Effect of soil bulk density on hydrolysis of surface-applied urea in unsaturated soils

In situ hydrolysis of broadcast urea occurs in unsaturated soils with different bulk densities. The effect of increasing soil bulk densities on the hydrolysis of urea was studied in open and in covered unsaturated soil columns incubated at 30°C. An increase in bulk density from 0.8 to 1.4 Mg/m³ markedly increased the hydrolysis of surface-applied urea in soils containing water > 6% up to near field capacity. Increased diffusion of urea to sorbed soil urease with an increase in bulk density may have enhanced formation of urease-urea complexes and therefore increased the hydrolysis. As urea diffused farther in more dense soils, the retarding effects of high urea concentration gradients on the hydrolysis probably decreased. In light-textured soils, increases in the bulk density had no apparent effect on the hydrolysis of surface-applied urea when evaporation occurred.     

Studies on urea hydrolysis in salt affected soils

In laboratory incubation studies, the kinetics of urea hydrolysis was analysed in seven soils widely differing in salinity and sodicity. The effects of the kind of salinity on urea hydrolysis was studied in a non-saline Tulewal Sl soil treated with solutions (100 me/1 to produce ECe values of approximately 10 m mhos/cm) of NaCl, NaSO₄, NaHCO₃ or NaCl + CaCl₂ salts. In another experiment the rates of urea hydrolysis in the soil samples collected from two recently reclaimed salt affected areas were also studied. The results showed considerable variations in the rates of urea hydrolysis in different soils. Urea hydrolysis was considerably delayed with increase in soil pH. The time required for complete hydrolysis to occur varied from 3 to 14 days. Urea hydrolysis seemed to follow first order reaction kinetics. The average time for one half of the hydrolysis to occur (t_1/2) ranged from 0.51 yo 4.55 days. The delay in urea hydrolysis was related to decrease in urease activity with increase in pH, decrease in organic matter (and total N). The Na HCO₃ treatment decreased the activity of urease and hence resulted in the maximum delay in urea hydrolysis followed by NaCl and Na₂SO₄ salts in the ascending order. Urea hydrolysis was faster in recently reclaimed sodic soils than in unreclaimed soils.     

In vitro effects of urease inhibitors on rate of urea hydrolysis in soils

We studied the effect of urease inhibitors on the urea hydrolysis in some Sundanese soils belonging to the orders of Vertisol and Entisol. The hydrolysis showed a lag period of about 3 days and its rate (Y) per unit time (t) could be described by a two constants exponential equation of the general form Y = K₁t^K ₂. Statistical analysis showed that the intercept K₁ (rate of urea hydrolysis) was significantly affected by soil type rather than treatment. It seems that K₁ is associated with the soils' initial urease activity as it closely correlates with the Michaelis constant (km).The gradient, K₂, being significantly affected by soil type as well as treatment is probably associated with the induced urease activity with time and it, therefore, varied with variations in soils and treatments. Of the so-called urease inhibitors used in this study Ca(OH)₂, p-benzoquinone (PBQ) and orthophosphoric acid (OP) only PBQ reduced urea hydrolysis while the other chemicals have effects possibly related to modifying the soil pH. Inhibitor treated soils had substantial amounts of unacounted for N which was believed to be present, presumably, in the form of carbamate.Contribution from the Department of Biochemistry and Soil Science, Faculty of Agriculture, Shambat, Sudan.     

Effect of urea granule size on ammonia volatilization from surface-applied urea

Urea powder and granules of varying size (1 to 8 mm diameter) were surface applied to a ryegrass/white clover pasture. Evolution of NH₃ was measured using a continuous air flow enclosure method. At 30 kg N ha^–1, the percentage of urea-N lost as NH₃ from powder or granules of 1–2, 3–4, 5.6 and 8 mm diameter was 18, 17, 20, 22 and 32 respectively. As the particle size increased, the rate of urea hydrolysis decreased and delayed the time at which the maximum rate of volatilization occurred. Mineral-N and soil surface pH measurements confirmed that during the period of volatilization, urea moved less than 30 mm from the application point.For the powder and 3–4 mm granule treatments, when the application rate was increased from 30 to 300 kg N ha^–1, the percentage of urea-N volatilized increased, but at any particular rate there was no significant difference in percentage loss between the powder and 3–4 mm granules.     

