研究

研究超临界二氧化碳萃取、内置超声提取、外置超声提取、普通醇提4种不同提取工艺制备的马尾松松针提取物（SCDEP、IUEP、OUEP,EEP）,分析4种提取物内总酚和总黄酮含量差异;同时研究4种松针提取物的抗氧化性能。结果表明：SCDEP提取物中总酚与总黄酮含量分别为22．18％和4．96％,含量最高;而EEP中总酚和总黄酮含量最低,分别为13．47％和2．98％。4种提取物具有较强抗氧化能力,SCDEP、IUEP、OUEP清除DPPH自由基和还原三价铁能力均强于丁基羟基甲苯（BHT）,而EEP还原三价铁能力弱于BHT。马尾松松针提取物中总酚及总黄酮含量与抗氧化性具有明显的量效关系。     

Differences in attraction to semiochemicals present in sympatric pine shoot beetles,Tomicus minor andT. piniperda

The chemical ecology of host- and mate-finding in the pine shoot beetles,Tomicus minor andT. piniperda, was studied in southern Sweden. Beetles were collected in the field from defined attack phases on Scots pine. Using gas chromatography-mass spectroscopy, a number of oxygen-containing monoterpenes, e.g., 3-carene-10-ol, myrtenol,trans-verbenol, and verbenone, were identified from hindgut extracts of both sexes of both species. Compared toT. minor,T. piniperda contained additional compounds and in larger amounts. The amounts were highest in both species at the time when the beetles had bored into contact with the resin-producing xylem-phloem tissue. The synthesis of (1S,6R)-3-carene-10-ol by photooxidatipn of (+)-(1S,6R)-3-carene is described. In comparative electroantennogram (EAG) measurements on males and females of both species, the most active of the tested compounds wastrans-verbenol. Laboratory bioassays of walking beetles showed thatT. piniperda was attracted to uninfestèd pine logs.T. minor was more strongly attracted to pine logs infested with females than to uninfested pine logs, indicating a female-produced aggregation pheromone. Field tests confirmed thatT. piniperda was strongly attracted to pine logs. The attraction ofT. minor to logs was significant only when logs were combined with racemictrans-verbenol and (1S,6R)-3-carene-10-ol.T. minor was also attracted to a combination of these monoterpene alcohols alone. We suggest that host and mate location inT. piniperda is achieved by means of a kairomone composed of host monoterpenes, whileT. minor utilizes a primitive pheromone synergized by host odors. Evolution of host colonization strategies of the two beetles are discussed.Coleoptera: Scolytidae.This study was made within the project Odour signals for control of pest insects.     

模拟降雨条件下岩溶地区马尾松林下地表径流特征

以贵州省贵阳市岩溶地区为例,通过野外人工模拟降雨试验,研究了不同坡度(15°、20°、25°)的径流小区在不同雨强(60、90、120mm/h)下马尾松林地表径流的变化特征。结果表明,岩溶地区马尾松林下,雨强对地表径流有明显影响;随着降雨持续进行,陡坡时的径流量增幅显著大于缓坡;随着雨强增加,坡度对累积径流量的影响变得显著;坡度对累积径流量的影响并非线性关系,而是坡度较陡时影响程度更大,但不同雨强条件下径流总量的增幅不一致;岩溶地区马尾松林地在中等雨强时地表径流大,大雨强时地表径流反而较小。     

Wind and slope effects on ROS during the fire propagation in East-Mediterranean pine forest litter

The paper presents data from laboratory experimental burns modelling the effects of slope of ground surface and wind velocity over the fire spread in the pine litter layer. Subjected to the study are samples from Pinus halepensis and Pinus pinaster pine needles collected in a specific region in Greece. Statistical processing of results obtained has also been carried out and equations have been drawn up presenting the relationship between the rate of spread and changes in wind velocity and slope of terrain. Statistical models for rate of fire spread (ROS) are based on the individual effects of the two factors over the increase in the rate of fire spread above its baseline value. The spread rates in P. halepensis were higher than in P. pinaster beds and the combustion process took place mainly on the fuel top surface. The most severe case of fire propagation has been monitored when the leading edge of the fire front was moving upslope and in matching direction with the wind. The rate of spread for a fire front moving upslope with back-wind direction has been influenced mainly by the slope; however, the negative value of the wind flow reduced the spread rate. The results obtained and equations produced provide a basis to carry out a risk analysis for fire spread in the studied vegetation species taking into account specific terrain features and climate characteristics in the specified geographic area.     

Genetic Control of the Enantiomeric Composition of Ipsdienol in the Pine Engraver, Ips pini

The genetic nature of pheromone variation within species has rarely been studied, and never for male-produced long-range pheromones. Males from western North American populations of Ips pini produce predominantly (R)-(−)-ipsdienol, whereas those from eastern North American populations produce higher proportions of (S)-(+)-ipsdienol. From a population in the hybrid zone, we divergently selected lines for the opposing pheromonal types and then created F1, F2, and backcross lines. We formed additional F1, F2, and backcross lines, first by using populations with low (+)-ipsdienol enantiomeric ratios near to and distant from the hybrid zone, and then by using populations with high (+)-ipsdienol enantiomeric ratios near to and distant from the hybrid zone. Three types of analysis were employed: (1) line means analysis; (2) Mendelian analysis of assigned high and low (+)-ipsdienol enantiomeric ratio phenotypes when applicable; and (3) Castle–Wright estimation of the number of effective factors. Dominance at one autosomal locus explains much of the variation in ipsdienol blend between the divergently selected lines. Thus, as in all previously studied female long-range pheromone systems, a major genetic element is implicated. The populations with low (+)-ipsdienol enantiomeric ratios near and distant to the hybrid zone differ negligibly for this trait. We confirmed previous studies showing slightly higher ratios of (+)-ipsdienol at the hybrid zone than in a distant eastern population and reveal a genetic basis for this difference.