不同热解温度生物质炭对羊粪堆肥过程氮素损失的减控效果

为探讨高温堆肥中氮素损失的有效控制技术，以2种不同热解温度制备的稻壳生物质炭为堆肥添加剂，与羊粪、食用菌渣混合，进行了43 d的堆肥试验。设置了3 个处理，羊粪与食用菌渣质量比9:1混合体作为预备物料，在预备物料上分别添加450、650 ℃热解的生物质炭（占预备物料质量百分比15%）为B1、B2处理，在预备物料上添加未热解的稻壳（与生物质炭等体积）为CK处理。监测了堆肥体的温度、NH3挥发、N2O排放、pH值等参数变化动态，分析了不同热解温度生物质炭在堆肥中的保氮效果。结果表明，B1、B2处理促进了堆肥初期的温度快速上升，堆肥体初次升温至55 ℃所需时间分别较CK 缩短了2、6 d，B2 处理的促升温、增温效应优于B1 处理；堆肥43 d 后，CK、B1 与B2处理的NH3挥发累积量分别为378.12、117.22、94.16 mg/kg，N2O排放累积量分别为13.9、26.3、23.6 mg/kg，氮素损失率分别为47.8%、34.1%，30.5%；B1、B2处理增加了堆肥体N2O排放，降低了堆肥体NH3挥发，整个堆肥过程中N2O排放累积量远小于NH3挥发累积量，添加生物质炭对堆肥过程氮素损失表现为正向的减控作用，B1、B2处理的氮素损失率分别较CK处理降低了28.6%、36.19%，B1、B2处理之间差异不显著（P＞0.05）。综合堆温快速上升、氮素损失控制等指标，B2处理对羊粪堆肥过程保氮效果优于B1处理；堆肥工程中应用生物质炭减控氮素损失及提高堆肥质量，优选热解温度650 ℃制备的生物质炭。     

Mixing of different mineral soil layers by endogeic earthworms affects carbon and nitrogen mineralization

The effect of the endogeic earthworm species Octolasion tyrtaeum (Savigny) on decomposition of uniformly ¹⁴C-labelled lignin (lignocellulose) was studied in microcosms with upper mineral soil (Ah-horizon) from two forests on limestone, representing different stages of succession, a beech- and an ash-tree-dominated forest. Microcosms with and without lower mineral soil (Bw-horizon) were set-up; one O. tyrtaeum was added to half of them. It was hypothesised that endogeic earthworms stabilise lignin and the organic matter of the upper mineral soil by mixing with lower mineral soil of low C content. Cumulative C mineralization was increased by earthworms and by the addition of lower mineral soil. Effects of the lower mineral soil were more pronounced in the beech than in the ash forest. Cumulative mineralization of lignin was strongly increased by earthworms, but only in the beech soil (+24.6%). Earthworms predominantly colonized the upper mineral soil; mixing of the upper and lower mineral soils was low. The presence of lower mineral soil did not reduce the rates of decomposition of organic matter and lignin; however, the earthworm-mediated increase in mineralization was less pronounced in treatments with (+8.6%) than in those without (+14.1%) lower mineral soil. These results indicate that the mixing of organic matter with C-unsaturated lower mineral soil by endogeic earthworms reduced microbial decomposition of organic matter in earthworm casts.     

改性HZSM-5催化生物质与塑料热解制备芳烃和生物炭

为了进一步提升生物油的品质,该研究采用竹材和低密度聚乙烯(Low-Density Polyethylene, LDPE)为原料,采用金属氧化物和HZSM-5(HZ)为催化剂催化生物质共热解,探索生物质与塑料的混合比例、金属氧化物的种类(HZSM-5、CaO、MgO、CeO_2、La_2O_3和SnO_2)、HZSM-5和MgO的混合比例以及组合方式(分层模式和混合模式)对生物质催化共热解制备生芳烃和生物炭的影响,同时对其添加效果进行分析。结果表明:LDPE和金属氧化物的添加可以有效的促进生物质的转化,降低了生物油的产率(9.76%～23.96%),提高生物油的品质和生物炭的石墨化程度,二者具有明显的协同效果,MgO促进了烷基酚的形成,CaO促进了烯烃的转化,而La_2O_3和SnO_2明显的促进是呋喃的生成。而且混合模式可以有效的提高芳烃的产率,当生物质:LDPE=1:1,HZSM-5:MgO=2:1时,芳烃含量最高为84.99%,苯、甲苯、二甲苯和乙苯(SBTXE)的总含量达到了60.09%,而甲苯和二甲苯含量分别达到了25.97%和16.91%,混合模式有效促进了苯、甲苯和二甲苯的选择性,分层模式有效促进了烷基苯的转化,且MgO的添加明显抑制了稠环芳烃的形成。     