Kinetic study of urease-catalysed urea hydrolysis

The kinetics of the urease-catalysed hydrolysis of urea in phosphate and citrate buffers have been studied. The effects of urease concentration, substrate concentration, pH and temperature of solutions, and particularly the concentrations of buffers and product on the reaction rate of urea hydrolysis have been examined. The activation energies in two buffer systems indicate that the reaction mechanism catalysed by urease may be the same in each case. A substrate inhibition model has been developed that describes the effect of substrate concentration ranging from 0.001 to 4 mol dm^?3. The experimental data indicated that the inhibition of urease by phosphate is of partially mixed type, whilst that by citrate is uncompetitive. In contrast ammonium ions exhibited no significant influence on the rate of urea hydrolysis by urease.     

A comparative study of urea hydrolysis rate and ammonia volatilization from urea and urea calcium nitrate

A comparing of urea hydrolysis and NH₃ volatilization from urea supergranules and urea calcium nitrate (UCN, a new fertilizer produced by Norsk Hydro A/S, Norway) was made on two different flooded soil types, a high-CEC clay loam (Ås) and an intermediate-CEC clay loam (Kinn).Nitrogen loss by ammonia volatilization was reduced from 17% by surface application of urea supergranules (USG) on flooded Ås soil to 3% and 6% by UCN briquettes at either the same urea or nitrogen concentration as USG. A significant reduction was even found with the surface application of prilled UCN, 12% and 18% N-loss for prilled UCN and urea, respectively. The floodwater pH and NH ₄ ⁺ content was lower with UCN than urea, which reduced the potential for ammonia volatilization.NH₃-loss (5%) was significantly less when USG was surface applied on Kinn soil, while NH₃-loss from UCN briquettes was independent of soil type. The reduction in NH₃-loss from USG on Kinn soil was due to a decrease in the pH and NH ₄ ⁺ content of the floodwater caused by a reduced rate of urea hydrolysis.The rate of urea hydrolysis was lower with UCN than USG in both soils, but the difference between UCN and USG was greater in the Ås soil than in the Kinn soil. Three days after deep placement (10 cm), 18% of UCN urea and 52% of USG urea were hydrolyzed in Ås soil, while only 12% UCN and 17% USG were hydrolyzed in the Kinn soil.The surface application of USG on flooded soil reduced the rate of urea hydrolysis as compared to deep placement. 30% and 17% of USG urea was hydrolyzed after four days on Ås and Kinn soil, respectively. During the first few days the rate of hydrolysis of UCN was more affected by the soil type than the application method. Four days after surface application 32% and 13% UCN urea was hydrolyzed on Ås and Kinn soil, respectively. The rate of urea hydrolysis exhibited a zero-order reaction when USG and UCN-briquettes were point placed in flooded soils.     

Ammonia losses from surface-applied urea as related to urea application rates,plant residue and calcium chloride addition

Volatile losses of NH₃ from surface-applied urea are known to decrease in the presence of soluble Ca-salts or with a decrease in easily decomposable organic matter content (EDOM), both of which influence urease activity. How these factors interact to affect NH₃ losses is not fully understood. Studies were conducted to determine the effect CaCl₂ in sand with varying rates of EDOM on NH₃ losses from surface applied urea. The same effects were examined on agricultural soils containing partially decomposed native organic matter (NOM). Determinations were made in the laboratory on field soils, sand free of organic matter and sand with known amounts of grass clippings (GC, EDOM). Low levels of GC in sand with low amounts of added urea resulted in little NH₃ loss. Ammonia loss increased as more N was applied at the low levels of GC. The loss was independent of urea application rates at high levels of GC. Ammonia losses were reduced more effectively at low EDOM and NOM in the presence of Ca. Incubation of sand with GC at low rates prior to urea addition increased NH₃ losses relative to high levels of non-incubated GC. For the above situation incubation for as high as 24 days resulted in equivalent NH₃ losses. The amount and state of decomposition of existing organic matter affected the degree of NH₃ loss from surface placed urea and its control by added Ca-salts. Microbial decomposition of EDOM, such as might occur in the spring prior to urea addition, led to greater NH₃ losses. Greater loss of NH₃ from urea might be an indication of a larger ureolytic microbial population leading to increased urease production.     

