胡敏酸吸附解吸Fe3+反应特征研究

采用C-25葡聚糖凝胶层析方法研究了在不同酸度、离子强度、温度条件下胡敏酸（HA）吸附解吸Fe3^＋特征.结果表明,在相同离子强度、反应温度条件下,随着pH的升高,HA对Fe（Ⅲ）最大吸附量Smax和吸附平衡常数k增加,标准摩尔自由能变△Gom绝对值减小.相同pH和温度下,离子强度从0.00到0.10mol L^-1,HA对Fe（Ⅲ）最大吸附量Smax和吸附亲和力常数k增加,自由能变△G^o m绝对值减小,但离子强度从0.10 mol L^-1继续上升到0.15 mol L^-1,则上述特征常数变化刚好相反.温度升高,胡敏酸吸附Fe3^＋的最大吸附量、吸附平衡常数k、自由能变△G^o m绝对值均较大幅度降低,表明升高温度对吸附反应不利.吸附反应的焓变△H^o m和熵变△S^o m均小于零,为放热反应,反应向更有序状态进行;在相同条件下,pH越大,焓变△H^o m和熵变△rS^θ m绝对值越大,表明pH越大,越有利于吸附反应的进行.随着pH的升高,Fe3^＋被还原的百分率η减小,用幂函数方程拟合,相关系数达到显著水平.随着pH的降低,胡敏酸铁Fe3^＋解吸率增大;对解吸率曲线进行拟合,线形方程具有显著的相关系数.胡敏酸吸附Fe3^＋的反应为包括胡敏酸内部和外部结合的“两相”反应.     

土壤有机/无机胶体凝聚的光散射研究

有机/无机复合体是土壤中最重要的物质形态。本文在不同浓度的CaCl2作用下,对黄壤、胡敏酸、黄壤/胡敏酸混合胶体的凝聚动力学和凝聚体结构特征进行了研究,结果表明:黄壤、胡敏酸、黄壤/胡敏酸混合胶体的凝聚与否均强烈地依赖于体系电解质CaCl2浓度,其临界絮凝浓度(Critical flocculation con-centration,CFC)分别为1.38 mmol L-1、45 mmol L-1、15 mmol L-1。当CaCl2浓度高于CFC时,3种胶体的凝聚均表现为快速的扩散控制团簇凝聚(Diffusion limited cluster-cluster aggregation,DLCA)机制,形成分形维数分别为1.45、1.76、1.46的疏松凝聚体;当CaCl2浓度低于CFC时,3种胶体的凝聚过程对电解质浓度非常敏感,表现为慢速的反应控制团簇凝聚(Reaction limited cluster-cluster aggregation,RLCA)机制,形成分形维数高至1.58、1.86、1.56的相对紧实的凝聚体。凝聚速率越快,形成的凝聚体越疏松。在悬液中黄壤胶体自凝聚形成的结构很疏松,但是非常不稳定,而胡敏酸自凝聚体的结构非常稳定。胡敏酸的参与没有改变黄壤胶体凝聚体的结构性质,但显著促进所形成的凝聚体结构的稳定。     

Na~+、Ca~(2+)及Na~+-Ca~(2+)混合离子对胡敏酸胶体稳定性的影响

以胡敏酸为研究对象,通过光散射技术比较土壤中常见盐基离子(Na~+、Ca~(2+)和Na~+-Ca~(2+)混合三种电解质)不同浓度条件下胡敏酸胶体凝聚动力学过程,明确不同价态离子界面行为和陪补离子效应对胡敏酸分散稳定性和凝聚体结构的影响。结果发现,Na~+和Ca~(2+)对胡敏酸胶体聚沉能力的差异远远大于舒尔策-哈迪(Schulze-Hardy)规则中因其化合价不同所引起的差异;Na~+-Ca~(2+)混合体系中Ca~(2+)主导凝聚过程,且Na~+-Ca~(2+)混合与Ca~(2+)两种离子体系中凝聚现象的差异随离子浓度的降低而增大;混合离子体系中Na~+作为陪补离子,其陪补离子效应对临界聚沉浓度、颗粒间活化能和胡敏酸凝聚体结构均有一定影响,尤以对凝聚体的结构特征影响显著;Na~+-Ca~(2+)混合体系中胡敏酸凝聚体的结构紧实程度介于单纯离子体系之间,因此可通过调节溶液中的离子组成实现对凝聚体结构紧实程度的调控。上述结果表明,Ca~(2+)对胡敏酸的聚沉不仅依赖于静电作用,还有Ca~(2+)在强电场中的极化诱导其与胡敏酸表面含氧官能团之间发生的共价键和桥键的贡献;此外,陪补离子Na~+与Ca~(2+)在胡敏酸胶体表面的竞争吸附抑制了Ca~(2+)对胡敏酸的聚沉作用,从而形成紧实程度适中的结构体。研究结果为探究胶体界面反应及土壤胶体凝聚机制提供新的思路和理论。     

