不同含羧基有机酸改性尿素在石灰性潮土中的转化特征

doi:10.3864/j.issn.0578-1752.2022.17.008

摘要/Abstract

摘要：

【目的】研究羧基与其他活性官能团组合的不同含羧基有机酸改性尿素在石灰性潮土中的转化特征,为高效氮肥的研制提供理论依据。【方法】将柠檬酸（羧基+羟基）、腐殖酸（羧基+酚羟基/羰基/醛基等）、聚谷氨酸（羧基+氨基）和聚丙烯酸（羧基）按照0.5%添加量加入熔融尿素中制得含柠檬酸尿素（CAU）、含腐殖酸尿素（HAU）、含聚谷氨酸尿素（PGAU）和含聚丙烯酸尿素（PAAU）4种含羧基有机酸改性尿素试验产品。设置不施肥处理（CK）及施用普通尿素（U）、CAU、HAU、PGAU和PAAU处理,采用土壤培养方法研究不同含羧基有机酸改性尿素对土壤中酰胺态氮、NH₄⁺-N、NO₃^–-N含量和土壤脲酶活性的影响。并结合普通尿素和不同含羧基有机酸改性尿素的傅里叶变换红外光谱（FTIR）,从化学结构上揭示不同含羧基有机酸改性尿素对尿素转化的影响机制。【结果】（1）与U处理相比,在6 h—2 d内4种含羧基有机酸改性尿素均能延缓尿素在土壤中的水解,HAU和PGAU处理效果较好、其土壤尿素态氮残留量平均提高22.3%和23.7%。（2）与U处理铵态氮峰值（第2天）相比,HAU处理铵态氮含量峰值推迟至第3天,在6 h—2 d内,HAU处理铵态氮含量平均降低16.9%,HAU处理在培养后期（3—14 d）可提高土壤铵态氮含量,平均提高3.2%。（3）与U处理相比,4种含羧基有机酸改性尿素在培养后期显著提高土壤NO₃^--N含量,并以HAU处理最高,平均提高17.4 mg·kg^-1。（4）与U处理相比,培养前期（1—2 d）,4种含羧基有机酸改性尿素均抑制了土壤脲酶活性,其中HAU处理抑制效果最强、脲酶活性较U处理降低30.9%,但却提高了培养后期（2—14 d）土壤脲酶活性。【结论】含羧基有机酸改性尿素可通过抑制培养前期脲酶活性延缓尿素在土壤中的水解与转化,延缓培养中期NH₄⁺-N向NO₃^--N转化,提高培养后期土壤NO₃^--N含量,减少氮损失。以上结果的产生主要是由于羧基及其他活性官能团可以与尿素发生反应。其中羧基与多种活性官能团（酚羟基/醛基/羰基）同时存在时与尿素的反应程度最深,对尿素的缓释效果最好。

关键词: 含羧基有机酸改性尿素, 尿素转化, 脲酶活性, 不同活性官能团, 土壤培养, 石灰性潮土

Abstract:

【Objective】 The conversion characteristics of different carboxyl-containing organic acids modified urea combined with carboxyl groups and other active functional groups in calcareous fluvo-aquic soil were investigated, so as to provide a theoretical basis for the development of high-efficiency nitrogen fertilizers.【Method】 The citric acid (carboxyl group + hydroxyl group), humic acid (carboxyl group + phenolic hydroxyl group/carbonyl group/aldehyde group, etc.), polyglutamic acid (carboxyl group + amino group) and polyacrylic acid (carboxyl group) were added into the molten urea at 0.5% addition amount, to prepare the test fertilizers, exactly, citric acid urea (CAU), humic acid urea (HAU), polyglutamic acid urea (PGAU) and polyacrylic acid urea (PAAU). The treatments of without urea (CK), common urea (U), CAU, HAU, PGAU and PAAU were set up to study the effects of different carboxyl-containing organic acids modified urea on the soil amide nitrogen, NH₄⁺-N, NO₃^--N and soil urease activity by using soil incubation method. The influence mechanism of different carboxy-containing organic acids modified urea in soil conversion was revealed with the results from Fourier transform infrared spectroscopy (FTIR) of U and different carboxy-containing organic acids modified urea.【Result】 (1) Compared with U, the four kinds of carboxyl-containing organic acids modified urea delayed the urea hydrolysis in the soil from 6 h to 2 d. HAU and PGAU had a better performance than other treatments, and their residual amount of soil urea nitrogen increased by 22.3% and 23.7% than that with U, respectively. (2) Compared with the appearing time of NH₄⁺-N content peak treat with U (2 d), HAU application delayed to the appearing time of NH₄⁺-N content peak to the third day. In 6 h-2 d, the average value of NH₄⁺-N content with HAU treatment decreased by 16.9% than that with U, while increased by 3.2% in 3-14 d. (3) Compared with U, four kinds of carboxyl-containing organic acids modified urea significantly increased soil NO₃^--N content in the later period of incubation, and the HAU treatment showed the highest value with an average increase of 17.4 mg·kg^-1 than the U treatment. (4) Compared with U, four kinds of carboxyl-containing organic acids modified urea inhibited soil urease activity in 1-2 d, among which HAU had the strongest inhibitory effect, and the urease activity was reduced by 30.9% compared with U. However, HAU enhanced the soil urease activity in 2-14 d.【Conclusion】 Carboxyl-containing organic acids modified urea could delay the hydrolysis and transformation of urea in the soil by inhibiting urease activity in the early stage of incubation delaying the transformation of NH₄⁺-N to NO₃^--N in the middle stage of incubation, and increase the NO₃^--N content of cultivated soil in the late stage of incubation to reduce nitrogen loss. The above results were mainly attributed to the reaction of carboxyl groups and other active functional groups with urea. The reaction degree with urea was the deepest when the carboxyl group and a variety of active functional groups (phenolic hydroxyl group/aldehyde group/carbonyl group) existed at the same time, which attributed the slow release of urea to the best.

Key words: carboxyl-containing organic acids modified urea, urea conversion, urease activity, different active functional groups, soil incubation, calcareous fluvo-aquic soil

张英强,张水勤,李燕婷,赵秉强,袁亮. 不同含羧基有机酸改性尿素在石灰性潮土中的转化特征[J]. 中国农业科学, 2022, 55(17): 3355-3364.

ZHANG YingQiang,ZHANG ShuiQin,LI YanTing,ZHAO BingQiang,YUAN Liang. Conversion Characteristics of Different Carboxyl-Containing Organic Acids Modified Urea in Calcareous Fluvo-Aquic Soil[J]. Scientia Agricultura Sinica, 2022, 55(17): 3355-3364.

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处理 Treatment	有机材料添加量 Addition of organic materials (%)	全氮含量 Total N content (%)
尿素 U	0	45.96
含柠檬酸尿素 CAU	0.5	45.62
含腐殖酸尿素 HAU	0.5	45.58
含聚谷氨酸尿素 PGAU	0.5	45.84
含聚丙烯酸尿素 PAAU	0.5	45.64