不同处理褐煤腐殖酸对磷吸附特性的研究

采用吸附等温线的试验方法,研究了平衡溶液中磷浓度、反应时间及介质pH对不同处理的2种褐煤腐殖酸吸附磷的影响及其规律性。结果表明:在试验pH范围内,pH的升高减缓了吸附反应进行的速度,对于未经硝酸处理的样品S1,在pH为4.7时,吸附量和分配系数有一最大值,而样品S2,随着pH的升高,吸附量和分配系数一直减小;经硝酸处理后,样品对磷的吸附能力降低,一定条件下其单位吸附量仅为处理前的5.33%。适宜的固液比例可提高2个不同处理供试样品对磷的单位吸附量,其等温吸附规律可用Langmuir方程来加以描述;其吸附动力学用Elovich方程描述最佳。     

无机酸处理对褐煤腐殖酸含量及特性的影响

研究了不同浓度的各种无机酸对褐煤中腐殖酸含量、CEC及其光学性质变化规律的影响。试验结果表明:H_3PO_4和HCl处理能在一定程度上提高阳离子交换能力,但对腐殖酸含量及光学性质基本无影响。一定强度的HNO_3能使腐殖酸含量增加25％以上,阳离子交换能力有了很大程度提高,且随硝酸强度的变化过程要明显滞后于腐殖酸含量的变化过程,光学性质发生了很大变化。不同褐煤达到最佳处理效果的条件也不尽相同。     

长期秸秆还田下土壤铵态氮的吸附解吸特征

【目的】研究长期秸秆还田对不同轮作区域耕层和亚耕层的土壤铵态氮 (NH₄+) 的吸附、解吸特征差异,通过 Langmuir 等温吸附方程拟合得到 NH₄+ 最大吸附量 (q_max) 和吸附系数 (b),分析长期秸秆还田对不同土壤 NH₄+ 的吸附、解吸特征差异及影响因素。 【方法】2015 年 10 月水稻收获后,在湖南望城 (稻–稻轮作)、江西进贤 (稻–稻轮作)、重庆北碚 (稻–麦轮作) 三个长期定位试验点 (25 年) 采集不施肥 (CK)、长期施用化肥 (NPK) 和长期秸秆还田配施化肥 (NPKS) 三个处理、0—20 cm 和 20—40 cm 两个土层的土样,进行土壤 NH₄+ 的吸附–解吸室内试验,吸附试验为添加不同浓度的 NH₄Cl 溶液振荡、离心后,测定滤液 NH₄+ 浓度;解吸试验采用吸附试验后的土壤样品,经无水乙醇淋洗至无 NH₄+ 后,再加入 0.01 mol/L 的 KCl 溶液振荡、离心后测定滤液 NH₄+ 浓度。 【结果】长期秸秆还田对不同试验点土壤 NH₄+ 吸附–解吸特征的影响差异较大。处理间的差异主要表现在耕层土壤。当平衡溶液 NH₄+ 浓度 < 400 mg/L 时,不同试验点耕层和亚耕层处理间差异均不明显;当平衡溶液浓度 > 400 mg/L 时,处理间耕层土壤对 NH₄+ 吸附表现出差异,其中望城试验点土壤对 NH₄+ 的吸附表现为 CK > NPK > NPKS,北碚试验点则表现为 CK > NPKS > NPK,且北碚试验点的紫色土对 NH₄+ 的吸附显著高于望城和进贤试验点的红壤性水稻土。进贤试验点不同处理间差异不明显,且土壤对 NH₄+ 的吸附量最低。 通过相关性分析发现,q_max和土壤 pH、阳离子交换量 CEC 呈显著正相关,而与土壤有机质和全氮含量呈显著负相关;b 与土壤性质的相关性与q_max 则相反。从土壤对 NH₄+ 的解吸曲线来看,耕层和亚耕层土壤对 NH₄+ 的解吸在各试验点不同处理间均表现为差异不显著,其中望城和进贤试验点的红壤性水稻土 NH₄+ 的最大解吸量高于其吸附量,而北碚试验点的紫色土 NH₄+ 的最大解吸量 (541.89～742.38 mg/kg) 则远低于其吸附量 (1003.83～2014.79 mg/kg)。 【结论】长期秸秆还田对不同土壤 NH₄+ 的吸附–解吸作用影响不同,对于土壤吸附位点较多且钾离子含量丰富的紫色土而言,长期秸秆还田有利于土壤对氮的吸附;而对于土壤偏酸性的红壤性水稻土而言,长期秸秆还田则可能因为增加了土壤有机质含量而减少了土壤对铵态氮的吸附位点,从而降低了土壤对氮的吸附保持能力。     

