Verhalten von Dünger-NH4 in Böden unterschiedlicher tonmineralischer Zusammensetzung im Inkubationsversuch

Fate of fertilizer ammonium in soils with different composition of clay minerals in an incubation experiment In an incubation experiment with three different soils (gray brown podsolic soil from loess, alluvial gley, and brown earth, derived from basalt) the specific adsorption (fixation) and release of fertilizer NH₄⁺ was investigated. In one treatment 120 mg NH₄–N/kg soil was added, while the other treatment (control) received no nitrogen. Soils samples were taken every ten days and analyzed for nonexchangeable and exchangeable NH₄⁺ and NO₃^?. The experimental results are showing that the specific adsorption of applied NH₄⁺ was related to the type of clay minerals. While the loess soil, rich in illite, and the alluvial soil, rich in expansible clay minerals, bound about 40% of the added NH₄⁺ specifically, the soil derived from basalt with mainly kaolinite bound only about 10 %. From the recently “fixed” fertilizer NH₄⁺ about a half was nitrified during the incubation period of about 9 weeks. In the control there was no significant release of specifically bound NH₄⁺. Obviously this NH₄⁺ is located more deeply in the interlayers of the clay minerals and not available to microorganisms.     

Fixed ammonium in some Bangladesh soils

Nitrogen is the most deficient element and the most limiting factor for crop production in Bangladesh. The total N content in Bangladesh soils ranges between 0.02 and 0.12% (Ahsan and Karim 1988). The low N content indicates the presence of a small organic N pool and suggests that inorganic N plays an important role as a N source for crops. Contribution of “fixed” or “nonexchangeable” NH₄ ⁺ to the N economy of soil has been reported for many tropical soils (Rodrigues 1954; Moore and Ayeke 1965; Dalal 1977; Sahrawat 1995). However, there are few reports on fixed NH₄ ⁺ status in Bangladesh. In the present study, therefore, attempts were made to collect data on fixed NH₄ ⁺ of some major soil series from the important physiographic units of Bangladesh.     

Studies on the mechanisms of fixation and release of ammonium in paddy soils after flooding. I. Effect of iron oxides on ammonium fixation

Experiments were conducted with two typical paddy soils from China and a vermiculite to study the influence of iron oxides on the fixation and release of ammonium. Removing iron oxides, especially amorphous iron oxides, from the soils favoured the release of non-exchangeable NH₄-N and stimulated the fixation of NH₄-N in the presence of added (NH₄)₂SO₄. Addition of artificial goethite and hematite to the original soils or to the soils free of iron oxides reduced the fixation of NH₄⁺-ions. This effect was also observed with vermiculite. We conclude that the coating of clay minerals with iron oxides has an impact on the diffusion of NH₄⁺-ions into and out of the interlayers of the clay minerals. The reduction and dissolution of iron oxides induced by low redox potential (E_h) after flooding of paddy soils is assumed to be an important mechanism controlling NH₄⁺-fixation in paddy fields.     

Ammonium fixation by soil and pure clay minerals

Abstract

Fixation of the ammonium ion (NH₄ ⁺) by clay minerals is an alternate way of building the nitrogen (N) pool in soil to optimize N crop recovery and minimize losses. Clay minerals (illite, montmorillonite, and vermiculite) and an illitic Portnoeuf soil were used to compare NH₄ ⁺ fixation abilities. Total N determination and X‐ray diffraction analysis were performed on each of the minerals and the Portnoeuf soil controls, and NH₄ ⁺ saturated batches were subsequently desorbed by potassium chloride (KCl) after 4096 hours. Total N was determined for each employing either Kjeldahl digestion only, or pretreating with hydrofluoric‐hydrochloric acid (HF‐HCl) before the Kjeldahl digestion. The total N for the soil was 38% more after pretreatment with HF‐HCl. The total N determined after pretreatment with HF‐HCl for the NH₄ ⁺ saturated and subsequently KCl desorbed minerals was found to be highest in vermiculite. The cation exchange acapacity (CEC) of each of the minerals was determined, and highest CEC was found in montmorillonite [83.07 cmol(+)/kg]. X‐ray diffraction analysis revealed collapse of the vermiculitic clay lattice from an initial d‐spacing of 13.1 angstrom to 10.4 angstrom after desorprion by KCl. This suggested the existence of sequestered NH₄ ⁺ between the 2: 1 vermiculitic clay interlayer lattice.     

