磁性纳米羟基磷灰石对污染土壤中镉的吸附-移除效果

doi:10.19741/j.issn.1673-4831.2021.0822

摘要/Abstract

摘要： 为从污染土壤中吸附移除重金属镉(Cd),将共沉淀法合成的磁性纳米羟基磷灰石(nHAP@Fe₃O₄)分别按0、0.1%、0.5%、1.0%、3.0%比例添加至土壤中,在修复21、30、45 d时,磁分离nHAP@Fe₃O₄与土壤,考察nHAP@Fe₃O₄对土壤Cd的去除、材料的回收效果及修复后土壤理化性质的变化。结果表明,w(Cd)为 2.510 mg·kg^-1的重污染稻田土壤中添加1.0% nHAP@Fe₃O₄,修复21 d时土壤Cd去除和材料回收效果最好,Cd平均去除率和材料回收率分别为16.45%和85.33%;nHAP@Fe₃O₄能明显降低土壤Cd的可交换态,促使其向较稳定的形态转化;经nHAP@Fe₃O₄修复后的土壤pH值升高,CEC有所降低,土壤颗粒间孔隙增大。利用磁性将nHAP@Fe₃O₄及其吸附的Cd从土壤中分离出来,以此实现对土壤Cd的吸附-移除。该方法对土壤理化性质影响较小,适宜修复重度污染程度的农田土壤。

关键词: 纳米羟基磷灰石, 磁性材料, 镉污染, 土壤修复

Abstract: In order to remove cadmium (Cd) from contaminated soil, magnetic nano hydroxyapatite (nHAP@Fe₃O₄) was synthesized by co-precipitation method under the soil water ratio of 1∶1 precursor. 0, 0.1%, 5%, 1.0% and 3.0% nHAP@Fe₃O₄ were then added to soil, respectively. After 21, 30 and 45 days of remediation, magnetic separation was used to separate nHAP@Fe₃O₄from soil, and the removal rates of Cd in soil, the recovery effect of materials and the changes of soil physical and chemical properties after remediation were then investigated. The results show that the average Cd removal rate and the material (nHAP@Fe₃O₄) recovery rate of heavy polluted paddy soil (containing 2.510 mg·kg^-1 of Cd) with the addition of 1% nHAP@Fe₃O₄ were 16.45% and 85.33%, respectively. The nHAP@Fe₃O₄ can significantly reduce the exchangeable and carbonate bound forms of soil Cd, and promote its transformation to a more stable form. After the remediation by nHAP@Fe₃O₄, the pH of the soil was increased, while the CEC decreased and the pore size between soil particles was increased. The removal of Cd from soil could be realized by using magnetic method to separate nHAP@Fe₃O₄ and adsorb Cd from the soil, which has little effect on soil physico-chemical properties. It is suitable for the remediation of severely polluted agicultural soil.

Key words: nano hydroxyapatite, magnetic material, cadmium pollution, soil remediation

中图分类号:

卢杰, 李玉娇, 杨志敏, 陈玉成. 磁性纳米羟基磷灰石对污染土壤中镉的吸附-移除效果[J]. 生态与农村环境学报, 2023, 39(6): 803-809.

LU Jie, LI Yu-jiao, YANG Zhi-min, CHEN Yu-cheng. Adsorption and Removal of Cd from Contaminated Soil by Magnetic Nano-hydroxyapatite[J]. Journal of Ecology and Rural Environment, 2023, 39(6): 803-809.

