3,5,6-三氯-2-吡啶醇在紫色土中的吸附特征与参数估计
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摘要
通过批量平衡实验和土柱实验获得了3,5,6-三氯-2-吡啶醇(简称TCP)在紫色土土壤中的吸附特征,并应用模型对上述吸附过程进行模拟。其中,吸附动力学参数通过准一阶、准二阶动力学方程、Elovich模型和粒子扩散模型反演;等温吸附参数应用Freundlic、Langmuir和Linear模型反演;土柱实验中的吸附参数基于Thomas与YoonNelson模型反演。结果表明:TCP在紫色土中的吸附动力学过程包含快速的表面物理吸附和慢速的内部化学扩散2个阶段,且粒子扩散模型表现最好。等温吸附过程可以通过Freundlic模型描述(R~2=0.94),获得的吸附容量常数K_f为0.79 mL/g,吸附水平较小说明TCP在紫色土中具有较大的迁移风险。TCP在土柱中达到平衡需要的时间约为1 215 min,土壤对TCP的吸附率为10.65%。Thomas与Yoon-Nelson模型能够较好地模拟TCP在紫色土中的动态吸附曲线(R~2≥0.84),获得的平衡浓度q0为0.008 6 mg/g。
The adsorption parameters of pesticide are one of the most important factors to determine its destination and pollution in the soil and water. However,these parameters varied substantially in different environments even though tested by the same soil samples. 3,5,6-trichloro-2-pyrdionl( TCP) is the main degradation product of pesticide chlorpyrifos and herbicide triclopyr,and it exhibits anti-degradation ability,high water solubility and high migration capability,which would lead to the soil and water pollution easily. This situation might be exacerbated in purple soil distributing regions because of the low organic matter content and large pores with high water conductivity of the soil. In order to provide more accurate data,the adsorption behaviors of TCP in purple soil were explored on the basis of three environments: isothermal adsorption and kinetic adsorption by bath equilibrium experiment,and soil column experiment by breakthrough curves. Then the parameters of these adsorption processes were simulated by their corresponding models. As for kinetic adsorption,the performance of four models was tested,which were pseudo-first-order,pseudo-second-order,Elovich,and intraparticle diffusion model,respectively; isothermal adsorption was fitted by Freundlic,Langmuir and Linear models; and the adsorption in soil column experiment was simulated by Thomas and Yoon-Nelson models. By comparing the performance of these methods,the appropriate models were identified,and the adsorption parameters in different environments were obtained through inversion simulation. The main conclusions were as follows: the kinetic adsorption of TCP in purple soil included two stages: both rapid physical adsorption on the surface and slow chemical diffusion inside,and intraparticle diffusion model performed the best with determination coefficient R~2 of 0. 99,implying the diffusion had important effect on the kinetic adsorption; as for isothermal adsorption,Freundilic model performed the best( with R~2 of 0. 94),and the inversion simulated parameter of K_fwas 0. 79 mL/g,which indicated a high risk of transportation in soil;in the soil column experiment,the equilibrium time was 1 215 min for breakthrough curve of TCP,and the adsorption rate was 10. 65%. The dynamic adsorption curves can be well simulated by Thomas and Yoon-Nelson models( R~2≥0. 84),from which the equilibrium concentration was obtained: q0 equaled to0. 008 6 mg/g. Therefore,this study identified the appropriate model to describe the adsorptions of TCP in purple soil in different environments,and the corresponding parameters were obtained by inversion simulation. These results were able to provide useful references for predicting the destination of TCP in purple soil,as well as other easy transporting pollutants.