不同原料生物炭对氮、磷、钾的吸附和解吸特性

【目的】通过三种不同原料生物炭 (玉米秆炭、稻壳炭、稻秆炭) 对氮、磷、钾的吸附解吸试验,了解不同材料来源的生物炭对无机养分的吸附和解吸特征,为将其作为添加物来调节有机肥的性质提供参考。【方法】在pH 6.75 ± 0.25、25℃下,采用Langmuir和Freundlich方程对三种不同原料生物炭 (玉米秆炭、稻壳炭、稻秆炭) 氮、磷、钾的等温吸附进行拟合。对吸附养分后的生物炭进行连续5次解吸,前4次采用水浸提,第5次浸提采用1 mol/L KCl浸提氮,0.5 mol/L的NaHCO₃浸提磷,1 mol/L的CH₃COONH₄浸提钾。【结果】1) Langmuir和Freundlich方程均可用来拟合生物炭对氮、磷、钾的等温吸附,Langmuir方程对氮、磷的吸附拟合较好,Freundlich方程对钾的吸附拟合较好。对不同原材料而言,稻秆炭对氮、磷、钾的吸附性能均较好,其最大吸附量q_m分别为 (2.44 ± 0.15) mg/g、(2.91 ± 0.12) mg/g和 (4.97 ± 0.22) mg/g。2) 不同原材料生物炭对氮、磷、钾的单次解吸率和总解吸率具有一定的差异。生物炭对阳离子 (铵根离子和钾离子) 的最大吸附量受阳离子交换量和酸性官能团的数量以及pH_pzc影响,对磷酸根的最大吸附量主要与阳离子交换量和碱性官能团的数量有关。【结论】所试三种生物炭对氮、磷、钾的吸附存在单分子层吸附和多分子层吸附,在单次解吸率和总解吸率上不同原料生物炭存在一定的差异性。在生物炭对氮和钾吸附的总量上,物理性吸附的贡献高于化学吸附;对磷的吸附总量上,化学吸附的贡献高于物理吸附。三种生物炭对氮、磷、钾的固储和缓释能力具有一定的差异,稻秆炭的保肥供肥能力优于玉米秆炭和稻壳炭。     

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.     

不同来源腐殖酸对铜吸附量和吸附机制的研究

本研究从三种供试材料:草炭、褐煤和风化煤中提取腐殖酸,采用NH4OAc和EDTA两种解吸剂,研究三种来源腐殖酸对Cu2+的吸附能力和吸附机制。研究结果表明:三种来源腐殖酸对Cu2+的吸附在吸附量上没有明显差异,但吸附机制却并不完全相同。三种来源腐殖酸对Cu2+的吸附均主要通过离子交换和络合(或螯合)作用,其中,草炭和褐煤提取的腐殖酸的离子交换作用显著大于风化煤提取的腐殖酸,而风化煤提取的腐殖酸的络合(或螯合)作用则明显大于草炭和褐煤提取的腐殖酸。     

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。     

不同电解质对牛粪生物质炭中腐殖酸吸附–解吸的影响

本文研究了NaCl、Na_2SO_4、Na_3PO_4 3种背景电解质对牛粪生物质炭中腐殖酸吸附和解吸的影响。结果表明:在这3种背景电解质作用下,牛粪生物质炭对腐殖酸的吸附量和吸附率随着加入液腐殖酸浓度的增加而增加,但是增加速度逐渐变缓。3种背景电解质相比,NaCl中牛粪生物质炭对腐殖酸的吸附量和吸附率均为最高,吸附量范围为0.13～6.10 mg/g,吸附率范围为25.40%～87.14%。随着加入液腐殖酸浓度的增加,吸附态腐殖酸的解吸量逐渐增加,解吸率逐渐减小。3种背景电解质相比,Na_2SO_4中牛粪生物质炭吸附的腐殖酸的解吸量最高,解吸量范围为0.15～0.78 mg/g。加入液腐殖酸浓度为140 mg/L,3种背景电解质中牛粪生物质炭吸附的腐殖酸的解吸量均达到最大值,解吸量的大小顺序为Na_2SO_4Na_3PO_4NaCl。Na_3PO_4对腐殖酸的解吸率影响最大,解吸率范围为17.24%～90.55%,NaCl对腐殖酸的解吸率影响最小,解吸率范围为8.22%～53.54%。用Langmuir拟合3种背景电解质中腐殖酸的等温吸附曲线和等温解吸曲线,其相关系数都达到显著水平。研究结果揭示了不同背景电解质对牛粪生物质炭吸附和解吸腐殖酸的影响,可为土壤保土保肥提供理论参考。     

