常规施肥对土壤水稳性团聚体镉吸附解吸特性及化学形态的影响研究

doi:10.16258/j.cnki.1674-5906.2022.12.015

生态环境学报 ›› 2022, Vol. 31 ›› Issue (12): 2403-2413.DOI: 10.16258/j.cnki.1674-5906.2022.12.015

常规施肥对土壤水稳性团聚体镉吸附解吸特性及化学形态的影响研究

秦秦¹^,²^,⁴(), 段海芹¹^,³, 宋科¹, 孙丽娟¹, 孙雅菲¹, 周斌¹, 薛永¹^,^*()

1.上海市农业科学院生态环境保护研究所，上海 201403
2.农业农村部绿色低碳重点实验室，上海 201403
3.上海海洋大学海洋生态与环境学院，上海 201306
4.上海市设施园艺艺术重点实验室，上海 201403

收稿日期:2022-06-08 出版日期:2022-12-18 发布日期:2023-02-15
通讯作者: *薛永，E-mail: exueyong@163.com
作者简介:秦秦（1987年生），女，副研究员，博士，主要研究方向为农田土壤修复与保育。E-mail: qinqin19870987@126.com
基金资助:
上海市科技兴农推广项目(沪农科推字 (2020) 第2-1号);上海市自然科学基金项目(17ZR1431200);上海市农业科学院卓越团队计划项目(沪农科卓 (2022) 008)

Effect of Conventional Fertilization on the Adsorption-desorption Characteristics and Chemical forms of Cadmium in Soil Water-stable Aggregates

QIN Qin¹^,²^,⁴(), DUAN Haiqin¹^,³, SONG Ke¹, SUN Lijuan¹, SUN Yafei¹, ZHOU Bin¹, XUE Yong¹^,^*()

1. Institute of Eco-Environment and Plant Protection, Shanghai Academy of Agricultural Sciences, Shanghai 201403, P. R. China
2. Key Laboratory of Low-carbon Green Agriculture, Ministry of Agriculture and Rural Affairs, Shanghai 201403, P. R. China
3. College of Marine Ecology and Environment, Shanghai Ocean University, Shanghai 201306, P. R. China
4. Shanghai Key Laboratory of Protected Horticultural Technology, Shanghai 201403, P. R. China

Received:2022-06-08 Online:2022-12-18 Published:2023-02-15

摘要/Abstract

摘要：

土壤团聚体是土壤颗粒的主要存在形式，对重金属在土壤中的富集和生物有效性具有重要影响。施肥方式会影响土壤团聚体的粒径分布和理化特性，但是不同粒径团聚体自身理化特性对重金属富集和赋存化学形态的影响仍缺乏系统研究。选取两种施肥处理（常规施肥和不施肥）的水稳性团聚体颗粒为研究对象，采用平衡等温法研究各粒级团聚体中镉（Cd）的吸附解吸特性和赋存化学形态，探讨施肥-团聚体理化特性-Cd吸附解吸及其赋存化学形态的内在关系。结果表明：相比未施肥处理，常规施肥处理能够显著增加大粒径团聚体（>53 μm）占比及其有机质、游离氧化铁（特别是无定形氧化铁）、全氮、有效磷和速效钾含量。与未施肥处理不同，常规施肥处理原土及各粒径团聚体对Cd²⁺的吸附解吸过程符合Freundlich方程，可达到非均匀多层吸附，其中2000—250 μm粒径团聚体对Cd²⁺的吸附、固持能力最强，随着粒径的减小，对Cd²⁺的吸附、固持能力均降低，主要与其游离氧化铁（特别是无定形氧化铁）、有机质、有效磷及全氮含量呈显著正相关。随着溶液中Cd²⁺初始浓度的增大，各粒径团聚体对Cd²⁺的吸附、解吸能力均增加。原土及各粒径团聚体固持Cd²⁺的化学形态以交换态为主，其中2000—250 μm粒径团聚体交换态Cd占比最低，为66.0%。常规施肥处理使各粒径团聚体中交换态Cd和有机结合态Cd含量显著降低，铁锰氧化物结合态Cd和残渣态Cd含量显著增加。由此可以得出，适当施肥处理能够增加团粒胶结物质含量，有利于大团聚结构生成，提高土壤颗粒对Cd²⁺的固持能力，促使固持的Cd²⁺向更稳定的形态转化，降低其生物活性和迁移能力。

