风化煤腐殖酸对氮、磷、钾的吸附和解吸特性

研究了风化煤腐殖酸在不同pH值条件下对氮、磷、钾的吸附和解吸特性。结果表明,1)在pH.4～8条件下,随着氮、磷、钾初始处理浓度的增加,腐殖酸对其吸附量和解吸量均呈上升趋势,但解吸率均呈下降趋势;2)在不同pH值的介质溶液中,腐殖酸对氮、磷、钾的吸附和解吸特性不尽相同,其中,在碱性条件下,腐殖酸对氮的吸附和解吸作用较强,在酸性条件下,腐殖酸对磷的吸附和解吸作用较强,而腐殖酸对钾的的吸附和解吸作用在中性条件下更易发生;3)腐殖酸对氮、磷、钾的等温吸附可用Linear、Langmuir和Freundlich三个吸附方程来拟合,相关性达显著或极显著水平,但以Freundlich方程为最优。     

Influence of Humic Acid on Water Adsorption Characteristics of Kaolin and Quartz

Water vapor adsorption isotherms were measured for samples of kaolin and quartz amended with different amounts of humic acid extracted from a Cambic Arenosol under forest. Applying the approximation of the adsorption isotherms with the BET equation the monolayer capacities (surface areas) for the studied systems were calculated. For kaolin systems the surface area decreased sharply at low humic acid additions and this slowly increased with the further rise of the humic acid content, whereas for the quartz the increase of surface area was only noted for high humic acid contents. Using an exponential isotherm equation with a local BET model, the adsorption energy distribution functions were calculated for kaolin systems. The shape of the adsorption energy distributions showed that the increase in humic acid content changed the character of the surface from more hydrophilic to more hydrophobic. For intermediate humic acid contents, the energy distribution function had two maxima – more polar and less polar. At high humic acid contents the energy distribution function tended to the estimated value for pure humic acid, indicating high surface coverage with organic material. As measured by the mercury intrusion porosimetry, for the kaolin samples the amount of the largest pores decreases and the amount of the smallest pores increases with the accumulation of humic acid. For the quartz systems only very high doses of humic acid are reflected in changes of pore size distribution.     

硝酸处理对褐煤中可提取性腐殖酸含量及其吸附特性的影响

采用硝酸氧化及一次平衡法,研究了硝酸处理对褐煤中的可提取性腐殖酸含量、CEC（阳离子交换量）、E₄/E₆及其对各种养分离子吸附规律变化的影响。结果表明:一定强度的HNO₃能使褐煤中可提取性腐殖酸含量增加45.8%以上,使其阳离子交换能力提高;随硝酸处理时间的不断延长,褐煤中可提取性腐殖酸含量和CEC均呈先增加后减小的趋势,但CEC达到最大值所需时间相对较长;硝酸处理后的褐煤腐殖酸光学性质也发生了很大的变化。经硝酸处理褐煤腐殖酸样品对铵、钾吸附能力分别可提高58.73%和41.53%,其等温吸附式分别符合Freundlich和Langmuir方程。而对磷的吸附能力降低,一定条件下其吸附量仅为处理前的5.33%,其等温吸附式用Langmuir方程描述最佳。上述结果表明,经硝酸处理后,褐煤腐殖酸更适宜作为缓效肥料基质使用。     

褐煤腐殖酸对铵的吸附特性研究

研究了铵浓度、处理时间及介质pH对2种褐煤腐殖酸吸附铵的影响及其规律。结果表明,褐煤腐殖酸对铵的吸附等温式可用Freundlich等温曲线描述,其动力学吸附方程用Elovich方程描述最佳。在pH7.04时,介质pH的升高有利于铵的吸附。当pH4.03时,主要以物理吸附为主;当4.03.     