The adsorption parameters of pesticide are one of the most important factors to determine its destination and pollution in the soil and water. However,these parameters varied substantially in different environments even though tested by the same soil samples. 3,5,6-trichloro-2-pyrdionl( TCP) is the main degradation product of pesticide chlorpyrifos and herbicide triclopyr,and it exhibits anti-degradation ability,high water solubility and high migration capability,which would lead to the soil and water pollution easily. This situation might be exacerbated in purple soil distributing regions because of the low organic matter content and large pores with high water conductivity of the soil. In order to provide more accurate data,the adsorption behaviors of TCP in purple soil were explored on the basis of three environments: isothermal adsorption and kinetic adsorption by bath equilibrium experiment,and soil column experiment by breakthrough curves. Then the parameters of these adsorption processes were simulated by their corresponding models. As for kinetic adsorption,the performance of four models was tested,which were pseudo-first-order,pseudo-second-order,Elovich,and intraparticle diffusion model,respectively; isothermal adsorption was fitted by Freundlic,Langmuir and Linear models; and the adsorption in soil column experiment was simulated by Thomas and Yoon-Nelson models. By comparing the performance of these methods,the appropriate models were identified,and the adsorption parameters in different environments were obtained through inversion simulation. The main conclusions were as follows: the kinetic adsorption of TCP in purple soil included two stages: both rapid physical adsorption on the surface and slow chemical diffusion inside,and intraparticle diffusion model performed the best with determination coefficient R~2 of 0. 99,implying the diffusion had important effect on the kinetic adsorption; as for isothermal adsorption,Freundilic model performed the best( with R~2 of 0. 94),and the inversion simulated parameter of K_fwas 0. 79 mL/g,which indicated a high risk of transportation in soil;in the soil column experiment,the equilibrium time was 1 215 min for breakthrough curve of TCP,and the adsorption rate was 10. 65%. The dynamic adsorption curves can be well simulated by Thomas and Yoon-Nelson models( R~2≥0. 84),from which the equilibrium concentration was obtained: q0 equaled to0. 008 6 mg/g. Therefore,this study identified the appropriate model to describe the adsorptions of TCP in purple soil in different environments,and the corresponding parameters were obtained by inversion simulation. These results were able to provide useful references for predicting the destination of TCP in purple soil,as well as other easy transporting pollutants.
引文
1 CHAPMAN R,HARRIS C R.Persistence of chlorpyrifos in a mineral and organic soil[J].Environment Science Health,Part B,1980,15(1):39-46.
2 RACKE K D,COATS J R,TITUS K R.Degradation of chlorpyrifos and its hydrolysis product 3,5,6-trichloro-2-pyridinol in soil[J].Journal of Environment Science Health,Part B,1988,23(6):527-539.
3 YANG H,WU X,ZHOU L X.Effect of dissolved organic matter on chlorotoluron sorption and desorption in soils[J].Pedosphere,2005,15(4):432-439.
4孙宝利.毒死蜱主要有毒代谢物3,5,6-TCP在土壤中的环境行为研究[D].北京:中国农业科学院,2011.SUN B L.Study on the soil environment behavior of the chlorpyrifos relevant-metabolite 3,5,6-TCP[D].Beijing:Chinese Academy of Agricultural Sciences,2011.(in Chinese)
5 FENG Y.Transformation of 3,5,6-trichloro-2-pyridinol,a metabolite of pyridine e-based pesticides[D].Pennsylvania:The Pennsylvania State University,1995.
6 FENG Y,RACKE K D,BOLLAG J M.Use of immobilized bacteria to treat industrial wastewater containing a chlorinated pyridinol[J].Applied Microbiology and Biotechnology,1997,47(1):73-77.
7 RACKE K D,ROBBINS S T.Factors affecting the degradation of 3,5,6-trichloro-2-pyridinol in soil[M]∥ACS Symposium Series,1991,459:93-107.
8 ARMBRUST K L.Chlorothalonil and chlorpyrifos degradation products in golf course leachate[J].Pest Management Science,2001,57(9):797-802.
9叶振华.化工吸附分离过程[M].北京:中国石油化工出版社,1992.
10钟璐.核桃壳与花生壳对模拟废水中Cr(Ⅵ)的吸附特性研究[D].上海:华东交通大学,2012.ZHONG L.Adsorption experimental study on removing Cr(Ⅵ)from simulated wastewater by walnut and peanut shells[D].Shanghai:East China Jiao Tong University,2012.(in Chinese)
11 NADDAFI K,RASTKARI N,NABIZADEH R.Adsorption of 2,4,6-trichlorophenol from aqueous solutions by a surfactantmodified zeolitic tuff:batch and continuous studies[J].Desalination and Water Treatment,2016,57(13):5789-5799.