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。     

中低分子量腐殖酸提高冬小麦磷吸收和产量的机理

  【目的】  研究不同分子量腐殖酸与磷肥复合制备的腐殖酸磷肥对作物和土壤磷有效性的影响,为腐殖酸磷肥研发和磷素高效利用提供理论依据。  【方法】  利用超滤分级方法,将风化煤腐殖酸分子量分为 > 100 kDa、10～100 kDa和 < 10 kDa 3个部分,获得高 (HA_H)、中 (HA_M)、低 (HA_L) 不同分子量的腐殖酸,采用磷酸与KOH反应法制备普通磷肥 (P)、未分级腐殖酸磷肥 (PHA)、高分子量腐殖酸磷肥 (PHA_H)、中分子量腐殖酸磷肥 (PHA_M) 和低分子量腐殖酸磷肥 (PHA_L) 5种磷肥。采用深100 cm、内径25 cm的土柱进行冬小麦栽培试验,按等磷量原则,设置P、PHA、PHA_H、PHA_M、PHA_L 5个施磷处理,同时设置与4个施磷处理对应的等量腐殖酸处理 (HA、HA_H、HA_M、HA_L),以不施磷肥为对照CK。测定小麦产量及产量构成因素、植株磷含量及不同层次土壤有效磷含量。  【结果】  1) 与CK相比,腐殖酸处理 (HA、HA_H、HA_M、HA_L) 小麦增产不明显。与普通磷肥相比,PHA、PHA_M和PHA_L处理产量显著提高了14.73%、18.84%、21.37% (P < 0.05),3 个处理间产量差异不显著,PHA_H增产不明显。PHA_L处理千粒重显著高于普通磷肥处理,其余3个腐殖酸磷肥处理增幅未达显著水平。2) PHA、PHA_M和PHA_L处理籽粒吸磷量较普通磷肥处理分别显著提高14.97%、19.45%、22.68%,而PHA_H增幅未达显著水平;腐殖酸磷肥处理间秸秆吸磷量没有显著差异。3) 与普通磷肥相比,PHA、PHA_H、PHA_M、PHA_L磷肥偏生产力和农学效率分别提高14.71%、6.01%、18.82%、21.35%和14.95%、1.66%、20.18%、23.03%,磷肥表观利用率分别提高2.93、0.51、4.52、5.41个百分点,也以中、低分子量腐殖酸磷肥效果最为明显,腐殖酸中的氧烷基碳、羧基/酰胺基碳、烷基碳结构与小麦籽粒产量和磷肥利用率具有正相关性,与芳香碳、芳香C―O负相关。4) 4个腐殖酸磷肥处理间及其与普通磷肥处理间 0—20、20—40、40—60 cm 土层土壤有效磷含量差异不显著。  【结论】  田间土柱栽培条件下,单施腐殖酸对小麦没有表现出明显的增产效果。腐殖酸中的氧烷基碳、羧基/酰胺基碳、烷基碳结构与小麦磷素吸收具有正相关性,低分子量腐殖酸具有较多的烷基碳、氧烷基碳、羧基/酰胺基碳结构,因而低分子量腐殖酸提高磷肥中磷素利用率的作用好于中分子量腐殖酸,而高分子量腐殖酸的效果不显著。     

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.     

Measurement of electrostatic and site-specific associations of alkali metal cations with humic acid

A discontinuous acidimetric titration method incorporating ultrafiltration was developed to measure the association of a soil humic acid with Li⁺ t, Na⁺ and K⁺ (pH 3 to 8). In addition, possible site-specific binding of these alkali metal cations was investigated using desorption experiments at pH 1. Li, Na and K cations behaved equivalently in the titrations and the amounts of these cations associated with the humic acid was measurable at all pH values between 3 and 8. Up to 90% of the total alkali metal cation was humate-associated at pH 8. The absolute amount of humic-associated cation did not depend on the alkali metal cation concentration, but rather on the solution alkalinity. In addition, the net charge of the humate polyanion made a negligible contribution to the electroneutrality of the bulk solution under all conditions. These results are consistent with a diffuse layer model of hydrated humic acid in which the alkali metal cations neutralize the humic charge. The association of Na+ andK+ with humic acid at pH 1 was successfully described by a Langmuir adsorption model. The number of sites per g of humic acid was very small, and greater for K+ than for Nat. Lithium cations exhibited no detectable humic association at pH 1. These differences suggest that humic acids may have a small number of specific binding sites for which the size of the hydrated cation is important.     