红外光谱法研究胡敏酸与Fe3+、Al3+、Mn2+金属离子配位机理

被称为土壤“精华”的土壤腐殖质影响着土壤的物理性质、化学性质和生物学性质;其中,腐殖酸是腐殖质的核心成分,由于含有大量的羧基、羟基等活性基团,具有很高的反应活性,对环境中金属离子具有强烈的结合力,使之成为环境中金属离子的重要络合剂和聚沉剂,从而对金属元素在环境中的迁移、转化和生物有效性起着十分重要的调控作用[1~4]。腐殖酸与金属离子的相互作用一直是土壤、生态、环保等领域研究的重点,不少学者从动力学或热力学的角度研究了腐殖酸对金属离子铜、铅、镉、汞等离子的吸附和络合作用[3~13];也正是由于腐殖酸结构中有机活性基团众多,对于腐殖酸与金属离子的相互作用的确切部位或反应机理至今依然未彻底弄清楚;     

不同pH条件下黄壤胶体凝聚的动态光散射研究

土壤胶体的凝聚或分散紧密地联系着许多环境问题,并受胶体表面电荷性质的调控.以黄壤为实验材料,利用动态光散射技术研究pH作用下该可变电荷胶体颗粒的凝聚动力学.结果发现:土壤胶体的凝聚与否强烈依赖于pH.不同浓度HNO3和KOH诱发的土壤胶体凝聚均表现出慢速和快速凝聚特征,在快速凝聚中,HNO3作用较KOH作用的黄壤胶体平均凝聚速率更高、变化更快,表明表面电荷中和诱发的凝聚远大于压缩双电层诱发的凝聚.通过快速平均凝聚速率变化的反转点对应的pH,估计电荷零点(Zero pointof charge,ZPC),提供了一个实验测定ZPC的新方法.     

电位计滴定法对Co2+, Ni2+, Cu2+ and Zn2+与胡敏酸和富里酸形成复合物时的结合常数的确定

The formation constants of Co^2 ,Ni^2 ,Cu^2 and Zn^2 complexes with humic acid(HA) and fulvic acid(FA) in red soil wrer determined by the potentiometric titration method.The constants as a function of composition of the complexation solutions were obtained by two graphical approaches respetively,The formation constants decreased with increasing concentration of metal in the solution,The results provide unambiguous evidence for the heterogeneity of the function groups of humic substances,the formation constants of FA were much smaller than those of HA,and the formation constants of Cu^2 were much greater than those of Co^2 ,Ni^2 and Zn^2 ,The potentiometric titration methon for determining formation constants are also discussed in the article.     

2︰1和1︰1型黏土矿物胶体凝聚中Hofmeister效应的比较研究

土壤胶体是土壤具备肥力与生态功能的物质基础,土壤胶体凝聚与分散影响着土壤中一系列微观过程和宏观现象。采用动态光散射技术比较研究三种碱金属阳离子(Li+、Na+、K+)引发不同类型黏土矿物(2︰1型蒙脱石和1︰1型高岭石)胶体凝聚中的Hofmeister效应。研究发现,Li+、Na+、K+作用下蒙脱石、高岭石胶体的凝聚速率、临界聚沉浓度及活化能都存在明显差异,表现出强烈的Hofmeister效应。当电解质浓度为20 mmol·L–1时,K+引发蒙脱石胶体凝聚的速率为66.61 nm·min–1,远高于Na+、Li+引发蒙脱石胶体凝聚速率(5.93、4.41 nm·min–1);而与之对应的临界聚沉浓度则呈现K+(蒙脱石21.8 mmol·L–1、高岭石34.6 mmol·L–1)低于Na+(蒙脱石57.6 mmol·L–1、高岭石85.8 mmol·L–1)低于Li+(蒙脱石81.8 mmol·L–1、高岭石113.9 mmol·L–1)规律,胶体凝聚中活化能可合理解释此现象。电解质浓度为25 mmol·L–1时,Li+、Na+、K+引发蒙脱石、高岭石胶体凝聚的活化能分别为1.97 kT、1.43 kT、0 kT和2.94 kT、1.71 kT、0.49 kT,说明蒙脱石、高岭石胶体凝聚过程中Hofmeister效应序列均为Li+相似文献   

