可生物降解螯合剂亚氨基二琥珀酸和谷氨酸N,N-二乙酸对重金属污染土壤的淋洗修复及动力学特征

doi:10.19741/j.issn.1673-4831.2020.0439

摘要/Abstract

摘要： 通过振荡淋洗研究了可生物降解螯合剂亚氨基二琥珀酸（IDS）和谷氨酸N，N-二乙酸（GLDA）对污染土壤中重金属Cd、Pb和Zn的淋洗动力学特征，分析了淋洗时间、淋洗剂浓度和pH对土壤重金属淋洗效率的影响，采用BCR连续提取法分析淋洗前后土壤重金属形态变化。结果表明，IDS和GLDA对Cd、Pb和Zn淋洗效率随淋洗时间（5~720 min）延长而增加，Elovich方程和双常数方程适合用于描述淋洗动力学过程，说明该淋洗解吸动力学过程为非均相扩散过程；淋洗剂浓度（0~20 mmol·L^-1）越大，淋洗效率就越高；随淋洗剂pH （3~10）的上升，淋洗效率呈现先增加后减少的变化。GLDA对Cd和Pb的淋洗去除能力大于IDS，而IDS对Zn的淋洗去除能力大于GLDA。在较佳淋洗条件下（IDS和GLDA浓度为10 mmol·L^-1，pH为5，分别淋洗240和360 min），IDS和GLDA对Cd淋洗效率分别为21.88%和66.12%，对Pb淋洗效率分别为17.47%和22.96%，对Zn淋洗效率分别为9.21%和8.11%，此时土壤中活性较高的酸溶态和可还原态重金属能够被有效去除。因此，IDS和GLDA淋洗可减少土壤重金属的环境风险。

关键词: 土壤淋洗, 重金属, 可生物降解螯合剂, 亚氨基二琥珀酸, 谷氨酸N,N-二乙酸, 淋洗动力学

Abstract: Batch experiments were carried out, to study the washing kinetics characteristics of heavy metals (Cd, Pb and Zn) from a contaminated soil with biodegradable chelating agents of imminodisuccinic acid (IDS) and Dl-2-(2-carboxymethyl) nitrilotriacetic acid (GLDA). The effects of washing time, concentrations and pH value of IDS and GLDA on the heavy metals removal efficiencies were also investigated. Afterwards, fractions of heavy metals in soil before and after washing were determined using the sequential extraction procedure of the optimized European Community Bureau of Reference (BCR). Results show that the removal efficiencies of Cd, Pb and Zn increased with the increasing of washing time (ranging from 5 to 720 min). Both Elovich equation and double-constant equation were suitable for describing the washing kinetic process, which suggested that the desorption of Cd, Pb and Zn from soil as a function of IDS and GLDA was regarded as the heterogeneous diffusion process. The removal efficiencies of Cd, Pb and Zn increased with the increasing of IDS and GLDA concentrations (ranging from 0 to 20 mmol·L^-1), however which increased first and then decreased with the increase of the pH of IDS and GLDA solution (ranging from 3 to 10). The removal efficiencies of Cd and Pb with GLDA were greater than that of IDS, while the removal efficiencies of Zn with IDS were better than that of GLDA. Under the optimal washing conditions (10 mmol·L^-1 IDS and GLDA with pH = 5 for 240 and 360 min, respectively), the removal efficiencies of Cd, Pb and Zn by IDS and GLDA were 21.88% and 66.12%, 17.47% and 22.96%, and 9.21% and 8.11%, respectively. BCR results demonstrate that the acid soluble and reducible fractions of heavy metals with high activity in soil can be effectively removed by using IDS and GLDA, respectively. Soil environmental risk induced by heavy metals could be reduced after washing with IDS and GLDA.

Key words: soil washing, heavy metal, biodegradable chelating agent, imminodisuccinic acid, Dl-2-(2-carboxymethyl) nitrilotriacetic acid, washing kinetic

中图分类号:

陈春乐, 杨婷, 邹县梅, 田甜. 可生物降解螯合剂亚氨基二琥珀酸和谷氨酸N,N-二乙酸对重金属污染土壤的淋洗修复及动力学特征[J]. 生态与农村环境学报, 2021, 37(3): 394-401.

CHEN Chun-le, YANG Ting, ZOU Xian-mei, TIAN Tian. Remediation of Heavy Metal Contaminated Soil by Biodegradable Chelating Agents of IDS and GLDA Washing and Their Washing Kinetics Characteristics[J]. Journal of Ecology and Rural Environment, 2021, 37(3): 394-401.

