土壤腐殖质各组分红外光谱研究

土壤腐殖质是土壤中所特有的一类特殊的高分子化合物,具有重要的肥力和环境调节功能。其中胡敏素的提取和纯化很困难,从而限制了对其性质和结构的研究。为揭示胡敏素的结构性质,本研究按Pallo分组,将胡敏酸(HA)分为焦磷酸钠提取的胡敏酸(HAP)、氢氧化钠提取的胡敏酸(HAS);富里酸(FA)分为焦磷酸钠提取的富里酸(FAP)和氢氧化钠提取的富里酸(FAS);胡敏素(HM)分为铁结合胡敏素(HMi)、粘粒结合胡敏素(HMc)和不溶性胡敏素(HMr)三个组分,采用红外光谱法对黑土、草甸土以及黑土底土加入大量玉米秸秆培养后腐殖质各组分的结构特征进行研究。腐殖质各组分按Pallo法分组。结果表明:铁结合胡敏素(HMi)、粘粒结合胡敏素(HMc)与胡敏酸(HA)、富里酸(FA)具有相似的光谱特征,但存在明显差异。黑土、草甸土中HMi和HMc的脂族性强于HA和FA;HMi与HMc相比,HMi具有较高的脂族性。黑土中氢氧化钠提取的胡敏酸(HAS)的脂族性强于焦磷酸钠提取的胡敏酸(HAP);NaOH提取的富里酸(FAS)的脂族性强于Na4P2O7提取的富里酸(FAP)。草甸土中HAP的脂族结构较多,而HAS脂族结构相对较少。在培养土中,新形成的FA脂族性强于HA、HMi和HMc组分。新形成的HMc脂族性强于HMi和HMc的脂族性强于HAP,而弱于HAS。     

酸碱解聚玉米秸秆分子结构的实验研究

以玉米秸秆为研究对象,分别采用5%H2SO4和5%NaOH溶液对秸秆进行解聚处理,并对解聚前后秸秆结构、化学组成、热稳定性等进行分析和表征。结果表明,与未处理前相比,经酸或碱解聚处理后,秸秆纤维结晶度由51.8%分别提高到63.5%和67.0%,秸秆中大部分半纤维素和部分木质素组分被脱除,半纤维素由29.10%分别降至7.02%和6.86%,木质素由38.12%分别降至32.21%和16.52%,而纤维素则由31.54%分别升至60.54%和76.15%。经酸碱处理后,秸秆表面形态结构变得疏松,出现小孔和裂缝,降解温度达到350℃,热稳定性能增加。上述结果说明,稀酸或稀碱均对玉米秸秆分子结构有一定程度的解聚作用,但就解聚溶出木质素而言,稀碱的解聚溶出效果要优于稀酸的。     

催化加氢不同预处理玉米秸秆制取多元醇的研究

以玉米秸秆为研究对象,采用5%硫酸和5%氢氧化钠对其进行预处理,通过对解聚前后玉米秸秆官能团表征和成分分析,发现酸、碱处理后秸秆中大部分半纤维素和木质素被脱除,其中先碱后酸、先酸后碱处理后秸秆的木质素含量由28.04%分别下降至11.54%和12.14%,而纤维素相对含量由42.02%分别增加到75.12%和77.68%。通过浸渍法制备的非贵金属5%Ni-15%W/MCM-41催化剂用于催化转化预处理秸秆制取多元醇,结果表明:与未经处理的玉米秸秆多元醇得率21.00%相比,先碱后酸、先酸后碱处理的玉米秸秆催化转化多元醇得率分别达到60.72%和61.40%。α-葡萄糖和β-葡萄糖的加氢结果显示乙二醇(EG)和1,2-丙二醇(1,2-PG)得率均相近,说明葡萄糖的旋光构型对催化加氢没有影响。与C6糖加氢产物分布比较,C5糖的产物中除了有EG和1,2-PG,同时还有丙三醇的生成,提出了糖加氢制取多元醇的可能机理。     

