腐殖酸磷肥中的腐殖酸对磷迁移的影响及机理

doi:10.3864/j.issn.0578-1752.2021.23.009

摘要/Abstract

摘要：

【目的】比较腐殖酸磷肥中的腐殖酸（PHA）与常规腐殖酸（HA）对肥料磷迁移、Ca²⁺及磷酸盐吸附特征的差异,明晰腐殖酸在磷肥增效过程中的作用。【方法】在实验室分别制备腐殖酸、腐殖酸磷肥及普通磷肥,利用腐殖酸“碱溶酸析”的原理,通过调节腐殖酸磷肥溶液pH分离得到PHA。研究磷肥配施两种添加量的HA和PHA对肥料磷迁移状况的影响,HA和PHA的配施量分别为施磷量的0.5%与5%,代号分别为0.5HA+P、0.5PHA+P、5HA+P及5PHA+P,同时设置单施磷肥（P）及不施肥（CK）两个处理。并通过HA和PHA对Ca²⁺及磷酸盐的吸附特征解释二者对肥料磷迁移存在差异的原因。【结果】HA和PHA配施磷肥,肥料磷的迁移距离与迁移量均高于P处理：P处理肥料磷可以迁移到距施肥层垂直距离42 mm处,而配施HA和PHA处理可以分别到达距施肥层46与50 mm处,这与HA和PHA对土壤Ca²⁺存在较高的吸附容量,进而减少土壤对磷的固定有关。距施肥层42 mm以后,土壤速效磷总量占总施磷量的累积百分数基本趋于不变,且0.5HA+P ≈ 5PHA+P>5HA+P>0.5PHA+P>P处理。PHA对肥料磷迁移的促进作用会随其添加量的提高而增强,而提高HA用量反而会减弱其对肥料磷迁移的促进作用,这与PHA移动性强于HA,对磷酸盐的吸附弱于HA有关。HA与PHA对Ca²⁺ 的吸附均是膜扩散与颗粒内扩散综合作用的结果,但是与HA相比,Ca²⁺向PHA颗粒表面扩散的难度降低,在PHA颗粒内部扩散的难度变大。Langmuir等温吸附模型可以很好地拟合HA或PHA和Ca²⁺的等温吸附曲线,HA对Ca²⁺理论最大吸附量高于PHA,然而PHA对Ca²⁺的吸附以化学吸附为主。【结论】腐殖酸磷肥中的腐殖酸与普通腐殖酸均对Ca²⁺存在一定的吸附能力,因此均可以促进肥料磷的迁移,但是磷肥配施腐殖酸磷肥中的腐殖酸,肥料磷的迁移距离大于常规腐殖酸,这可能是腐殖酸磷肥中腐殖酸增效磷肥的一个原因。

关键词: 腐殖酸磷肥, 腐殖酸, 肥料磷迁移, 钙离子, 吸附

Abstract:

【Objective】The difference between HA (raw humic acid) and PHA (humic acid which extracted from humic acid enhanced phosphate fertilizers, HAP) on fertilizer-phosphorus migration, Ca²⁺ and phosphate adsorption characteristics was systematically compared to provide the theoretical basis for the study on high-efficiency mechanism of humic acid enhanced phosphate fertilizer. 【Method】 In this study, HA, HAP, and conventional phosphate fertilizer were prepared in the laboratory, and PHA was extracted by adjusting the pH of HAP’s solution based on the method of alkali-extraction acid-precipitation. The addition of HA or PHA accounted for 0.5% and 5% of the application amount of phosphate fertilizer, and marked with 0.5HA+P, 0.5PHA+P, 5HA+P, and 5PHA+P, respectively. Only phosphate fertilizer application (P) and no fertilizer application (CK) were arranged at the same time. Then, the effects of HA and PHA applicated with phosphate fertilizer on the migration of fertilizer-phosphorus in soil was investigated. In addition, the adsorption characteristics of HA or PHA on Ca²⁺ and phosphate were studied to reveal the mechanism that HA and PHA showed different performance on phosphorus migration. 【Result】Both HA and PHA could promote the migration of fertilizer-phosphorus. Phosphorus could migrate to 42 mm vertical distance from the fertilizer layer under the treatment of P. However, when phosphate fertilizers application combined with HA and PHA, it could reach 46 mm and 50 mm away from the fertilizer layer, respectively. This result was due to the fact that HA or PHA had a higher adsorption capacity on soil Ca²⁺, while the application of HA or PHA reduced phosphorus fixation. The cumulative percentage of soil available P in total P application tended to be stable after 42 mm away from the fertilizer layer, and 0.5 HA+P ≈ 5PHA+P>5HA+P>0.5PHA + P>P. The promotion effect of PHA on fertilizer-phosphorus migration would be enhanced with the addition of PHA increase, while HA was the opposite, which might be related to the stronger mobility and the weaker phosphate adsorption of PHA than that of HA. The adsorption of Ca²⁺ by HA and PHA was the result of membrane diffusion and intra-particle diffusion. However, the difficulty of Ca²⁺ diffusion to the surface of PHA particles was lower than that of HA, and the difficulty of Ca²⁺ diffusion in the interior of PHA particles was higher than that of HA. Langmuir isothermal adsorption model could well fit the isothermal adsorption curves of HA or PHA on Ca²⁺, and the theoretical maximum adsorption capacity of HA on Ca²⁺ was higher than that of PHA, but the adsorption of PHA on Ca²⁺ was mainly chemical adsorption.【Conclusion】Both HA and PHA had certain ability to adsorb Ca²⁺, so they could promote the migration of fertilizer-phosphorus in the soil. However, the migration distance of fertilizer-phosphorus of PHA was longer than that of HA, when phosphate application was combined with HA or PHA. This might be one reason why PHA could improve the use efficiency of phosphate fertilizer.

Key words: humic acid enhanced phosphate fertilizer, humic acid, fertilizer-phosphorus migration, calcium ion, adsorption

景建元,袁亮,张水勤,李燕婷,赵秉强. 腐殖酸磷肥中的腐殖酸对磷迁移的影响及机理[J]. 中国农业科学, 2021, 54(23): 5032-5042.

JING JianYuan,YUAN Liang,ZHANG ShuiQin,LI YanTing,ZHAO BingQiang. Effects and Mechanism of Humic Acid in Humic Acid Enhanced Phosphate Fertilizer on Fertilizer-Phosphorus Migration[J]. Scientia Agricultura Sinica, 2021, 54(23): 5032-5042.

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样品 Sample	比表面积 BET surface area (m²·g^-1)	凝聚限度 Flocculation limit (meg·L^-1)
HA	0.36	1.75
PHA	1.59	1.85

	准一级动力学方程 Pseudo first order kinetic equation			准二级动力学方程 Pseudo second order kinetic equation			Weber-Morris模型Weber-Morris model
	准一级动力学方程 Pseudo first order kinetic equation			准二级动力学方程 Pseudo second order kinetic equation			附段1 Stage1			附段2 Stage2
	q_e,cal(mg·g^-1)	k₁(h^-1)	R²	q_e,cal(mg·g^-1)	k₂(h^-1)	R²	k_i	C	R²	k_i	C	R²
HA	5.63	26.89	0.99	5.70	17.27	0.94	1.41	4.71	0.81	0.01	5.62	0.42
PHA	5.33	28.38	0.89	5.39	19.16	0.99	1.18	4.52	0.95	0.02	5.33	0.34

	Langmuir等温吸附模型			Freundlich等温吸附模型
	q_max (mg·g^-1)	b	R²	k_F	n	R²
HA	14.84	0.76	0.996	6.06	2.81	0.93
PHA	12.79	0.80	0.989	5.40	2.83	0.97

	准一级动力学方程 Pseudo first order kinetic equation			准二级动力学方程 Pseudo second order kinetic equation
	q_e,cal(mg·g^-1)	k₁(h^-1)	R²	q_e,cal(mg·g^-1)	k₂(h^-1)	R²
HA	3.83	9.49	0.93	3.99	4.45	0.94
PHA	1.88	5.71	0.95	1.98	4.63	0.87