不同施肥处理土壤胡敏酸及其级分 与 Fe2+的络合特征 Ⅰ.胡敏酸原样与 Fe2+的络合特征

采用 17年不同施肥处理 (无肥、化肥、秸秆、厩肥 )土耕层土样 ,在对土壤胡敏酸性质研究的基础上 ,着重研究不同施肥处理土壤胡敏酸与Fe2+的络合特征 ,揭示络合作用与胡敏酸性质以及环境条件的关系。结果表明 ,不同施肥处理土壤胡敏酸与Fe2+的络合能力不同。和无肥处理相比 ,化肥处理胡敏酸的络合能力加强 ,logk值 (络合稳定常数 )增大 ,有机肥处理则使胡敏酸的络合能力下降 ,logk值减小。logk值大小与胡敏酸的羧基、酚羟基以及总酸度有关。pH值、温度、离子强度是影响络合稳定常数大小的环境因素 ,pH值由 4到 7,各处理胡敏酸的logk值增大 ,络合配位数也有增加趋势。温度升高 ,离子强度增大 ,logk值降低。胡敏酸与Fe2+络合反应是一个自发的放热反应 ,络合后整个体系的有序性增强 ,熵值减小。     

Fe2+与胡敏酸的络合特征及其抗氧化性和生物有效性研究

在研究不同来源胡敏酸性质的基础上,研究了Fe2+与胡敏酸的络合特征以及络合态Fe2+的抗氧化性和生物有效性。结果表明,来源于土的胡敏酸属于A型,而来源于腐解秸秆、粪肥的胡敏酸属于RP型。A型胡敏酸与Fe2+络合能力大于RP型。HA-Fe2+络合物的络合稳定常数越大,络合物中Fe2+抗氧化性越强,玉米叶片中全铁含量也越高,但存在活性铁含量和全铁含量不一致现象。     

几种胡敏酸和富里酸分子结构模型的三维可视化与特性研究

针对已提出的几种胡敏酸和富里酸的二维分子结构模型,应用HyperChem软件转换为三维结构并进行几何优化,计算了这些三维模型的能量以及定量构效关系(QSAR)参数。结果表明:几种模型在三维结构和特性上都各不相同,这为从空间角度更直观地认识腐殖物质的分子结构提供了可能性。     

光散射技术在土壤胶体颗粒相互作用研究中的应用

由于测试手段的限制,目前对土壤中粒径为0·001～1μm的"超微粒子"之间相互作用的微观效应研究还未引起足够的重视。本文从散射角和悬液颗粒密度两个方面讨论了光散射技术在土壤胶体研究中的应用条件,探讨了土壤胶体颗粒凝聚动力学机制及形成的聚合体结构特征。结果表明:(1)对于本实验所用黄壤悬液,应用光散射准确测定的散射角范围为90°～135°,初始颗粒密度范围为1·90×10-3～0·119gL-1。(2)在自相关曲线平滑地衰减至基线且散射光强保持不变的条件下,可以用光散射技术准确测定土壤胶体颗粒凝聚过程中有效直径、最可几粒径及粒径分布的变化,反映凝聚动力学规律。(3)在298K、90mmolL-1KNO3体系中用动态光散射测得黄壤胶体颗粒凝聚动力学为扩散控制团簇聚集机制,用静态光散射测得形成的聚合体分形维数为1·56±0·02。     

腐殖酸对钾在褐土中迁移和转化的影响

采用室内土柱实验研究了腐殖酸与钾共施时腐殖酸对钾在褐土施肥点附件微域中迁移和形态转化的影响。研究结果表明,与单施KCl处理相比,共施腐殖酸没有明显改变肥料钾在褐土中的迁移距离,在培养7天时增加了肥际微域中的水溶性钾含量,而在培养28天时则降低了其含量;共施腐殖酸明显增加了交换性钾含量以及在土壤中的迁移量,但减少了非交换性钾的含量和迁移量。说明共施腐殖酸减少了土壤晶格对钾离子的固定,提高了外源钾在褐土中的有效性。     

Nickel adsorption in two Oxisols and an Alfisol as affected by pH,nature of the electrolyte,and ionic strength of soil solution

