复合药剂对不同类型重金属污染土壤的固化修复
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摘要
为了考察复合药剂对Pb、Hg、Cr、Cd、Zn、Cu和Ni污染土样的固化修复效果,以重污染企业用地、冶炼厂河道底泥和自配土壤为污染土样进行试验,试验中的普适复合药剂主要为含磷酸盐沉淀剂、黏土和水泥,视情况辅以无机还原助剂和有机络合助剂。在普适药剂(相对原土样的质量分数<15%)、还原剂(<5%)和有机助剂(<2%)的组配下,处理后的重金属浸出质量浓度低于GB 18598—2001标准值。普适药剂对Pb、Cd、Zn、Cu、Ni的固化有效,磷酸盐是促成Pb固化的关键成分,黏土和水泥分别起到吸附固定和物理包封的作用。无机助剂中的还原/络合性成分和硫化物分别对Cr(VI)和Hg的固化有明显的促进作用。对于Pb、Cd、Zn、Cu复合污染土壤的修复,分析了重金属浸出质量浓度随普适药剂投加量变化的特征曲线,结果表明,Pb比Cu的曲线斜率更大,表明Pb的固化效率更高;Cd和Zn具有相似的曲线形状,推测二者具有类似的固化机理。
The paper is to devote itself to the research on the immobilization and remediation mechanism of the heavy metal contamination in the soils via the composite agents.For the said purpose,we have chosen a series of composite agents to immobilize such heavy metal contaminants of Pb,Hg,Cr,Cd,Zn,Cu,and Ni in the soil samples from the nearby manufacturing spots,the river-course sediments and the synthetic land soils by choosing the normal components of the composite agents including soluble phosphate,calcium montmorillonite clay,and the fly-ash Portland cement.We have also added inorganic reductants including ferrous sulfate and calcium sulfide,and a thiol-based organic complexant,to the composite agents as adjuvants in case they are needed.The remediation process we have adopted included the pretreatment of soil samples,the addition of the composite agents with blending,and the incubation.Effective remediation of the soil samples were obtained,and the leaching concentrations of the heavy metal contaminants from the soil samples,too,in accordance with the Chinese national standard GB 18598—2001,can also be expected to achieve proper dosage of the composite agents(normal components,and/or inorganic adjuvants),so as to reduce the rate of the normal components content,inorganic adjuvants content,and organic adjuvants content to less than 15%,5%,and 2% of their original soil weight,respectively.The normal components of the composite agents were found to be effective in immobilizing the contaminants of Pb,Cd,Zn,Cu,and Ni,for in this case,phosphate tends to play a key function in precipitating Pb,whereas clay and cement are vital for adsorbing and enveloping the aforementioned heavy metal residuals.What is more,the inorganic adjuvants may play their roles in the reduction and complexation of Cr and in the sulfidation of Hg.Therefore,we have made a proposal to remediate for the pollution with multiple heavy-metal composite agents,to relieve the characteristic curves of the leaching concentrations as the function of dosage,which tends to be instructive for optimizing the dosage and exploring the immobilization mechanism.Hence,it can be inferred from the slopes of the curves that Pb can be more effectively stabilized by the composite agents than can Cu.The similar curve forms for Cd and Zn may still imply that they are likely to give similar response to the process of immobilization.
The paper is to devote itself to the research on the immobilization and remediation mechanism of the heavy metal contamination in the soils via the composite agents.For the said purpose,we have chosen a series of composite agents to immobilize such heavy metal contaminants of Pb,Hg,Cr,Cd,Zn,Cu,and Ni in the soil samples from the nearby manufacturing spots,the river-course sediments and the synthetic land soils by choosing the normal components of the composite agents including soluble phosphate,calcium montmorillonite clay,and the fly-ash Portland cement.We have also added inorganic reductants including ferrous sulfate and calcium sulfide,and a thiol-based organic complexant,to the composite agents as adjuvants in case they are needed.The remediation process we have adopted included the pretreatment of soil samples,the addition of the composite agents with blending,and the incubation.Effective remediation of the soil samples were obtained,and the leaching concentrations of the heavy metal contaminants from the soil samples,too,in accordance with the Chinese national standard GB 18598—2001,can also be expected to achieve proper dosage of the composite agents(normal components,and/or inorganic adjuvants),so as to reduce the rate of the normal components content,inorganic adjuvants content,and organic adjuvants content to less than 15%,5%,and 2% of their original soil weight,respectively.The normal components of the composite agents were found to be effective in immobilizing the contaminants of Pb,Cd,Zn,Cu,and Ni,for in this case,phosphate tends to play a key function in precipitating Pb,whereas clay and cement are vital for adsorbing and enveloping the aforementioned heavy metal residuals.What is more,the inorganic adjuvants may play their roles in the reduction and complexation of Cr and in the sulfidation of Hg.Therefore,we have made a proposal to remediate for the pollution with multiple heavy-metal composite agents,to relieve the characteristic curves of the leaching concentrations as the function of dosage,which tends to be instructive for optimizing the dosage and exploring the immobilization mechanism.Hence,it can be inferred from the slopes of the curves that Pb can be more effectively stabilized by the composite agents than can Cu.The similar curve forms for Cd and Zn may still imply that they are likely to give similar response to the process of immobilization.
