天然矿物复配腐植酸对农田镉的钝化机理研究
|
摘要
采用田间试验研究了改良剂(腐植酸)及由膨润土、硅藻土、氧化镁组配的钝化剂对土壤镉(Cd)的钝化效果及对土壤理化性质的影响,并借助红外光谱仪(FTIR)、扫描电镜联用能谱分析仪(SEM-EDS)和比表面分析仪(BET),分析探讨了钝化改良剂对镉的钝化机理。结果表明:不同钝化改良剂处理初始有效态镉浓度为0.0836 mg/kg的菜地土壤70 d后,镉的钝化效率由高到低依次为:10 g/kg钝化剂+0.4 g/kg改良剂>10 g/kg钝化剂>5 g/kg钝化剂+0.4 g/kg改良剂>5 g/kg钝化剂>0.4 g/kg改良剂,其中10 g/kg钝化剂+0.4 g/kg改良剂对有效态镉的钝化效率达到60.2%。表征分析显示,钝化剂表面结构疏松,其表面的Na~+、Ca~(2+)、Mg~(2+)等离子可与Cd~(2+)发生离子交换反应,改良剂中含有醌基、醇羟基、羧基、羰基和C=C键,能与Cd~(2+)发生配位络合作用,化学吸附是复配钝化改良剂降低土壤镉有效性的主要原因。
The stabilizing effects of improved bentonite-diatomite-magnesia-humic acid composite curing agent on soil available Cd and its influence on soil physicochemical properties were investigated, and the related mechanisms were also studied by adopting FTIR, SEM-EDS and BET analyses. Results showed that after 70-day treatment, the concentration of available Cd in soil, which was initially 0.083 6 mg/kg, decreased significantly. The stabilizing efficiencies of different composite curing agents were in an order of 10 g/kg curing agent +0.4 g/kg humic acid > 10 g/kg curing agent > 5 g/kg curing agent + 0.4 g/kg humic acid> 5 g/kg curing agent > 0.4 g/kg humic acid. In particular, the stabilizing efficiency reached 60.2% for 10 g/kg curing agent + 0.4 g/kg humic acid treatment. SEM-EDS and BET analyses revealed that the curing agent exhibited loose surface structure, the existence of ions on the surface, which included Na~+, Ca~(2+), Mg~(2+), could contribute to chemical adsorption through ion exchange.Besides, functional groups such as quinone, alcohol, hydroxyl, carboxyl, carbonyl and C=C bond in humic acid could coordinate with Cd~(2+). Chemical absorption is the main reason to reduce the availability of soil Cd.
The stabilizing effects of improved bentonite-diatomite-magnesia-humic acid composite curing agent on soil available Cd and its influence on soil physicochemical properties were investigated, and the related mechanisms were also studied by adopting FTIR, SEM-EDS and BET analyses. Results showed that after 70-day treatment, the concentration of available Cd in soil, which was initially 0.083 6 mg/kg, decreased significantly. The stabilizing efficiencies of different composite curing agents were in an order of 10 g/kg curing agent +0.4 g/kg humic acid > 10 g/kg curing agent > 5 g/kg curing agent + 0.4 g/kg humic acid> 5 g/kg curing agent > 0.4 g/kg humic acid. In particular, the stabilizing efficiency reached 60.2% for 10 g/kg curing agent + 0.4 g/kg humic acid treatment. SEM-EDS and BET analyses revealed that the curing agent exhibited loose surface structure, the existence of ions on the surface, which included Na~+, Ca~(2+), Mg~(2+), could contribute to chemical adsorption through ion exchange.Besides, functional groups such as quinone, alcohol, hydroxyl, carboxyl, carbonyl and C=C bond in humic acid could coordinate with Cd~(2+). Chemical absorption is the main reason to reduce the availability of soil Cd.