12 KHITOUS M,MOUSSOUS S,SELATNIA A,et al.Biosorption of Cd(Ⅱ)by Pleurotus mutilus biomass in fixed-bed column:experimental and breakthrough curves analysis[J].Desalination and Water Treatment,2016,57(35):16559-16570.
13 RANGABHASIYAM S,SUGANYA E,SELVARAJU N.Packed bed column investigation on hexavalent chromium adsorption using activated carbon prepared from Swietenia Mahogani fruit shells[J].Desalination and Water Treatment,2016,57(28):13048-13055.
14 SKODRAS G,DIAMANTOPOULOU I,PANTOLEONTOS G.Kinetic studies of elemental mercury adsorption in activated carbon fixed bed reactor[J].Journal of Hazardous Materials,2008,158(1):1-13.
15李兵,蒋海涛,张立强,等.SO2在活性炭表面的吸附平衡和吸附动力学[J].煤炭学报,2012,37(10):1737-1742.LI B,JIANG H T,ZHANG L Q,et al.Adsorption equilibrium and kinetics of SO2on activated carbon[J].Journal of China Coal Society,2012,37(10):1737-1742.(in Chinese)
16尹艳山,张军,盛昌栋,等.NO在活性炭表面的吸附平衡和动力学研究[J].中国电机工程学报,2010,30(35):49-54.YIN Y S,ZHANG J,SHENG C D,et al.Adsorption equilibrium and kinetics of NO removal on activated carbons[J].Proceedings of the CSEE,2010,30(35):49-54.(in Chinese)
17 OZCAN A S,OZCAN A.Adsorption of acid dyes from aqueous solutions onto acid-activated betonies[J].Journal of Colloid and Interface Science,2004,276(1):39-46.
18 WANG S B,LI H T.Dye adsorption on unburned carbon:kinetics and equilibrium[J].Journal of Hazardous Materials,2005,126(1-3):71-77.
19周强,段钰锋,冒咏秋,等.活性炭汞吸附动力学及吸附机制研究[J].中国电机工程学报,2013,33(29):10-17.ZHOU Q,DUAN Y F,MAO Y Q,et al.Kinetics and mechanism of activated carbon adsorption for mercury removal[J].Proceedings of the CSEE,2013,33(29):10-17.(in Chinese)
20杜衍红,蒋恩臣,李志宇,等.稻壳炭对铵态氮的吸附机理研究[J/OL].农业机械学报,2016,47(2):193-199.http:∥www.j-csam.org/jcsam/ch/reader/view_abstract.aspx?file_no=20160225&flag=1.DOI:10.6041/j.issn.1000-1298.2016.02.025.DU Y H,JIANG E C,LI Z Y,et al.Adsorption mechanism of ammonium nitrogen onto rice husk biochar[J/OL].Transactions of the Chinese Society for Agricultural Machinery,2016,47(2):193-199.(in Chinese)
21摄晓燕,魏孝荣,魏艳春,等.砒砂岩改良风沙土对铵态氮吸附特性影响研究[J/OL].农业机械学报,2015,46(11):165-172.http:∥www.j-csam.org/jcsam/ch/reader/view_abstract.aspx?file_no=20151123&flag=1.DOI:10.6041/j.issn.1000-1298.2015.11.023.SHE X Y,WEI X R,WEI Y C,et al.Effects of soft rock modified sandy soil on NH+4-N adsorption characteristics[J/OL].Transactions of the Chinese Society for Agricultural Machinery,2015,46(11):165-172.(in Chinese)
22李允超,王贤华,隋海清,等.竹炭对生物油模型组分的吸附特性试验[J/OL].农业机械学报,2013,44(11):154-159.http:∥www.j-csam.org/jcsam/ch/reader/view_abstract.aspx?file_no=20131128&flag=1.DOI:10.6041/j.issn.1000-1298.2013.11.028.LI Y C,WANG X H,SUI H Q,et al.Adsorption properties of model component of bio-oil from aqueous solution by bamboo charcoal[J/OL].Transactions of the Chinese Society for Agricultural Machinery,2013,44(11):154-159.(in Chinese)
23 ACHHEAMPONG M A,PAKSHIRAJAN K,ANNACHATRE A P.Removal of Cu(Ⅱ)by biosorption onto coconut shell in fixed-bed column systems[J].Journal of Industrial&Engineering Chemistry,2013,19(3):841-848.