参考文献

[1] WANG Y T,BJÃRN L O.Heavy Metal Pollution in Guangdong Province,China,and the Strategies to Manage the Situation[J].Frontiers in Environmental Science,2014,2:9.
[2] QU J H,TIAN X,JIANG Z,et al.Multi-component Adsorption of Pb(Ⅱ),Cd(Ⅱ) and Ni(Ⅱ) onto Microwave-Functionalized Cellulose:Kinetics,Isotherms,Thermodynamics,Mechanisms and Application for Electroplating Wastewater Purification[J].Journal of Hazardous Materials,2020,387:121718.
[3] YANG J,MOSBY D.Field Assessment of Treatment Efficacy by Three Methods of Phosphoric Acid Application in Lead-contaminated Urban Soil[J].Science of the Total Environment,2006,366(1):136-142.
[4] 赵述华,陈志良,张太平,等.重金属污染土壤的固化/稳定化处理技术研究进展[J].土壤通报,2013,44(6)1531-1536.[ZHAO Shu-hua,CHEN Zhi-liang,ZHANG Tai-ping,et al.Advances in Solidification/Stabilization Technology Treatment of Heavy Metals in Contaminated Soils［J].Chinese Journal of Soil Science,2013,44(6)1531-1536.］
[5] 冯敬云,聂新星,刘波,等.镉污染农田原位钝化修复效果及其机理研究进展[J].农业资源与环境学报,2021(5):764-777.[FENG J Y,NIE X X,LIU B,et al.Efficiency of in-situ Passivation Remediation in Cadmium-Contaminated Farmland Soil and Its Mechanism:A Review［J].Journal of Agricultural Resources and Environment,2021(5):764-777.］
[6] 胡红青,黄益宗,黄巧云,等.农田土壤重金属污染化学钝化修复研究进展[J].植物营养与肥料学报,2017,23(6)1676-1685.[HU Hong-qing,HUANG Yi-zong,HUANG Qiao-yun,et al.Research Progress of Heavy Metals Chemical Immobilization in Farm Land［J].Plant Nutrition and Fertilizer Science,2017,23(6)1676-1685.］
[7] 任春溶.磁性纳米复合材料的制备及其对重金属离子的吸附性能研究[D].杭州:浙江大学,.[REN Chun-rong.Preparation of Magnetic Nanocomposites and Their Adsorption Properties for Heavy Metal Ions［D].Hangzhou:Zhejiang University.］
[8] LI Y J,YANG Z M,CHEN Y C,et al.Adsorption,Recovery,and Regeneration of Cd by Magnetic Phosphate Nanoparticles[J].Environmental Science and Pollution Research,2019,26(17):17321-17332.
[9] 梁媛,王晓春,曹心德.基于磷酸盐、碳酸盐和硅酸盐材料化学钝化修复重金属污染土壤的研究进展[J].环境化学,2012,31(1):16-25.[LIANG Yuan,WANG Xiao-chun,CAO Xin-de.Immobilization of Heavy Metals in Contaminated Soils with Phosphate-,Carbonate-,and Silicate-Based Amendments:a Review［J].Environmental Chemistry,2012,31(1)16-25.］
[10] 聂新星,刘骏龙,欧阳光明,等.一种磁性固体螯合材料对农田土壤Cd的移除修复效果研究[J].农业资源与环境学报,2017,34(6):525-530.[NIE Xin-xing,LIU Jun-long,OUYANG Guang-ming,et al.Removal and Remediation Effects of Cd from Cadmium-Contaminated Farmland Soils by a Magnetic Solid Chelator［J].Journal of Agricultural Resources and Environment,2017,34(6):525-530.］
[11] 刘骏龙,欧阳光明,聂新星,等.磁性固体螯合材料对农田土壤中镉去除的影响因素[J].农业资源与环境学报,2018,35(1)11-16.[LIU Jun-long,OUYANG Guang-ming,NIE Xin-xing,et al.Influences Factors of the Cadmium Removal by Magnetic Solid Chelator Powder(MSC) in Soil［J].Journal of Agricultural Resources and Environment,2018,35(1)11-16.］
[12] FAN L R,SONG J Q,BAI W B,et al.Chelating Capture and Magnetic Removal of Non-magnetic Heavy Metal Substances from Soil[J].Scientific Reports,2016,6(1):1-9.
