零价铁粉对水稻土中六价铬的还原作用及其影响因素研究
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摘要
【目的】研究雷州半岛水稻土吸附Cr(Ⅵ)反应特征以及零价铁粉对水稻土中Cr(VI)的还原作用,分析相关因素对上述过程的影响。【方法】通过批处理等温吸附和动力学实验,考察反应物浓度、时间、pH、离子强度和陪伴离子等因素对Cr(Ⅵ)吸附量和还原比例的影响,并用相关反应模型对数据进行拟合分析。【结果】在所研究的0.1～2.0 mmol/L初始浓度范围内,水稻土对Cr(Ⅵ)吸附未达到饱和,吸附等温线可用Langmuir方程拟合(R2=0.9963)。提高pH和离子强度将抑制C(Ⅵ)吸附,且吸附动力学曲线可用假一级反应动力学方程拟合(R2=0.9935)。在所研究的反应条件下(初始溶液pH_4.0、0.20 mmol/L Cr(Ⅵ)、0.01 mmol/L NaCl、5.0 g土+0.25 g零价铁粉、体系总体积250 mL),Cr(Ⅵ)还原比例可达100%。溶液中Cr质量衡算表明,所生成的Cr(Ⅲ)可部分被吸附到固体表面。磷酸根和邻菲罗啉的存在均可降低Cr(Ⅵ)还原比例,提高反应体系pH不利于Cr(VI)还原,其比例可从pH_4.34时的100%下降至pH6.87时的56.3%。【结论】水稻土吸附Cr(Ⅵ)反应机理包含静电吸附,高pH条件所导致的土壤表面对Cr(VI)的静电斥力增加以及背景电解质中阴离子的竞争吸附均可减少水稻土对Cr(Ⅵ)的吸附量;零价铁粉对水稻土中Cr(Ⅵ)的还原比例随pH升高逐渐减少,且磷酸根的存在有抑制作用。
【Objective】The present study aimed to reveal the reaction characteristics of Cr( Ⅵ) adsorbed by paddy soil and examine the reduction effect of Cr( Ⅵ) by zero-valent iron( ZVI,) in the soil, and analyze the effect of relative factors on the above-mentioned process. 【Method】The batch isotherm adsorption and kinetics experiments were performed to investigate the effects of reactant concentration, reacting time, pH, ionic strength and accompanying anions on the adsorption and reduction of Cr( Ⅵ) in the mixed system of paddy soil and ZVI. The experimental data was also analyzed with adsorption and kinetic model.【Result】The adsorption saturation was not obtained with the initial concentrations ranging from 0.1 to 2.0 mmol/L and the adsorption isotherm could be well fitted by Langmuir equation(R2=0.9963). The increase in pH and ionic strength was unfavourable for Cr( Ⅵ) adsorption and the kinetic curve could be properly fitted by pseudo-first-order kinetic equation(R2=0.9935). With the introduction of ZVI, the added Cr( Ⅵ)(0.20 mmol/L) was totallytransformed to Cr( Ⅲ) under the present reaction condition, and the calculation of aqueous Cr mass balance indicated that a certain amount of the generated Cr( Ⅲ) were adsorbed by the solid surface. The presence of phosphate and 1,10-phenanthroline could inhibit the Cr( Ⅵ) reduction. Moreover, Cr(VI) reduction would be suppressed as the solution pH increased, evidenced by the reduction percentage decreased from 100% at pH 4.34 to 56.3% at pH 6.87. 【Conclusion】The electrostatic adsorption was involved in Cr( Ⅵ) adsorption by the paddy soil. The enhancement of electrostatic repulsion between the soil surface and Cr( Ⅵ) and the competitive adsorption between Cr( Ⅵ) and chloride ions contained in the supporting electrolyte could jointly decrease the Cr( Ⅵ) adsorption in the soil. Low pH was favourable for the occurrence of Cr( Ⅵ) reduction by ZVI in the soil, and the reduction would be inhibited in the presence of phosphate and 1,10-phenanthroline.