遗传算法模拟计算Pb^2＋—FA—SO^2—4体系的化学形态分布

研究了水体中重要污染元素铅在富里酸（ＦＡ），ＳＯ＾２－４共同存在的化学形态分布，根据物料平衡和化学平衡建立了Ｐｂ＾２＋－ＦＡ－ＳＯ＾２－４的化学模型，用Ｐｂ＾２＋滴定络合剂ＦＡ和ＳＯ＾２－４的混合溶液，使用ＡＳＶ测定阳极溶出电流并采用遗传算法（ＧＡ）对铅的化学形态进行了模拟计算，用成对ｔ检验的结果表明，阳极溶出电流的计算值和实测值之间的无显著性差异。     

碱解聚对玉米秸秆的影响

以玉米秸秆为研究对象,氢氧化钠为解聚剂,研究了碱解聚前后玉米秸秆组份、表面形态、化学官能团和纤维结晶度的变化。结果表明:玉米秸秆中木质素的主要组成单体是H-木质素,解聚液中的酚类物质有4-羟基苯甲醛、香草醛、紫丁香醛、对香豆酸和阿魏酸。玉米秸秆经碱解聚,表面形态变得疏松而多孔,红外光谱下木质素的特征吸收峰消失,85%的木质素和52%的半纤维素被脱除,而纤维素的相对含量增加,结晶度增大。说明碱解聚有利于后续酶解和(或)其它生化方法的实施,以实现秸秆纤维的高值转化。     

有氧烘焙对生物质气化及碱金属迁移转化特性的影响

本工作研究了有氧烘焙对玉米秸秆组成成分、烘焙产率、化学结构及微观结构等理化特性及气化特性的影响,同时考察了玉米秸秆烘焙及气化过程中碱金属的迁移转化规律。结果表明,烘焙可有效提高玉米秸秆中固定碳含量,降低H/C、O/C。相较于惰性烘焙,有氧烘焙具有更好的提质效果,结合H/C、O/C、质量产率和能量产率发现,氧气体积分数为6%时较合适。烘焙玉米秸秆气化气中CO含量、气体产率及热值随烘焙气氛中氧气含量的增加呈先上升后下降的趋势,在氧气体积分数为6%时气化品质相对较好,此时气体组分中CO体积分数为14.73%、气体产率达到1.09 L/g、气体热值达到4.93 MJ/m³。烘焙过程中碱金属在玉米秸秆中富集,并促进部分水溶态钾向醋酸铵溶态钾转化,有助于气化过程中生成更多不溶态钾,且有氧烘焙促进作用更明显。研究结果可为生物质有氧烘焙提质及气化产气的技术推广提供基础数据及技术支持。     

水中天然有机物富里酸的光催化氧化研究

以粉末态TiO2为催化剂对水中天然有机物富里酸（FA）进行了光催化氧化的研究，考察了在光催化-超滤反应器中直接光氧化、曝气条件、错流速度、催化剂浓度、初始pH等因素对富里酸氧化的影响。结果表明，光催化氧化明显优于直接光氧化对富里酸的影响，另外在空气曝气、pH减小以及增大错流速度的条件下均能有效提高富里酸的去除率。     

微波辅助DMSO/AmimCl复合溶剂预处理玉米秸秆的酶解影响

为了实现玉米秸秆纤维素的高效糖化, 设计利用微波加热辅助的离子液体1-烯丙基-3-甲基咪唑氯盐(AmimCl)/二甲基亚砜(DMSO)复合溶剂生物质预处理体系, 破坏玉米秸秆天然结构, 提高纤维素酶解效率. 研究发现, 15% (w)DMSO, 110℃, 60 min 及4 g 秸秆/100 g 复合溶剂为最适预处理条件. 在此条件下, 秸秆溶解率、提取率可分别达46.6%和22.9%; 提取物纤维素酶解率14 h 可达71.4%, 相较于天然玉米秸秆的20 h 酶解率12.5%有极大提高. 通过XRD,SEM及¹H NMR 分析发现:秸秆预处理后, 提取物纤维素晶型由Ⅰ 型变为Ⅱ 型, 残渣纤维素相对结晶度明显降低, 有利于纤维素酶解的进行, 达到了生物质预处理的目的; 预处理过程中使用的AmimCl 离子液体经简单回收再生, 结构及秸秆溶解性能未发生变化, 可循环使用. 为玉米秸秆生物质预处理提供了一个新的方案.     