关键词: 施肥, 团聚体, 镉（Cd）, 吸附, 解吸, 化学形态

Abstract:

Soil aggregates are the main from of soil particles, which have important effects on the enrichment and bioavailability of heavy metals in soil. Fertilization can affect the particle size distribution and physicochemical characteristics of soil aggregates. However, the effects of physicochemical characteristics of soil aggregates with different particle sizes on the enrichment and chemical forms of heavy metals are still unclear. In this study, a number of equilibrium isothermal adsorption-desorption experiments were conducted to study the adsorption-desorption characteristics and chemical forms of cadmium (Cd) in different particle sizes (< 53 μm，53?250 μm and 250?2000 μm) of water-stable aggregates fractions extracted from the agricultural soil treated with no fertilizer or conventional fertilization, and reveal the relationship between the physicochemical characteristics of soil aggregates with/without fertilization treatments and adsorption-desorption characteristics and chemical forms of Cd²⁺ in these aggregate fractions. The results showed that compared to no fertilizer treatment, conventional fertilization treatment significantly increased the proportion of 2000?250 μm aggregates and the contents of organic matter (OM), free iron oxide (especially amorphous iron oxide), total nitrogen, available phosphorus and available potassium in each aggregate component, especially 2000?250 μm aggregates. The adsorption and desorption of Cd²⁺ on different size fraction aggregate and bulk soil with conventional fertilization treatment was in accordance with Freundlich equation, and was dominated by heterogeneous multi-surface adsorption. Among them, 2000?250 μm aggregates had the strongest adsorption and retention ability for Cd²⁺. With the size fraction increase, adsorption and retention ability decreased, being significantly positively correlated with free iron oxides (especially amorphous iron oxide), OM, available phosphorus and total nitrogen. With the initial concentration of Cd²⁺ in the solution increase, the adsorption and desorption capacity of every size fraction on Cd²⁺ increased. Cd²⁺ retained in different particles were dominated by exchangeable Cd, and the proportion of exchangeable Cd in 2000?250 μm aggregates was the lowest, accounting for 66.0%. The exchangeable fraction and organic bound fraction of Cd significantly decreased, and the Fe/Mn oxide bound fraction and the residual fraction of Cd significantly increased in particle size fractions collected from soil samples with the conventional fertilization treatment. Findings above showed that the application of fertilizers could increase the ratio of large size aggregates and their organic matters and free iron oxides contents, which could decrease the migration and bioavailability of Cd²⁺ in these aggregates.

Key words: fertilization, aggregates, cadmium (Cd), adsorption, desorption, chemical forms

中图分类号:

X53
X131.3

秦秦, 段海芹, 宋科, 孙丽娟, 孙雅菲, 周斌, 薛永. 常规施肥对土壤水稳性团聚体镉吸附解吸特性及化学形态的影响研究[J]. 生态环境学报, 2022, 31(12): 2403-2413.

QIN Qin, DUAN Haiqin, SONG Ke, SUN Lijuan, SUN Yafei, ZHOU Bin, XUE Yong. Effect of Conventional Fertilization on the Adsorption-desorption Characteristics and Chemical forms of Cadmium in Soil Water-stable Aggregates[J]. Ecology and Environment, 2022, 31(12): 2403-2413.

图/表 11

参考文献 37

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处理 Treatment	有机肥 Organic manure (N-P₂O₅-K₂O）	尿素 Urea (N)	过磷酸钙 Calcium superphosphate (P₂O₅)	硫酸钾 Potassium sulfate (K₂O)
未施肥 No fertilizer	0	0	0	0
常规施肥 Conventional fertilization	4950 (99-40-114)	660 (304)	131 (79)	330 (172)

处理 Treatment	有机肥 Organic manure (N-P₂O₅-K₂O）	尿素 Urea (N)	过磷酸钙 Calcium superphosphate (P₂O₅)	硫酸钾 Potassium sulfate (K₂O)
未施肥 No fertilizer	0	0	0	0
常规施肥 Conventional fertilization	4950 (99-40-114)	660 (304)	131 (79)	330 (172)