【Objective】The present study aimed to reveal the reaction characteristics of Cr( Ⅵ) adsorbed by paddy soil and examine the reduction effect of Cr( Ⅵ) by zero-valent iron( ZVI,) in the soil, and analyze the effect of relative factors on the above-mentioned process. 【Method】The batch isotherm adsorption and kinetics experiments were performed to investigate the effects of reactant concentration, reacting time, pH, ionic strength and accompanying anions on the adsorption and reduction of Cr( Ⅵ) in the mixed system of paddy soil and ZVI. The experimental data was also analyzed with adsorption and kinetic model.【Result】The adsorption saturation was not obtained with the initial concentrations ranging from 0.1 to 2.0 mmol/L and the adsorption isotherm could be well fitted by Langmuir equation(R2=0.9963). The increase in pH and ionic strength was unfavourable for Cr( Ⅵ) adsorption and the kinetic curve could be properly fitted by pseudo-first-order kinetic equation(R2=0.9935). With the introduction of ZVI, the added Cr( Ⅵ)(0.20 mmol/L) was totallytransformed to Cr( Ⅲ) under the present reaction condition, and the calculation of aqueous Cr mass balance indicated that a certain amount of the generated Cr( Ⅲ) were adsorbed by the solid surface. The presence of phosphate and 1,10-phenanthroline could inhibit the Cr( Ⅵ) reduction. Moreover, Cr(VI) reduction would be suppressed as the solution pH increased, evidenced by the reduction percentage decreased from 100% at pH 4.34 to 56.3% at pH 6.87. 【Conclusion】The electrostatic adsorption was involved in Cr( Ⅵ) adsorption by the paddy soil. The enhancement of electrostatic repulsion between the soil surface and Cr( Ⅵ) and the competitive adsorption between Cr( Ⅵ) and chloride ions contained in the supporting electrolyte could jointly decrease the Cr( Ⅵ) adsorption in the soil. Low pH was favourable for the occurrence of Cr( Ⅵ) reduction by ZVI in the soil, and the reduction would be inhibited in the presence of phosphate and 1,10-phenanthroline.
引文
[1]刘仕业,岳昌盛,彭犇,邱桂博,郭敏,张梅.铬污染毒性土壤清洁修复研究进展与综合评价[J].工程科学学报,2018,40(11):1275-1287.doi:10.13374/j.issn2095-9389.2018.11.001.LIU S Y,YUE C S,PENG B,QIU G B,GUO M,ZHANG M.Research progress on remediation technologies of chromium-contaminated soil:a review[J].Chinese Journal of Engineering,2018,40(11):1275-1287.doi:10.13374/j.issn2095-9389.2018.11.001.
[2]ERTANI A,MIETTO A,BORIN M,NARDI S.Chromium in agriculture soils and crops:A review[J].Water Air and Soil Pollution,2017,228:190.doi:l10.1007/s11270-017-3356-y.
[3]金晓丹,马华菊,颜增光,张超兰,吴昊,区永杰,杨子杰.典型制革厂周边农田土壤重金属污染特征[J],广西大学学报(自然科学版),2018,43(5):2079-2087.doi:10.13624/j.cnki.issn.1001-7445.2018.2079.JIN X D,MA H J,YAN Z G,ZHANG C L,WU H,OU Y J,YANG Z J.Characteristics of heavy metal pollution on farmland soil surrounding representative tannery[J].Journal of Guangxi University(Natural Science Edition),2018,43(5):2079-2087.doi:10.13624/j.cnki.issn.1001-7445.2018.2079.
[4]CHOPPALA G,BOLAN N,LAMB D,KUNHIKRISHNAN A.Comparative sorption and mobility of Cr(Ⅲ)and Cr(Ⅵ)species in a range of soils:Implication of bioavalability[J].Water Air and Soil Pollution,2013,224:1699.doi:10.1007/s11270-013-1699-6.
[5]DHAL B,THATOI H N,DAS N N,PANDEY B D.Chemical and microbial remediation of hexavalent chromium from contaminated soil and mining/metallurgical solid waster:A review[J].Journal of Hazardous Materials,2013(250-251):272-291.doi:10.1016/j.jhazmat.2013.01.048.
[6]马健伟,任淑鹏,宋亚瑞,王东升,门彬,赵海谦.零价铁技术在废水处理领域的应用研究进展[J].化学通报,2019,82(1):3-11.doi:10.13624/j.cnki.issn.1001-7445.2018.2079.MA J W,REN S P,SONG Y R,WANG D S,MENG B,ZHAO H Q.Advances in the application of zero-valent iron technology in the field of wastewater treatment[J].Bulletin of the Chemical Society of Chinese,2019,82(1):3-11.doi:10.13624/j.cnki.issn.1001-7445.2018.2079.
[7]张永祥,马晓敏.纳米零价铁去除水中六价铬的研究[J].应用化工,2018,47(8):1569-1573.doi:10.16581/j.cnki.issn1671-3206.2018.08.002.ZhaNG Y X,MA X M.Removal of chromium(Ⅵ)from water by modified nano zero-valent iron[J].Applied Chemical Industry,2018,47(8):1569-1573.doi:10.16581/j.cnki.issn1671-3206.2018.08.002.