引文
[1]环境保护部,国土资源部.全国土壤污染状况调查公报[R].中国:环境保护部国土资源部,2014
[2]Dudka S,Adriano D C.Environmental impacts of metal ore mining and processing:A review[J].Journal of Environmental Quality,1997,26(3):516-528
[3]Wu L H,Luo Y M,Christie P,et al.Effects of EDTA and low molecular weight organic acids on soil solution properties of a heavy metal polluted soil[J].Chemosphere,2003,50(6):819-822
[4]唐秋香,缪新.土壤镉污染的现状及修复研究进展[J].环境工程,2013(1):747-750
[5]陈杰,宋靖珂,张晶,等.不同钝化剂对铜污染土壤原位钝化修复[J].土壤,2016,48(4):742-747
[6]Mercier L,Detellier C.Preparation,characterization,and applications as heavy metals sorbents of covalently grafted thiol functionalities on the interlamellar surface of montmorillonite[J].Environmental Science&Technology,1995,29(5):1318-1323
[7]熊琼仙,陈文,朱霞萍,等.巯基功能化膨润土吸附Pb2+的动力学和热力学研究[J].离子交换与吸附,2012,28(5):432-441
[8]Namor A F D D,Gamouz A E,Frangie S,et al.Turning the volume down on heavy metals using tuned diatomite.Areview of diatomite and modified diatomite for the extraction of heavy metals from water[J].Journal of Hazardous Materials,2012,241/242(4):14-31
[9]Meng F,Yuan G,Jing W,et al.Humic substances as a washing agent for Cd-contaminated soils[J].Chemosphere,2017,181:461-467
[10]Reed B E,Carriere P C.Moore R.Flushing of a Pb(II)contaminated soil using HCl,EDTA and CaCl2[J].Journal of Environmental Engineering,1998,122(1):48-50
[11]Bassi R,Prasher S O,Simpson B K.Extraction of metals from a contaminated sandy soil using citric acid[J].Environmental Progress&Sustainable Energy,2010,19(4):275-282
[12]Giannis A,Gidarakos E.Washing enhanced electrokinetic remediation for removal cadmium from real contaminated soil[J].Journal of Hazardous Materials,2005,123(1):165-175
[13]Benschoten J E V,Reed B E,Matsumoto M R,et al.Metal removal by soil washing for an iron oxide coated sandy soil[J].Water Environment Research,1994,66(2):168-174
[14]Abumaizar R J,Smith E H.Heavy metal contaminants removal by soil washing[J].Journal of Hazardous Materials,1999,70(1/2):71-86
[15]赖胜强,林亲铁,项江欣,等.氧化镁基固化剂对铅离子的吸附作用及其影响因素[J].环境工程学报,2016,10(7):3859-3865
[16]中华人民共和国农业部.土壤pH的测定:NY/T 1377-2007[S].北京:中国标准出版社,2007
[17]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.土壤质量有效态铅和镉的测定原子吸收法:GB/T 23739-2009[S].北京:中国标准出版社,2009
[18]环境保护部.土壤和沉积物金属元素总量的消解微波消解法:HJ 832-2017[S].北京:中国标准出版社,2017
[19]环境保护部.土壤有效磷的测定碳酸氢钠浸提-钼锑抗分光光度法:HJ704-2014[S].北京:中国标准出版社,2014
[20]全国农业技术推广服务中心.土壤分析技术规范(第二版)[M].北京:中国农业出版社,2006
[21]中华人民共和国农业部.土壤检测第6部分:土壤有机质的测定:NY/T 1121.6-2006[S].北京:中国标准出版社,2006
[22]杨秀敏,钟子楠,潘宇,等.重金属离子在钠基膨润土中的吸附特征与机理[J].环境工程学报,2013,7(7):2775-2780
[23]程文婷,陈亚芬,李扬,等.片层花状氧化镁的制备及其吸附性能研究[J].无机化学学报,2013,29(9):1793-1798
[24]Chen C L,Wang X K.Influence of pH,soil humic/fulvic acid,ionic strength and foreign ions on sorption of thorium(IV)ontoγ-Al2O3[J].Applied Geochemistry,2007,22(2):436-445
[25]Putra E K,Pranowo R,Sunarso J,et al.Performance of activated carbon and bentonite for adsorption of amoxicillin from wastewater:mechanisms,isotherms and kinetics[J].Water Research,2009,43(9):2419-2430