Urease immobilization on an ion‐exchange textile for urea hydrolysis

Ion‐exchange textiles are used as organic supports for urease immobilization with the aim of developing reactive fibrous materials able to promote urea removal. A non‐woven, polypropylene‐based cation‐exchange textile was prepared using UV‐induced graft polymerization. Urease was covalently immobilized onto the cation‐exchange textile using three different coupling agents: N‐(3‐dimethylaminopropyl)‐N′‐ethylcarbodiimide hydrochloride (EDC), N‐cyclohexyl‐N′‐(b‐[N‐methylmorpholino]ethyl)carbodiimide p‐toluenesulfonate (CMC), and glutaraldehyde (GA). The immobilized biocatalyst was characterized by means of FT‐IR spectrometry, SEM micrographs, dependence of the enzyme activity on pH and temperature, and according to the kinetic constants of the free and immobilized ureases. The biotextile prepared with EDC in the presence of N‐hydroxysuccinimide performs best. The optimum pH was 7.2 for the free urease and 7.6 for the immobilized ureases. The reactivity was maximal at 45 °C for free urease, 50 °C for biotextiles prepared using EDC or CMC, and 55 °C for biotextiles prepared with GA. The activation energy for the immobilized ureases was 4.73–5.67 kcal mol^?1, which is somewhat higher than 4.3 kcal mol^?1 for free urease. The urea conversion for a continuous‐flow immobilized urease reactor is nearly as good as a continuously stirred tank reactor having a much longer residence time, suggesting that the packed bed reactor had sufficient diffusive mixing and residence time to reach nearly optimal results. Urease immobilized on a biotextile using EDC has good storage and operational stability. Copyright © 2006 Society of Chemical Industry     

Effects of initial soil calcium content on ammonia losses from surface-applied urea and calcium-urea

Ammonia loss from surface-applied urea occurs because urea hydrolysis increases the pH of the placement site microenvironment. Addition of Ca-salts with urea will control or reduce the microsite pH, thus reducing NH₃ losses. The degree of Ca-saturation of the cation exchange sites may influence the ratio of calcium:urea required to control ammonia loss. A laboratory study was conducted to determine if adsorbed Ca or CaCO₃ additions (acid soils only) had a measureable impact on Ca control of NH₃ loss from surface applied urea at various Ca:urea ratios.With urea alone applied to the soil surface varying the adsorbed Ca content of the treatment soil did not influence NH₃ loss. The addition of CaCl₂ with urea on the same pretreated soils generally resulted in NH₃ losses reflecting the initial pH of the soil. The Ca-saturated acid soils and those acid soils receiving CaCO₃ had higher NH₃ losses than untreated soils in the presence of urea with soluble CaCl₂. It was noted that increasing the calcium:urea ratios progressively depressed the NH₃ loss from all soils. Increasing the percent Na-saturation of the calcareous Harkey soil to 25 and 50% (ESP) reduced Ca control of NH₃ loss due to Ca being exchanged for Na on the cation exchange sites.Inclusion of CaCl₂ with the urea mixture on the surface of the pretreated acid soils resulted in stepwise differences in NH₃ loss concuring with the increases in pretreatment soil pH values (differing exchangeable Ca content). Other parameters that influence the amount of NH₃ loss, such as acidic buffer capacity and CEC, appeared more important than anticipated for control of NH₃ loss with the calcium:urea mixture. On Ca enriched soils the calcium:urea mixture was only slightly less effective in its ability to control NH₃ losses than on untreated soils.Contribution from the Texas Agric. Exp. Sta., Texas A&M University System, College Station, TX 77843, USA     