三峡库区水体溶解有机质的荧光光谱特性

利用荧光发射和三维荧光光谱(EEM)研究了三峡库区(TGRA)长江干流及嘉陵江、乌江两支流水体溶解有机质(DOM)的荧光特性.结合采样段面溶解有机碳(DOC)、氧化还原电位(ORP)、pH等参数,考察了干流、两支流及其汇合后各水体DOM的荧光指数f450/500和类腐殖酸与类富里酸强度比值rC/D变化,分析了类腐殖酸、类富里酸及类蛋白质在库区支流与干流、上游与下游水体的来源、组成、分布及环境行为.实验表明: 干流水体中DOM以类富里酸、类蛋白质荧光有机质为主;嘉陵江水体DOM以类蛋白质为主,富里酸次之; 在朝天门与长江汇合后,类蛋白峰强减弱而类腐殖酸有一定增加;乌江以类富里酸为主,汇合干流后,富里酸和类蛋白质峰增强;库区上游水体DOM主要受嘉陵江影响;干流DOM受陆源性影响.初步揭示了水体DOM的EEM特性与库区水质参数的相关性,为水体监测与分析提供参考.     

SO^2—4／TiO2和SO^2—4／Fe2O3固体超强酸研究

用ＸＲＤ、ＴＧ－ＤＴＧ、ＳＥＭ和化学分析等手段研究了浸渍Ｈ２ＳＯ４的无定形ＴｉＯ２和Ｆｅ２Ｏ３在焙烧过程中的晶化、相变、失水及失硫情况，总结出ＳＯ＾２－４／ＭｘＯｙ型固体超强酸具有与ＳＯ＾２－４／ＺｒＯ２体系相同的形成规律。用ＩＲ光谱和常温正戊烷异构化反应对ＳＯ＾２－４／ＴｉＯ２／Ｆｅ２Ｏ３的超强酸性进行了表征，表明它们与ＳＯ＾２－４／ＺｒＯ２体系具有相似的表面酸位结构，无水状态主要为Ｌ酸位，吸水     

The structural composition of humic compounds as indicator of organic carbon sources

Various analytical techniques ((13)C-NMR, FTIR, elemental analysis) have been used to study the structures of humic compounds present in the sediments of Martignano lake located 50 km from Roma city (Italy). The total amount of humic compounds present in the upper layer of sediments is practically constant; instead, considering humic (HA) and fulvic acids (FA) separately, it can be noticed that while HA increase remarkably from A(1) to A(3), FA diminish, probably as a result of the continuous transformation of algal debris, present in large amount in A(1), from compounds which are in an early stage of decomposition to more highly degraded organic matter. In deeper layers the percentage both of HA and FA is constant and slightly lower than that found in the upper layer, except for two sampling points. In these stations the amount of both HA and FA are very high and the carbohydrate peak areas of HA and FA increase along with the depth, reflecting the presence of a well localized source of organic carbon or different environmental conditions.     