钾对铵离子在蛭石矿物表面吸附与层间固定的影响

在K+、NH4+不同施用顺序的情况下研究了蛭石对NH4+的晶层固定 ,证实了K+的存在对NH4+的矿物晶层固定不具有影响。在Ca2+-NH4+二元系统和Ca2+-NH4+-K+三元系统中 ,对NH4+在蛭石表面的吸附进行了研究 ,结果同样显示 ,K+对NH4+在蛭石表面的吸附位点不具有竞争作用。     

Beziehung zwischen dem Stickstoff-Entzug der Pflanzen und der Abnahme von spezifisch gebundenem NH4-N im Boden

Relationship between the N uptake of plants and the mobilization of nonexchangeable NH₄-N In a pot experiment with ryegrass (Lolium multiflorum) the relationship between the release of nonexchangeable NH₄⁺ and the N uptake of plants was studied. For this purpose the surface soil of an alluvial soil and of a grey brown podsolic soil was labelled with ¹⁵NH₄-N. The following results were obtained: After treating the soil with 15-N the alluvial soil contained 4,55 mg and the grey brown podsolic soil 1,64 mg nonexchangeable ¹⁵NH₄-N/100 g soil. In the alluvial soil 72% and in the grey brown podsolic soil 66% of the nonexchangeable ¹⁵NH₄⁺ had been released during the growing season when ryegrass was planted. However, without plants there was no change in the content of labelled nonexchangeable NH₄⁺ in the alluvial soil or only a slight decrease in the grey brown podsolic soil. A highly significant correlation was found between the ¹⁵NH₄-N released and the ¹⁵N uptake of ryegrass in the alluvial soil (r = 0,78⁺⁺⁺) as well as in the grey brown podsolic soil (r = 0,98⁺⁺⁺).     

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.     

Kinetics of Competitive Fixation of Potassium and Ammonium Ions by Silt Component of Soils from Different Agro-Climatic Regions

Potassium (K⁺) and nitrogen [N, as the form of ammonium (NH₄⁺)] are major nutrients for plant growth. Although there have been a number of studies on the kinetic fixation of potassium and ammonium ions in soils and clays, however, investigations on the kinetics of competitive fixation of these ions have been few, if any, especially by taking into account silt component of the soils. In this study, the kinetics of potassium and ammonium fixation were examined in the silt components of several soil samples. The results revealed that considerable amounts of K⁺ and in lesser amounts, NH₄⁺ ions were fixed by silt components of the soils. Potassium fixation was strongly preferred over ammonium. To describe the fixation kinetics, seven mathematically models were evaluated. A comparison of the models showed that pseudo-second-order equation properly described the fixation of these ions by the silt components.     

Release of nonexchangeable NH4-N after planting of ryegrass in relation to soil content and as affected by nitrate supply

The uptake of N by ryegrass grown in pot culture on a range of soils differing widely in content of nonexchangeable NH₄-N (topsoils: 117 to 354 mg kg^?1 soil; subsoils: 117 to 270 mg kg^?1 soil) was measured to indicate whether the amounts of NH₄-N released from clay minerals were correlated with soil NH₄-N. After two cuts soil analysis revealed that the amounts of mobilized nonexchangeable NH₄-N were between 3.5 and 25.2 mg kg^?1 from topsoils and between 0 and 8.2 mg kg^?1 from subsoils. There was no correlation between soil nonexchangeable NH₄-N content and release. The NH₄-N extracted with 1 N HCl and the actual N uptake of the plants correlated highly significant. Assuming that the whole of the NH₄-N released was taken up by ryegrass, NH₄-N accounted for 11.2 to 75.0% of total N uptake from topsoils and 0 to 37.3% from subsoils. The release of nonexchangeable NH₄-N was increased by the application of nitrate.     

Increase in the Capacity of Interlayer Sites in a Paddy Soil as a Possible Factor Affecting the Dynamics of Fixed Ammonium at the Initial Stage of Anaerobic Incubation

To evaluate whether the capacity of interlayer sites affects the dynamics of fixed ammonium (NH₄⁺) in a paddy soil, a combination of potassium (K)–saturation treatment and stepwise extraction of nonexchangeable K with 0.01 mol L^?1 hydrochloric acid was applied to a soil incubated anaerobically up to 70 days. The capacity of interlayer sites increased with an increase of weakly fixed NH₄⁺ during the initial 28 days (r = 0.78, P < 0.01), and remained stable thereafter. On the other hand, the concentration of exchangeable NH₄⁺ increased curvilinearly during the whole incubation period, which was correlated with an increase of weakly fixed NH₄⁺ (r = 0.85, P < 0.01). These results suggested that the dynamics of weakly fixed NH₄⁺ in a paddy soil is regulated not only by the chemical equilibrium between exchangeable and weakly fixed NH₄⁺ but also by the capacity of interlayer sites within a few weeks after flooding.     