[26]Zhu L,Zhu R.Simultaneous sorption of organic compounds and phosphate to inorganic-organic bentonites from water[J].Separation&Purification Technology,2007,54(1):71-76
[27]刘国良,朱一民,房鑫,等.不同粒度纳米氧化镁的制备及其红外吸收特性[J].东北大学学报(自然科学版),2010,31(8):1192-1195
[28]顾志忙,王晓蓉,顾雪元,等.傅里叶变换红外光谱和核磁共振法对土壤中腐殖酸的表征[J].分析化学,2000,10(3):314-317
[29]Sun Y B,Li Y,Xu Y M,et al.In situ stabilization remediation of cadmium(Cd)and lead(Pb)co-contaminated paddy soil using bentonite[J].Applied Clay Science,2015,105/106:200-206
[30]王秀丽,梁成华,马子惠,等.施用磷酸盐和沸石对土壤镉形态转化的影响[J].环境科学,2015,36(4):1437-1444
[31]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(4):141-166
[32]白玲玉,陈世宝,华珞,等.腐植酸与Cd、Zn的络合特性研究[J].核农学报,2000,14(1):44-48
[33]曾维爱,曾敏,周航,等.腐植酸和硫酸铁配施改良偏碱烟田土壤的研究[J].水土保持学报,2013,27(3):170-173
[34]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(6):1531-1536
[35]Kulikowska D,Gusiatin Z M,Bu?kowska K,et al.Feasibility of using humic substances from compost to remove heavy metals(Cd,Cu,Ni,Pb,Zn)from contaminated soil aged for different periods of time[J].Journal of Hazardous Materials,2015,300:882-891
[36]王磊,应蓉蓉,石佳奇,等.土壤矿物对有机质的吸附与固定机制研究进展[J].土壤学报,2017,54(4):805-818
[37]宋贤威,赵秀兰,张进忠,等.蒙脱石对有机物料施入土壤磷形态和有效性的影响[J].环境科学,2016,37(10):4020-4029
[38]林琼,吴昭珍,邱孝煊,等.施肥条件下白云石粉对菜地土壤氮素转化的影响[J].福建农业科技,2014,1(1):35-37
[39]王宇霞,郝秀珍,苏玉红,等.不同钝化剂对Cu、Cr和Ni复合污染土壤的修复研究[J].土壤,2016,48(1):123-130
[40]辜娇峰,周航,杨文弢,等.复合改良剂对镉砷化学形态及在水稻中累积转运的调控[J].土壤学报,2016,53(6):1576-1585
[2]Dudka S,Adriano D C.Environmental impacts of metal ore mining and processing:A review[J].Journal of Environmental Quality,1997,26(3):516-528
[3]Wu L H,Luo Y M,Christie P,et al.Effects of EDTA and low molecular weight organic acids on soil solution properties of a heavy metal polluted soil[J].Chemosphere,2003,50(6):819-822
[4]唐秋香,缪新.土壤镉污染的现状及修复研究进展[J].环境工程,2013(1):747-750
[5]陈杰,宋靖珂,张晶,等.不同钝化剂对铜污染土壤原位钝化修复[J].土壤,2016,48(4):742-747
[6]Mercier L,Detellier C.Preparation,characterization,and applications as heavy metals sorbents of covalently grafted thiol functionalities on the interlamellar surface of montmorillonite[J].Environmental Science&Technology,1995,29(5):1318-1323
[7]熊琼仙,陈文,朱霞萍,等.巯基功能化膨润土吸附Pb2+的动力学和热力学研究[J].离子交换与吸附,2012,28(5):432-441
[8]Namor A F D D,Gamouz A E,Frangie S,et al.Turning the volume down on heavy metals using tuned diatomite.Areview of diatomite and modified diatomite for the extraction of heavy metals from water[J].Journal of Hazardous Materials,2012,241/242(4):14-31
[9]Meng F,Yuan G,Jing W,et al.Humic substances as a washing agent for Cd-contaminated soils[J].Chemosphere,2017,181:461-467
[10]Reed B E,Carriere P C.Moore R.Flushing of a Pb(II)contaminated soil using HCl,EDTA and CaCl2[J].Journal of Environmental Engineering,1998,122(1):48-50
[11]Bassi R,Prasher S O,Simpson B K.Extraction of metals from a contaminated sandy soil using citric acid[J].Environmental Progress&Sustainable Energy,2010,19(4):275-282
