生物质炭对华北平原4种典型土壤冬小麦生育前期氨挥发的影响

为了探明生物质炭对华北平原土壤氨挥发的影响,以该区域4种典型土壤(水稻土、砂姜黑土、褐土、潮土)为研究对象进行微区试验,设置了对照(CK)、单施化肥(NPK)、单施生物质炭(BC)、化肥配施生物质炭(BC+NPK)4个处理,于冬小麦生育前期观测土壤氨挥发损失,分析土壤矿质氮含量、土壤pH和温度对土壤氨挥发的影响。结果表明,4种土壤单施化肥处理氨挥发累积损失分别为2.70、3.14、2.90、4.00 kg N·hm~(-2),占施氮量的比例(氨挥发损失率)为3.3%、3.8%、3.5%、4.9%。与单施化肥相比,化肥配施生物质炭可以降低砂姜黑土(15.3%)和潮土(14.8%)的氨挥发损失,但增加了水稻土(3.0%)和褐土(6.9%)氨挥发。添加生物质炭显著提升土壤pH值和土壤温度,相关性分析表明,土壤pH值是决定生物质炭对土壤氨挥发增减的关键因素。综上所述,在华北平原砂姜黑土和潮土施用生物质炭可以有效降低小麦生育前期土壤氨挥发。     

硫酸铵与DMPP配施对石灰性褐土氮素转化及N2O、CO2排放的影响

为合理利用工业副产硫酸铵,探究3,4—二甲基吡唑磷酸盐(DMPP)配施硫酸铵对石灰性褐土中氮素转化及N_2O和CO_2排放的影响。通过室内培养试验,研究不同剂量DMPP与硫酸铵配施后,石灰性褐土中铵态氮(NH_4~+-N)含量、硝态氮(NO_3~--N)含量、土壤pH、N_2O和CO_2排放通量和累计排放量的动态变化,并进行了相关性分析。结果表明:单施硫酸铵的ASN处理在培养的前15天硝化作用强烈,第15天时,土壤NH_4~+-N含量降低了477.28 mg/kg, NO_3~--N含量增高了177.03 mg/kg。添加DMPP可以明显抑制硫酸铵NH_4~+-N向NO_3~--N转化。培养30天后,0.75%～1.75%剂量的DMPP处理的土壤NO_3~--N含量低于ASN处理174.02～177.00 mg/kg,硝化抑制率为94.92%～95.30%,且在0.75%～1.75%浓度范围内未表现出明显的剂量差异效应。各剂量DMPP在试验期间的硝化抑制效果表现较好,其作用时长为30天以上。培养30天时,与空白CKII处理相比,单施硫酸铵T1处理的N_2O和CO_2的累计排放量分别显著增加了975.3%,126.66%(P0.05),而添加了DMPP的T2处理相较于单施硫酸铵T1处理,N_2O和CO_2累计排放量分别显著降低了76.8%,6.22%(P0.05)。相关性分析表明,CO_2排放通量与N_2O排放通量呈正相关关系,土壤pH与N_2O、CO_2排放通量呈负相关关系。硫酸铵与0.75%DMPP配合施用在一定程度上可以抑制土壤酸化,同时短期内可以显著降低N_2O和CO_2累计排放量(P0.05)。     