[8]刘涛,祝方,赵晋宇,任文涛.降雨条件下纳米零价铁镍对污染土壤中六价铬迁移的影响[J].环境化学,2017,36(4):812-820.LIU T,ZHU F,ZHAO J Y,REN W T.Effect of zero valent iron/nickel under rain condition on the transportation of hexavalent chromium in contaminated soil[J].Environmental Chemistry,2017,36(4):812-820.
[9]FI ZA A,SILVA A,CARVALHO G,DE LA FUENTE A V,DELERUE-MATOS C.Heterogeneous kinetics of the reduction of chromium(Ⅵ)by elemental iron[J].Journal of Hazardous Materials,2010,175(1-3):1042-1047.doi:10.1016/j.jhazmat.2009.10.116.
[10]VILARDI G,PALMA L D,VERDONE N.A physical-based interpretation of mechanism and kinetics of Cr(Ⅵ)reduction in aqueous solution by zero-valent iron nanoparticle[J].Chemosphere,2019,220:590-599.doi:10.1016/j.chemosphere.2018.12.175.
[11]樊明德,王睿哲,贾时雨,杨青,贾子豪,邢浩云.蒙脱石负载型零价铁纳米颗粒吸附水体中Cr(Ⅵ)污染物实验研究[J].岩石矿物学杂志,2018,37(5):860-868.FAN M D,WANG R Z,JIA S Y,YANG Q,JIA Z H,XING H Y.Montmorillonite-supported zero-valent iron nanoparticles for remoⅥng Cr(Ⅵ)from aqueous solutions[J].Acta Petrologica et Mineralogica,2018,37(5):860-868.
[12]谢华俊,陈华林,张永普,周江敏,黄卉林,郑乾送,王晶晶.纳米零价铁对水溶液中Cr(Ⅵ)的去除效果[J].环境监测管理与技术,2018,30(5):68-71.doi:10.19501/j.cnki.1006-2009.20180912.015.XIE H J,CHEN H L,ZHANG Y P,ZHOU J M,HUANG H L,ZHENGQ S,WANG J J.Removal efficiency of chromium(Ⅵ)from waste water by nanoscale zero-valent iron(nZVI)[J].Environmental Monitoring Management and Technology,2018,30(5):68-71.doi:10.19501/j.cnki.1006-2009.20180912.015.
[13]CHANG D Y,CHEN T H,LIU H B,XI Y F,QING C S,XIE Q Q,FROST R L.A new approach to prepare ZVI and its application in removal of Cr(Ⅵ)from aqueous solution[J].Chemical Engineering Journal,2014,244:264-272.doi:10.1016/j.cej.2014.01.095.
[14]SPARKS D L,PAGE A L,HELMKE P A,LOPPERT R H,SOITANPOUR P N,TABATABAI M A,JOHNSTON C T,SUMNER ME.Methods of Soil Analysis.Part 3.Chemical Methods[M].Madison:Soil Science Society of America,Inc,1996.
[15]夏瑶,娄运生,杨超光,梁永超.几种水稻土对磷的吸附与解吸特性研究[J].中国农业科学,2002,35(11):1369-1374.XIA Y,LOU Y S,YANG C G,LIANG Y C.Characteristics of phosphate adsorption and desorption in paddy soils[J].Scientia Agricultura Sinica,2002,35(11):1369-1374.
[16]RAMSEY J D,XIA L,KENDIG M W,MCCREERY R L.Raman spectroscopic analysis of the speciation of dilute chromate solutions[J].Corrosion Science,2001,43(8):1557-1572.doi:10.1016/S0010-938X(00)00145-1.
[17]SPOSITO G.The Chemistry of Soils(Second Edition)[M].New York:Oxford University Press,Inc.,2008.
[18]李欣雨,夏建国,姜强,李雪柔.水稻土壤组分去除有机质和游离氧化铁后对吸附解吸特征的影响[J].安全与环境学报,2017,17(4):1483-1490.doi:10.13637/j.issn.1009-6094.2017.04.053.LI X Y,XIA J G,JIANG Q,LI X R.Effects of organic matter and free iron oxide removal from the soil components on As5+adsorptiondesorption in the padd fields[J].Journal of Safety and Environment,2017,17(4):1483-1490.doi:10.13637/j.issn.1009-6094.2017.04.053.
[19]XIE J Y,GU X Y,TONG F,ZHAO Y P,TAN Y Y.Surface complexation modeling of Cr(Ⅵ)adsorption at the goethite-water interface[J].Journal of Colloid and Interface Science,2015,455:55-62.doi:10.1016/j.jcis.2015.05.041.