Fixed ammonium and potassium release from two soils

Abstract

Release of native and added K⁺ and NH⁺ ₄ from two soils was monitored during a 166 day incubation/leaching experiment. One soil (Brookston) represented a major soil series In Ontario whereas the other (Harriston) was suspected having a relatively large fixation capacity. Treatments were imposed involving addition of 50 μM g^‐1 soil of K⁺(KCl) or NH⁺ ₄ (NH₄Cl) only or one added after the other on successive days. The addition of either K⁺ or NH⁺ ₄ on day 2 tended to inhibit the release of the other added on day I. Also the addition of either K⁺ or NH⁺ ₄ on day 1 tended to inhibit the sorption or fixation of the other on day 2. The release rate of K⁺ during the 10 to 166 day period was almost constant and not affected by the addition of NH⁺ ₄. Alternatively, the addition of K⁺ on day 2 slowed the release rate of NH⁺ ₄ measured by NO^? ₃ appearance from day 10 to 40 but had no effect thereafter. At the end of the experiment considerably more K⁺ than NH⁺ ₄ was retained suggesting that K⁺ was more firmly fixed. However, the continuing nitrification of NH⁺ ₄ must be contrasted with periodic removal of K⁺ by leaching with 0.01 M CaCl₂ solution since the equilibrium between exchangeable and fixed ions was affected. There were no notable differences between the two soils inspite of a considerable difference in clay content.     

Kinetics of nonexchangeable‐potassium release and plant response in some calcareous soils

Nonexchangeable K⁺ constitutes a slowly available reserve that may significantly influence K⁺ fertility of soils. Laboratory and greenhouse experiments were conducted to characterize the K⁺ supply and nonexchangeable K⁺–release kinetics in 10 calcareous soils using 0.01 M CaCl₂ and 0.01 M oxalic acid extractions. Total K⁺ uptake by wheat (Triticum aestivum L.) grown in the greenhouse was used to measure plant‐available K⁺. The release of K⁺ was characterized by an initial fast rate followed by a slower rate. The nonlinear relationship in the early stages of the K⁺ release may be attributed to the edge sites, and release of K⁺ from interlayer exchange sites may be responsible for the second part of the K⁺ release. Kinetics of K⁺ release was described best with power function, which showed the best fit of the four models tested. Parameters of kinetics models in 0.01 M CaCl₂ were significantly related to K⁺ uptake by wheat. Potassium release was also correlated to initial NH₄OAc‐extratable K⁺ and to HNO₃‐extractable K⁺.     

Ammonium-calcium exchange equilibria in soils and weathered pumices that differ in cationexchange materials

The retention of NH₄+ and Ca²+ on soil and weathered pumice samples containing constant and/or variable charge components was measured in different NH₄CI-CaCl₂ solutions. The NH₄+/Ca²+ selectivity of each sample was evaluated using a quotient of the partition of NH₄+ on the exchange sites and in the solution relative to that of Ca²+. It increased with decreasing pH and increasing NH₄Cl-CaCl₂ concentration for a given equivalent fraction of NH₄+ in the solution. These effects were quantitatively explained in terms of the changes of NH₄+ and Ca²+ concentrations in the solution and in the diffuse double-layer of the ion-exchange material as predicted by the law of mass action and the electric double layer theory. The NH₄+/Ca²+ selectivity of different exchange materials showed a similar variation among their exchange sites and increased in the order humus, allophane and imogolite (Si/Al ratio 0.5) < allophane (Si/Al ratio 1.0), montmorillonite < vermiculite, illite < halloysite. The origin of negative charge, the steric features around the exchange sites and clay-humus interaction are suggested as being important in determining the NH₄+/Ca²+ selectivity.     