引文
[1]Ministry of Environmental Protection of the People's Republic of China(中华人民共和国环境保护部),Ministry of Land and Resources of the People's Republic of China(中华人民共和国国土资源部).Report on the national general survey of soil contamination(全国土壤污染状况调查公报)[R].[2015-07-04].http://www.zhb.gov.cn/gkml/hbb/qt/201404/W020140417558995804588.pdf.
[2]HUANG Yizong(黄益宗),HAO Xiaowei(郝晓伟),LEI Ming(雷鸣),et al.The remediation technology and remediation practice of heavy metals-contaminated soil[J].Journal of Agro-Environment Science(农业环境科学学报),2013,32(3):409-417.
[3]XU Lulu(徐露露),MA Youhua(马友华),MA Tiezheng(马铁铮),et al.Passivating agents on remediation of heavy metal pollution in soils[J].Journal of Agricultural Resources and Environment(农业资源与环境学报),2013,30(6):25-29.
[4]ZHAO Shuhua(赵述华),CHEN Zhiliang(陈志良),ZHANG Taiping(张太平),et al.Advances in solidification/stabilization technology treatment of heavy metals in contaminated soils[J].Chinese Journal of Soil Science(土壤通报),2013,44(6):1531-1536.
[5]CAO Xinde(曹心德),WEI Xiaoxin(魏晓欣),DAI Gelian(代革联),et al.Combined pollution of multiple heavy metals and their chemical immobilization in contaminated soils:a review[J].Chinese Journal of Environmental Engineering(环境工程学报),2011,5(7):1441-1453.
[6]U.S.Environmental Protection Agency.Technology performance review:selecting and using solidification/stabilization treatment for site remediation,EPA/600/R-09/148[R].Cincinnati:U.S.Environmental Protection Agency,2009.
[7]LIANG Yuan(梁媛),WANG Xiaochun(王晓春),CAO Xinde(曹心德).Immobilization of heavy metals in contaminated soils with phosphate-,carbonate-,and silicate-based amendments:a review[J].Environmental Chemistry(环境化学),2012,31(1):16-25.
[8]HU Xingming(胡星明),YUAN Xinsong(袁新松).In-situ remediation of mine tailing soil contaminated by heavy metals in Tongling City[J].Resources and Environment in the Yangtze Basin(长江流域资源与环境),2011,20(11):1378-1382.
[9]SERRANO S,VLASSOPOULOS D,BESSINGER B,et al.Immobilization of Hg(II)by coprecipitation in sulfate-cement systems[J].Environmental Science&Technology,2012,46(12):6767-6775.
[10]ZHANG Lijie(张丽洁),ZHANG Yu(张瑜),LIU Dehui(刘德辉).Remediation of soils contaminated by heavy metals with different amelioration materials[J].Soils(土壤),2009,41(3):420-424.
[11]WANG Changwei(王长伟),XU Yingming(徐应明),WANG Lin(王林),et al.Amendment effects of cadmium and lead to the co-contaminated soils through sepiolite and phosphate[J].Journal of Safety and Environment(安全与环境学报),2010,10(4):42-45.
[12]RUBY M V,SCHOOF R,BRATTIN W,et al.Advances in evaluating the oral bioavailability of inorganics in soil for use in human health risk assessment[J].Environmental Science&Technology,1999,33(21):3697-3705.
[13]WANG L,PUTNIS C V,RUIZ-AGUDO E,et al.Coupled dissolution and precipitation at the cerussite-phosphate solution interface:implications for immobilization of lead in soils[J].Environmental Science&Technology,2013,47(23):13502-13510.
[14]DU Y J,WEI M L,REDDY K R,et al.New phosphate-based binder for stabilization of soils contaminated with heavy metals:leaching,strength and microstructure characterization[J].Journal of Environmental Management,2014,146:179-188.
[15]MATZAPETAKIS M,GHOSH D,WENG T C,et al.Peptidic models for the binding of Pb(II),Bi(III)and Cd(II)to mononuclear thiolate binding sites[J].Journal of Biological Inorganic Chemistry,2006,11(7):876-890.
[16]ZHANG Haijun(张海军),YU Ying(于颖),NI Yuwen(倪余文),et al.Stabilization of heavy metals in municipal solid waste incineration fly ash with the thiol collectors[J].Environmental Science(环境科学),2007,28(8):1899-1904.
