微生物降解褐煤产生的腐植酸化学特性研究

本文对微生物降解褐煤产生的腐植酸的化学特性进行了分析.结果表明,褐煤经微生物降解后其腐植酸与降解前相比,氢和氧百分含量增加,碳百分含量减少,分子量减小 ,而絮凝极限明显增大,红外吸收光谱也发生明显变化.     

堆肥处理对污泥腐殖物质组成和光谱学特征的影响

采用凝胶(Sephadex G-75)色谱、荧光光谱和红外光谱法研究了污泥堆肥的HA和FA在堆制前后的组成与结构特征变化．凝胶色谱分析表明,污泥经过63d堆腐后,HA中大分子组分含量明显提高;而FA则由不同分子量物质组成,其中小分子量物质占主要部分,在堆腐以后,FA中大分子物质含量下降30％,小分子量物质含量则相对增加．同时,荧光光谱、红外光谱的结果表明：随着污泥堆肥的进行,HA中有机物不饱和结构的多聚化或联合程度增大,芳香结构物质含量增加;但经过堆制的FA具有更多的结构简单的低分子量物质和更低的芳构化水平．     

大骨节病病区饮水中自由基的测定

大骨节病病区饮水中有机物——腐植酸的黄腐酸级分浓度偏高,已知腐植酸含有具有生物功能的半醌自由基。为配合病因研究,本文建立了一种简易的饮水中自由基浓度的测定方法;以GDX-102树脂吸附饮水中的有机物,干燥后以ESR谱仪直接测定,文中对干扰及测定条件进行了研究,并用之测定了内蒙、黑、吉、冀等省部分病区饮水中自由基浓度。结果表明,病区饮水中自由基浓度明显高于非病区。     

硝化褐煤对铬离子溶液的吸附研究

利用硝酸与龙口褐煤反应制得硝化褐煤，使其有效吸附质腐植酸含量提高。用该湖化褐煤对铬离子进行吸附试验，研究吸附剂的吸附量、吸附动力学、吸附模型和溶液的pH值对吸附的影响。结果表明：硝化褐煤对铬离子具有良好的吸附特性，其静态等温吸附符合Langmuir等温议程。     

秸秆腐解剂在秸秆还田中的效果研究初报

在大田、微区和盆栽条件下，研究了秸秆腐解剂对小麦、水稻生长及产量的影响，同时研究了秸秆腐解剂对小麦、水稻秸秆腐解速率及对土壤肥力的影响。结果表明，稻、麦秸秆还田时施用秸秆腐解剂对提高稻、麦产量具有明显的增产效果，增产的原因是穗数和粒数增加；稻、麦秸秆还田量不同时，还田量大且配施秸秆腐解剂的效果较还田量小好；麦秸秆还田方式不同时，麦秸以栽稻前耕翻还田且配施秸秆腐解剂的效果较好，上水沤制的效果较差；秸秆腐解剂能促进稻、麦秸秆较快腐解，减轻和防止多量秸秆还田给作物生长带来不利影响，并可稳定和提高土壤养分含量。     

沼气发酵液对西瓜苯丙氨酸解氨酶的诱导

为了研究沼气发酵液抑制西瓜枯萎病（ Ｆｕｓａｒｉｕｍ ｏｘｙｓｐｏｒｕｍ ｆ．ｓｐ ． ｎｉｖｅｕｍ） 的作用机理,使用不同来源和不同浓度的沼气发酵液处理西瓜植株,发现处理的植株体内的苯丙氨酸解氨酶（ Ｐ Ａ Ｌ） 的活性有显著升高,不同来源的沼气发酵液对植株的 Ｐ Ａ Ｌ活性都有不同程度的增加,并与黄腐酸的含量有一定相关性．用黄腐酸处理西瓜植株也可以诱导 Ｐ Ａ Ｌ 的产生     