Responses of biotic and abiotic effects on conservation and supply of fertilizer N to inhibitors and glucose inputs

Fertilizer N can be conserved through immobilization by microorganisms (biotic process) and fixation by soil clay minerals (abiotic process), and then subsequently remineralized and released. These processes are significantly affected by inhibitors, and available C application. In this study, a 96-day incubation experiment was conducted to assess the effects of microbial immobilization and ammonium fixation on conservation and supply of urea-N with the nitrification inhibitor (DMPP: 3,4-dimethylpyrazole phosphate), urease inhibitor (NBPT: N-(n-butyl) thiophosphoric triamide), and glucose additions. The results showed that urea-derived soil microbial biomass nitrogen (SMBN) consistently increased with DMPP input, whereas NBPT increased urea-derived SMBN in the absence of glucose but decreased it in the presence of glucose. Both inhibitors enhanced the effects of fixed NH₄⁺ on conservation and supply of urea-N in all cases, and retarded the release of fixed NH₄⁺. Glucose addition intensified the competition for NH₄⁺ between microbial immobilization and mineral fixation, as well as reduced the availability of urea-N and native soil N, resulting in a negative added N interaction at the initial incubation stage. From 12 to 96 days, the release of fixed NH₄⁺ was 2.6-fold greater than the mineralization of organic N (including SMBN and non-microbial organic N) in the non-glucose treatments, whereas the latter was 2.7-fold greater than the former in the glucose treatments. Taken together, our study indicates both microbial immobilization and mineral fixation are important processes by which N is stabilized in soil. Clarification of fertilizer N transformation induced by these biotic and abiotic processes can provide helpful implications for quantifying N cycle and optimizing agricultural nutrient management.     

Bestimmung von nichtaustauschbarem Ammonium in Böden mit einer Halbmikromethode

Determination of non exchangeable Ammonia in Soils by a semicro method A semi-micro version (sample weight 0,1 g) for the determination of nonexchangeable NH₄⁺ of soils, based on the method of Silva and Bremner (1966) is described. The results of the semi-micro version are compared with the original method. The regression-coefficient is r = 0,9906. Analysis time is reduced by a factor of 2, reagent needs approximately by a factor of 20. Exactness and reproducibility are satisfactory for routine measurements. Pampean soils from Argentina, analyzed with the semi-micro method contain between 50 and 90 ppm nonexchangeable NH₄⁺.     

Blocking the release of potassium from clay interlayers by small concentrations of NH4+ and Cs+

To understand the process and the kinetics of potassium release from the clay interlayer in natural and arable soils in more detail, I tested the hypotheses that large, monovalent cations, especially NH₄⁺ and Cs⁺, can reduce the release rates of K⁺ which is exchanged by Ca²⁺, even if these monovalent cations are present in concentrations of only a few μm . Percolation experiments were carried out with different illitic soil materials, some containing vermiculite, with 5 m m CaCl₂ at pH 5.8 and 20°C, in some cases for over 7000 h. NH₄⁺ and Cs⁺ both caused a large decrease in the rate at which K⁺ was released, Cs⁺ especially. Suppression began at 5 μm NH₄⁺ Blocking by 20 μm NH₄⁺ was easily reversible: the release rates readily increased when NH₄⁺ was omitted from the exchange solution. Blocking by 2 μm Cs⁺ was equal to approximately 90% of that at 10 μm Cs^+. Larger concentrations of Cs⁺ than 10 μm did not further reduce release but rather caused a slight increase, probably because of enhanced exchange of K⁺ by Cs⁺ without exfoliation of the interlayer space. Blocking by Cs⁺ was not reversible within > 7000 h of percolation by 5 m m CaCl₂. The blocking effect was reproduced in several different soil materials using 10 μm Cs⁺ but was most pronounced in vermiculite-rich samples. As NH₄⁺ is present in most arable soils, at least in concentrations of a few μm , I conclude that the observed effects are of significance in the K dynamics processes in soils, for example near the roots of plants. Further, very small concentrations of Cs⁺ in exchange solutions containing a large background of Ca²⁺ appear to be useful for suppressing K⁺ release from the interlayer in laboratory studies, probably without significantly altering the exchange at outer mineral surfaces.     

Added nitrogen interaction as affected by soil nitrogen pool size and fertilization – significance of displacement of fixed ammonium