24 THOMAS H G.Chromatography:a problem in kinetics[J].Annals of the New York Academy of Sciences,1948,49:161-182.
25 YOON Y H,NELSON J H.Application of gas adsorption kinetics I.a theoretical model for respirator cartridge service life[J].American Industrial Hygiene Association Journal,1984,45(8):509-516.
26钟祥浩.山地学概论与中国山地研究[M].成都:四川科技出版社,2000.
27 TANG X Y,ZHU B,KATOU H.A review of rapid of pesticides from sloping farmland to surface waters:processes and mitigation strategies[J].Journal of Environmental Sciences-China,2012,24(3):351-361.
28熊建飞.高效液相色谱法、离子色谱法在环境分析和食品分析中的应用研究[D].重庆:西南大学,2013.XIONG J F.Study on high performance liquid chromatography and ion chromatography to environmental analysis and food analysi[D].Chongqing:Southwest University,2013.(in Chinese)
29 HASAN S H,RANJAN D,TALAT M.Agro-industrial waste‘wheat bran’for the biosorptive remediation of selenium through continuous up-flow fixed-bed column[J].Journal of Hazardous Materials,2010,181(1-3):1134-1142.
30 FUTALAN C M,KAN C C,DALIDA M L.Fixed-bed column studies on the removal of copper using chitosan immobilized on bentonite[J].Carbohydrate Polymers,2010,83(1-3):697-704.
31 AHMAD A A,HAMEED B H.Fixed-bed adsorption of reactive azo dye onto granular activated carbon prepared from waste[J].Journal of Hazardous Materials,2010,175(1-3):298-303.
32周尊隆,卢媛,孙红文.菲在不同性质黑炭上的吸附动力学和等温线研究[J].农业环境科学学报,2010,29(3):476-480.ZHOU Z L,LU Y,SUN H W.Sorption kinetics and isotherms of phenanthrene in charcoals with different properties[J].Journa of Agro-Environment Science,2010,29(3):476-480.(in Chinese)
33杨丽华.二氯喹啉酸在几种矿物和土壤中的吸附-解吸及机理研究[D].长沙:湖南农业大学,2014.YANG L H.The adsorption-desorption of quinclorac on some minerals and soils and its mechanism[D].Changsha:Hunan Agricultural University,2014.(in Chinese)
34 ZHANG Z,MOGHADDAM L,O’HARA I M.Congo red adsorption by ball-milled sugarcane bagasse[J].Chemical Engineerin Journal,2011,178:122-128.
2 RACKE K D,COATS J R,TITUS K R.Degradation of chlorpyrifos and its hydrolysis product 3,5,6-trichloro-2-pyridinol in soil[J].Journal of Environment Science Health,Part B,1988,23(6):527-539.
3 YANG H,WU X,ZHOU L X.Effect of dissolved organic matter on chlorotoluron sorption and desorption in soils[J].Pedosphere,2005,15(4):432-439.
4孙宝利.毒死蜱主要有毒代谢物3,5,6-TCP在土壤中的环境行为研究[D].北京:中国农业科学院,2011.SUN B L.Study on the soil environment behavior of the chlorpyrifos relevant-metabolite 3,5,6-TCP[D].Beijing:Chinese Academy of Agricultural Sciences,2011.(in Chinese)
5 FENG Y.Transformation of 3,5,6-trichloro-2-pyridinol,a metabolite of pyridine e-based pesticides[D].Pennsylvania:The Pennsylvania State University,1995.