钾肥和腐殖酸互作对烤烟有机钾盐指数的影响

以烤烟品种金神农1号为材料,采用钾肥与腐殖酸双因子大田试验,分析了不同钾肥和腐殖酸水平及其互作对烤烟干物质量、化学成分、香味物质及有机钾盐指数的影响。结果表明:在同一钾肥水平下增施腐殖酸及在同一腐殖酸水平下增施钾肥均可增加烤烟前期的总干物质和烘烤后烟叶的总香味物质量,改善烟叶化学成分,提高有机钾盐指数;钾肥和腐殖酸互作对烟叶还原糖、总氮、氮碱比、钾及有机钾盐指数均有显著的正效应,而对烤烟干物质量及其余化学成分指标的影响则未达到显著水平;较高水平的钾肥和腐殖酸配施相对于较低水平两者配施有利于改善烤烟品质,提高烟叶钾含量和有机钾盐指数。     

Adsorption and desorption of Cd on humic acid fraction of soils

The adsorption of ionic Cd has been investigated on three humic acids isolated from podzol, rendzina and brown Mediterranean soils of Tuscany. The adsorption isotherms have been determined at 5 and 25°C. Cadmium adsorption was described by the Langmuir adsorption equation. Langmuir parameters were related to the functional groups content of humic acids and decreased in the following order: rendzina>brown Mediterranean soil>podzol. Adsorption was independent on temperature and increased with pH. Desorption experiments with 0.1 N NH₄OAc and 0.25 M Cu (OAc)₂ proved that Cd is adsorbed on humic acid about 50% in an exchangeable form and 50% in coordination complexes.     

褐煤腐植酸对钾的吸附特性研究

为给褐煤的有效利用和腐植酸缓效肥的研制提供理论依据,本试验采用吸附等温线的试验方法,探讨了K⁺平衡溶液浓度、平衡时间、pH值及固液比对褐煤腐植酸钾吸附的影响。结果表明：介质pH值升高有利于腐植酸样品对钾的吸附,且能加快吸附反应的速度;当pH<4.4时,K_d1>K_d2,此时以物理吸附为主。当7.12K_d1<K_d2,化学交换占主导地位。其等温吸附曲线符合Langmuir吸附形式,动力学吸附用Elovich方程描速最佳。经硝酸处理后的褐煤腐植酸样品对钾的吸附能力有了一定程度的提高。适宜的固液比能提高2种样品对钾的单位吸附量,分别在固液比为0.06和0.04时达最大,其单位吸附量分别为0.079 g/g和0.094 g/g。     

Retention of coumaric acid by soil and its colloidal components

In this study of the behavior of coumaric acid added to soil, the disappearance of the acid was found to be due to adsorption plus microbial degradation, and was influenced by the concentration and contact time. Adsorption experiments set up with soils varying widely in their chemical and physical properties, showed that the Freundlich isotherm fits the data quite well and that among the different soil factors, only the pH was closely and negatively correlated with coumaric acid adsorption. Approximately at pH > 7 no adsorption occurred, perhaps due to the repulsion between the negatively charged soil colloids and the dissociated acidic groups of coumaric acid. Adsorption experiments carried out with different adsorbents showed that the hydroxy-Fe compound was the most effective in retaining coumaric acid, followed by humic acid, illite, kaolinite and vermiculite, in this order.     

Caesium sorption—desorption in clay—humic acid systems

Soaking for 7 d with 0.05 M NaCl resulted in less caesium being sorbed by bentonite and kaolinite, but more by illite, compared to soaking for 2 d prior to addition of Cs. Overall the amount of Cs sorbed by the three clays was in the order bentonite > illite > kaolinite. Addition of humic acid to the clays depressed the sorption of Cs by all three clays, with illite showing the greatest effect. Desorption of added Cs was not totally reversible. The presence of humic acid resulted in an enhanced desorption of Cs from bentonite and to a lesser extent kaolinite. This enhanced desorption in the presence of humic acid was not seen for illite. The order of Cs retention following desorption for both clay and clay/ humic-acid mixtures was illite > bentonite > kaolinite. A single K_d value could not describe the whole isotherm, but individual values were calculated at different Cs concentrations to cover the range of the isotherm. K_d values for desorption were higher than the corresponding K_d for sorption. For both sorption and desorption, the presence of humic acid resulted in lower K_d values than in its absence.     

腐植酸与尿素结合工艺对尿素在潮土中转化的影响

通过研究腐植酸与尿素结合工艺对尿素在土壤中转化的影响,为腐植酸尿素生产工艺的选择提供科学依据.在石灰性潮土上进行土壤培养试验,设置8个处理:不施尿素(CK)、普通熔融尿素(U)、0.5％添加量的腐植酸(HA0.5)、5％添加量的腐植酸(HA5)、腐植酸添加量为0.5％的掺混腐植酸尿素(HA+U0.5)、腐植酸添加量为0...     