Fluorescence analysis of humic and fulvic acids from two Brazilian oxisols as affected by biosolid amendment

Conventional monodimensional fluorescence spectroscopy in the emission, excitation, and synchronous-scan modes and total luminescence spectroscopy have proven to be sensitive techniques for characterization and differentiation of humic acid (HA) and fulvic acid (FA) fractions isolated from an aerobically and anaerobically digested and limed biosolid, two layers of a sandy and a clayey Brazilian oxisol, and the corresponding biosolid-amended soils. The spectral patterns and the relative fluorescence intensities suggest greater molecular heterogeneity, less aromatic polycondensation, and less humification of biosolid HA and FA compared with soil HA and FA. However, the differences are smaller for the FA fractions than for the HA fractions. Fluorescence properties of soil HA and FA differ slightly as a function of soil type and soil layer. Biosolid application causes a shift to shorter wavelengths of the main fluorescence peaks and marked variation of the relative fluorescence intensities of HA and FA isolated from amended soils. These results suggest that molecular components of relatively small molecular size, with a low level of aromatic polycondensation, and low degree of humification present in biosolid HA and FA are partially and variously incorporated into amended soil HA and FA. In general, these modifications seem to be smaller in HA and FA from the clayey soil layers than in those from the sandy soil layers, possibly because of protective effects exerted by clay minerals of native soil HA and FA against disturbances caused by biosolid application.     

Sorption of thorium(IV) from aqueous solutions by graphene oxide

Graphene oxide (GO) is one of the most important carbon nano-materials. In this paper, GO was synthesized from flake graphite and characterized by transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. The sorption of Th(IV) on GO was investigated as a function of contact time, solid-to-liquid ratio, pH, ionic strength, and in the presence of fulvic acid (FA) and humic acid (HA) by batch experiments. The sorption percentage of Th(IV) on GO decreased with increasing ionic strength and decreasing solid-to-liquid ratio. The sorption edge of Th(IV) in the presence of FA/HA is much lower than that in the absence of FA/HA. Furthermore, the sorption processes of Th(IV) can be described by a pseudo-second order rate model. Based on the Langmuir model, the maximum sorption capacities (Cs_max) of Th(IV) were about 5.80 × 10^?4 mol/L. From thermodynamic investigation, sorption of Th(IV) on GO is spontaneous and endothermic in nature. The rapid sorption rate and high sorption capacity suggest that GO is a promising adsorbent for Th(IV).     

Humic acid fractionation upon sequential adsorption onto goethite

Mineral-humic complexes are commonly distributed in natural environments and are important in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study investigated the structural and conformational changes of humic acid (HA) and mineral-HA complexes after sequential HA adsorption by goethite, using UV-visible spectroscopy, high performance size exclusion chromatography (HPSEC), Fourier transform infrared (FT-IR) spectroscopy, and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The HA remaining in the solution after adsorption showed low polarity index values ((N+O)/C), which indicates that polar functional moieties are likely to adsorb on the goethite surface. In addition, we observed decreased E4/E6 and E2/E3 ratios of unbound HA with increasing number of coatings, implying that aliphatic rich HA fractions with polar functional moieties readily adsorb to the goethite surface. According to IR spectra, carbohydrate carbon would be the important fractions associated with goethite. NMR spectra provided evidence for HA fractionation during adsorption onto the mineral surface; that is, aliphatic fractions were preferentially adsorbed by goethite while aromatic fractions were left in solution. Relatively small molecular weight (MW) HA fractions had a greater affinity for the goethite surface based on analyses of the HPSEC chromatograms, which differs from the results reported in the literature. Finally, our results suggest that the polar aliphatic fractions of HA were mainly adsorbed to goethite via electrostatic attraction and/or ligand exchange reactions.     