[20]YIRSAW B D,MEGHARAJ M,CHEN Z L,NAIDU R.Multifunctional kaolinite-supported nanoscale zero-valent iron used for the adsorption and degradation of crystal violet in aqueous solution[J].Journal of Environmental Sciences,2016,44:88-98.doi:10.1016/j.jcis.2013.02.020.
[21]JAMES B R,PETURA J C,ROCK J.Vitale R J,Mussoline G R.Hexavalent chromium extraction from Soils:A comparison of five methods[J].Environmental Science&Technology,1995,29(9):2377-2381.doi:10.1021/es00009a033.
[22]ZHU F,LI L W,MA S Y,SHANG Z F.Effect factors,kinetics and thermodynamics of remediation in the chromium contaminated soils by nanoscale zero valent Fe/Cu bimetallic particles[J].Chemical Engineering Journal,2016,302:663-669.doi:10.1016/j.cej.2016.05.072.
[2]ERTANI A,MIETTO A,BORIN M,NARDI S.Chromium in agriculture soils and crops:A review[J].Water Air and Soil Pollution,2017,228:190.doi:l10.1007/s11270-017-3356-y.
[3]金晓丹,马华菊,颜增光,张超兰,吴昊,区永杰,杨子杰.典型制革厂周边农田土壤重金属污染特征[J],广西大学学报(自然科学版),2018,43(5):2079-2087.doi:10.13624/j.cnki.issn.1001-7445.2018.2079.JIN X D,MA H J,YAN Z G,ZHANG C L,WU H,OU Y J,YANG Z J.Characteristics of heavy metal pollution on farmland soil surrounding representative tannery[J].Journal of Guangxi University(Natural Science Edition),2018,43(5):2079-2087.doi:10.13624/j.cnki.issn.1001-7445.2018.2079.
[4]CHOPPALA G,BOLAN N,LAMB D,KUNHIKRISHNAN A.Comparative sorption and mobility of Cr(Ⅲ)and Cr(Ⅵ)species in a range of soils:Implication of bioavalability[J].Water Air and Soil Pollution,2013,224:1699.doi:10.1007/s11270-013-1699-6.
[5]DHAL B,THATOI H N,DAS N N,PANDEY B D.Chemical and microbial remediation of hexavalent chromium from contaminated soil and mining/metallurgical solid waster:A review[J].Journal of Hazardous Materials,2013(250-251):272-291.doi:10.1016/j.jhazmat.2013.01.048.
[6]马健伟,任淑鹏,宋亚瑞,王东升,门彬,赵海谦.零价铁技术在废水处理领域的应用研究进展[J].化学通报,2019,82(1):3-11.doi:10.13624/j.cnki.issn.1001-7445.2018.2079.MA J W,REN S P,SONG Y R,WANG D S,MENG B,ZHAO H Q.Advances in the application of zero-valent iron technology in the field of wastewater treatment[J].Bulletin of the Chemical Society of Chinese,2019,82(1):3-11.doi:10.13624/j.cnki.issn.1001-7445.2018.2079.
[7]张永祥,马晓敏.纳米零价铁去除水中六价铬的研究[J].应用化工,2018,47(8):1569-1573.doi:10.16581/j.cnki.issn1671-3206.2018.08.002.ZhaNG Y X,MA X M.Removal of chromium(Ⅵ)from water by modified nano zero-valent iron[J].Applied Chemical Industry,2018,47(8):1569-1573.doi:10.16581/j.cnki.issn1671-3206.2018.08.002.
[8]刘涛,祝方,赵晋宇,任文涛.降雨条件下纳米零价铁镍对污染土壤中六价铬迁移的影响[J].环境化学,2017,36(4):812-820.LIU T,ZHU F,ZHAO J Y,REN W T.Effect of zero valent iron/nickel under rain condition on the transportation of hexavalent chromium in contaminated soil[J].Environmental Chemistry,2017,36(4):812-820.
[9]FI ZA A,SILVA A,CARVALHO G,DE LA FUENTE A V,DELERUE-MATOS C.Heterogeneous kinetics of the reduction of chromium(Ⅵ)by elemental iron[J].Journal of Hazardous Materials,2010,175(1-3):1042-1047.doi:10.1016/j.jhazmat.2009.10.116.
[10]VILARDI G,PALMA L D,VERDONE N.A physical-based interpretation of mechanism and kinetics of Cr(Ⅵ)reduction in aqueous solution by zero-valent iron nanoparticle[J].Chemosphere,2019,220:590-599.doi:10.1016/j.chemosphere.2018.12.175.
