黄荣^1,,
徐应明^1,,,
黄青青¹,
孙国红²,
尹秀玲³,
梁学峰¹,
秦旭¹
1.农业部环境保护科研监测所/农业部产地环境质量重点实验室 天津 300191
2.天津农学院工程技术学院 天津 300384
3.吉林大学环境与资源学院 长春 130012
基金项目: 中国农业科学院创新工程项目2017-cxgc-xym
农业部农业生态环境保护项目2017-sthj-xym
天津市科技支撑计划项目14ZCZDSF00004
天津市农业科技成果转化与推广项目201404100
国家现代农业产业技术体系CARS-03

详细信息

作者简介:黄荣, 主要从事施肥对农田土壤重金属镉污染修复影响研究。E-mail:huangrong1992@163.com

通讯作者:徐应明, 主要从事农田土壤重金属污染钝化修复技术研究。E-mail:ymxu1999@126.com

中图分类号:X131.2;X53

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出版历程

收稿日期:2017-12-06
录用日期:2018-04-13
刊出日期:2018-08-01

Effect of potassium fertilizers on immobilization remediation of Cd-polluted soils using sepiolite

HUANG Rong^1,,
XU Yingming^1,,,
HUANG Qingqing¹,
SUN Guohong²,
YIN Xiuling³,
LIANG Xuefeng¹,
QIN Xu¹
1. Institute of Ago-Environmental Protection of Ministry of Agriculture/Key Laboratory of Original Agro-Environmental Quality, Ministry of Agriculture, Tianjin 300191, China
2. College of Engineering and Technology, Tianjin Agricultural University, Tianjin 300384, China
3. College of Environment and Resources, Jilin University, Changchun 130012, China
Funds: the Agricultural Science and Technology Innovation Project of Chinese Academy of Agricultural Sciences2017-cxgc-xym
the Agricultural Eco-Environmental Protection Project of the Ministry of Agriculture of China2017-sthj-xym
the Science and Technology Support Project of Tianjin, China14ZCZDSF00004
the Agricultural Science and Technology Achievement Transformation and Promotion Project of Tianjin, China201404100
the Modern Agricultural Industry Technology System of ChinaCARS-03

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Corresponding author:XU Yingming, E-mail:ymxu1999@126.com

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摘要
摘要:为了揭示钾肥对Cd污染土壤钝化修复效果的影响，为土壤钝化修复过程中合理施钾肥提供理论依据。本文选取不同剂量（含量以K₂O计算，分别为0.1 g·kg^-1、0.2 g·kg^-1和0.3 g·kg^-1）的KCl和K₂SO₄作为典型钾肥，以海泡石（10 g·kg^-1）作为钝化材料，通过油菜盆栽试验，研究了两种钾肥在海泡石钝化条件下对Cd污染土壤修复效应的影响。结果表明：K₂SO₄显著增加了油菜的生物量，其增幅为6.06%~10.05%。与单施海泡石钝化相比，在海泡石钝化时施用KCl和K₂SO₄两种钾肥，油菜地上部茎叶Cd含量分别增加16.38%~60.73%和15.62%~25.19%；施用KCl和K₂SO₄对土壤pH未产生显著性影响，却显著地增加了土壤有效态Cd含量，其增幅分别为25.51%~34.65%和18.5%~24.96%。添加海泡石可使土壤的Zeta电位向负值方向移动，提高土壤对Cd的负载能力；但添加海泡石下施用KCl和K₂SO₄均能提高土壤的Zeta电位，降低土壤对Cd的负载能力。等温吸附试验同样表明，添加KCl和K₂SO₄均能降低海泡石对Cd的吸附量，在水溶液中海泡石对Cd的最大吸附量为5.30 mg·kg^-1，添加KCl和K₂SO₄后吸附量分别降低至2.87 mg·g^-1和4.92 mg·g^-1。KCl和K₂SO₄显著改善了土壤中K、Mn、Cu和Zn等营养元素的有效态含量。从上述结果可以发现，在海泡石钝化修复Cd污染土壤过程中，施K₂SO₄对钝化效果的影响小于施KCl。
关键词:钾肥/
海泡石/
镉污染土壤/
油菜/
钝化/
原位修复
Abstract:Cadmium (Cd) is one of the most toxic pollutants in soil environments because of its persistence, toxicity and potential for bioaccumulation. Natural sepiolite has recently been found as a cost-effective material for immobilization remediation of metal-contaminated soils due to its low cost, high cation exchange capacity, and high specific surface area associated with the small particle sizes. In agricultural production, the application of various fertilizers is vital, but the effects of fertilizer addition to polluted soils on immobilization remediation have been little investigated. In previous studies on immobilization experiments, only remediation effects were emphasized. The effects of nutrient elements on remediation process promotion or inhibition has been largely ignored. For large application of immobilization remediation in different areas with various fertilizer forms, the impact of fertilizers on the process must be determined. In this research, natural sepiolite (10 g·kg^-1) was used as immobilization agent and meanwhile potassium chloride (KCl) and potassium sulphate (K₂SO₄) used as representative potassic fertilizers in rape pot experiments to determine the effects of potassic fertilizers on the process of immobilization remediation of Cd-polluted soil. The potassium fertilizer content was calculated as K₂O, with 0.1 g·kg^-1, 0.2 g·kg^-1 and 0.3 g·kg^-1, respectively. The results showed that rape biomass significantly increased (by 6.06%-10.05%) after the application of K₂SO₄, compared with sole sepiolite treatment. Cd contents in shoot increased respectively by 16.38%-60.73% and 15.62%-25.19% after the application of KCl and K₂SO₄. KCl and K₂SO₄ had little effects on soil pH, but increased exchangeable Cd concentration significantly (respectively by 25.51%-34.65% and 18.5%-24.96%). Sepiolite conduced Zeta potential of soil samples to shift in negative direction, while the addition of KCl and K₂SO₄ made the Zeta potential of soil samples increase. The maximum adsorption of Cd by sepiolite in aqueous solution was 5.30 mg·g^-1, but KCl and K₂SO₄ reduced sorption of Cd on sepiolite, with maximum sorption of respectively 2.87 mg·g^-1 and 4.92 mg·g^-1. Bioavailable fractions of K, Mn, Cu and Zn were enhanced significantly by the additions of KCl and K₂SO₄. Considering the various factors during passivation of sepiolite to Cd-contaminated soils therefore, the effect of application of K₂SO₄ on passivation was less than that of application of KCl. On the whole, K₂SO₄, rather than KCl, was recommended potassic fertilizer for remediation of Cd-contaminated soils using sepiolite.
Key words:Potassic fertilizer/
Sepiolite/
Cd-polluted soil/
Rape/
Passivation/
In-situ remediation