Background, aim, and scope  The retention of potentially toxic metals in highly weathered soils can follow different pathways that variably affect their mobility and availability in the soil–water–plant system. This study aimed to evaluate the effects of pH, nature of electrolyte, and ionic strength of the solution on nickel (Ni) adsorption by two acric Oxisols and a less weathered Alfisol. Materials and methods  The effect of pH on Ni adsorption was evaluated in surface and subsurface samples from a clayey textured Anionic ‘Rhodic’ Acrudox (RA), a sandy-clayey textured Anionic ‘Xantic’ Acrudox (XA), and a heavy clayey textured Rhodic Kandiudalf (RK). All soil samples were equilibrated with the same concentration of Ni solution (5.0 mg L⁻¹) and two electrolyte solutions (CaCl₂ or NaCl) with different ionic strengths (IS) (1.0, 0.1 and 0.01 mol L⁻¹). The pH of each sample set varied from 3 to 10 in order to obtain sorption envelopes. Results and discussion  Ni adsorption increased as the pH increased, reaching its maximum of nearly pH 6. The adsorption was highest in Alfisol, followed by RA and XA. Competition between Ni²⁺ and Ca²⁺ was higher than that between Ni²⁺ and Na⁺ in all soil samples, as shown by the higher percentage of Ni adsorption at pH 5. At pH values below the intersection point of the three ionic strength curves (zero point of salt effect), Ni adsorption was generally higher in the more concentrated solution (highest IS), probably due to the neutralization of positive charges of soil colloids by Cl⁻ ions and consequent adsorption of Ni²⁺. Above this point, Ni adsorption was higher in the more diluted solution (lowest ionic strength), due to the higher negative potential at the colloid surfaces and the lower ionic competition for exchange sites in soil colloids. Conclusions  The effect of ionic strength was lower in the Oxisols than in the Alfisol. The main mechanism that controlled Ni adsorption in the soils was the ionic exchange, since the adsorption of ionic species varied according to the variation of pH values. The ionic competition revealed the importance of electrolyte composition and ionic strength on Ni adsorption in soils from the humid tropics. Recommendations and perspectives  The presence of NaCl or CaCl₂ in different ionic strengths affects the availability of heavy metals in contaminated soils. Therefore, the study of heavy metal dynamics in highly weathered soils must consider this behavior, especially in soils with large amounts of acric components.     

鸡分腐解过程腐殖质络合态铜的变化及其淋溶特征

Chicken manure was composted for 110 d to evaluate changes in organic carbon (C) and humic substance-complexed copper (HS-Cu) extracted with water, sodium hydroxide (NaOH), and sodium pyrophosphate and sodium hydroxide mixture (Na₄P₂O₇-NaOH). The average HS-Cu content from the Na₄P₂O₇-NaOH extraction accounted for 46.8% of the total Cu in the compost, followed by those from the NaOH and water extractions, which accounted for 34.5% and 6% of the total Cu in the compost, respectively. NaOH-Na₄P₂O₇-extractable HS-Cu increased throughout the composting process. NaOH-extractable HS-Cu increased during the first 50 d of composting and then leveled off. Water-extractable HS-Cu enhanced during the first 21 d and then decreased. Water-extractable HS-Cu was not correlated to NaOH-or NaOH-Na₄P₂O₇-extractable organic C. The average amount of Cu leached from the compost was about 20% of the total Cu in the chicken manure and Cu leaching increased during the first 35 d of composting and then decreased. Leaching of Cu was significantly correlated to the concentrations of HS-Cu extracted with NaOH and water, but was not correlated to the concentration of HS-Cu extracted with NaOH-Na₄P₂O₇. Thus, NaOH-and water-extractable HS-Cu were relatively labile and NaOH-Na₄P₂O₇-extractable HS-Cu was relatively immobile. Composting process after rapid decomposition could result in low potential of Cu leaching because of formation of more NaOH-Na₄P₂O₇-extractable HS-Cu.     

Photodegradation of the surfactants Na-dodecylbenzenesulfonate and dodecylpyridinium-chloride as affected by humic substances

Surfactants account for a great proportion of organic xenobiotica released into the environment by anthropogenic action. In natural waters and sewage sludge they can be removed from solution by different reactions, including adsorption to solid phases, biodegradation and abiotic photolytic degradation. In the present investigation we found that photodegradation of Na- dodecylbenzenesulfonate (LAS) was reduced by humic substances by a factor of 2 or more. In contrast, photodegradation of dodecylpyridinium-chloride (LPC) was increased in the presence of humic substances by a factor of 1.16–1.43. These differences were explained by the strong bonding of LPC but not of LAS to the humics. Photolytic degradation of LAS begins at the aliphatic side chains followed by aromatic ring cleavage. Photodegradation of LPC mainly associated with the humics showed similarity to that of pyridine. The experimental data demonstrate strong effects of photodegradation on the persistence of surfactants and the relevance of humic-surfactants associations for photolytic processes.     