玉米芯的热解特性及气相产物的释放规律

为了全面掌握不同热解条件下玉米芯的热解特性及热解过程中气相产物随温度变化的释放规律,深刻理解玉米芯的热解行为及反应机理,该文采用热重-质谱联用技术对玉米芯进行了氮气气氛下的热解特性试验研究,对比研究了不同升温速率(5、10、20℃/min)、不同粒度(74、154、280、450μm)、不同气体流速(30、60、90 m L/min)等因素对玉米芯热解行为的影响,发现非等温失重过程可分为4个阶段:失水、预热解过渡、挥发分析出和炭化阶段。通过质谱分析研究了热解过程小分子气相产物(CO、CO2、CH4、O2、H2、H2O)的释放规律,并计算了挥发分释放指数。升温速率升高,热解反应越易进行;在粒度小于450μm范围内,试样热解的总失重率随粒度的增大而增加,而且颗粒越大,挥发分产物开始逸出的温度越低。粒度为154~450μm的试样的热解过程主要受颗粒内部热传递影响,而粒度154μm的试样的热解主要受内在反应动力学速率控制;随着气体流速升高,试样热解的总失重率和初始温度增大,但增幅很小,最大失重速率对应的温度也有向高温段移动的趋势。利用Coats-Redfern方法计算出玉米芯的热解动力学参数,说明玉米芯热解的挥发分析出阶段可用单段一级反应描述。该研究对于优化以玉米芯为原料的热化学转化工艺参数和提高燃料产物的产量与品质等具有重要意义,对于设计和开发高效的生物质能转化设备也可提供参考。     

土壤呼吸对生物炭添加的短期响应：发酵后处理和无机氮的影响

The biodegradability of chars derived from pyrolysis and hydrothermal carbonisation (HTC) was studied in short-term dynamic incubation experiments under controlled conditions. Carbon dioxide C (CO$_{2}$) emissions from soil-char mixtures in combination with solid digestate or mineral nitrogen (N) fertiliser were measured in dynamic chambers for 10 d.~Compared to the original material (maize straw), pyrolysis and HTC chars showed significantly lower CO$_{2}$ emissions and slower decay dynamics; and compared to the soil control, HTC char increased soil respiration to a significant extent, while pyrolysis char did not. The addition of mineral N resulted in a delayed respiration dynamics for HTC char, while the addition of digestate resulted in an increase in the respired CO$_{2}$ for pyrolysis char and a decrease for HTC char. For the first time, a peculiar two-stage decay kinetics was observed for HTC char, indicating a highly inhomogeneous substrate consisting at least of two C pools.     

Chemical stabilization of soil organic nitrogen by phenolic lignin residues in anaerobic agroecosystems

This review summarizes independent reports of yield decreases in several agricultural systems that are associated with repeated cropping under wet or submerged soil conditions. Crop and soil data from most of these agroecosystems have led researchers to attribute yield decreases to a reduction in crop uptake of N mineralized from soil organic matter (SOM). These trends are most evident in several long-term field experiments on continuous lowland rice systems in the Philippines, but similar trends are evident in a continuous rice rotation in Arkansas, USA and with no-till cropping systems in North American regions with cool, wet climatic conditions in Spring. Soil analyses from some of these systems have found an accumulation of phenolic lignin compounds in SOM. Phenolic compounds covalently bind nitrogenous compounds into recalcitrant forms in laboratory conditions and occurrence of this chemical immobilization under field conditions would be consistent with field observations of reduced soil N supply. However, technological shortcomings have precluded its demonstration for naturally formed SOM. Through recent advances in nuclear magnetic resonance spectroscopy, agronomically significant quantities of lignin-bound N were found in a triple-cropped rice soil in the Philippines. A major research challenge is to demonstrate in the anaerobic agroecosystems that these lignin residues bind sufficient quantities of soil N to cause the observed yield decreases. A key objective will be to elucidate the cycling dynamics of lignin-bound N relative to the seasonal pattern of crop N demand. Anaerobic decomposition of crop residues may be the key feature of anaerobic cropping systems that promotes the accumulation of phenolic lignin residues and hence the covalent binding of soil N. Potential mitigation options include improved timing of applied N fertilizer, which has already been shown to reverse yield decreases in tropical rice, and aerobic decomposition of crop residues, which can be accomplished through field drainage or timing of tillage operations. Future research will evaluate whether aerobic decomposition promotes the formation of phenol-depleted SOM and greater in-season N mineralization, even when the soil is otherwise maintained under flooded conditions during the growing season.     

Structural studies on soil nitrogen by Curie-point pyrolysis — gas chromatography/mass spectrometry with nitrogen-selective detection

Curie-point pyrolysis-gas chromatography mass spectrometry with N-selective detection was used to characterize the structure of organic N compounds in four mineral soils. The technique was found suitable for the fast, sensitive, and highly specific identification of N-containing pyrolysis products from whole soils with total N contents between 0.08 and 0.46%. In order to optimize the methodology, one agricultural soil was pyrolyzed at final temperatures of 573, 773, and 973 K. Almost no chemical alterations to identifiable pyrolysis products were observed when the final pyrolysis temperature was increased from 573 to 973 K. More than 50 N-containing pyrolysis products were identified, and were divided into compound classes chracterized by specific molecular-chemical structures. These included pyrroles, imidazoles, pyrazoles, pyridines, pyrimidines, pyrazines, indoles, quinolines, N derivatives of benzene, alkyl nitriles, and aliphatic amines. Three additional soil samples different in origin and N content were analyzed at 773 K and each showed a specific thermosensitive N-selective chromatogram. Many N-containing pyrolysis products were identified in all samples, which indicated general qualitative regularities in the thermal release of N-containing pyrolysis products from the four soils. In the pyrolyzates of the investigated soils a number of compounds were identified, which is usually not detectable in pyrolysis-gas chromatography spectrometry analyses with N-selective detection of plants and microorganisms. Among these were N derivatives of benzene and long-chain alkyl nitriles, which appear to be soil-specific and suggest significant transformations of organic N in soils. Thus, our results contribute to a better understanding of the molecular-chemical structure of unknown N.     