腐植酸促进植物生长的机理研究进展

【目的】腐植酸在我国农业生产中发挥了重要作用,许多研究证实,腐植酸具有促进植物生长的功能,本文从腐植酸刺激植物根系生长、调控土壤与肥料养分转化及肥料利用率和影响土壤微生物和酶活性方面,系统总结了国内外施用腐植酸促进植物生长的途径,阐述了腐植酸对植物生长促进作用的机理,旨在梳理腐植酸促进植物生长机理的研究现状,为腐植酸的进一步研究和应用提供参考依据。[主要进展]1）腐植酸能够对植物产生类似生物刺激素的效应。它能够提高植物根系H+-ATP酶等的活性、刺激植物根伸长和侧根生长点的增加,从而增加根系活力及植物根系与土壤养分的接触面积,增加植物对养分的吸收;2）逆境胁迫下,腐植酸能够通过调节植物体内的新陈代谢并改善植物生长环境,缓解甚至消除逆境胁迫对植物的伤害,从而促进植物生长;3）腐植酸能够通过与氮素、磷素和钾素发生结合效应,与磷酸盐产生竞争效应和对钾离子的吸附作用固持与活化土壤与肥料中的养分,提高土壤肥料有效性和缓释性能,提高肥料利用率,从而促进植物生长;4）腐植酸还能够影响土壤中与养分转化相关的酶活性和微生物群落结构及数量,在活化养分的同时,保蓄养分,降低养分的损失,为植物生长保障持久的养分供应;5）腐植酸对植物生长的促进效应受腐植酸结构特征、添加量和供试植物种类等因素的影响。[建议与展望]由于技术手段的限制和研究技术的差异,人们对腐植酸促进植物生长机理的认识还不够系统和深入,因此,腐植酸的基本特征、影响腐植酸作用的主控因子、土壤-植物系统中腐植酸促进植物生长的主要途径和腐植酸对土壤功能性微生物等的影响都将成为未来研究的重要方向。     

Adsorption of humic acid fractions with different molecular weight by magnetic polyacrylic anion exchange resin

Purpose

Anion exchange resin has been shown to be efficient for adsorption of humic acid (HA). However, the mechanism of the effect(s) of the molecular weight (MW) of HA on the adsorption by anion exchange resin needs to be further explored. The objective of this work was to investigated the effect(s) of HA MW on their adsorption and desorption behavior by interacting with anion exchange resin.

Materials and methods

HA fractions with different MW were obtained by ultrafiltration and characterized. For adsorption kinetic study, the magnetic polyacrylic anion exchange resin (NDMP) was shaken with each HA fraction. The amounts of HA in the solutions at different sampling times were obtained by measurement of the total organic carbon. For isotherm study, batch experiments were performed to obtain the isotherms of each HA fractions. The effects of pH value and the regeneration efficiency for HA fractions with different MW were all investigated.

Results and discussion

The characterization reveals that aromaticity of HA increases as the MW rises, while the negative charge follows the order: HA3 (2,500–1,000 Da)?>?HA4 (>10,000 Da)?>?HA2 (1,000–2,500 Da)?>?HA1 (<1,000 Da). The adsorption amount of HA increases as the negative surface charge rises. Thus, HA3 has the largest adsorption amount by NDMP resin among HA fractions, while the adsorption amount of HA1 is the smallest. HA2 adsorption could be modeled by Freundlich equation, suggesting the interaction between HA2 and NDMP is a heterogeneous process. However, the adsorption isotherms of HA3 and HA4 were both better described by Langmuir equation than Freundlich equation. In addition, the resin fouling follows the order: HA2?>?HA1?>?HA4?>?HA3.

Conclusions

The aromaticity of HA freactions increases as MW rises. HA fractions with 1,000?–?2,500 Da have the largest surface negative charge, while the fractions with MW lower than 1,000 Da are almost electroneutral. The adsorptions of HA fractions onto NDMP suggest there is little effect of size exclusion on adsorption, and the adsorption behavior mainly depends on the negative charge of HAs.     