处理 Treatment	粒径 Particle size/ μm	质量分数 Mass percentage/ %	有机质 w_{(Organic matter)}/ (g∙kg⁻¹)	游离氧化铁 w_{(Free iron oxide)}/ (g∙kg⁻¹)	无定形氧化铁 w_{(Amorphous iron oxide)}/ (g∙kg⁻¹)	全氮 w_{(Total nitrogen)}/ (g∙kg⁻¹)	有效磷 w_{(Available phosphorus)}/ (mg∙kg⁻¹)	速效钾 w_{(Available potassium)}/ (mg∙kg⁻¹)	pH
常规施肥 Conventional fertilization	原土	—	26.30±0.91ab	9.02±0.08c	4.60±0.01b	1.53±0.02c	74.75±3.95b	306.10±5.69c	6.76±0.02a
	2000‒250	40.84±0.32c	29.91±1.06b	8.83±0.05bc	4.82±0.06c	1.67±0.07d	106.06±2.54c	242.19±17.13b	7.53±0.01c
	250‒53	34.74±0.66b	25.79±4.65ab	8.74±0.01b	4.71±0.01bc	1.30±0.01b	70.36±5.64b	167.52±25.69a	7.7±0.01d
	<53	20.13±0.80a	21.11±0.62a	8.43±0.02a	4.42±0.10a	1.01±0.02a	31.08±1.41a	240.17±14.27b	7.47±0.03b
未施肥 No fertilizer	原土	—	14.95±0.06b	8.92±0.03d	3.71±0.01c	1.16±0.01d	20.10±0.56a	125.16±2.27b	6.99±0.03b
	2000‒250	44.47±0.48c	16.39±1.54b	7.61±0.02c	3.90±0.02d	0.85±0.01b	31.87±1.41b	153.38±5.71c	7.38±0.01c
	250‒53	31.41±1.00b	12.07±0.42a	6.50±0.01b	3.32±0.04b	0.98±0.02c	20.10±2.26a	115.04±8.56b	7.32±0.02c
	<53	13.24±0.23a	9.71±0.81a	5.62±0.02a	3.17±0.02a	0.74±0.04a	15.52±0.84a	94.86±8.56a	6.79±0.01a

处理 Treatment	粒径 Particle size/ μm	质量分数 Mass percentage/ %	有机质 w_{(Organic matter)}/ (g∙kg⁻¹)	游离氧化铁 w_{(Free iron oxide)}/ (g∙kg⁻¹)	无定形氧化铁 w_{(Amorphous iron oxide)}/ (g∙kg⁻¹)	全氮 w_{(Total nitrogen)}/ (g∙kg⁻¹)	有效磷 w_{(Available phosphorus)}/ (mg∙kg⁻¹)	速效钾 w_{(Available potassium)}/ (mg∙kg⁻¹)	pH
常规施肥 Conventional fertilization	原土	—	26.30±0.91ab	9.02±0.08c	4.60±0.01b	1.53±0.02c	74.75±3.95b	306.10±5.69c	6.76±0.02a
	2000‒250	40.84±0.32c	29.91±1.06b	8.83±0.05bc	4.82±0.06c	1.67±0.07d	106.06±2.54c	242.19±17.13b	7.53±0.01c
	250‒53	34.74±0.66b	25.79±4.65ab	8.74±0.01b	4.71±0.01bc	1.30±0.01b	70.36±5.64b	167.52±25.69a	7.7±0.01d
	<53	20.13±0.80a	21.11±0.62a	8.43±0.02a	4.42±0.10a	1.01±0.02a	31.08±1.41a	240.17±14.27b	7.47±0.03b
未施肥 No fertilizer	原土	—	14.95±0.06b	8.92±0.03d	3.71±0.01c	1.16±0.01d	20.10±0.56a	125.16±2.27b	6.99±0.03b
	2000‒250	44.47±0.48c	16.39±1.54b	7.61±0.02c	3.90±0.02d	0.85±0.01b	31.87±1.41b	153.38±5.71c	7.38±0.01c
	250‒53	31.41±1.00b	12.07±0.42a	6.50±0.01b	3.32±0.04b	0.98±0.02c	20.10±2.26a	115.04±8.56b	7.32±0.02c
	<53	13.24±0.23a	9.71±0.81a	5.62±0.02a	3.17±0.02a	0.74±0.04a	15.52±0.84a	94.86±8.56a	6.79±0.01a

