我国西北黄土对阿特拉津的吸附行为及影响因素
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摘要
为了探讨ATZ(阿特拉津)在黄土中的吸附/解吸行为及主要影响因素,以我国西北黄土为供试土样,采用批量试验法研究了黄土对ATZ的吸附动力学和热力学行为特征.结果表明:黄土对ATZ的吸附动力学过程更符合准二级动力学模型,吸附热力学过程更符合线性分配的Henry吸附模型(R2>0.90),吸附过程中ΔGθ(吉布斯自由能)及ΔHθ(焓变)均小于0、ΔSθ(熵变)大于0,25~45℃温度范围内E(吸附平均自由能)为0.86~1.30 k J/mol,表明黄土对ATZ的吸附过程以物理吸附为主,属于自发放热过程且导致吸附体系混乱度增加.黄土对ATZ的吸附影响因素分析结果显示,随着系统温度的升高,ATZ在黄土中的饱和吸附量下降;pH在2~10范围内变化时,ATZ在黄土中的饱和吸附量随pH的增加呈明显降低趋势;初始ρ(ATZ)从2.5 mg/L增至10.0 mg/L时,黄土对ATZ的饱和吸附量也相应地从0.082 5 mg/g增至0.621 0 mg/g.结果显示,ATZ在黄土中的吸附速率受内部扩散、表面吸附和液膜扩散的共同影响,并且吸附过程主要受到土壤有机质疏水性分配作用的影响.
Batch experiments were performed to understand the sorption kinetics and thermodynamics of atrazine( ATZ) onto loess soil.Meanwhile,the effects of the systemic temperature,pH value and the initial concentration of ATZ were also investigated for the adsorption of ATZ onto loess soil. The results indicate that the adsorption kinetic of ATZ onto loess soil could be better described by the pseudosecond-order model,and the boundary layer control and intraparticle diffusion were both involved in the adsorption kinetic process. The adsorption thermodynamics of ATZ onto loess soil were linear,and were fitted well with the Henry model( R2> 0. 90). Thermodynamic parameter analysis showed that Gibbs free energy( ΔGθ) and Entropy( ΔHθ) were less than zero,while Enthalpy( ΔSθ) was greater than zero,which tended to prove the spontaneous nature of the adsorption process,the endothermic nature of the adsorption and the increased randomness at the solid-solution interface due to the adsorption of ATZ. The average adsorption free energy E was between 0. 86-1. 30 k J/mol when the temperature increased from 25 to 45 ℃. This indicated that adsorption was dominated by physical adsorption. The adsorption capacity of ATZ tended to decrease with the increase of pH value between 2 and 10. When the initial concentration of ATZ increased from 2. 5 to 10. 0 mg/L,the adsorption capacity of ATZ increased from 0. 0825 to 0. 6210 mg/g. The results indicate that the adsorption rate of ATZ onto loess involved a surface adsorption,diffusion within the particles and external film diffusion mechanism. The adsorption processes of ATZ onto loess were mainly affected by the hydrophobic effect of soil organic distribution.
Batch experiments were performed to understand the sorption kinetics and thermodynamics of atrazine( ATZ) onto loess soil.Meanwhile,the effects of the systemic temperature,pH value and the initial concentration of ATZ were also investigated for the adsorption of ATZ onto loess soil. The results indicate that the adsorption kinetic of ATZ onto loess soil could be better described by the pseudosecond-order model,and the boundary layer control and intraparticle diffusion were both involved in the adsorption kinetic process. The adsorption thermodynamics of ATZ onto loess soil were linear,and were fitted well with the Henry model( R2> 0. 90). Thermodynamic parameter analysis showed that Gibbs free energy( ΔGθ) and Entropy( ΔHθ) were less than zero,while Enthalpy( ΔSθ) was greater than zero,which tended to prove the spontaneous nature of the adsorption process,the endothermic nature of the adsorption and the increased randomness at the solid-solution interface due to the adsorption of ATZ. The average adsorption free energy E was between 0. 86-1. 30 k J/mol when the temperature increased from 25 to 45 ℃. This indicated that adsorption was dominated by physical adsorption. The adsorption capacity of ATZ tended to decrease with the increase of pH value between 2 and 10. When the initial concentration of ATZ increased from 2. 5 to 10. 0 mg/L,the adsorption capacity of ATZ increased from 0. 0825 to 0. 6210 mg/g. The results indicate that the adsorption rate of ATZ onto loess involved a surface adsorption,diffusion within the particles and external film diffusion mechanism. The adsorption processes of ATZ onto loess were mainly affected by the hydrophobic effect of soil organic distribution.