[13] 范力仁,宋吉青,周洋,等.磁性固体螯合剂(MSC-IDA)对土壤镉污染的移除净化[J].环境化学,2017,36(6):1204-1212.[FAN Li-ren,SONG Ji-qing,ZHOU Yang,et al.Cd Removal from Contaminated Soil by Magnetic Solid Chelator Microparticles (MSC-IDA)［J].Environmental Chemistry,2017,36(6):1204-1212.］
[14] 王碧玲,谢正苗.磷对铅、锌和镉在土壤固相-液相-植物系统中迁移转化的影响[J].环境科学,2008,29(11):3225-3229.[WANG Bi-ling,XIE Zheng-miao.Effects of Phosphorus Application on Transiocation of Lead,Zinc and Cadmium in the Soil-plant System［J].Environmental Science,2008,29(11):3225-3229.］
[15] VIIPSI K,SJÖBERG S,TÕNSUAADU K,et al.Hydroxy- and Fluorapatite as Sorbents in Cd(Ⅱ)-Zn(Ⅱ) Multi-Component Solutions in the Absence/Presence of EDTA[J].Journal of Hazardous Materials,2013,252/253:91-98.
[16] ZHELTOVA V,VLASOVA A,BOBRYSHEVA N,et al.Fe₃O₄@HAp Core-shell Nanoparticles as MRI Contrast Agent:Synthesis,Characterization and Theoretical and Experimental Study of Shell Impact on Magnetic Properties[J].Applied Surface Science,2020,531:147352.
[17] MA J Z,XIA M Z,ZHU S D,et al.A New Alendronate Doped HAP Nanomaterial for Pb²⁺,Cu²⁺ and Cd²⁺ Effect Absorption[J].Journal of Hazardous Materials,2020,400:123143.
[18] 叶兴银,张卫,龙精华,等.人工纳米颗粒输入对稻田土壤Cd形态转化及生物有效性的影响[J].环境工程学报,2018,12(12):3426-3432.[YE X Y,ZHANG W,LONG J H,et al.Impact of Engineered Nanoperticles on Cd Chemical Speciation and Bioavailability in Paddy Soil［J].Chinese Journal of Environmental Engineering,2018,12(12):3426-3432.］
[19] MISHRA P M,NAIK G K,NAYAK A,et al.Facile Synthesis of Nano-structured Magnetite in Presence of Natural Surfactant for Enhanced Photocatalytic Activity for Water Decomposition and Cr (Ⅵ) Reduction[J].Chemical Engineering Journal,2016,299:227-235.
[20] TESSIER A,CAMPBELL P G C,BISSON M.Sequential Extraction Procedure for the Speciation of Particulate Trace Metals[J].Analytical Chemistry,1979,51(7):844-851.
[21] MA H,PU S Y,HOU Y Q,et al.A Highly Efficient Magnetic Chitosan "Fluid" Adsorbent with a High Capacity and Fast Adsorption Kinetics for Dyeing Wastewater Purification[J].Chemical Engineering Journal,2018,345:556-565.
[22] ZHENG L C,DANG Z,YI X Y,et al.Equilibrium and Kinetic Studies of Adsorption of Cd(Ⅱ) from Aqueous Solution Using Modified Corn Stalk[J].Journal of Hazardous Materials,2010,176(1/2/3):650-656.
[23] NIE X X,ZHANG Z Y,XIA X G,et al.Magnetic Removal/Immobilization of Cadmium and Zinc in Contaminated Soils Using a Magnetic Microparticle Solid Chelator and Its Effect on Rice Cultivation[J].Journal of Soils and Sediments,2020,20(4):2043-2052.
[24] 乔建晨.钝化材料对设施土壤镉稳定性和盐基离子动态变化的影响研究[D].保定:河北大学,2020.[QIAO Jian-chen.Effects of Passivation Materials on Cadmium Stability and Dynamic Changes of Base Ions in Protected Soil［D].Baoding:Hebei University,2020.］
[25] WANG B L,XIE Z Y.Effects of Phosphorus Application on Translocation of Lead,Zinc and Cadmium in the Soil-Plant System[J].Environmental Science,2008,29(11):3225-3229.