Geochemical Fractionation and Adsorption Characteristics of Zinc in Thai Major Calcareous Soils

Zinc (Zn) is a vital plant nutrient that is widely deficient in Thai cultivated calcareous soils. The chemical fractionation and adsorption of Zn are among the most important solid- and liquid-phase interactions that determine the retention of Zn in the soils. This study aimed to investigate the fractionation and adsorption isotherms of Zn in cultivated Thai calcareous soils. The results of sequential extractions showed that Zn is mainly distributed in residual fractions followed by organic-bound, iron and manganese oxides-bound, carbonate-bound, and exchangeable Zn, respectively. Zinc adsorption was well fitted by the Langmuir and Freundlich isotherms. Thai calcareous soils had high Zn adsorption capacity. Soil pH, organic carbon, calcium carbonate, cation exchange capacity, and extractable calcium were the major soil properties that affected the Zn adsorption isotherms in these soils. Zinc hydroxide was the solid precipitate and the Zn hydroxide ion (ZnOH⁺) was the dominant Zn ion in alkaline equilibrium solution.     

胡敏酸对铵钾在粘土矿物上交互作用的影响

Interaction of ammonium (NH+4) and potassium (K+) is typical in field soils. However, the effects of organic matter on interaction of NH+4 and K+have not been thoroughly investigated. In this study, we examined the changes in major physicochemical properties of three clay minerals (kaolinite, illite, and montmorillonite) after humic acid (HA) coating and evaluated the influences of these changes on the interaction of NH+4 and K+on clay minerals using batch experiments. After HA coating, the cation exchange capacity (CEC) and specific surface area (SSA) of montmorillonite decreased significantly, while little decrease in CEC and SSA occurred in illite and only a slight increase in CEC was found in kaolinite. Humic acid coating significantly increased cation adsorption and preference for NH+4, and this effect was more obvious on clay minerals with a lower CEC. Results of Fourier transform infrared spectrometry analysis showed that HA coating promoted the formation of H-bonds between the adsorbed NH+4 and the organo-mineral complexes. HA coating increased cation fixation capacity on montmorillonite and kaolinite, but the opposite occurred on illite. In addition, HA coating increased the competitiveness of NH+4 on fixation sites. These results showed that HA coating affected both the nature of clay mineral surfaces and the reactions of NH+4 and K+with clay minerals, which might influence the availability of nutrient cations to plants in field soils amended with organic matter.     

Adsorption and Desorption of Boron as Influenced by Soil Properties in Temperate Soils of Lesser Himalayas

Boron (B) adsorption increased with increasing concentration. Langmuir adsorption isotherm was curvilinear. The maximum value of adsorption maxima (b1) was observed Sagipora soil and maximum bonding energy (k) constant was in Anantnag soil. The Langmuir isotherm best explains the adsorption trend at low adsorbent concentrations. A significant correlation among b1, clay, and cation exchange capacity was observed. Linear affiliation was observed in all the soils at all concentration, indicating that B adsorption data conform to the Freundlich equation. Soils with greater affinity for B adsorption, like Sagipora, tended to desorb less B. Boron desorption was positively and significantly correlated with sand content and negatively with clay content and cation exchange capacity. The maximum value of 50.76 mg g^?1 for desorption maxima (Dm) was observed in Sagipora soil, and mobility constant (Kd) was maximum in Khag soil (0.412 ml kg^?1).     

Removal of Cu2+ and Cd2+ from Aqueous Solution by Bentonite Clay Modified with Binary Mixture of Goethite and Humic Acid

Pre-modification of bentonite clay with goethite, humic acid, and a binary mixture of goethite and humic acid reagents increased its cation exchange capacity from 95 to 105.32, 120.4, and 125.8 meq/100 g of bentonite clay, respectively. The effective pre-modification of bentonite clay with goethite, humic acid, and goethite–humic acid reagents was confirmed from their Fourier transform infrared spectra which suggested that modification was effective on the AlAlOH and Si–O sites for goethite and humic acid modification and AlAlOH for goethite–humic acid modification. The presence of 0.001 M NaNO₃ electrolyte increased the adsorption capacity of bentonite clay. Temperature was observed to favor the adsorption of Cu²⁺ and Cd²⁺ onto both the raw and modified bentonite clay samples. The goethite–humic acid-modified bentonite gave the best adsorption capacity of ≈10 and 16 mg/g at 30 and 50°C, respectively, for both metal ions. The inner sphere complexation mechanism was suggested for the adsorption of both metal ions onto the modified adsorbents. Modifying bentonite clay with a binary mixture of goethite and humic acid reduced the selectivity of bentonite clay for either Cu²⁺ or Cd²⁺. Preadsorbed goethite and humic acid on bentonite clay will further reduce the mobility of heavy metal ions in soils and in aquatic environments.