[11]樊明德,王睿哲,贾时雨,杨青,贾子豪,邢浩云.蒙脱石负载型零价铁纳米颗粒吸附水体中Cr(Ⅵ)污染物实验研究[J].岩石矿物学杂志,2018,37(5):860-868.FAN M D,WANG R Z,JIA S Y,YANG Q,JIA Z H,XING H Y.Montmorillonite-supported zero-valent iron nanoparticles for remoⅥng Cr(Ⅵ)from aqueous solutions[J].Acta Petrologica et Mineralogica,2018,37(5):860-868.
[12]谢华俊,陈华林,张永普,周江敏,黄卉林,郑乾送,王晶晶.纳米零价铁对水溶液中Cr(Ⅵ)的去除效果[J].环境监测管理与技术,2018,30(5):68-71.doi:10.19501/j.cnki.1006-2009.20180912.015.XIE H J,CHEN H L,ZHANG Y P,ZHOU J M,HUANG H L,ZHENGQ S,WANG J J.Removal efficiency of chromium(Ⅵ)from waste water by nanoscale zero-valent iron(nZVI)[J].Environmental Monitoring Management and Technology,2018,30(5):68-71.doi:10.19501/j.cnki.1006-2009.20180912.015.
[13]CHANG D Y,CHEN T H,LIU H B,XI Y F,QING C S,XIE Q Q,FROST R L.A new approach to prepare ZVI and its application in removal of Cr(Ⅵ)from aqueous solution[J].Chemical Engineering Journal,2014,244:264-272.doi:10.1016/j.cej.2014.01.095.
[14]SPARKS D L,PAGE A L,HELMKE P A,LOPPERT R H,SOITANPOUR P N,TABATABAI M A,JOHNSTON C T,SUMNER ME.Methods of Soil Analysis.Part 3.Chemical Methods[M].Madison:Soil Science Society of America,Inc,1996.
[15]夏瑶,娄运生,杨超光,梁永超.几种水稻土对磷的吸附与解吸特性研究[J].中国农业科学,2002,35(11):1369-1374.XIA Y,LOU Y S,YANG C G,LIANG Y C.Characteristics of phosphate adsorption and desorption in paddy soils[J].Scientia Agricultura Sinica,2002,35(11):1369-1374.
[16]RAMSEY J D,XIA L,KENDIG M W,MCCREERY R L.Raman spectroscopic analysis of the speciation of dilute chromate solutions[J].Corrosion Science,2001,43(8):1557-1572.doi:10.1016/S0010-938X(00)00145-1.
[17]SPOSITO G.The Chemistry of Soils(Second Edition)[M].New York:Oxford University Press,Inc.,2008.
[18]李欣雨,夏建国,姜强,李雪柔.水稻土壤组分去除有机质和游离氧化铁后对吸附解吸特征的影响[J].安全与环境学报,2017,17(4):1483-1490.doi:10.13637/j.issn.1009-6094.2017.04.053.LI X Y,XIA J G,JIANG Q,LI X R.Effects of organic matter and free iron oxide removal from the soil components on As5+adsorptiondesorption in the padd fields[J].Journal of Safety and Environment,2017,17(4):1483-1490.doi:10.13637/j.issn.1009-6094.2017.04.053.
[19]XIE J Y,GU X Y,TONG F,ZHAO Y P,TAN Y Y.Surface complexation modeling of Cr(Ⅵ)adsorption at the goethite-water interface[J].Journal of Colloid and Interface Science,2015,455:55-62.doi:10.1016/j.jcis.2015.05.041.
[20]YIRSAW B D,MEGHARAJ M,CHEN Z L,NAIDU R.Multifunctional kaolinite-supported nanoscale zero-valent iron used for the adsorption and degradation of crystal violet in aqueous solution[J].Journal of Environmental Sciences,2016,44:88-98.doi:10.1016/j.jcis.2013.02.020.
[21]JAMES B R,PETURA J C,ROCK J.Vitale R J,Mussoline G R.Hexavalent chromium extraction from Soils:A comparison of five methods[J].Environmental Science&Technology,1995,29(9):2377-2381.doi:10.1021/es00009a033.
[22]ZHU F,LI L W,MA S Y,SHANG Z F.Effect factors,kinetics and thermodynamics of remediation in the chromium contaminated soils by nanoscale zero valent Fe/Cu bimetallic particles[J].Chemical Engineering Journal,2016,302:663-669.doi:10.1016/j.cej.2016.05.072.
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