Exogenous application of humic acid and salicylic acid to alleviate seedling drought stress in two corn (Zea mays L.) hybrids

Efficacy of 1?mM humic (HA) and salicylic (SC) acids on SC 260 and SC 705 corn seedlings to alleviate drought stress via polyethylene glycol was studied via hydroponics at Shiraz University, Iran in a factorial, randomized design, with four replicates each. Under stress, SC 260 had higher electrolyte leakage compared to SC 705, and exogenous application of HA combined with SA decreased SC 705 electrolyte leakage. As a general trend, photosynthetic pigment content, relative water content, root and shoot length, mean number and diameter of central and peripheral root metaxylem, and K⁺ accumulation were higher in SC 705 treated with HA and SA compared to SC 260. Application of HA with SA could be an effective and low cost approach to ensure seedling establishment and plant growth in fields affected by soil drought in the early season, especially for the SC 705 corn hybrid in semi-arid regions.     

腐殖酸对磷在石灰性土壤中迁移的影响

When humic acid (HA) and phosphorus (P) fertilizer are simultaneously applied to soil, HA may affect the movement of P. A laboratory incubation experiment was conducted to quantify the effects of a commercial HA product co-applied with monocalcium phosphate (MCP) on the distance of P movement and the concentration of P in various forms at different distances from the P fertilizer application site in a calcareous soil from northern China. Fertilizer MCP (at a rate equivalent to 26.6 kg P ha-1 ) was applied alone or in combination with HA (at 254.8 kg HA ha-1 ) to the surface of soil packed in cylinders (150 mm high and 50 mm internal diameter), and then incubated at 320 g kg-1 moisture content for 7 and 28 d periods. Extraction and analysis of each 2 mm soil layer in columns showed that the addition of HA to MCP increased the distance of P movement and the concentrations of water-extractable P, acid-extractable P and Olsen P in soil. The addition of HA to MCP could enhance P availability by increasing the distance of P movement and the concentration of extractable P in soil surrounding the P fertilizer.     

The fate of catechol in soil as affected by earthworms and clay

The effect of endogeic earthworms (Octolasion tyrtaeum) and the availability of clay (Montmorillonite) on the mobilization and stabilization of uniformly ¹⁴C-labelled catechol mixed into arable and forest soil was investigated in a short- and a long-term microcosm experiment. By using arable and forest soil the effect of earthworms and clay in soils differing in the saturation of the mineral matrix with organic matter was investigated. In the short-term experiment microcosms were destructively sampled when the soil had been transformed into casts. In the long-term experiment earthworm casts produced during 7 days and non-processed soil were incubated for three further months. Production of CO₂ and ¹⁴CO₂ were measured at regular intervals. Accumulation of ¹⁴C in humic fractions (DOM, fulvic acids, humic acids and humin) of the casts and the non-processed soil and incorporation of ¹⁴C into earthworm tissue were determined.Incorporation of ¹⁴C into earthworm tissue was low, with 0.1 and 0.44% recovered in the short- and long-term experiment, respectively, suggesting that endogeic earthworms preferentially assimilate non-phenolic soil carbon. Cumulative production of CO₂-C was significantly increased in casts produced from the arable soil, but lower in casts produced from the forest soil; generally, the production of CO₂-C was higher in forest than in arable soil. Both soils differed in the pattern of ¹⁴CO₂-C production; initially it was higher in the forest soil than in the arable soil, whereas later the opposite was true. Octolasion tyrtaeum did not affect ¹⁴CO₂-C production in the forest soil, but increased it in the arable soil early in the experiment; clay counteracted this effect. Clay and O. tyrtaeum did not affect integration of ¹⁴C into humic fractions of the forest soil. In contrast, in the arable soil O. tyrtaeum increased the amount of ¹⁴C in the labile fractions, whereas clay increased it in the humin fraction.The results indicate that endogeic earthworms increase microbial activity and thus mineralization of phenolic compounds, whereas clay decreases it presumably by binding phenolic compounds to clay particles when passing through the earthworm gut. Endogeic earthworms and clay are only of minor importance for the fate of catechol in soils with high organic matter, clay and microbial biomass concentrations, but in contrast affect the fate of phenolic compounds in low clay soils.     

Insights into sorption and leaching behavior of sulfadiazine in soil as affected by humic acid

Journal of Soils and Sediments - Sulfonamides with high mobility in the soil pose a significant threat to environmental ecology and human health. Organic matter is known to affect the sorption and...