竹红菌甲素与血红蛋白相互作用光谱

竹红菌甲素与血红蛋白相互作用光谱;马心血红蛋白;竹红菌甲素;相互作用;UV-Vis吸收光谱;荧光光谱;荧光猝灭动力学常数     

Binding constants of lead by humic and fulvic acids studied by anodic stripping square wave voltammetry

A better understanding of metal ion binding to soil organic substances is of fundamental importance in geochemical modeling of environments. Fulvic acids (FA) and humic acids (HA) make up an important part of soil organic matter, and their binding capacity affects the fate of metal ions and plays an important role in their mobility. Binding constants of Pb(II) to HA and FA were evaluated by anodic stripping square wave voltammetry (ASSWV) where the binding reaction was performed at pH 4.5 in a medium of 0.020 mol l⁻¹ KNO₃. Results showed that ASSWV technique was well suited for the estimation of the binding capacity of a natural organic matter towards heavy metals. Based on the voltammetric titration curves, binding constants of Pb(II) complexes formed with HA and FA were 0.78 × 10⁶ and 0.15 × 10⁶ mol⁻¹ l, which indicated that complex of Pb²⁺ with HA was more stable than with FA. The average molecular weight of HA and FA prepared from soil samples were also found to be 1821 g mol⁻¹ and 805 g mol⁻¹, respectively.     

Nano‐hydroxyapatite Surfaces Grafted with Electroactive Aniline Tetramers for Bone‐Tissue Engineering

An electroactive amino/carboxyl‐capped aniline tetramer (AT) is covalently grafted to the surface of hydroxyapatite (HA) nanoparticles to generate novel electroactive HA‐AT nanoparticles. The amount of AT ranges from 16.5 to 34.0 wt% and is characterized by thermogravimetric analysis (TGA). The HA‐AT nanoparticles are characterized by Fourier transform IR (FTIR) spectroscopy, X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction, and scanning electron microscopy (SEM). For the excellent electroactivity of HA‐AT, the mixture of HA‐AT and PLA shows much better adhesion ability and proliferation ability than that of HA and a PLA matrix. At a 15 wt% AT grafting amount, the matrix shows the best biocompatibility.

     

Effects of acid rain on soil humic compounds

The modifications induced by acid rain on the solubility, molecular configuration and molecular weight distribution of humic (HA) and fulvic (FA) acids were studied. A natural soil was subjected to simulated acid rain until a soil pH of 4 was obtained; HA and FA acids were then extracted and characterised. The results obtained were compared both with those of natural soil and with those of a soil subjected to acid rain. Elute analysis indicates the continuous release of soluble organic compounds as a consequence of acid rain simulation, although no relationship was found with the process of soil acidification. The yields of HA and FA show that HA values are the same while FA amount is higher in the natural soil; in acid soils their water solubility increases. The molecular weight distribution shows that HA consist of a mixture of compounds of different molecular weights; they are molecules for the most part larger than 100 kDa and their distribution is not changed by soil acidification. FA can be considered to form a much more homogeneous system; in natural soil, the molecules are larger than 50 kDa, while in acidified soil they are for the most part smaller than 3 kDa.     

Adsorption of humic acids onto goethite: effects of molar mass, pH and ionic strength

In this paper, the LCD (ligand charge distribution) model is applied to describe the adsorption of (Tongbersven) humic acid (HA) to goethite. The model considers both electrostatic interactions and chemical binding between HA and goethite. The large size of HA particles limits their close access to the surface. Part of the adsorbed HA particles is located in the compact part at the goethite surface (Stern layers) and the rest in the less structured diffuse double layer (DDL). The model can describe the effects of pH, ionic strength, and loading on the adsorption. Compared to fulvic acid (FA), adsorption of HA is stronger and more pH- and ionic-strength-dependent. The larger number of reactive groups on each HA particle than on a FA particle results in the stronger HA adsorption observed. The stronger pH dependency in HA adsorption is related to the larger number of protons that are coadsorbed with HA due to the higher charge carried by a HA particle than by a FA particle. The positive ionic-strength dependency of HA adsorption can be explained by the conformational change of HA particles with ionic strength. At a higher ionic strength, the decrease of the particle size favors closer contact between the particles and the surface, leading to stronger competition with electrolyte ions for surface charge neutralization and therefore leading to more HA adsorption.     

硝酸氧解法提高泥炭中黄腐酸的产率

硝酸氧解法提高泥炭中黄腐酸的产率;腐植酸;硝酸氧化降解