不同活化处理腐植酸–尿素对褐土小麦–玉米产量及有机碳氮矿化的影响

腐植酸–尿素是一种新型有机无机肥料,不同活化方式对其肥效的发挥具有重要作用。本研究利用田间定位试验和室内培养试验,设计不施肥处理(CK)、无机肥处理(U)、腐植酸–尿素直接掺混处理(U+HA1)、腐植酸–尿素硫化活化处理(U+HA2)、腐植酸–尿素硫化加超声波处理(U+HA3),在褐土上研究不同活化处理腐植酸–尿素肥料对小麦–玉米产量和土壤有机碳氮矿化的影响。结果表明:施用腐植酸–尿素显著提高小麦–玉米产量,小麦、玉米产量分别比U处理增产15%~28%、8%~10%,比CK处理增产63%~81%、55%~57%。U+HA3处理比U+HA1和U+HA2处理具有更强的增产效果。土壤养分在不同施肥处理间存在差异,土壤NO3–-N含量的变化趋势为U+HA1、U+HA3U+HA2UCK。土壤NH4+-N含量在不同处理间与NO3–-N含量具有相似的趋势,其中U+HA1处理土壤NH4+-N含量较其他两种腐植酸–尿素处理有显著的降低。施肥处理提高了土壤有效磷、速效钾含量,但是腐殖酸–尿素处理与U处理的影响未见差异。腐殖酸-尿素处理对土壤有机碳含量未产生显著影响,但提高了土壤有机碳的矿化速率与累积矿化量,其中U+HA3处理比U+HA1和U+HA2处理效果明显。土壤有机碳的累积矿化量与作物总产量、土壤速效氮、有效磷、速效钾含量具有显著的正相关关系。与CK处理相比,腐植酸的添加对土壤有机氮矿化比率影响不显著,但U处理土壤有机氮矿化比率显著提高。通过本研究验证腐植酸-尿素肥料比无机肥料具有更强的提高土壤生产力和肥力的作用,硫化超声波活化处理效果比其他两种活化处理效果显著。硫化超声波活化处理腐植酸-尿素肥料是值得推广的新型肥料,对丰富肥料资源具有重要作用。     

活化腐植酸–尿素施用对小麦–玉米轮作土壤氮肥利用率及其控制因素的影响

腐植酸-尿素是近年来的一种新型有机无机复合肥料,其增产效应显著,但是在小麦-玉米轮作中该肥料的利用率和环境调控因素尚不清楚。本研究通过田间定位与室内培养试验,以不施肥处理(Control)和单施尿素处理(Urea)为对照,研究腐植酸-尿素直接掺混处理(U+HA1)、腐植酸-尿素活化处理(U+HA2)和腐植酸-尿素活化催化处理(U+HA3)对小麦和玉米生长、土壤理化性质、氮肥利用率和土壤氮转化及土壤脲酶含量的影响。研究结果表明:活化腐植酸-尿素处理的小麦、玉米籽粒产量分别较Urea处理增产15%~28%和8%~10%。活化腐植酸-尿素施用显著地降低土壤容重、p H和土壤颗粒粒径的中位粒径,提高了土壤的比表面积、电导率、有机碳含量和矿质态氮含量。小麦季活化腐植酸-尿素处理下氮肥回收利用率较Urea处理显著增加,增加幅度为37%~91%,玉米季的增加幅度为78%~93%。活化腐植酸-尿素处理下小麦和玉米的氮肥农艺利用率和偏生产力均较Urea处理高。此外,回归分析表明活化腐植酸-尿素的氮肥当季回收利用率随土壤硝化比率、有机氮的矿化量及脲酶含量的增加而降低,而随土壤颗粒比表面积的增大而提高。本研究结果明确了腐植酸-尿素活化处理对小麦、玉米的增产效果较好,可改善土壤理化性质,其中腐植酸-尿素活化催化处理(U+HA3)的效果最好。研究结果为活化腐植酸-尿素肥料的深入研发与推广提供基础资料。     

腐植酸对土壤氮素转化及氨挥发损失的影响

采用培养试验方法研究腐植酸添加量(0、5%、10%、25%、50%、75%HA)对土壤氮素转化及其损失的影响。结果表明:与CK对比,1)腐植酸可显著降低氨挥发量,各处理平均降低12.08%,且随着腐植酸添加量的增加对氨挥发的抑制作用增大;2)培养前期,5%~50%添加量范围内腐植酸能提高土壤脲酶活性,至5 d时平均提高了35.13%,75%腐植酸添加量的土壤脲酶活性降低了13.23%,但培养后期(14 d后)腐植酸处理均能提高土壤脲酶活性;3)添加腐植酸使土壤铵态氮含量增加,且随着腐植酸添加量的增大,土壤铵态氮含量呈增加趋势,至培养112 d时,腐植酸处理的土壤铵态氮含量平均增加了39.63%;4)在整个培养期间,腐植酸处理的土壤表观硝化率平均降低了17.20%,且腐植酸的添加量越大,土壤表观硝化率越低。这些结果充分表明腐植酸能够调控土壤氮素去向、减少氮素损失,对提高氮肥利用率具有重要意义。     