碳酸盐岩山地土壤施用有机肥的溶蚀作用探讨

选择碳酸盐岩山地常见耕植、未耕植土层,通过概化制作为系列模拟柱试验土层,按当地正常施肥方法,向土层定量施入有机肥并浇灌及控制其它相关条件变化,再定期观测预埋土层不同深度碳酸岩石片的溶蚀量和土层其它指标的变化,作了施用有机肥的土中碳酸岩石溶蚀变化研究。结果揭示,在未耕植红黏土表层施用有机肥,大大减弱了土中碳酸岩石的溶蚀作用,且减弱程度随土深加大而降低。但对其下伏碱性岩粉层而言,施肥又引起了溶蚀量的微小增加变化;另在耕植土表层施用有机肥,对其土中碳酸岩石的溶蚀作用改变不大,且无论施肥与否溶蚀作用随土深加大又略显增大变化。而其下部红黏土中碳酸岩石的溶蚀量要远大于耕植土中的溶蚀量,并受施肥的影响较小。表明,农业施肥对未耕植土土中包被、包裹的碳酸岩石溶蚀影响较大,对下伏碱性岩粉层的层中、层下碳酸岩石的溶蚀影响较小。同时,施肥对耕植土土中、土下碳酸岩石的溶蚀影响不大。人类可采取禁令开垦较薄土层措施,来有效规避耕作施肥对土中碳酸岩石溶蚀作用的抑制,减少反石漠化的不利因素。此将为丰富碳酸盐岩山地成土演化理论和石漠化灾害的防治提供依据。     

花岗岩风化壳的不均一性与海岸带的可蚀性研究——以南海北大陆海岸带为例

海岸带岩土动力学特征的差异是影响海岸侵蚀过程与方向的重要因素之一。南海北大陆海岸带主要由花岗岩风化边坡组成。通过对该海岸带的北东翼及西南翼典型花岗岩风化壳剖面的黏土矿物及风化指标研究发现,两者存在不均一性：横向上,北东翼黏土矿物主要以高岭石、伊利石为主;西南翼黏土矿物主要以高岭石、伊利石和绿泥石为主,两翼均未见较明显的蒙脱石。相同层位比较,西南翼黏土矿物总量高于北东翼。垂向上,自地表到深部,北东翼黏土矿物组合及总量无明显的分层性,而西南翼则呈明显的分层性且地表含量明显高于深部。海岸带的风化作用也存在明显的不均一性：表现为横向上,北东翼海岸带风化程度要稍弱于西南翼;垂向上,北东翼化学风化指标n（Al2O3）/n（SiO2）,n（Fe2O3＋Al2O3）/n（SiO2）,n（TiO2）/n（Al2O3）、CIA在风化壳中呈无规律变化,而西南翼则呈明显的分层性,这种分层基本与表土层、红土层及砂土层成一定的对应关系。从化学可蚀性指标来看,由南海北大陆海岸带花岗岩风化壳演化而成的土壤均为强抗蚀性,但相同层位比较,北东翼可蚀性要稍弱于西南翼剖面。研究认为,组成南海北大陆海岸带的花岗岩风化壳之黏土矿物与风化作用的不均一性可很大程度影响海岸带的可蚀性。     

生物质炭对根际土壤中镉形态转化及水稻镉累积的影响

采用盆栽试验和Tessier连续形态分析方法,研究了不同镉污染水平下(1.0、2.5、5.0 mg·kg-1),施入不同量的生物质炭(0.0、2.5、5.0、10.0 g·kg-1)对根际与非根际土壤中镉形态转化及水稻镉累积的影响。结果表明,(1)施入生物质炭后,根际与非根际土壤中镉的有效性降低。施入生物质炭后,根际与非根际土壤可交换态、碳酸盐结合态、铁锰氧化物结合态以及有机物结合态镉最大可分别降低34.64%和28.15%、49.27%和63.82%、34.58%和24.59%、60.04%和49.00%,残渣态镉最大可分别增加14.79%和16.57%。10.0 g·kg-1生物质炭处理影响效果最显著。在不同处理下,镉形态变化显著且根际与非根际之间的变化呈显著性差异。中低镉污染水平下,施入生物质炭,根际与非根际土壤中镉形态变化趋于一致但镉形态含量存在差异。高镉污染水平下,生物质炭引起根际与非根际土壤中镉形态变化但不显著。(2)施入生物质炭可显著降低水稻各部分镉含量且水稻根部镉含量大于地上部镉含量。在不同镉污染程度下,不同施入量生物质炭处理与对照相比,地上部、根部镉含量最大可分别降低42.51%、22.86%;根部镉含量最大是地上部的2.63倍。10.0 g·kg-1生物质炭对水稻各部分镉含量降低效果最明显。     

煤矸石风化物不同粒级中重金属镉含量及其形态变化

对抚顺西露天矿煤矸石山表层煤矸石风化母岩进行多点取样,风化物筛分成>2 mm、2～0.25 mm和<0.25 mm等3个粒级,分析测定了矸石山表层母岩及其风化物不同粒级中Cd含量及其形态变化特征.结果表明:煤矸石母岩及其风化物中cd含量超过土壤环境质量2级标准,页岩、泥岩及其风化物pH值7.2～8.6,但燃后泥岩pH值4.9.碳质页岩2～0.25 mm粒级风化物中Cd损失最多,为73.6%;<0.25 mm细粒级Cd损失较少,为17.0%,这与细颗粒的表面吸附作用有关;泥岩及其各粒级风化物Cd元素不易损失,其Cd含量变化也相对较小;但燃后泥岩风化物中的Cd较容易损失.煤矸石风化物各样品类型中的Cd均以残渣态为主,可还原态和弱酸可提取态所占比例次之,可氧化态所占比例最小.弱酸可提取态Cd在细颗粒风化物中所占比例较高.     