尿素深度水解技术的应用

概述了尿素生产中所产生的废液的回收、利用和符合国家环保机制的废水处理的特点,分析了运行过程中产生的效益和存在的弊端,并提出了合理的建议。     

Transport and hydrolysis of urea in a reactor–separator combining an anion-exchange membrane and immobilized urease

A membrane reactor–separator, in which an anion-exchange membrane and a urease-immobilized poly(vinyl alcohol) (PVA) membrane were clamped together to separate the feed solution and the stripping solution of a dialysis cell, was constructed. The urea in the feed solution passed through the anion-exchange membrane, water film, and then was hydrolyzed to ammonium carbamate in the urease-immobilized PVA membrane. The experimental results showed that no ammonium ion was found in the feed solution under either phosphate or citrate buffer systems at 0·05–0·2 mol dm^?3 and pH 6–9, and various initial concentrations of urea in the feed solution (20–200 mmol dm^?3). This indicates that the water film between two membranes allows the carbamate ions to decompose into ammonium and carbonate ions completely before entering the anion-exchange membrane. The device therefore can be used for the removal of urea from feed solution, while preventing the backflow of ammonium ions from the stripping solution or water film into feed solution. It has significant potential in the development of a wearable or portable artificial kidney. The properties of the urease-immobilized PVA membrane were examined. A kinetic model describing the transport-reaction behavior of urea in the membrane reactor–separator was developed, and the optimum values of the reactor parameters were obtained.     

Recent research on problems in the use of urea as a nitrogen fertilizer

Recent research on the NH₃ volatilization, NO ₂ ^- accumulation, and phytotoxicity problems encountered in the use of urea fertilizer is reviewed. This research has shown that the adverse effects of urea fertilizers on seed germination and seedling growth in soil are due to NH₃ produced through hydrolysis of urea by soil urease and can be eliminated by addition of a urease inhibitor to these fertilizers. It also has shown that the leaf burn commonly observed after foliar fertilization of soybean with urea results from accumulation of toxic amounts of urea in soybean leaves rather than formation of toxic amounts of NH3 through hydrolysis of urea by leaf urease. It further showed that this leaf burn is accordingly increased rather than decreased by addition of a urease inhibitor to the urea fertilizer applied. N-(n-butyl)thiophosphoric triamide (NBPT) is the most effective compound currently available for retarding hydrolysis of urea fertilizer in soil, decreasing NH3 volatilization and NO ₂ ^- accumulation in soils treated with urea, and eliminating the adverse effects of urea fertilizer on seed germination and seedling growth in soil. NBPT is a poor inhibitor of plant or microbial urease, but it decomposes quite rapidly in soil with formation of its oxon analog N-(n-butyl) phosphoric triamide, which is a potent inhibitor of urease activity. It is not as effective as phenylphosphorodiamidate (PPD) for retarding urea hydrolysis and ammonia volatilization in soils under waterlogged conditions, presumably because these conditions retard formation of its oxon analog. PPD is a potent inhibitor of urease activity but it decomposes quite rapidly in soils with formation of phenol, which is a relatively weak inhibitor of urease activity. Recent studies of the effects of pesticides on transformations of urea N in soil indicate that fungicides have greater potential than herbicides or insecticides for retarding hydrolysis of urea and nitrification of urea N in soil.     

含镍配合物的合成、表征及其对尿素水解的影响

报道了对称六齿配体N,N,N′,N′, 四(2′ 苯并咪唑甲基)乙二胺(EDTB)的一种含镍(II)配合物[Ni(EDTB)·C6H5COO(OH)]·ClO4·CH3CH2OH·H2O的合成、表征及其对尿素水解的影响。根据配合物元素分析、摩尔电导、紫外 可见、红外、ESR谱和循环伏安(CV)等性质,与已测X 射线单晶结构的同种配体含铜(Ⅱ)单核配合物比较,推测此配合物中的Ni(Ⅱ)离子被配体EDTB的4个苯并咪唑氮和1个烷胺氮与水杨酸根的1个羧基氧配位,形成一种畸变八面体几何构型,并用气相色谱法观测了此配合物对尿素水解的影响,结果表明,它具有催化尿素水解的活性。     