引文
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[12]张丹蓉,管仪庆.批实验中土壤对阿特拉津的吸附差异性研究[J].河海大学学报(自然科学版),2004,32(5):492-495.ZHANG Danrong,GUAN Yiqing.Difference of atrazine sorption by soils in batch experiments[J].Journal of Hohai University(Science Edition),2004,32(5):492-495.
[13]ARNAUD B,RICHARD C,MICHEL S.A comparison of five pesticides adsorption and desorption processes in thirteen contrasting field soils[J].Chemosphere,2005,61:668-676.
[14]KODEOVR,KOˇCREK M,KODEV,et al.Pesticide adsorption in relation to soil properties and soil type distribution in regional scale[J].Journal of Hazardous Materials,2011,186(1):540-550.
[15]DIVINCENZO J P,SPARKS D L.Slow sorption kinetics of pentachlorophenol on soil:concentration effects[J].Environmental Science&Technology,1997,31:977-983.
[16]HO Y S,MCKAY G.Sorption of dye from aqueous solution by peat[J].Chemical Engineering Journal,1998,70:115-124.
[17]HO Y S,MCKAY G.The kinetics of sorption of basic dyes from aqueous solution by sphagnum moss peat[J].Canadian Journal of Chemical Engineering,1998,76:822-827.
[18]HO Y S,MCKAY G.Kinetic models for the sorption of dye from aqueous solution by wood[J].Journal of Environmental Science and Health Part B:Process Safety and Environmental Protection,1998,76(2):183-191.
[19]WEBER W J,MORRISS J C.Kinetics of adsorption on carbon from solution[J].Journal of Sanitary Engineering Division:American Society of Civil Engineering,1963,89:31-60.
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[21]FREUNLICH H.Uber die adsorption in losungen(adsorption in solution)[J].Physical Chemistry Periodical,1906,57:384-470.
[22]DUBININ M M,ZAVERINA E D,RADUSHKEVICH L V.Sorption and structure of active carbons.Ⅰ:adsorption of organic vapors[J].Russian Journal of Bioorganic Chemistry,1947,21:1351-1362.
[23]JIANG Y F,SUN H,YVES U J,et al.Impact of biochar produced from post-harvest residue on the adsorption behavior of diesel oil on loess soil[J].Environmental Geochemistry and Health,2016,38(1):243-253.
[24]XING B,PIGNATELLO J J.Time-dependent isotherm shape of organic compounds in soil organic matter:implications for sorption mechanism[J].Environmental Toxicology and Chemistry,1996,15(8):1282-1288.
[25]邓建才,蒋新,胡维平,等.吸附反应时间对除草剂阿特拉津吸附行为的影响[J].生态环境,2007,16(2):402-406.DENG Jiancai,JIANG Xin,HU Weiping,et al.Effect of sorption reaction time on behavior of herbicide atrazine[J].Ecology and Environment,2007,16(2):402-406.
[26]KARAPANAGIOTI H K,KLEINEIDAM S,SABATINI D A,et al.Impacts of heterogeneous organic matter on phenanthrene sorption:equilibrium and kinetic studies with aquifer material[J].Environmental Science&Technology,2000,34(3):406-414.
[27]NASSAR M M.Intraparticle diffusion of basic red and basic yellow dyes on palm fruit bunch[J].Water Science&Technology,1999,40(7):133-139.
[28]CHANG M Y,JUANG R S.Adsorption of tannic acid,humic acid,and dyes from water using the composite of chitosan and activated clay[J].Journal of Colloid and Interface Science,2004,278(1):18-25.
[29]王连生.有机污染化学[M].北京:高等教育出版社,2004.