Studies of Thermal Transformation of Humic and Fulvic Acids in Soils Ii. Thermogravimetry

The thermogravimetry and differential curves of the humic and fulvic acids in the soils from five areas of China were determined and the peaks of these curves were classified according to the results of infra-red (IR) spectra at high temperature and pyrolysis-mass spectra (Py/Ms). the kinetic parameters for heat-degradation of these humic and fulvic acids were calculated by the Coast-Redfern method. the initial temperatures, the final temperatures, and the peaks of DTG curves, the activation energies, the reaction orders and the percentages of weight loss at different reaction stages for these samples were analysed. Thus, the similarity of thermal transformation of humic and fulvic acids in the soils from different areas of China was demonstrated. in addition, the DTA curves of red earth HA and FA were determined.     

Soil organic matter chemistry. Part 1. Characterization of several humic preparations by proton and carbon‐13 nuclear magnetic resonance spectroscopy

Both laboratory and commercial preparations of humic substances (HSs) such as fulvic acids and humic acids along with HC1‐HF preparation of Manitoba peat soil organic matter were characterized using Fourier Transformation (FT) proton (¹H) and carbon‐13 (¹³C) nuclear magnetic resonance (NMR) spectroscopy. All the samples were dissolved in a solution of 0.4 N NaOD in D₂O. In the case of ‘H‐NMR spectroscopy, all the investigated humic samples displayed resonance absorption peaks in the region of 1–4 ppm indicating the likely presence of aliphatic protons in the preparations. However, with the exception of one fulvic acid preparation (extracted from Manitoba Carrol clay‐loam soil with 0.5 N NaOH), ¹H‐NMR spectra of all other samples provided evidence for strong aromatic character. The aliphatic and aromatic characteristics of such samples of HSs were further confirmed with the aid of ¹³C‐NMR spectra.     

交替冻融对东北典型土壤腐殖质的影响

以受季节性冻融过程影响显著的东北地区的黑土、暗棕壤和水稻土为例,采用实验室模拟的方法,研究交替冻融循环过程（分别在-20℃和20℃下处理）对土壤腐殖质的影响。研究表明：交替冻融后,黑土和暗棕壤松结态腐殖质质量分数分别增加了39%和28%,HA/FA分别上升了45%和35%;水稻土松结态腐殖质质量分数和HA/FA分别下降了18%和31%。三维荧光结果进一步验证,黑土、暗棕壤在交替冻融中土壤芳香化程度增高,HA/FA上升,而水稻土则相反。黑土和暗棕壤松结态腐殖质和HA/FA升高,主要是微生物分解作用和土壤大团聚体破坏等原因造成,水稻土松结态腐殖质和HA/FA降低,主要是水稻土的缺氧环境造成。     

Variation in humic and fulvic acids during thermal sludge treatment assessed by size fractionation,elementary analysis,and spectroscopic methods

Thermal pretreatment can be applied to sludge anaerobic digestion or dewatering. To analyze the variation in humic substances during thermal sludge treatment, sludge humic and fulvic acids were extracted before and after 30-min thermal treatment at 180℃, and then their contents, molecular weight distributions, elementary compositions, and spectral characteristics were compared. The results showed that the total contents of humic and fulvic acids in the sludge almost remained constant during thermal treatment, but 35% ofhumic and fulvic acids were dissolved from the sludge solids. Moreover, both humic and fulvic acids were partly decomposed and 32% of humic acids were converted to fulvic acids. The median value of the molecular weights of humic acids decreased from 81 to 41 kDa and that of fulvic acids decreased from 15 to 2 kDa. Besides the reduction in molecular size, the chemical structures of humic and fulvic acids also exhibited a slight change, i.e. some oxygen functional groups disappeared and aromatic structures increased after thermal sludge treatment.     