处理 Treatment	粒径 Particle size/μm	Langmuir			Freundlich
处理 Treatment	粒径 Particle size/μm	K_L	Q_max	r²	K_F	n	r²
常规施肥 Conventional fertilization	原土	0.441	2257.10	0.603	660.802	0.639	0.603
	2000‒250	0.689	4089.67	0.958	1699.788	0.748	0.962
	250‒53	0.579	3792.11	0.974	1350.562	0.651	0.960
	<53	0.545	3055.37	0.989	1020.904	0.719	0.998
未施肥 No fertilizer	原土	0.405	1290.72	0.912	361.971	0.514	0.859
	2000‒250	0.406	2611.26	0.954	704.912	0.648	0.932
	250‒53	0.363	2428.97	0.966	609.095	0.634	0.944
	<53	0.229	2308.04	0.954	458.056	0.752	0.948

常规施肥对土壤水稳性团聚体镉吸附解吸特性及化学形态的影响研究

Effect of Conventional Fertilization on the Adsorption-desorption Characteristics and Chemical forms of Cadmium in Soil Water-stable Aggregates

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处理 Treatment	pH	有机质 Organic matter	全氮 Total nitrogen	有效磷 Available phosphorus	速效钾 Available potassium	游离氧化铁 Free iron oxide	无定形氧化铁Amorphous iron oxide
常规施肥 Conventional fertilization	0.232	0.867^*	0.985^**	0.992**	0.033	0.959^**	0.975^**
未施肥 No fertilizer	0.823*	0.933^**	0.294	0.986**	0.989**	0.979^**	0.967^**

溶液初始浓度 Initial centration of Cd²⁺/ (mg∙L⁻¹)	原土 Bulk soil		2000‒250 µm		250‒53 µm		<53 µm
溶液初始浓度 Initial centration of Cd²⁺/ (mg∙L⁻¹)	常规施肥 Conventional fertilization	未施肥 No fertilizer	常规施肥 Conventional fertilization	未施肥 No fertilizer	常规施肥 Conventional fertilization	未施肥 No fertilizer	常规施肥 Conventional fertilization	未施肥 No fertilizer
2	0.37	1.01	—	15.88	—	24.32	3.54	33.87
5	17.34	11.11	3.23	37.08	7.53	42.76	13.83	47.76
10	12.54	13.14	11.92	46.94	19.80	56.04	26.57	64.80
20	12.29	14.11	10.52	23.58	13.47	27.44	16.46	31.36
30	13.51	19.73	14.18	52.53	17.22	57.73	20.12	63.33

处理 Treatment	pH	有机质 Organic matter	全氮 Total nitrogen	有效磷 Available phosphorus	速效钾 Available potassium	游离氧化铁 Free iron oxide	无定形氧化铁 Amorphous iron oxide
常规施肥 Conventional fertilization	−0.102	−0.815^*	−0.992^**	−0.978^**	−0.054	−0.935^**	−0.944^**
未施肥 No fertilizer	−0.826^*	−0.931^**	−0.527	−0.904^**	−0.869^*	−0.91^**	−0.861^**

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处理 Treatment	粒径 Particle size/μm	Langmuir			Freundlich
处理 Treatment	粒径 Particle size/μm	K_L	Q_max	r²	K_F	H	r²
常规施肥 Conventional fertilization	原土	0.20	371.11	0.99	62.52	1.11	0.99
	2000‒250	0.28	359.92	0.93	14.55	2.54	0.96
	250‒53	0.19	475.15	0.94	31.32	2.01	0.97
	<53	0.14	608.64	0.96	37.71	1.63	0.99
未施肥 No fertilizer	原土	0.26	332.20	0.96	51.58	2.02	0.85
	2000‒250	0.020	3105.19	0.99	44.20	1.62	0.99
	250‒53	0.017	3668.98	0.99	45.29	1.64	0.99
	<53	0.014	4412.69	0.99	44.61	1.37	0.99

处理 Treatment	粒径 Particle size/μm	Langmuir			Freundlich
处理 Treatment	粒径 Particle size/μm	K_L	Q_max	r²	K_F	H	r²
常规施肥 Conventional fertilization	原土	0.20	371.11	0.99	62.52	1.11	0.99
	2000‒250	0.28	359.92	0.93	14.55	2.54	0.96
	250‒53	0.19	475.15	0.94	31.32	2.01	0.97
	<53	0.14	608.64	0.96	37.71	1.63	0.99
未施肥 No fertilizer	原土	0.26	332.20	0.96	51.58	2.02	0.85
	2000‒250	0.020	3105.19	0.99	44.20	1.62	0.99
	250‒53	0.017	3668.98	0.99	45.29	1.64	0.99
	<53	0.014	4412.69	0.99	44.61	1.37	0.99