[17]DE PABLO L,CHVEZ M L,ABATAL M.Adsorption of heavy metals in acid to alkaline environments by montmorillonite and Camontmorillonite[J].Chemical Engineering Journal,2011,171(3):1276-1286.
[18]LI L,SCHECKEL K G,ZHENG L.Immobilization of lead in soil influenced by soluble phosphate and calcium:lead speciation evidence[J].Journal of Environmental Quality,2014,43(2):468-474.
[19]SERRANO S,VLASSOPOULOS D,BESSINGER B,et al.Immobilization of Hg(II)by coprecipitation in sulfate-cement systems[J].Environmental Science&Technology,2012,46(12):6767-6775.
[20]ZHANG X Y,WANG Q C,ZHANG S Q,et al.Stabilization/solidification(S/S)of mercury-contaminated hazardous wastes using thiol-functionalized zeolite and Portland cement[J].Journal of Hazardous Materials,2009,168(2/3):1575-1580.
[21]PIAO H,BISHOP P L.Stabilization of mercury-containing wastes using sulfide[J].Environmental Pollution,2006,139(3):498-506.
[22]PAPASSIOPI N,VAXEVANIDOU K,CHRISTOU C,et al.Synthesis,characterization and stability of Cr(III)and Fe(III)hydroxides[J].Journal of Hazadous Materials,2014,264:490-497.
[23]SZULCZEWSKI M D,HELMKE P A,BLEAM W F.XANES spectroscopy studies of Cr(VI)reduction by thiols in organosulfur compounds and humic substances[J].Environmental Science&Technology,2001,35(6):1134-1141.
[24]MIGNARDI S,CORAMI A,FERRINI V.Evaluation of the effectiveness of phosphate treatment for the remediation of mine waste soils contaminated with Cd,Cu,Pb,and Zn[J].Chemosphere,2012,86(4):354-360.
[25]HALE B,EVANS L,LAMBERT R.Effects of cement or lime on Cd,Co,Cu,Ni,Pb,Sb and Zn mobility in field-contaminated and aged soils[J].Journal of Hazardous Materials,2012,199/200:119-127.
[26]GREENWOOD N N,EARNSHAW A.Chemistry of the elements[M].2nd ed.Oxford:Butterworth-Heinemann,1997.
[27]SELIM H M.Competitive sorption and transport of heavy metals in soils and geological media[M].Boca Raton:Taylor&Francis Group,2012.
[28]ZHU J,COZZOLINO V,PIGNA M,et al.Sorption of Cu,Pb and Cr on Na-montmorillonite:competition and effect of major elements[J].Chemosphere,2011,84(4):484-489.
[29]GARCA-SNCHEZ A,ALASTUEY A,QUEROL X.Heavy metal adsorption by different minerals:application to the remediation of polluted soils[J].Science of the Total Environment,1999,242(1/2/3):179-188.
[2]HUANG Yizong(黄益宗),HAO Xiaowei(郝晓伟),LEI Ming(雷鸣),et al.The remediation technology and remediation practice of heavy metals-contaminated soil[J].Journal of Agro-Environment Science(农业环境科学学报),2013,32(3):409-417.
[3]XU Lulu(徐露露),MA Youhua(马友华),MA Tiezheng(马铁铮),et al.Passivating agents on remediation of heavy metal pollution in soils[J].Journal of Agricultural Resources and Environment(农业资源与环境学报),2013,30(6):25-29.
[4]ZHAO Shuhua(赵述华),CHEN Zhiliang(陈志良),ZHANG Taiping(张太平),et al.Advances in solidification/stabilization technology treatment of heavy metals in contaminated soils[J].Chinese Journal of Soil Science(土壤通报),2013,44(6):1531-1536.
[5]CAO Xinde(曹心德),WEI Xiaoxin(魏晓欣),DAI Gelian(代革联),et al.Combined pollution of multiple heavy metals and their chemical immobilization in contaminated soils:a review[J].Chinese Journal of Environmental Engineering(环境工程学报),2011,5(7):1441-1453.
[6]U.S.Environmental Protection Agency.Technology performance review:selecting and using solidification/stabilization treatment for site remediation,EPA/600/R-09/148[R].Cincinnati:U.S.Environmental Protection Agency,2009.
[7]LIANG Yuan(梁媛),WANG Xiaochun(王晓春),CAO Xinde(曹心德).Immobilization of heavy metals in contaminated soils with phosphate-,carbonate-,and silicate-based amendments:a review[J].Environmental Chemistry(环境化学),2012,31(1):16-25.
[8]HU Xingming(胡星明),YUAN Xinsong(袁新松).In-situ remediation of mine tailing soil contaminated by heavy metals in Tongling City[J].Resources and Environment in the Yangtze Basin(长江流域资源与环境),2011,20(11):1378-1382.