Characterization of fulvic acids during olive mill waste composting (Elemental,Thermal and fluorescence analyses)

Elemental analysis, fluorescence spectroscopy and differential scanning calorimetry (DSC) were applied to the study of fulvic acids isolated from different stages during olive mill waste composting. The fulvic extracted acids are characterized by a high nitrogen content and O/C ratio values that may result from the high degree of humification and the synthesis of more condensed humic complexes. This was confirmed by fluorescence spectroscopy in the synchronous-scan mode by the decrease of shoulder intensities at intermediate wavelengths indicating the increase of polycondensation and conjugation of unsaturated structures and the greater uniformity of fluorophores. Fluorescence spectra in the emission, excitation and synchronous modes became simpler with compost maturation. This was confirmed by DSC results which proved the high degree of polycondensation of aromatic nuclei of fulvic acid molecules during olive mill waste composting.     

Characterization of fulvic acids during olive mill waste composting (Elemental, Thermal and fluorescence analyses)

Elemental analysis, fluorescence spectroscopy and differential scanning calorimetry (DSC) were applied to the study of fulvic acids isolated from different stages during olive mill waste composting. The fulvic extracted acids are characterized by a high nitrogen content and O/C ratio values that may result from the high degree of humification and the synthesis of more condensed humic complexes. This was confirmed by fluorescence spectroscopy in the synchronous-scan mode by the decrease of shoulder intensities at intermediate wavelengths indicating the increase of polycondensation and conjugation of unsaturated structures and the greater uniformity of fluorophores. Fluorescence spectra in the emission, excitation and synchronous modes became simpler with compost maturation. This was confirmed by DSC results which proved the high degree of polycondensation of aromatic nuclei of fulvic acid molecules during olive mill waste composting.     

Studies of Thermal Transformations of Humic and Fulvic Acids in Soils I. Infrared Spectroscopy and Temperature-Programmed Pyrolysis Mass Spectrometry

Temperature-programmed pyrolysis mass spectrometry and Fourier-transform infrared spectroscopy have been used to monitor structural changes of humic and fulvic acids isolated from soils in China, in the temperature range of 25-550°C. in this work, we found that decarboxylation is obvious as the main reaction with dehydration reaction from 150°C to 400°C, the anhydride can be identified from FT-IR spectra at temperature range from 200°C to 400°C; there are evident changes of the aromatic nucleus of humic and fulvic acids above 400°C, even remaining up to 550°C. Besides, some changes of adsorption water can be distinguished before 200°C, and the mass signal of sulphur dioxide was detected.     

Studies of Thermal Transformations of Humic and Fulvic Acids in Soils I. Infrared Spectroscopy and Temperature-Programmed Pyrolysis Mass Spectrometry

Temperature-programmed pyrolysis mass spectrometry and Fourier-transform infrared spectroscopy have been used to monitor structural changes of humic and fulvic acids isolated from soils in China, in the temperature range of 25-550°C. in this work, we found that decarboxylation is obvious as the main reaction with dehydration reaction from 150°C to 400°C, the anhydride can be identified from FT-IR spectra at temperature range from 200°C to 400°C; there are evident changes of the aromatic nucleus of humic and fulvic acids above 400°C, even remaining up to 550°C. Besides, some changes of adsorption water can be distinguished before 200°C, and the mass signal of sulphur dioxide was detected.     

Scanning Electron Microscopy of Humic Substances Produced During Cellulose Decomposition

Humic substances (HS) produced during the aerobic decomposition of polysaccharides still need to be recognized as such and characterized. Humic (HA) and fulvic (FA) acids extracted at different time intervals during composting of cotton residues from carding, where no decomposition of lignin occurred, were investigated by scanning electron microscopy (SEM) size exclusion chromatography and infrared spectroscopy. Throughout the experiment, fulvic acids possessed a larger number of carboxyl groups but a lower number of weak acidic groups (negatively charged acid groups at pH 11) than humic acids. the number of carboxyl groups increased with time in both fulvic and humic acids, while that of phenolic groups decreased. Infrared spectra showed that the ratio between carboxyl and methyl groups decreased from 8.5 to 4 in FA after 18 days. This change corresponded with the disappearance of flat sheet structures observed by SEM at pH 6. Our results suggest that the shape of humic molecules as observed by SEM reflects the strength of hydrophilic/hydrophobic interactions with the solvent molecules. About 80% of FA molecules had a molecular weight lower than 3500 as deduced from column calibration with HS standards obtained by ultrafiltration. About 40% of humic acids were composed of small molecules; only 20% HA had a molecular weight larger than 45000. Polysaccharide-derived HS may not be limited to the high molecular weight poorly transformed fraction containing bonded polysaccharide structures, but may also consist of low molecular weight components with no structural similarity to the original material.