腐植酸尿素氨挥发特性及影响因素研究

采用室内模拟,研究了腐植酸尿素在土壤培养条件下其氨挥发特性及其与土壤脲酶活性、氮溶出率以及土壤铵态氮、硝态氮含量变化的关系。结果表明,研制的4种腐植酸尿素氨挥发量分别比普通尿素降低了48.14%、 47.99%、 30.89%、 59.22%,其中水溶性腐植酸含量11.78%的腐植酸尿素降低最多。腐植酸尿素降低氨挥发量与其养分释放模式和形成的土壤环境密切相关。土壤氨挥发总量与脲酶活性在培养前期相关系数较高,培养48和96 h分别达到0.825和0.808; 土壤氨挥发总量与肥料累积溶出量相关系数为0.903; 培养前期,土壤氨挥发量与铵态氮含量相关系数达到0.869。     

腐植酸氮肥对玉米产量、氮肥利用及氮肥损失的影响

【目的】 通过研究新型腐植酸氮肥对玉米产量、氮肥吸收利用和分配及氮肥在土壤中分布以及损失的影响,为促进新型肥料的应用,减少环境污染,提高作物产量提供理论依据。 【方法】 采用固定装置,应用同位素示踪技术进行田间试验。试验共设 4 个处理:CK1 (不施氮肥)、CK2 (普通尿素 N 225 kg/hm2)、HA1 (脲基活化腐植酸氮肥 N 225 kg/hm2)、HA2 (常规掺混腐植酸氮肥 N 225 kg/hm2)。采集玉米播种前、施肥前和收获后 0—20 cm、20—40 cm、40—60 cm 土壤样品,采用静态箱体内置硼酸吸收池法测定氨挥发,氧化亚氮通过静态箱体收集、真空瓶贮存后气相色谱仪测定。玉米成熟后采集地上部植株样品,将营养器官与籽粒分离,计产并测定产量构成指标。 【结果】 籽粒中氮素 34.6%～36.2% 来自肥料,营养器官中氮素 14.6%～17.4% 来自肥料。CK2、HA1 和 HA2 处理的氮肥利用率分别为 25.1%、30.9%、28.5%,氮肥损失率分别为 38.1%、19.8%、27.2%。与 CK2 相比:1) 施用 HA1 能提高玉米产量;2) HA1 和 HA2 处理的氮素吸收总量分别增加 25.8 和 16.3 kg/hm2,氮肥利用率分别提高 5.8 个百分点和 3.4 个百分点,氮肥损失率分别减少 18.3 个百分点和 10.9 个百分点;3) HA1 和 HA2 处理 0—60 cm 土壤氮素残留率分别增加 12.5 个百分点和 7.5 个百分点;4) 施用腐植酸氮肥明显提高 0—20、20—40 cm 土壤铵态氮和硝态氮含量。 【结论】 腐植酸氮肥能显著提高玉米产量和氮肥利用率,促进玉米对土壤氮素的吸收利用,显著增加 0—20 cm 土壤氮素残留量和 0—40 cm 土壤无机态氮含量,减缓氮素向深层土壤迁移,从而减少淋溶损失。腐植酸氮肥能改善氮素在土壤中的分布,满足作物根系需肥特性;腐植酸氮肥能显著降低氧化亚氮产生量和其它途径的氮素损失,从而减少氮素损失量。其中,脲基活化腐植酸氮肥作用效果更加明显。      