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图1海泡石及钾肥施用对Cd污染土壤上油菜生物量的影响
CK:对照; S:海泡石钝化; S+K₁.L:海泡石+低剂量(0.1 g·kg^-1)KCl; S+K₁.M:海泡石+中剂量(0.2 g·kg^-1)KCl; S+K₁.H:海泡石+高剂量(0.3 g·kg^-1)KCl; S+K₂.L:海泡石+低剂量(0.1 g·kg^-1)K₂SO₄; S+K₂.M:海泡石+中剂量(0.2 g·kg^-1)K₂SO₄; S+K₂.H:海泡石+高剂量(0.3 g·kg^-1)K₂SO₄。图中不同字母表示不同处理间差异显著(P < 0.05)。
Figure1.Effects of sepiolite and potassium fertilizers application on biomasses of rape grown in Cd-polluted soils
CK: control; S: sepiolite; S+K₁.L: sepiolite + low-dose (0.1 g·kg^-1) KCl; S+K₁.M: sepiolite + middle-dose (0.2 g·kg^-1) KCl; S+K₁.H: sepiolite + high-dose (0.3 g·kg^-1) KCl; S+K₂.L: sepiolite + low-dose (0.1 g·kg^-1) K₂SO₄; S+K₂.M: sepiolite + middle-dose (0.2 g·kg^-1) K₂SO₄; S+K₂.H: sepiolite + high-dose (0.3 g·kg^-1) K₂SO₄. Different letters mean significant differences among different treatments (P < 0.05).


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图2海泡石及钾肥施用对Cd污染土壤上油菜地上部中Cd含量影响
CK:对照; S:海泡石钝化; S+K₁.L:海泡石+低剂量(0.1 g·kg^-1) KCl; S+K₁.M:海泡石+中剂量(0.2 g·kg^-1)KCl; S+K₁.H:海泡石+高剂量(0.3 g·kg^-1)KCl; S+K₂.L:海泡石+低剂量(0.1 g·kg^-1)K₂SO₄; S+K₂.M:海泡石+中剂量(0.2 g·kg^-1)K₂SO₄; S+K₂.H:海泡石+高剂量(0.3 g·kg^-1)K₂SO₄。图中不同字母表示不同处理间差异显著(P < 0.05)。
Figure2.Effects of sepiolite and potassium fertilizers application on shoot Cd contents of rape grown in Cd-polluted soils
CK: control; S: sepiolite; S+K₁.L: sepiolite + low-dose (0.1 g·kg^-1) KCl; S+K₁.M: sepiolite + middle-dose (0.2 g·kg^-1) KCl; S+K₁.H: sepiolite + high-dose (0.3 g·kg^-1) KCl; S+K₂.L: sepiolite + low-dose (0.1 g·kg^-1) K₂SO₄; S+K₂.M: sepiolite + middle-dose (0.2 g·kg^-1) K₂SO₄; S+K₂.H: sepiolite + high-dose (0.3 g·kg^-1) K₂SO₄. Different letters mean significant differences among different treatments (P < 0.05).