Effects of fungal inocula on the decomposition of lignin and structural polysaccharides in Pinus sylvestris litter

 Litter bags containing sterile Scots pine (Pinus sylvestris) needles (19.8% lignin, 26.5% cellulose and 0.34% N) were inoculated with two species of fungi in the laboratory and then placed in the litter layer of a pine plantation. Marasmius androsaceus, which can degrade lignocellulose, was initially displaced by other fungal colonisers and was not detected in the litter after 2–3 months; but was re-isolated from the needles after 12 months. Trichoderma viride, which is a cellulolytic species and also antagonistic to other fungi, dominated the litter throughout the experiment. The control litter was naturally colonised by litter fungi. After 12 months, mass losses were similar at 52% for M. androsaceus and 48% for T. viride, compared with 36% for the control litter colonised by a more complex fungal community. Lignin concentrations increased with time in control litter and with T. viride because mass losses of carbohydrates were greater than those of lignin. Litter inoculated with M. androsaceus showed significant lignin decomposition throughout the experiment but cellulose concentrations showed a proportional increase in the first 6 months, suggesting that the fungus was preferentially exploiting hemicellulose and non-structural carbohydrates. Analysis of TFA-extractable sugars (mainly from hemicellulose) and CuO-derived phenylpropanoid moieties from lignin confirmed the differential patterns of resource decomposition which were not evident from total mass losses. During the initial stages of decomposition, T. viride was as effective in utilising structural polysaccharides as the complex fungal community in the control litter. Furthermore, M. androsaceus not only exhibited unexpectedly low cellulolytic activity but also facilitated lignin depolymerisation after the fungus was no longer detectable in the litter. The pre-inoculation of litter with these two fungal species therefore affected the overall dynamics of decomposition at a biochemical level. This study illustrates the importance of understanding the effects and interactions of specific fungi, rather than assumptions about the functional competence of diverse communities, on the processes of litter decomposition. Received: 5 July 2000     

Forms and solubility of plant nutrient elements in tropical plant waste biochars

Thailand is an agriculture‐based country which produces large amounts of agricultural waste. Making biochar from this waste can reduce pollution, decrease costs of production, and increase C sequestration. The agronomic benefits of biochar are partly derived from the available plant nutrients in biochar. This study investigated the fertilizer value of biochars manufactured by slow pyrolysis. Pyrolysis temperature and feedstock type affect nutrient concentrations and nutrient element speciation in biochar. The physio‐chemical, mineralogical and structural properties of biochars made from 14 agriculture wastes (soybean cake, corncob, lemon peel, sugar palm fibre, durian shell, tamarind wood, coconut fibre, coconut shell, bamboo wood, rice husk, eucalyptus wood, oil palm fruit, coffee waste, and bagasse) were investigated. The plant nutrients in biochar mostly occurred in crystalline minerals which were present on the surface and inside the cell structure of biochar. Most biochars examined in this research contained calcite (CaCO₃). The presence in biochars of several K‐minerals [archerite (KH₂PO₄), chlorocalcite (KCaCl₃), kalicinite (KHCO₃), pyrocoproite (K₂MgP₂O₇), struvite‐K (KMgPO₄ · 6 H₂O), and sylvite (KCl)] encourages the use of biochar as a K‐fertilizer. Fibre, fruit and wood biochars contained considerable amounts of K, Ca, and P. Sugar palm and coconut fibres also contained high level of Na in halite. This study recommends the utilization of biochars manufactured from sugar palm fibre, coconut fibre, durian shell, and oil palm fruit as fertilizers. With their appreciable contents of plant nutrients in highly to moderately soluble compounds these biochars should be effective fertilizers, especially for use by organic farmers who cannot use any chemical fertilizers.     

竹材热解特性研究

主要研究了竹材在快速热解与常规热解下液相、固相及气相产品的得率差异。快速热解下升温28℃／s，停留时间0．76s，温度500℃，液相产品竹焦油得率为48．5％，主要组分为2，6-二甲氧基苯酚和2-甲氧基苯酚（愈疮木酚），在常规热解下升温速率1℃／min，温度500℃，液相得率为30％（包括水），组分主要为乙酸。在常规或缓慢热解中，固相产物，炭的微孔结构中，当热解温度低于550℃的情况下，主要孔径在6．0-22．0nm，当热解温度在650～750℃，主要孔径〈2nm。