腐植酸钾与磷肥施用方式对土壤磷素移动性的影响

为探明腐植酸与磷肥施用方式对土壤磷素移动性和淋失量的影响,通过室内土柱淋溶试验,分别设计了不施肥(CK)、基施腐植酸钾追施/不追施磷肥(HA-P、HA)、基施磷肥追施/不追施腐植酸钾(P-HA、P)和磷肥腐植酸钾共同基施(P+HA)共6个处理,来探讨将腐植酸水溶性肥料中的主要原料腐植酸钾与磷肥按照不同施用方式施入土壤后对土壤磷素剖面迁移能力和淋出的影响。结果表明:在相同的灌溉条件下,HA-P处理显著增加了土壤磷素的淋出,分别比P-HA、P和P+HA3个处理的磷素淋出总量高244.08%、78.51%和35.34%,而P-HA则显著降低了土壤磷素的淋出量;P+HA和P-HA处理土壤剖面的速效磷和全磷含量均随土层深度的增加而显著增加,与P处理结果相似,而HA-P处理剖面各层土壤的速效磷和全磷含量差异较小;HA处理会使土壤磷素淋出略有增加。研究表明,腐植酸钾与磷肥等量输入时,以腐植酸钾为基肥、磷溶液进行追肥的施用方式对土壤磷素移动的促进作用最大,有较高的淋失风险,而基施磷肥、追施腐植酸钾则可以显著控制土壤剖面磷素移动,降低土壤磷素的淋出量。     

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...     

长期施肥对黄淮海平原小麦氮素吸收及氨挥发的影响

黄淮海平原是我国重要的粮食主产区,针对该区域氮肥利用率低且损失率高等问题,以国家土壤质量新乡观测实验站为研究平台,监测长期不同施肥模式下小麦玉米轮作体系土壤氮素损失规律,探讨减少黄淮海平原土壤氨挥发的科学施肥方式,为提高氮肥利用效率提供理论依据。设置了对照(CK)、单施化肥(NPK)、单施有机肥(M)、秸秆还田配施化肥 (NPK+S)、化肥增施有机肥(NPK+M)5个处理,于小麦季观测潮土氨挥发损失,分析土壤矿质氮含量、pH值对氨挥发的影响。结果表明,长期施肥对小麦产量及氮素吸收有显著影响。各施肥处理小麦产量均显著高于CK处理,且籽粒、秸秆和颖壳产量以NPK+M处理最高,分别达11.6、13.38和3.34 t·hm-2,较NPK处理分别增加15.6%、39.1%和18.4%。各处理的小麦地上部吸氮量以NPK+M处理最大,达306.67 kg·hm-2,较NPK、NPK+S处理分别提高14.3%、44.7%。不同施肥处理对土壤氨挥发有显著影响,小麦季土壤氨挥发速率峰值主要在施肥后1～4 d 内,其中NPK+S处理观测到的峰值高达N 0.40 kg·hm-2·d-1,     

Adsorption mechanisms of nicotine on humic acid and clay humic acid complex

The adsorption isotherm of nicotine on humic acid - surface was found to be multiphase according to the applied concentrations of nicotine. Each phase was characterized by its own change in free energy and represented a mechanism of interaction. At low concentrations, the isotherm showed a H-curve of high affinity between both reactants as a result of protonation of the pyrrolidine nitrogen atom of nicotine, the second phase was that of flat adsorption in which the nitrogen atoms of nicotine acted as electron donor. The third phase was that of the rearrangement of the nicotine from flat to side adsorption on the humic surface, after which the phase of multilayer formation followed. The adsorption on the surface of the humic acid-clay complex showed no distinct phases but an isotherm looks like the L-type, although it could not verify Langmuir's equation. Probably the isotherm was the resultant of two mechanisms one due to the adsorption of the humic acid part and the other due to the clay part in the complex. Comparison of the constants of Freundlich's equation showed that the capacity of the adsorption humic surface was greater than that of the complex.     

Deformation of humic acid by acid treatment

In our previous report (1) we had proposed the method to fractionate humic acid into three parts using organic solvents, and had advocated the new theory on the process of humification in volcanic ash soils from the results of the fractionation.     

Viscosimetric characteristics of humic acid

One of the authors, KUMADA (I), has proposed a new classification of humic acids based on their colour and spectral characteristics in the visible and ultra-violet regions. Humic acids can be grouped into four major types by this procedure (A, B, Rp and P types) and evidence for a classification diagram based on the values ΔlogK and RF has recently been presented (2). It is clearly important that the usefulness of this new classification should be investigated by considering other chemical and physical properties of humic acids.     