火电厂脱硝用尿素水解中试试验

为降低火电厂NO_x排放造成的环境污染,采用尿素水解法制备烟气脱硝还原剂,在自主研发尿素水解反应器和尿素水解制氨工艺的基础上,搭建产氨量10kg/h规模的尿素水解中试试验台。结果表明,尿素水解反应速率是由温度控制的单调递增函数,蒸汽耗量随反应压力的增加而增加,当反应压力大于0.6MPa时加剧,装置经济性降低。提高进料浓度可减少过量水吸热造成的能量损失,有益于降低装置运行成本。多批次测试期间,进料浓度为40%~60%,操作压力与温度为0.6MPa、160℃,装置最大产氨量为16kg/h,水解率均大于98%,产品气氨气质量分率22.6%~34%(体积分率28.5%~48%),装置性能良好。     

Penetration depth of broadcast urea granules in puddled wetland rice soils

The efficiency of urea in wetland rice cultivation is known to be increased by placement below the soil surface. The penetration of broadcast urea into puddled soil might be a way to achieve placement of urea in soil. This paper combines an analysis of the free fall of urea granules in the atmosphere and a layer of water on the soil surface with measurements of granule penetration into puddled soils. The process of free fall can be described in terms of the height of fall in air, the depth of the water layer, and the terminal velocities and characteristic distances for free fall in air and water. The penetration depth of a particular granule with a particular velocity at the water/soil interface depends on the type of soil and its physical condition. Granule mass ranged from 0.1 to 0.5 g, granule velocity from 1 to 10 m s^–1, depth of the water layer from 0 to 30 mm and penetration depth from 0 to 35 mm. There is some indication that the penetration depth is proportional to the square root of the kinetic energy at the water/soil interface.     

A study on the removal of urea from aqueous solution with immobilized urease and electrodialysis

A five-compartment electrodialyzer with immobilized urease was developed for the removal of urea from aqueous solution. The immobilized urease, supported on polyurethane foam, was placed in the central (dilute) compartment, where urea was hydrolyzed and the products NH₄⁺ and CO₃^2-/HCO₃^? were removed simultaneously by electrodialysis. The system was studied both under constant current and under constant voltage. The effects of urea concentration and applied current or voltage on the removal of urea and ammonium ions from the dilute solution were investigated. The variations of the pH of dilute solution, the current or voltage of system, and current efficiency were also examined during reaction-electrodialysis. The removal of urea by enzymic reaction was not affected significantly by the applied electric field. The current effieiencies for removing ammonium ions from dilute solution were mostly within 40-80%, and the removal percentage of ammonium ions was dependent on current density and current efficiency.     

Immobilization of urease and estimation of effective diffusion coefficients of urea in HEMA and VP copolymer matrices

Enzyme urease was immobilized in copolymer matrices of 2-hydroxyethyl methacrylate (HEMA) and N-vinyl pyrrolidone (VP). The activities of immobilized urease stored in phosphate buffer solution of pH 7.0 at 4°C were examined periodically for up to 90 days. For the matrices of higher VP/HEMA mole ratio in the structure, a higher volume increase and enhanced apparent activity were observed, while HEMA polymer alone proved to have the most stable matrix for prolonged activity. No appreciable amount of enzyme leakage was experienced for any of the matrices prepared. The effective diffusion coefficients of urea through these polymer matrices were calculated with a ‘diffusion and reaction’ model and the highest effective diffusion coefficient was found with pure HEMA matrix, possibly due to its laminated structure.     

Nitrogen transformations during hydrolysis and nitrification of urea

Nitrogen transformations occurring in ten soils fertilized with urea were determined during incubation in the laboratory for four weeks. Urea was applied at one rate, but with different placement methods. Urea was applied in solution, as prills with a 1 cm grid spacing and as prills with no spacing. Unfertilized soils and soils amended with KNO₃ solution were included as controls.Nitrite accumulated in the majority of soils treated with urea, and the maximum nitrite concentration measured was directly related to initial soil pH. Cumulative gaseous N losses as percentages of applied N were: NH₃, 0-59.6; N₂, 0-4.9; N₂O, 0-9.9; KMnO₄-N, 0-1.3; CH₃ONO, 0-<0.1. No gaseous N evolution was detected in control treatments. Gaseous N losses were correlated with soil pH (NH₃) maximum NO ₂ ^- concentration (N₂, N₂O, KMnO₄-N) and organic C content (N₂, N₂O). Fertilizer placement effects were generally not significant and were small in comparison with differences between soils.