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图3海泡石及钾肥施用对Cd污染土壤pH和0.025 mol·L^-1 HCl可交换态Cd含量的影响
CK:对照; S:海泡石钝化; S+K₁.L:海泡石+低剂量(0.1 g·kg^-1)KCl; S+K₁.M:海泡石+中剂量(0.2 g·kg^-1)KCl; S+K₁.H:海泡石+高剂量(0.3 g·kg^-1)KCl; S+K₂.L:海泡石+低剂量(0.1 g·kg^-1)K₂SO₄; S+K₂.M:海泡石+中剂量(0.2 g·kg^-1)K₂SO₄; S+K₂.H:海泡石+高剂量(0.3 g·kg^-1)K₂SO₄。图中不同字母表示不同处理间差异显著(P < 0.05)。
Figure3.Effect of sepiolite and potassium fertilizers application on pH and exchangeable Cd contents of Cd-polluted soils
CK: control; S: sepiolite; S+K₁.L: sepiolite + low-dose (0.1 g·kg^-1) KCl; S+K₁.M: sepiolite + middle-dose (0.2 g·kg^-1) KCl; S+K₁.H: sepiolite + high-dose (0.3 g·kg^-1) KCl; S+K₂.L: sepiolite + low-dose (0.1 g·kg^-1) K₂SO₄; S+K₂.M: sepiolite + middle-dose (0.2 g·kg^-1) K₂SO₄; S+K₂.H: sepiolite + high-dose (0.3 g·kg^-1) K₂SO₄. Different letters mean significant differences among different treatments (P < 0.05).


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图4海泡石及钾肥施用对Cd污染土壤有效态K、Cu、Zn和Mn影响
CK:对照; S:海泡石钝化; S+K₁.L:海泡石+低剂量(0.1 g·kg^-1)KCl; S+K₁.M:海泡石+中剂量(0.2 g·kg^-1)KCl; S+K₁.H:海泡石+高剂量(0.3 g·kg^-1)KCl; S+K₂.L:海泡石+低剂量(0.1 g·kg^-1)K₂SO₄; S+K₂.M:海泡石+中剂量(0.2 g·kg^-1)K₂SO₄; S+K₂.H:海泡石+高剂量(0.3 g·kg^-1)K₂SO₄。图中不同字母表示不同处理间差异显著(P < 0.05)。
Figure4.Effects of sepiolite and potassium fertilizers on exchangeable K, Cu, Zn and Mn contents in Cd-polluted soil
CK: control; S: sepiolite; S+K₁.L: sepiolite + low-dose (0.1 g·kg^-1) KCl; S+K₁.M: sepiolite + middle-dose (0.2 g·kg^-1) KCl; S+K₁.H: sepiolite + high-dose (0.3 g·kg^-1) KCl; S+K₂.L: sepiolite + low-dose (0.1 g·kg^-1) K₂SO₄; S+K₂.M: sepiolite + middle-dose (0.2 g·kg^-1) K₂SO₄; S+K₂.H: sepiolite + high-dose (0.3 g·kg^-1) K₂SO₄. Different letters mean significant differences among different treatments (P < 0.05).


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图5海泡石及钾肥施用对Cd污染土壤Zata电位的影响
CK:对照; S:海泡石钝化; S+K₁.L:海泡石+低剂量(0.1 g·kg^-1)KCl; S+K₁.M:海泡石+中剂量(0.2 g·kg^-1)KCl; S+K₁.H:海泡石+高剂量(0.3 g·kg^-1)KCl; S+K₂.L:海泡石+低剂量(0.1 g·kg^-1)K₂SO₄; S+K₂.M:海泡石+中剂量(0.2 g·kg^-1)K₂SO₄; S+K₂.H:海泡石+高剂量(0.3 g·kg^-1)K₂SO₄。
Figure5.Effects of sepiolite and potassium fertilizers application on Zeta potentials of Cd-polluted soils
CK: control; S: sepiolite; S+K₁.L: sepiolite + low-dose (0.1 g·kg^-1) KCl; S+K₁.M: sepiolite + middle-dose (0.2 g·kg^-1) KCl; S+K₁.H: sepiolite + high-dose (0.3 g·kg^-1) KCl; S+K₂.L: sepiolite + low-dose (0.1 g·kg^-1) K₂SO₄; S+K₂.M: sepiolite + middle-dose (0.2 g·kg^-1) K₂SO₄; S+K₂.H: sepiolite + high-dose (0.3 g·kg^-1) K₂SO₄.


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图6KCl和K₂SO₄对海泡石吸附Cd等温平衡的影响
S:海泡石; S+K₁:海泡石+KCl; S+K₂:海泡石+K₂SO₄。
Figure6.Effects of KCl and K₂SO₄ on adsorption isotherms of Cd of sepiolite
S: sepiolite; S+K₁: sepiolite + KCl; S+K₂: sepiolite + K₂SO₄.


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表1KCl和K₂SO₄影响下海泡石对Cd的吸附等温线方程拟合参数
Table1.Parameters of Langmuri equations for Cd²⁺ adsorption by sepiolite under application of KCl and K₂SO₄

	Langmuri方程: C/Q=1/A×k+C/A
	A	k	R2 (n=8)
S	5.303	0.962	0.982
S+K1	2.872	0.266	0.928
S+K2	4.921	0.147	0.983
S:海泡石; S+K1:海泡石+KCl; S+K2:海泡石+K2SO4。S: sepiolite; S+K1: sepiolite + KCl; S+K2: sepiolite + K2SO4.

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