Wettability of humic acid and its salts

Homoionic humates are well wetted by hydrocarbons (apolar liquid) and water (polar liquid). By wetting with hydrocarbons low heats of immersion (or wetting) are registered, whereas by wetting with water high heats of immersion are registered and colloidal solutions are formed. Humic acid is well wetted by hydrocarbons, producing low heats. It floats on the water surface, but once wetted by water it produces the heat of immersion. Studies of the properties of humic acid and humate permit to conclude that their surfaces are covered by hydrophilic and hydrophobic sites. By adsorption of butanol molecules it is established that humic acid and humate contain nearly two hydrophobic sites per 100 Ų.     

Sorption of cadmium by complexes of kaolinite with humic acid

Abstract

Levels of cadmium (Cd) in New Zealand pastoral soils have increased due to Cd impurities in applied fertilisers. As there is little information on the interaction of Cd with soil mineral‐organic matter complexes, the sorption of Cd by complexes of kaolinite with humic acid has been investigated. Sorption was measured at pH and ionic strength values typically found for solutions of pastoral soils in New Zealand. Sorption increased with the content of humic acid in the complex, and as the pH of the medium was raised from 4.2 to 6.3. Sorption was also influenced by the ionic strength of the ambient solution, notably by the nature of the cation in the added electrolyte. The experimental data were interpreted in terms of the effect of solution pH and ionic composition on the charge characteristics of kaolinite and humic acid. These factors, in turn, influence clay particle association as well as the clay‐humic and metal‐humic interaction.     

锌腐酸肥料对冬小麦群体、产量及品质的影响

通过大田微喷灌节水灌溉方式研究锌腐酸肥料对冬小麦群体、产量及品质的影响。采用磷肥种类为锌腐酸磷酸二铵和普通磷酸二铵;氮肥种类为锌腐酸尿素和普通尿素;不施肥为对照。结果表明:底施普通尿素和磷酸二铵处理的拔节期总茎数和单株茎数均较高;底施普通尿素和磷酸二铵,拔节期追施锌腐酸尿素产量最高,达6 730.5 kg/hm~2。拔节期追施锌腐酸尿素处理的籽粒产量均高于追施普通尿素,增产主要与成穗数和穗粒数增加有关;底施锌腐酸尿素和锌腐酸磷酸二铵,追施锌腐酸尿素的小麦籽粒品质指标最高,拔节期追施锌腐酸尿素的提质效果优于普通尿素。     

凹凸棒土-腐植酸复合体对Pb（Ⅱ）的吸附特性及机理研究

通过吸附实验,研究了凹凸棒土-腐植酸复合体对Pb（Ⅱ）的吸附特性及机理。结果表明,复合体对Pb（Ⅱ）的吸附量显著高于各自单一的吸附量;当pH〉4,凹凸棒土-腐植酸复合体对Pb（Ⅱ）的吸附量有所增加,这与其等电点有关;凹凸棒土-腐植酸复合体较凹凸棒土上Pb（Ⅱ）的解吸率小,且解吸率随Pb（Ⅱ）吸附浓度升高而降低;凹凸棒土-腐植酸复合体溶液中溶解态腐植酸的量较单一腐植酸溶液有显著增加;红外光谱（IR）表明凹凸棒土-腐植酸复合体在吸附Pb（Ⅱ）后,大量特征峰变宽或消失,而腐植酸吸附Pb（Ⅱ）后仍可发现羟基等基团特征峰,说明腐植酸、凹凸棒土-腐植酸复合体的某些表面基团虽然相同,但混合物的基团更易与Pb（Ⅱ）结合。     

Influence of humic acid on adsorption and desorption of atrazine, hydroxyatrazine, deethylatrazine, and deisopropylatrazine onto a clay-rich soil sample

Adsorption and desorption properties of atrazine and some of its metabolites, hydroxyatrazine (AT-OH), deethylatrazine (DEA), and deisopropylatrazine (DIA), were studied with a clay-rich soil sample (clay content of 53%). A part of this soil was treated with humic acid (Soil-HA) to assess the influence of this important component of natural organic matter on adsorption and desorption processes. This study was performed using the batch approach with 1.0 g of soil, or Soil-HA, in 5.0 mL of 0.010 mol L(-)(1) CaCl(2) solution containing the herbicide and the metabolites in a concentration range between 0.010 and 5.0 mg L(-)(1). After 24 h of contact time, the suspensions were centrifuged and the four compounds were quantified in the supernatant phases by high-performance liquid chromatography. The adsorption and desorption data of both Soil and Soil-HA were properly fitted by the linearized Freundlich equation. For the untreated soil, the adsorption affinity order evaluated as a function of the K(f) values was AT-OH > AT > DIA > DEA, while desorption followed the order DEA > DIA approximately AT > AT-OH. The presence of humic acid increased significantly the adsorption of all compounds, following the same affinity order observed for the untreated soil. Increase in adsorption was especially high for AT-OH and AT. On the other hand, the dealkylated metabolites, DEA and DIA, were more easily desorbed from the Soil-HA sample, suggesting that natural organic matter facilitates the leaching of these compounds. Desorption order in the presence of humic acid was DEA > DIA > AT > AT-OH.     