[30]KIRAN I,AKAR T,OZCAN A S,et al.Biosorption kinetics and isotherm studies of Acid Red 57 by dried Cephalosporium aphidicola cells from aqueous solutions[J].Biochemical Engineering Journal,2006,31:197-203.
[31]王树伦,蒋煜峰,周敏,等.汽油在西北黄土上吸附特性的研究[J].环境科学学报,2013,33(6):1642-1647.WANG Shulun,JIANG Yufeng,ZHOU Min,et al.Adsorption characteristics of gasoline on loess soil[J].Acta Scientiae Circumstantiae,2013,33(6):1642-1647.
[32]CABRERA A,COX L,SPOKAS K,et al.Influence of biochar amendments on the sorption-desorption of aminocyclopyrachlor,bentazone and pyraclostrobin pesticides to an agricultural soil[J].Science of the Total Environment,2014,470/471:438-443.
[2]张涛,徐冰冰,吴丰昌.腐殖酸对苯并三唑的吸附动力学及热力学研究[J].环境科学研究,2014,27(5):540-546.ZHANG Tao,XU Bingbing,WU Fengchang.Kinetics and thermodynamics of benzotriazole adsorption on humic acids[J].Research of Environmental Sciences,2014,27(5):540-546.
[3]高敏苓,宋文华,依艳丽.棕壤不同粒径组分对阿特拉津吸附-解吸作用的影响[J].南开大学学报(自然科学版),2009,42(6):92-98.GAO Minling,SONG Wenhua,YI Yanli.Effect of different particlesize separates of brown soil on the sorption and desorption of atrazine[J].Acta Scientiarum Naturalium Universitatis Nankaiensis(Science Edition),2009,42(6):92-98.
[4]司友斌,孟雪梅.除草剂阿特拉津的环境行为及其生态修复研究进展[J].安徽农业大学学报,2007,34(3):451-455.SI Youbin,MENG Xuemei.Advance in environmental fate and ecological remediation of the herbicide atrazine[J].Journal of Anhui Agricultural University,2007,34(3):451-455.
[5]弓爱军,叶常明.除草剂阿特拉津(Atrazine)的环境行为综述[J].环境科学进展,1997,5(2):38-45.GONG Aijun,YE Changming.Behavior of herbicide atrazine in environment[J].Advances of Environmental Science,1997,5(2):38-45.
[6]BUSTER H R.Atrazine and other s-trazine herbicides in lakes and rains in Switzerland[J].Environmental Science&Technology,1990,24:1049-1058.
[7]叶常明,雷志芳,王杏君,等.除草剂阿特拉津的多介质环境行为[J].环境科学,2001,22(2):69-73.YE Changming,LEI Zhifang,WANG Xingjun,et al.Multimedia environmental behaivor of herbicide atrazine[J].Environmental Science,2001,22(2):69-73.
[8]杨炜春,王琪全,刘维平.除草剂阿特拉津在土壤-水环境中的吸附及其机理[J].环境科学,2000,21(4):94-97.YANG Weichun,WANG Qiquan,LIU Weiping.Adsorption of herbicide atrazine on soils[J].Environmental Science,2000,21(4):94-97.
[9]SPARK K M,SWIFT R S.Effect of soil composition and dissolved organic matter on pesticide sorption[J].Science of the Total Environment,2002,298(1/2/3):147-161.
[10]屈梦雄.阿特拉津在东北冻融土壤中的吸附降解行为研究[D].大连:大连理工大学,2014.
[11]GEVAO B,SEMPLE K T,JONES K C.Bound pesticide residues in soils:a review[J].Environmental Pollution,2000,108(1):3-14.
[12]张丹蓉,管仪庆.批实验中土壤对阿特拉津的吸附差异性研究[J].河海大学学报(自然科学版),2004,32(5):492-495.ZHANG Danrong,GUAN Yiqing.Difference of atrazine sorption by soils in batch experiments[J].Journal of Hohai University(Science Edition),2004,32(5):492-495.
[13]ARNAUD B,RICHARD C,MICHEL S.A comparison of five pesticides adsorption and desorption processes in thirteen contrasting field soils[J].Chemosphere,2005,61:668-676.