参考文献

[1] WANG B B,DUAN X L,FENG W Y,et al.Health Risks to Metals in Multimedia via Ingestion Pathway for Children in a Typical Urban Area of China[J].Chemosphere,2019,226:381-387.
[2] 张又文,韩建华,涂棋,等.天津市郊农田土壤重金属积累特征及评价[J].生态与农村环境学报,2019,35(11):1445-1452.[ZHANG You-wen,HAN Jian-hua,TU Qi,et al.Accumulation Characteristics and Evaluation of Heavy Metals in Suburban Farmland Soils of Tianjin[J].Journal of Ecology and Rural Environment,2019,35(11):1445-1452.]
[3] BOLAN N,KUNHIKRISHNAN A,THANGARAJAN R,et al.Remediation of Heavy Metal(Loid)s Contaminated Soils:To Mobilize or to Immobilize?[J].Journal of Hazardous Materials,2014,266:141-166.
[4] YAO Z T,LI J H,XIE H H,et al.Review on Remediation Technologies of Soil Contaminated by Heavy Metals[J].Procedia Environmental Sciences,2012,16:722-729.
[5] KO I,CHANG Y Y,LEE C H,et al.Assessment of Pilot-scale Acid Washing of Soil Contaminated with As,Zn and Ni Using the BCR Three-step Sequential Extraction[J].Journal of Hazardous Materials,2005,127(1/2/3):1-13.
[6] DI PALMA L,FERRANTELLI P.Copper Leaching from a Sandy Soil:Mechanism and Parameters Affecting EDTA Extraction[J].Journal of Hazardous Materials,2005,122(1/2):85-90.
[7] MAO X H,JIANG R,XIAO W,et al.Use of Surfactants for the Remediation of Contaminated Soils:A Review[J].Journal of Hazardous Materials,2015,285:419-435.
[8] KOŁODYŃSKA D.Application of a New Generation of Complexing Agents in Removal of Heavy Metal Ions from Different Wastes[J].Environmental Science and Pollution Research,2013,20(9):5939-5949.
[9] COKESA Ž,LAKNER S,KNACKMUSS H J,et al.A Stereoselective Carbon-nitrogen Lyase from Ralstonia sp.SLRS7 Cleaves Two of Three Isomers of Iminodisuccinate[J].Biodegradation,2004,15(4):229-239.
[10] KOODYNSKA D.Chelating Agents of a New Generation as an Alternative to Conventional Chelators for Heavy Metal Ions Removal from Different Waste Waters[M]//Expanding Issues in Desalination.[s. l.]:InTech,2011:339-371.
[11] WU Q,DUAN G Q,CUI Y R,et al.Removal of Heavy Metal Species from Industrial Sludge with the Aid of Biodegradable Iminodisuccinic Acid as the Chelating Ligand[J].Environmental Science and Pollution Research,2015,22(2):1144-1150.
[12] HAUTHAL H G.Sustainable Detergents and Cleaners,Progress on Ingredients,Nanoparticles,Analysis,Environment[J].Tenside Surfactants Detergents,2009,46:53-62.
[13] BEGUM Z A,RAHMAN I M M,TATE Y,et al.Remediation of Toxic Metal Contaminated Soil by Washing with Biodegradable Aminopolycarboxylate Chelants[J].Chemosphere,2012,87(10):1161-1170.
[14] WU Q,CUI Y R,LI Q L,et al.Effective Removal of Heavy Metals from Industrial Sludge with the Aid of a Biodegradable Chelating Ligand GLDA[J].Journal of Hazardous Materials,2015,283:748-754.
[15] 徐大勇,洪亚军,唐海,等.柠檬酸和谷氨酸N,N-二乙酸优化处理污泥重金属[J].化工学报,2017,68(6):2535-2545.[XU Da-yong,HONG Ya-jun,TANG Hai,et al.Optimization Treatment of Sludge Heavy Metals by Citric Acid and GLDA[J].CIESC Journal,2017,68(6):2535-2545.]
[16] 胡造时,莫创荣,戴知友,等.螯合剂GLDA对土壤Cr的淋洗修复研究[J].西南农业学报,2016,29(10):2422-2426.[HU Zao-shi,MO Chuang-rong,DAI Zhi-you,et al.Leaching Chromium from Soil Using GLDA as Eluting Agent[J].Southwest China Journal of Agricultural Sciences,2016,29(10):2422-2426.]
[17] 卫泽斌,吴启堂,龙新宪,等.可生物降解螯合剂GLDA和磷素活化剂促进东南景天提取土壤重金属的潜力[J].农业环境科学学报,2014,33(7):1402-1404.[WEI Ze-bin,WU Qi-tang,LONG Xin-xian,et al.Efficiency of Biodegradable Chelate GLDA and Phosphorus Activators on Heavy Metals Phytoextraction with Sedum alfredii Hance[J].Journal of Agro-environment Science,2014,33(7):1402-1404.]