矿物源腐植酸肥料中可溶性腐植酸快速检测方法研究

采用分光光度法检测矿物源腐植酸肥料中可溶性腐植酸含量，讨论在检测过程中样品的称取质量、离心条件、重铬酸钾浓度以及氧化时间对检测结果的影响。进行了方法验证，计算出方法检出限为4.27%，相对标准偏差为2.1%～11.6%，加标回收率为95%～106%。     

A model for a type humic acid

In the preceding papers (1,2,3,4), the author studied some chemical properties of soil humic acids, and compared various so-called artificial humic acids with soil humic acids in respect to their absorption spectra and stabilities. According to these experimental results, it is Presumed that soil humic acids, especially A type, must contain not only benzene ring, but also condensed aromatic rings as their structural units.     

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 antimony species by humic acid

The retention of antimony (a potential toxin) in polluted soils or waterway sediments can involve interaction with several component phases. One of these, humic acid, has been found to adsorb antimony (III) from solutions of Sb(OH)₃ or potassium antimonyl tartrate (C₈H₄K₂Sb₂O₁₂) in accordance with Langmuir type isotherms. Using Sb(OH)₃ solutions (initial Sb levels < 10 μM) the bonding constant value (at pH 4) was 6 × 10⁵, with a calculated saturation capacity of 23 μmol g^?1. In the antimonyl tartrate systems (initial Sb levels 0.5 to 75 μM) the bonding constant value for the sorbed species was 1.6 × 10⁵ and the saturation capacity 53 μmol g^?1. Addition of small amounts of HCl or NaOH (to vary the pH between 3.1 and 5.4) had little effect on the amount sorbed from KSbT solutions but with Sb(OH)₃ solutions uptake was reduced (by about 15%). In the presence of NaCl (0.5 or 0.05M) Sb uptake increased (by about 15%). Antimony (V) (introduced as KSb (OH)₆) was not sorbed from solutions < 10 μM in this salt. Using more concentrated solutions, uptake gradually increased, reaching a plateau value of around 8 μmol g^?1 with solutions initially 50 or 75 μM.     

Susceptibility of humic acid towards sodium amalgam

Three humic acids (HA-I) of different degrees of humification were treated with HCl (1:1). The hydrolyzed humic acids (HA-II) were subsequently degraded with Na-amalgam. The reduction products were divided into the following fractions: humic acid residues (HA-III), fulvic acid (FA), and ether-extractable lubstances (Et),

The humic acids used in this study were extracted from the following three soils; Inogashira (Volcanic ash soil), Kuragari (Drown forest soil, B_D type), and Higashiyama (Brown forest soil, rB_B type).

The experimental results are summarized as follows:

1. The RF values of HA-II, in the case of Inogashira and Kuragari, were higher, and the △log K values were lower than those of HA-I. The carbon and oxygen contents of HA-II were higher while the hydrogen, and nitrogen contents were lower than those of HA-I.

2. The total amount of carbon in HA-III. FA and Et added up to about 90% of the carbon present in HA-II. The carbon of HA-III found in HA-III after reduction tended to increase in the order: Inogashira>Kuragari>Higashiyama. In FA and Et, the opposite trend was followed.

In the case of Inogashira about 60% of the carbon of HA-II was found in HA-III.

3. The dark coloration of humic acid largely disappeared during the reductive treatment. As for the amorphous carbon-like structure detected in Inogashira, it was not found in the HA-III after reduction.

Therefore, it was presumed that the structures destroyed or saturated during the reductive treatment were the ones responsible for the essential properties of humic acid.     

Identification of amino acids in humic acid

Davidson, Sowden and Atkinson^l) in 1951 reported on the amino acids in the three soil organic matter fractions, and Stevenson, Marks, Varner and Martin~) in 1952 reported on the identification of eight amino acids from clay-adsorbed organic colloids in Brookstom slity clay loam. Also, some investigations on these amino acids have been carried out in our laboratory.