Displacement of NH₄⁺ fixed in clay minerals by fertilizer ¹⁵NH₄⁺ is seen as one mechanism of apparent added nitrogen interactions (ANI), which may cause errors in ¹⁵N tracer studies. Pot and incubation experiments were carried out for a study of displacement of fixed NH₄⁺ by ¹⁵N‐labeled fertilizer (ammonium sulfate and urea). A typical ANI was observed when ¹⁵N‐labeled urea was applied to wheat grown on soils with different N reserves that resulted from their long‐term fertilization history: Plants took up more soil N when receiving fertilizer. Furthermore, an increased uptake of ¹⁵N‐labeled fertilizer, induced by increasing unlabeled soil nitrogen supply, was found. This ANI‐like effect was in the same order of magnitude as the observed ANI. All causes of apparent or real ANI can be excluded as explanation for this effect. Plant N uptake‐related processes beyond current concepts of ANI may be responsible. NH₄⁺ fixation of fertilizer ¹⁵NH₄⁺ in sterilized or non‐sterile, moist soil was immediate and strongly dependent on the rate of fertilizer added. But for the tested range of 20 to 160 mg ¹⁵NH₄⁺‐N kg^–1, the NH₄⁺ fixation rate was low, accounting for only up to 1.3 % of fertilizer N added. For sterilized soil, no re‐mobilization of fixed ¹⁵NH₄⁺ was observed, while in non‐sterile, biologically active soil, 50 % of the initially fixed ¹⁵NH₄⁺ was released up to day 35. Re‐mobilization of ¹⁵NH₄⁺ from the pool of fixed NH₄⁺ started after complete nitrification of all extractable NH₄⁺. Our results indicate that in most cases, experimental error from apparent ANI caused by displacement of fixed NH₄⁺ in clay is unlikely. In addition to the low percentage of only 1.3 % of applied ¹⁵N, present in the pool of fixed NH₄⁺ after 35 days, there were no indications for a real exchange (displacement) of fixed NH₄⁺ by ¹⁵N.     

湖南几种耕地土壤固定添加铵的动力学研究

通过野外调查取样、室内培养试验和分析测定，研究了湖南省几种成土母质发育的旱地土壤和稻田土壤固定添加铵的动力学特性。结果表明，供试土壤对添加铵的固定速度很快，尤其在反应的前8～12h内速度更快，12h后速度逐渐变慢，24h以后，土壤对外源铵的固定已基本达到平衡。数学拟合表明，一级动力学方程和Elovich方程两种动力学模型能较好地拟合供试土壤固定添加铵的动力学特性，经统计均达极显著水平，抛物扩散方程也有较好的拟合效果，零级方程较差。由一级动力学方程求得的不同土壤固铵动力学参数：理论最大固铵量（A）、反应速率常数（b）以及反应半时值明显不同。耕型石灰性紫色土、耕型酸性紫色土、耕型棕色石灰土和耕型石灰岩红壤的理论最大固铵量和反应半时值分别为212．3mg kg^-1、179．0mg kg^-1、142．9mg kg^-1.13．7mg kg^-1和29．75h、25．96h、27．18h、23．49h；紫泥田、河沙泥、灰泥田和红黄泥的理论最大固铵量和反应半时值分别为86．2mg kg^-1、68．7mg kg^-1,31．8mg kg^-1、19．1mg kg^-1和14．50h、15．10h、15．51h、18．43h。耕型石灰性紫色土、耕型酸性紫色土、耕型棕色石灰土和耕型石灰岩红壤的反应速率常数分别为0．0233 h^-1、0．0267h^-1、0．0255h^-1、0．0295h^-1；紫泥田、河沙泥、灰泥田和红黄泥的反应速率常数分别为0．0478h^-1、0．0459h^-1、0．0447h^-1、0．0376h^-1.除耕型石灰岩红壤以外，旱地土壤的理论最大固铵量和反应半时值均明显大于水田土壤，而反应速率常数明显小于水田土壤。     

Does the potential ammonium fixation of soils have an impact on the optimum nitrogen fertilizer rate?

Field experiments were conducted to determine the effect of nitrogen (N) fertilizer forms and doses on wheat (Triticum aestivum L.) on three soils differing in their ammonium (NH₄) fixation capacity [high = 161 mg fixed NH₄-N kg^?1 soil, medium = 31.5 mg fixed NH₄-N kg^?1 soil and no = nearly no fixed NH₄-N kg^?1 soil]. On high NH₄⁺ fixing soil, 80 kg N ha^?1 Urea+ ammonium nitrate [NH₄NO₃] or 240 kg N ha^?1 ammonium sulfate [(NH₄)₂SO₄]+(NH₄)₂SO₄, was required to obtain the maximum yield. Urea + NH₄NO₃ generally showed the highest significance in respect to the agronomic efficiency of N fertilizers. In the non NH₄⁺ fixing soil, 80 kg N ha^?1 urea+NH₄NO₃ was enough to obtain high grain yield. The agronomic efficiency of N fertilizers was generally higher in the non NH₄⁺ fixing soil than in the others. Grain protein was highly affected by NH₄⁺ fixation capacities and N doses. Harvest index was affected by the NH₄⁺ fixation capacity at the 1% significance level.