6 FENG Y,RACKE K D,BOLLAG J M.Use of immobilized bacteria to treat industrial wastewater containing a chlorinated pyridinol[J].Applied Microbiology and Biotechnology,1997,47(1):73-77.
7 RACKE K D,ROBBINS S T.Factors affecting the degradation of 3,5,6-trichloro-2-pyridinol in soil[M]∥ACS Symposium Series,1991,459:93-107.
8 ARMBRUST K L.Chlorothalonil and chlorpyrifos degradation products in golf course leachate[J].Pest Management Science,2001,57(9):797-802.
9叶振华.化工吸附分离过程[M].北京:中国石油化工出版社,1992.
10钟璐.核桃壳与花生壳对模拟废水中Cr(Ⅵ)的吸附特性研究[D].上海:华东交通大学,2012.ZHONG L.Adsorption experimental study on removing Cr(Ⅵ)from simulated wastewater by walnut and peanut shells[D].Shanghai:East China Jiao Tong University,2012.(in Chinese)
11 NADDAFI K,RASTKARI N,NABIZADEH R.Adsorption of 2,4,6-trichlorophenol from aqueous solutions by a surfactantmodified zeolitic tuff:batch and continuous studies[J].Desalination and Water Treatment,2016,57(13):5789-5799.
12 KHITOUS M,MOUSSOUS S,SELATNIA A,et al.Biosorption of Cd(Ⅱ)by Pleurotus mutilus biomass in fixed-bed column:experimental and breakthrough curves analysis[J].Desalination and Water Treatment,2016,57(35):16559-16570.
13 RANGABHASIYAM S,SUGANYA E,SELVARAJU N.Packed bed column investigation on hexavalent chromium adsorption using activated carbon prepared from Swietenia Mahogani fruit shells[J].Desalination and Water Treatment,2016,57(28):13048-13055.
14 SKODRAS G,DIAMANTOPOULOU I,PANTOLEONTOS G.Kinetic studies of elemental mercury adsorption in activated carbon fixed bed reactor[J].Journal of Hazardous Materials,2008,158(1):1-13.
15李兵,蒋海涛,张立强,等.SO2在活性炭表面的吸附平衡和吸附动力学[J].煤炭学报,2012,37(10):1737-1742.LI B,JIANG H T,ZHANG L Q,et al.Adsorption equilibrium and kinetics of SO2on activated carbon[J].Journal of China Coal Society,2012,37(10):1737-1742.(in Chinese)
16尹艳山,张军,盛昌栋,等.NO在活性炭表面的吸附平衡和动力学研究[J].中国电机工程学报,2010,30(35):49-54.YIN Y S,ZHANG J,SHENG C D,et al.Adsorption equilibrium and kinetics of NO removal on activated carbons[J].Proceedings of the CSEE,2010,30(35):49-54.(in Chinese)
17 OZCAN A S,OZCAN A.Adsorption of acid dyes from aqueous solutions onto acid-activated betonies[J].Journal of Colloid and Interface Science,2004,276(1):39-46.
18 WANG S B,LI H T.Dye adsorption on unburned carbon:kinetics and equilibrium[J].Journal of Hazardous Materials,2005,126(1-3):71-77.