[12]Giannis A,Gidarakos E.Washing enhanced electrokinetic remediation for removal cadmium from real contaminated soil[J].Journal of Hazardous Materials,2005,123(1):165-175
[13]Benschoten J E V,Reed B E,Matsumoto M R,et al.Metal removal by soil washing for an iron oxide coated sandy soil[J].Water Environment Research,1994,66(2):168-174
[14]Abumaizar R J,Smith E H.Heavy metal contaminants removal by soil washing[J].Journal of Hazardous Materials,1999,70(1/2):71-86
[15]赖胜强,林亲铁,项江欣,等.氧化镁基固化剂对铅离子的吸附作用及其影响因素[J].环境工程学报,2016,10(7):3859-3865
[16]中华人民共和国农业部.土壤pH的测定:NY/T 1377-2007[S].北京:中国标准出版社,2007
[17]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.土壤质量有效态铅和镉的测定原子吸收法:GB/T 23739-2009[S].北京:中国标准出版社,2009
[18]环境保护部.土壤和沉积物金属元素总量的消解微波消解法:HJ 832-2017[S].北京:中国标准出版社,2017
[19]环境保护部.土壤有效磷的测定碳酸氢钠浸提-钼锑抗分光光度法:HJ704-2014[S].北京:中国标准出版社,2014
[20]全国农业技术推广服务中心.土壤分析技术规范(第二版)[M].北京:中国农业出版社,2006
[21]中华人民共和国农业部.土壤检测第6部分:土壤有机质的测定:NY/T 1121.6-2006[S].北京:中国标准出版社,2006
[22]杨秀敏,钟子楠,潘宇,等.重金属离子在钠基膨润土中的吸附特征与机理[J].环境工程学报,2013,7(7):2775-2780
[23]程文婷,陈亚芬,李扬,等.片层花状氧化镁的制备及其吸附性能研究[J].无机化学学报,2013,29(9):1793-1798
[24]Chen C L,Wang X K.Influence of pH,soil humic/fulvic acid,ionic strength and foreign ions on sorption of thorium(IV)ontoγ-Al2O3[J].Applied Geochemistry,2007,22(2):436-445
[25]Putra E K,Pranowo R,Sunarso J,et al.Performance of activated carbon and bentonite for adsorption of amoxicillin from wastewater:mechanisms,isotherms and kinetics[J].Water Research,2009,43(9):2419-2430
[26]Zhu L,Zhu R.Simultaneous sorption of organic compounds and phosphate to inorganic-organic bentonites from water[J].Separation&Purification Technology,2007,54(1):71-76
[27]刘国良,朱一民,房鑫,等.不同粒度纳米氧化镁的制备及其红外吸收特性[J].东北大学学报(自然科学版),2010,31(8):1192-1195
[28]顾志忙,王晓蓉,顾雪元,等.傅里叶变换红外光谱和核磁共振法对土壤中腐殖酸的表征[J].分析化学,2000,10(3):314-317
[29]Sun Y B,Li Y,Xu Y M,et al.In situ stabilization remediation of cadmium(Cd)and lead(Pb)co-contaminated paddy soil using bentonite[J].Applied Clay Science,2015,105/106:200-206
[30]王秀丽,梁成华,马子惠,等.施用磷酸盐和沸石对土壤镉形态转化的影响[J].环境科学,2015,36(4):1437-1444
[31]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(4):141-166
[32]白玲玉,陈世宝,华珞,等.腐植酸与Cd、Zn的络合特性研究[J].核农学报,2000,14(1):44-48
[33]曾维爱,曾敏,周航,等.腐植酸和硫酸铁配施改良偏碱烟田土壤的研究[J].水土保持学报,2013,27(3):170-173
[34]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(6):1531-1536
[35]Kulikowska D,Gusiatin Z M,Bu?kowska K,et al.Feasibility of using humic substances from compost to remove heavy metals(Cd,Cu,Ni,Pb,Zn)from contaminated soil aged for different periods of time[J].Journal of Hazardous Materials,2015,300:882-891
[36]王磊,应蓉蓉,石佳奇,等.土壤矿物对有机质的吸附与固定机制研究进展[J].土壤学报,2017,54(4):805-818
[37]宋贤威,赵秀兰,张进忠,等.蒙脱石对有机物料施入土壤磷形态和有效性的影响[J].环境科学,2016,37(10):4020-4029
[38]林琼,吴昭珍,邱孝煊,等.施肥条件下白云石粉对菜地土壤氮素转化的影响[J].福建农业科技,2014,1(1):35-37
[39]王宇霞,郝秀珍,苏玉红,等.不同钝化剂对Cu、Cr和Ni复合污染土壤的修复研究[J].土壤,2016,48(1):123-130
[40]辜娇峰,周航,杨文弢,等.复合改良剂对镉砷化学形态及在水稻中累积转运的调控[J].土壤学报,2016,53(6):1576-1585