白浆土对腐殖酸的吸附等温线和动力学研究

白浆土是吉林省和黑龙江省东部地区的主要农田土壤之一,研究白浆土对腐殖酸的吸附作用,可为探究白浆土的固碳潜力提供理论依据。采用批量平衡法,分析不同有机碳含量的白浆土及其组分(包括去有机质土壤、粉粒、黏粒)对腐殖酸的吸附动力学和等温吸附特性。结果表明:随吸附时间的延长,白浆土及其各组分对腐殖酸的吸附量逐渐增加;整个吸附动力学过程可划分为快速(0～30 min)和慢速(30～480 min)反应阶段,伪二级动力学方程的拟合效果优于Elovich、双常数和伪一级动力学方程。白浆土及其各组分对腐殖酸的吸附量随腐殖酸初始浓度的增加逐渐增大,Langmuir方程的拟合效果通常优于Freundlich方程和Temkin方程。随白浆土有机碳含量的增加,其对腐殖酸的最大吸附量分别为26.9,24.1,15.6 mg/g。而白浆土不同组分相比,最大吸附量的顺序依次为黏粒>去有机质土壤>粉粒,黏粒对腐殖酸的吸附量分别是原土的2.15～3.88倍,去有机质土壤的1.61～2.21倍,粉粒土壤的7.90～8.65倍。有机碳含量低的白浆土对腐殖酸具有更强的吸附能力,黏粒含量高的白浆土对腐殖酸的吸附潜力更大。     

铁氧化物-胡敏酸复合物对磷的吸附吸附

本试验通过设置不同磷酸根浓度、 pH和不同电解质及电解质强度梯度,研究磷酸根在针铁矿-胡敏酸（HA）复合物和赤铁矿-胡敏酸（HA）复合物表面的吸附特性。X射线衍射（XRD）、 扫描电镜（SEM）和红外光谱（FTIR）图谱显示: 铁氧化物包覆胡敏酸后其内部结构特性保持不变; 氧化铁与胡敏酸通过氢键形成粒径大、 表面光滑的铁氧化物-HA复合微粒,且复合物比表面减小; 形成的氧化铁-胡敏酸复合物对磷的吸附能力增强,且针铁矿复合物的吸附能力大于赤铁矿复合物,均为多层吸附过程; pH增高抑制铁氧化物复合物对磷的吸附,同时电解质浓度增加促进复合体对磷的吸附,且反应后体系pH随之降低。     

熔融造粒腐植酸尿素的缓释性能研究

运用碱处理风化煤得到水溶性腐植酸和沉淀混合物以及未处理的风化煤细粉（80目）分别与熔融尿素混合造粒,制得3种类型的腐植酸尿素产品,利用土柱淋洗方法研究不同腐植酸尿素产品的缓释性能。结果表明,除添加10%的未处理风化煤处理外,其余腐植酸尿素产品与普通尿素相比,均表现出具有氮缓释性能。其中,以添加水溶性腐植酸的产品缓释性最强;且当水溶性腐植酸与尿素比例为3∶7时,肥料的缓释效率最高。在本试验条件下,风化煤类腐植酸熔融造粒工艺下制成腐植酸复合尿素的缓释性能,与添加腐植酸的数量呈正相关;水溶性腐植酸添加比例与腐植酸复合尿素缓释性能相关性较低。3种类型的腐植酸复合尿素,以添加水溶性腐植酸的肥料质量最稳定。对风化煤进行活化后提取水溶性腐植酸,适量添加到熔融尿素中进行造粒,可生产出具有较好缓释性能的腐植酸尿素产品。