19周强,段钰锋,冒咏秋,等.活性炭汞吸附动力学及吸附机制研究[J].中国电机工程学报,2013,33(29):10-17.ZHOU Q,DUAN Y F,MAO Y Q,et al.Kinetics and mechanism of activated carbon adsorption for mercury removal[J].Proceedings of the CSEE,2013,33(29):10-17.(in Chinese)
20杜衍红,蒋恩臣,李志宇,等.稻壳炭对铵态氮的吸附机理研究[J/OL].农业机械学报,2016,47(2):193-199.http:∥www.j-csam.org/jcsam/ch/reader/view_abstract.aspx?file_no=20160225&flag=1.DOI:10.6041/j.issn.1000-1298.2016.02.025.DU Y H,JIANG E C,LI Z Y,et al.Adsorption mechanism of ammonium nitrogen onto rice husk biochar[J/OL].Transactions of the Chinese Society for Agricultural Machinery,2016,47(2):193-199.(in Chinese)
21摄晓燕,魏孝荣,魏艳春,等.砒砂岩改良风沙土对铵态氮吸附特性影响研究[J/OL].农业机械学报,2015,46(11):165-172.http:∥www.j-csam.org/jcsam/ch/reader/view_abstract.aspx?file_no=20151123&flag=1.DOI:10.6041/j.issn.1000-1298.2015.11.023.SHE X Y,WEI X R,WEI Y C,et al.Effects of soft rock modified sandy soil on NH+4-N adsorption characteristics[J/OL].Transactions of the Chinese Society for Agricultural Machinery,2015,46(11):165-172.(in Chinese)
22李允超,王贤华,隋海清,等.竹炭对生物油模型组分的吸附特性试验[J/OL].农业机械学报,2013,44(11):154-159.http:∥www.j-csam.org/jcsam/ch/reader/view_abstract.aspx?file_no=20131128&flag=1.DOI:10.6041/j.issn.1000-1298.2013.11.028.LI Y C,WANG X H,SUI H Q,et al.Adsorption properties of model component of bio-oil from aqueous solution by bamboo charcoal[J/OL].Transactions of the Chinese Society for Agricultural Machinery,2013,44(11):154-159.(in Chinese)
23 ACHHEAMPONG M A,PAKSHIRAJAN K,ANNACHATRE A P.Removal of Cu(Ⅱ)by biosorption onto coconut shell in fixed-bed column systems[J].Journal of Industrial&Engineering Chemistry,2013,19(3):841-848.
24 THOMAS H G.Chromatography:a problem in kinetics[J].Annals of the New York Academy of Sciences,1948,49:161-182.
25 YOON Y H,NELSON J H.Application of gas adsorption kinetics I.a theoretical model for respirator cartridge service life[J].American Industrial Hygiene Association Journal,1984,45(8):509-516.
26钟祥浩.山地学概论与中国山地研究[M].成都:四川科技出版社,2000.
27 TANG X Y,ZHU B,KATOU H.A review of rapid of pesticides from sloping farmland to surface waters:processes and mitigation strategies[J].Journal of Environmental Sciences-China,2012,24(3):351-361.
28熊建飞.高效液相色谱法、离子色谱法在环境分析和食品分析中的应用研究[D].重庆:西南大学,2013.XIONG J F.Study on high performance liquid chromatography and ion chromatography to environmental analysis and food analysi[D].Chongqing:Southwest University,2013.(in Chinese)
29 HASAN S H,RANJAN D,TALAT M.Agro-industrial waste‘wheat bran’for the biosorptive remediation of selenium through continuous up-flow fixed-bed column[J].Journal of Hazardous Materials,2010,181(1-3):1134-1142.
30 FUTALAN C M,KAN C C,DALIDA M L.Fixed-bed column studies on the removal of copper using chitosan immobilized on bentonite[J].Carbohydrate Polymers,2010,83(1-3):697-704.
31 AHMAD A A,HAMEED B H.Fixed-bed adsorption of reactive azo dye onto granular activated carbon prepared from waste[J].Journal of Hazardous Materials,2010,175(1-3):298-303.
32周尊隆,卢媛,孙红文.菲在不同性质黑炭上的吸附动力学和等温线研究[J].农业环境科学学报,2010,29(3):476-480.ZHOU Z L,LU Y,SUN H W.Sorption kinetics and isotherms of phenanthrene in charcoals with different properties[J].Journa of Agro-Environment Science,2010,29(3):476-480.(in Chinese)
33杨丽华.二氯喹啉酸在几种矿物和土壤中的吸附-解吸及机理研究[D].长沙:湖南农业大学,2014.YANG L H.The adsorption-desorption of quinclorac on some minerals and soils and its mechanism[D].Changsha:Hunan Agricultural University,2014.(in Chinese)
34 ZHANG Z,MOGHADDAM L,O’HARA I M.Congo red adsorption by ball-milled sugarcane bagasse[J].Chemical Engineerin Journal,2011,178:122-128.