[14]KODEOVR,KOˇCREK M,KODEV,et al.Pesticide adsorption in relation to soil properties and soil type distribution in regional scale[J].Journal of Hazardous Materials,2011,186(1):540-550.
[15]DIVINCENZO J P,SPARKS D L.Slow sorption kinetics of pentachlorophenol on soil:concentration effects[J].Environmental Science&Technology,1997,31:977-983.
[16]HO Y S,MCKAY G.Sorption of dye from aqueous solution by peat[J].Chemical Engineering Journal,1998,70:115-124.
[17]HO Y S,MCKAY G.The kinetics of sorption of basic dyes from aqueous solution by sphagnum moss peat[J].Canadian Journal of Chemical Engineering,1998,76:822-827.
[18]HO Y S,MCKAY G.Kinetic models for the sorption of dye from aqueous solution by wood[J].Journal of Environmental Science and Health Part B:Process Safety and Environmental Protection,1998,76(2):183-191.
[19]WEBER W J,MORRISS J C.Kinetics of adsorption on carbon from solution[J].Journal of Sanitary Engineering Division:American Society of Civil Engineering,1963,89:31-60.
[20]LANGMUIR I.The adsorption of gases on plane surfaces of glass,mica and platinum[J].Journal of American Chemical Society,1918,40:1361-1403.
[21]FREUNLICH H.Uber die adsorption in losungen(adsorption in solution)[J].Physical Chemistry Periodical,1906,57:384-470.
[22]DUBININ M M,ZAVERINA E D,RADUSHKEVICH L V.Sorption and structure of active carbons.Ⅰ:adsorption of organic vapors[J].Russian Journal of Bioorganic Chemistry,1947,21:1351-1362.
[23]JIANG Y F,SUN H,YVES U J,et al.Impact of biochar produced from post-harvest residue on the adsorption behavior of diesel oil on loess soil[J].Environmental Geochemistry and Health,2016,38(1):243-253.
[24]XING B,PIGNATELLO J J.Time-dependent isotherm shape of organic compounds in soil organic matter:implications for sorption mechanism[J].Environmental Toxicology and Chemistry,1996,15(8):1282-1288.
[25]邓建才,蒋新,胡维平,等.吸附反应时间对除草剂阿特拉津吸附行为的影响[J].生态环境,2007,16(2):402-406.DENG Jiancai,JIANG Xin,HU Weiping,et al.Effect of sorption reaction time on behavior of herbicide atrazine[J].Ecology and Environment,2007,16(2):402-406.
[26]KARAPANAGIOTI H K,KLEINEIDAM S,SABATINI D A,et al.Impacts of heterogeneous organic matter on phenanthrene sorption:equilibrium and kinetic studies with aquifer material[J].Environmental Science&Technology,2000,34(3):406-414.
[27]NASSAR M M.Intraparticle diffusion of basic red and basic yellow dyes on palm fruit bunch[J].Water Science&Technology,1999,40(7):133-139.
[28]CHANG M Y,JUANG R S.Adsorption of tannic acid,humic acid,and dyes from water using the composite of chitosan and activated clay[J].Journal of Colloid and Interface Science,2004,278(1):18-25.
[29]王连生.有机污染化学[M].北京:高等教育出版社,2004.
[30]KIRAN I,AKAR T,OZCAN A S,et al.Biosorption kinetics and isotherm studies of Acid Red 57 by dried Cephalosporium aphidicola cells from aqueous solutions[J].Biochemical Engineering Journal,2006,31:197-203.
[31]王树伦,蒋煜峰,周敏,等.汽油在西北黄土上吸附特性的研究[J].环境科学学报,2013,33(6):1642-1647.WANG Shulun,JIANG Yufeng,ZHOU Min,et al.Adsorption characteristics of gasoline on loess soil[J].Acta Scientiae Circumstantiae,2013,33(6):1642-1647.
[32]CABRERA A,COX L,SPOKAS K,et al.Influence of biochar amendments on the sorption-desorption of aminocyclopyrachlor,bentazone and pyraclostrobin pesticides to an agricultural soil[J].Science of the Total Environment,2014,470/471:438-443.