[9]SERRANO S,VLASSOPOULOS D,BESSINGER B,et al.Immobilization of Hg(II)by coprecipitation in sulfate-cement systems[J].Environmental Science&Technology,2012,46(12):6767-6775.
[10]ZHANG Lijie(张丽洁),ZHANG Yu(张瑜),LIU Dehui(刘德辉).Remediation of soils contaminated by heavy metals with different amelioration materials[J].Soils(土壤),2009,41(3):420-424.
[11]WANG Changwei(王长伟),XU Yingming(徐应明),WANG Lin(王林),et al.Amendment effects of cadmium and lead to the co-contaminated soils through sepiolite and phosphate[J].Journal of Safety and Environment(安全与环境学报),2010,10(4):42-45.
[12]RUBY M V,SCHOOF R,BRATTIN W,et al.Advances in evaluating the oral bioavailability of inorganics in soil for use in human health risk assessment[J].Environmental Science&Technology,1999,33(21):3697-3705.
[13]WANG L,PUTNIS C V,RUIZ-AGUDO E,et al.Coupled dissolution and precipitation at the cerussite-phosphate solution interface:implications for immobilization of lead in soils[J].Environmental Science&Technology,2013,47(23):13502-13510.
[14]DU Y J,WEI M L,REDDY K R,et al.New phosphate-based binder for stabilization of soils contaminated with heavy metals:leaching,strength and microstructure characterization[J].Journal of Environmental Management,2014,146:179-188.
[15]MATZAPETAKIS M,GHOSH D,WENG T C,et al.Peptidic models for the binding of Pb(II),Bi(III)and Cd(II)to mononuclear thiolate binding sites[J].Journal of Biological Inorganic Chemistry,2006,11(7):876-890.
[16]ZHANG Haijun(张海军),YU Ying(于颖),NI Yuwen(倪余文),et al.Stabilization of heavy metals in municipal solid waste incineration fly ash with the thiol collectors[J].Environmental Science(环境科学),2007,28(8):1899-1904.
[17]DE PABLO L,CHVEZ M L,ABATAL M.Adsorption of heavy metals in acid to alkaline environments by montmorillonite and Camontmorillonite[J].Chemical Engineering Journal,2011,171(3):1276-1286.
[18]LI L,SCHECKEL K G,ZHENG L.Immobilization of lead in soil influenced by soluble phosphate and calcium:lead speciation evidence[J].Journal of Environmental Quality,2014,43(2):468-474.
[19]SERRANO S,VLASSOPOULOS D,BESSINGER B,et al.Immobilization of Hg(II)by coprecipitation in sulfate-cement systems[J].Environmental Science&Technology,2012,46(12):6767-6775.
[20]ZHANG X Y,WANG Q C,ZHANG S Q,et al.Stabilization/solidification(S/S)of mercury-contaminated hazardous wastes using thiol-functionalized zeolite and Portland cement[J].Journal of Hazardous Materials,2009,168(2/3):1575-1580.
[21]PIAO H,BISHOP P L.Stabilization of mercury-containing wastes using sulfide[J].Environmental Pollution,2006,139(3):498-506.
[22]PAPASSIOPI N,VAXEVANIDOU K,CHRISTOU C,et al.Synthesis,characterization and stability of Cr(III)and Fe(III)hydroxides[J].Journal of Hazadous Materials,2014,264:490-497.
[23]SZULCZEWSKI M D,HELMKE P A,BLEAM W F.XANES spectroscopy studies of Cr(VI)reduction by thiols in organosulfur compounds and humic substances[J].Environmental Science&Technology,2001,35(6):1134-1141.
[24]MIGNARDI S,CORAMI A,FERRINI V.Evaluation of the effectiveness of phosphate treatment for the remediation of mine waste soils contaminated with Cd,Cu,Pb,and Zn[J].Chemosphere,2012,86(4):354-360.
[25]HALE B,EVANS L,LAMBERT R.Effects of cement or lime on Cd,Co,Cu,Ni,Pb,Sb and Zn mobility in field-contaminated and aged soils[J].Journal of Hazardous Materials,2012,199/200:119-127.
[26]GREENWOOD N N,EARNSHAW A.Chemistry of the elements[M].2nd ed.Oxford:Butterworth-Heinemann,1997.
[27]SELIM H M.Competitive sorption and transport of heavy metals in soils and geological media[M].Boca Raton:Taylor&Francis Group,2012.
[28]ZHU J,COZZOLINO V,PIGNA M,et al.Sorption of Cu,Pb and Cr on Na-montmorillonite:competition and effect of major elements[J].Chemosphere,2011,84(4):484-489.
[29]GARCA-SNCHEZ A,ALASTUEY A,QUEROL X.Heavy metal adsorption by different minerals:application to the remediation of polluted soils[J].Science of the Total Environment,1999,242(1/2/3):179-188.
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