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Resumo Foram determinadas, durante incubação em laboratório por quatro semanas, as transformações do nitrogênio ocorridas em dez solos fertilizados com uréia. A uréia foi aplicada a um só nivel, mas com diferentes métodos de aplicação: em solução e em grânulos com 1 cm de espaçamento de grade e em grânulos sem espaçamento. Solos não fertilizados e solos corrigidos com solução de KNO₃ foram incluidos como controles.O nitrito acumulado na maioria dos solos tratados com uréia e a concentração máxima de nitrito medido foram diretamente relacionados ao pH inicial do solo. As perdas cumulativas de N gasoso tomadas em percentagens de N aplicado foram: NH₃, 0-59.6; N₂, 0-4.9; N₂O; 0-9.9; KMnO₄-N, 0-1.3; CH₃ONO, 0-<0.1. Não foi detectada liberação de N gasoso nos tratamentos de controle. As perdas de N gasoso foram relacionadas com o pH do solo (NH₃), concentração máxima de NO ₂ ^- (N₂, N₂O, KMnO₄-N) e teor de C orgânico (N₂, N₂O). Efeitos da aplicação de fertilizante não foram de um modo geral significativos e foram pequenos em comparação com as diferenças entre os solos.

     

非热等离子体强化TiO2催化尿素分解副产物水解性能的研究

尿素-选择性催化还原技术低温下运行时尿素分解不彻底,易形成缩二脲、三聚氰酸和三聚氰胺等副产物。本研究将TiO₂催化剂与介质阻挡放电等离子体相结合,在程序升温条件下考察了载气中有无O₂时引入等离子体前后TiO₂催化尿素分解副产物水解的性能。结果表明：TiO₂表面缩二脲、三聚氰酸和三聚氰胺分别在43~261℃、217~300℃和199~300℃水解生成NH₃和CO₂,载气中有无O₂对催化水解过程几乎无影响。引入等离子体后缩二脲、三聚氰酸和三聚氰胺水解所需温度显著降低,载气中无O₂时引入等离子体NH₃产率变化不大,副产物仅有少量N₂O和NO,有O₂时NH₃产率显著降低,且生成较多N₂O、NO、NO₂及少量NH₄NO₂和NH₄NO₃。未来需从优化放电条件和催化剂组成等方面解决引入等离子体导致副产物形成等问题。     

Use of phenylphosphorodiamidate and N-(n-butyl)thiophosphorictriamide to reduce ammonia loss and increase grain yield following application of urea to flooded rice

Ammonia (NH₃) volatilization is an important mechanism for nitrogen (N) loss from flooded rice fields following the application of urea into the floodwater. One method of reducing losses is to use a urease inhibitor that retards the hydrolysis of urea by soil urease and allows the urea to diffuse deeper into the soil. The two chemicals that have shown most promise in laboratory and greenhouse studies are phenylphosphorodiamidate [PPD] and N-(n-butyl)thiophosphorictriamide [NBPT], but they seldom work effectively in the field. PPD decomposes rapidly when the pH departs from neutrality, and NBPT must be converted to the oxygen analogue [N-(n-butyl)phosphorictriamide, NBPTO] for it to be effective. Our field studies in Thailand showed that NH₃ loss is markedly reduced when PPD is added with the algicide terbutryn. The studies also showed that a mixture of PPD and NBPT was even more effective than either PPD or NBPT alone. It appears that initially PPD inhibited urease activity, and during this time at least part of the NBPT was converted to NBPTO; then as the activity of PPD declined, NBPTO inhibited the hydrolysis of urea. The combined urease inhibitor treatment reduced NH₃ loss from 15 to 3% of the applied N, and increased grain yield from 3.6 to 4.1 t ha^–1.