[18] 袁江,李晔,许剑臣,等.可生物降解螯合剂GLDA和植物激素共同诱导植物修复重金属污染土壤研究[J].武汉理工大学学报,2016,38(2):82-86,92.[YUAN Jiang,LI Ye,XU Jian-chen,et al.Enhanced Phytoremediation of Heavy Metal Polluted Soil from Contaminated Soils Using Plant by Biodegradable Chelate GLDA in Combination with Plant Hormones[J].Journal of Wuhan University of Technology,2016,38(2):82-86,92.]
[19] 卫泽斌,陈晓红,吴启堂,等.可生物降解螯合剂GLDA诱导东南景天修复重金属污染土壤的研究[J].环境科学,2015,36(5):1864-1869.[WEI Ze-bin,CHEN Xiao-hong,WU Qi-tang,et al.Enhanced Phytoextraction of Heavy Metals from Contaminated Soils Using Sedum alfredii Hance with Biodegradable Chelate GLDA[J].Environmental Science,2015,36(5):1864-1869.]
[20] 中华人民共和国生态环境部.中华人民共和国国家标准:土壤环境质量农用地土壤污染风险管控标准:GB 15618-2018[S].北京:中国环境科学出版社,2018:1-4.[Ministry of Ecology and Environment of the People's Republic of China.Soil Environmental Quality:Risk Control Standard for Soil Contamination of Agricultural Land:GB 15618-2018[S].Beijing:China Environmental Science Press,2018:1-4.]
[21] 鲍士旦.土壤农化分析[M].3版.北京:中国农业出版社,2000:25-380.[BAO Shi-dan.Soil and Agricultural Chemistry Analysis[M].3rd ed.Beijing:Chinese Agriculture Press,2000:25-380.]
[22] PUEYO M,MATEU J,RIGOL A,et al.Use of the Modified BCR Three-step Sequential Extraction Procedure for the Study of Trace Element Dynamics in Contaminated Soils[J].Environmental Pollution,2008,152(2):330-341.]
[23] FENG C,ZHANG S R,LI L X,et al.Feasibility of Four Wastes to Remove Heavy Metals from Contaminated Soils[J].Journal of Environmental Management,2018,212:258-265.
[24] MARTELL A E,SMITH R M,MOTEKAITIS R J.NIST Standard Reference Database 46:NIST Critically Selected Stability Constants of Metal Complexes Database (Version 8.0 for Windows)[DB].College Station,TX:Texas A & M University,2004.
[25] BEGUM Z A,RAHMAN I M M,TATE Y,et al.Formation and Stability of Binary Complexes of Divalent Ecotoxic Ions (Ni,Cu,Zn,Cd,Pb) with Biodegradable Aminopolycarboxylate Chelants[Dl-2-(2-Carboxymethyl)Nitrilotriacetic Acid,GLDA,and 3-Hydroxy-2,2'-Iminodisuccinic Acid,HIDS]in Aqueous Solutions[J].Journal of Solution Chemistry,2012,41(10):1713-1728.
[26] BEGUM Z A,RAHMAN I M M,SAWAI H,et al.Effect of Extraction Variables on the Biodegradable Chelant-assisted Removal of Toxic Metals from Artificially Contaminated European Reference Soils[J].Water,Air,& Soil Pollution,2013,224(3):1-21.
[27] 侯沁言,彭雅茜,张世熔,等.HPAA、MSA和SPP 3种可生物降解螯合剂对污染土壤中重金属的淋洗效率[J].四川农业大学学报,2019,37(4):525-532.[HOU Qin-yan,PENG Ya-xi,ZHANG Shi-rong,et al.Effects of HPAA,MSA and SPP Biodegradable Chelators on Removal Efficiencies of Heavy Metals from Contaminated Soils[J].Journal of Sichuan Agricultural University,2019,37(4):525-532.]
[28] BAJDA T.Dissolution of Mimetite Pb₅(AsO₄)₃Cl in Low-molecular-weight Organic Acids and EDTA[J].Chemosphere,2011,83(11):1493-1501.
[29] CAO Y R,ZHANG S R,WANG G Y,et al.Removal of Pb,Zn,and Cd from Contaminated Soil by New Washing Agent from Plant Material[J].Environmental Science and Pollution Research International,2017,24(9):8525-8533.
[30] WANG G Y,ZHANG S R,XU X X,et al.Efficiency of Nanoscale Zero-valent Iron on the Enhanced Low Molecular Weight Organic Acid Removal Pb from Contaminated Soil[J].Chemosphere,2014,117:617-624.
[31] OTTOSEN L M,HANSEN H K,JENSEN P E.Relation between pH and Desorption of Cu,Cr,Zn,and Pb from Industrially Polluted Soils[J].Water,Air,and Soil Pollution,2009,201(1/2/3/4):295-304.
[32] JELUSIC M,LESTAN D.Effect of EDTA Washing of Metal Polluted Garden Soils:Part I:Toxicity Hazards and Impact on Soil Properties[J].Science of the Total Environment,2014,475:132-141.
[33] 余春瑰,张世熔,姚苹,等.四种生物质材料水浸提液淋洗镉污染土壤及其废水处理研究[J].土壤,2015,47(6):1132-1138.[YU Chun-gui,ZHANG Shi-rong,YAO Ping,et al.Cadmium Contaminated Soil Washing by Leaching Liquid of Four Biomass Materials and Their Wastewater Treatment[J].Soils,2015,47(6):1132-1138.]