纳米羟基磷灰石对镉的吸附解吸及对镉污染土壤修复研究
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摘要
镉是我国土壤的首位污染元素,镉钝化修复技术是解决当前我国耕地面积减少、镉污染面广问题的有效手段。通过吸附解吸及盆栽试验,研究了纳米羟基磷灰石(nHAP)对镉的固定行为及油菜吸收的影响。结果表明:nHAP对镉的吸附符合二级动力学模型,且促进土壤对Cd~(2+)的吸附,在pH为5.6和7的解吸溶液下,Cd~(2+)的解吸率分别为3.3%和0.3%。同时,nHAP施加可改善土壤性质,促进植物生长。油菜收获后,施加0.2%、0.5%、1%的nHAP处理,油菜株高分别比对照组增加85.5%、99.1%和76.8%,土壤过氧化氢酶活性可分别提高0.86,1.19,1.54倍。添加1%nHAP土壤的pH值提高13.1%,有利于土壤镉向稳定态转换,降低了镉的生物毒性,表明nHAP对镉具有较好的稳定性,在促进植物生长、改善土壤生物质量、降低镉植物毒害方面有较好的应用前景。
Cadmium is the key element in heavy metal contaminated soil,and immobilization technology is a practical solution to the current reduction of arable land and cadmium pollution problem. The adsorption-desorption behavior of Cd on the surface of nHAP and the effect of Cd accumulation in rape were studied by the adsorption-desorption tests and pot experiments. The results showed that adsorption of cadmium by nano hydroxyapatite was in accordance with the pseudo-second-order kinetic model and nHAP could enhance the adsorption of Cd~(2+)in soil. The desorption rate of Cd~(2+)was 3. 3% at pH 5. 6,and 0. 3%at pH 7,respectively. The pot experiments demonstrate that nHAP also effectively increased the plant biomass compared with the control; the treatment of 0. 2%,0. 5%,1%( content) with nHAP in soil was increased by 85. 5%,99. 1% and 76. 8%,compared with the control; moreover,soil catalase activity increased by 0. 86,1. 19,1. 54 times; soil pH value increased by13. 1% with 1% of nHAP after rape harvested,which could promote the conversion of cadmium to more stable state,and reduced the biological toxicity of cadmium in plant and soil. Our work proved that nHAP application could alleviate the detrimental effect of cadmium on plants grown and soil enzyme activities,as well as soil microbial diversity.
Cadmium is the key element in heavy metal contaminated soil,and immobilization technology is a practical solution to the current reduction of arable land and cadmium pollution problem. The adsorption-desorption behavior of Cd on the surface of nHAP and the effect of Cd accumulation in rape were studied by the adsorption-desorption tests and pot experiments. The results showed that adsorption of cadmium by nano hydroxyapatite was in accordance with the pseudo-second-order kinetic model and nHAP could enhance the adsorption of Cd~(2+)in soil. The desorption rate of Cd~(2+)was 3. 3% at pH 5. 6,and 0. 3%at pH 7,respectively. The pot experiments demonstrate that nHAP also effectively increased the plant biomass compared with the control; the treatment of 0. 2%,0. 5%,1%( content) with nHAP in soil was increased by 85. 5%,99. 1% and 76. 8%,compared with the control; moreover,soil catalase activity increased by 0. 86,1. 19,1. 54 times; soil pH value increased by13. 1% with 1% of nHAP after rape harvested,which could promote the conversion of cadmium to more stable state,and reduced the biological toxicity of cadmium in plant and soil. Our work proved that nHAP application could alleviate the detrimental effect of cadmium on plants grown and soil enzyme activities,as well as soil microbial diversity.
引文
[1]钱翌,褚兴飞.纳米羟基磷灰石修复镉铅污染土壤的效果评价[J].环境科学与技术,2011,34(11):176-179.
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[6]Houben D,Evrard L,Sonnet P.Benefical effects of biochar application to contaiminated soils on the bioavailability of Cd,Pb and Zn and the biomass production of papeseed[J].Biomass and Bioenergy,2013,57:196-204.
[7]Akeem A O,Mustafa G.Uptake of Ni2+and rhodamine B by nano-hydroxyapatite/alginate composite beads:Batch and continuous-flow systems[J].Toxicological and Environmental Chemistry,2016,98(2):189-203.
[8]Mobasherpour E,Salahi M,Pazouki.Comparative of the removal of Pb2+,Cd2+and Ni2+by nano crystallite hydroxyapatite from aqueous solutions:Adsorption isotherm study[J].Arabian Journal of Chemistry,2010(5):439-446.
[9]Smiciklas I,Dimovic S,Plecas I,et al.Removal of CO2-from aqueous solutions by hydroxyapatite[J].Water Research,2006,40(12):2267-2274.
[10]崔红标,田超,周静,等.纳米羟基磷灰石对重金属污染土壤Cu/Cd形态分布及土壤酶活性影响[J].农业环境科学学报,2011,30(5):874-880.
[11]Doan H D,Lohi A,Dang V B H,et al.Removal of Zn2+and Ni2+by adsorption in a fixed bed of wheat straw[J].Process Safety and Environment Protection,2008,86(4):259-267.
[12]Wei W,Cui J.Effects of low molecular weight organic acids on the immobilization of aqueous Pb2+using phosphate rockband different crystallized hydroxyapatite[J].Chemosphere,2014,105:14-23.
[13]Smiciklas I,Onjia A,Raicevic S,et al.Factors influencing the removal of divalent cations by hydroxyapatite[J].Journal of Hazard Materials,2008,152(2):876-884.
[14]Fernane F,Mecherri M O,Sharrock P,et al.Sorption of cadmium and copper ions on natural and synthetic hydroxyapatite particles[J].Materials Characterization,2008,59(5):554-559.
[15]Mehrnaz A,Sharifah M,Ismail Y,et al.Immobilization of Pb,Cd,and Zn in a contaminated soil using eggshell and banana stem amendments:Metal leachability and a sequential extraction study[J].Environmental Science and Pollution Research,2015,22(1):223-230.
[16]陈杰华,王玉军,王汉卫,等.基于TCLP法研究纳米羟基磷灰石对污染土壤重金属的固定[J].农业环境科学学报,2009,28(4):645-648.
[17]刘文霞,郭华武,李博,等.铅与丁草胺的交互作用对油麦菜生长和抗氧化酶活性的影响[J].环境科学学报,2011,31(10):2282-2289.
[18]王维,仓龙,俞元春,等.纳米羟基磷灰石对土壤镉化学形态和水稻镉吸收的影响[J].广东农业科学,2014(9):83-87.
[19]Cui H B,Zhou J,Zhao Q G,et al.Fractions of Cu,Cd,and enzyme activities in a contaminated soil as affected by applications of micro-and nanohydroxyapatite[J].Journal of Soils and Sediments,2013,4(13):742-752.
[20]Zhang L D,Fang M.Nanomaterials in pollution trace detection and environmental improvement[J].Nano Today,2010,5(2):128-142.
[21]He M,Shi H,Zhao X Y,et al.Immobilization of Pb and Cd in contaminated soil using nanocrystallite hydroxyapatite[J].Procedia Environmental Sciences,2013(8):657-665.
[2]张亚丽,沈其荣,姜洋.有机肥料对镉污染土壤的改良效应[J].土壤学报,2001,38(2):212-218.
[3]Esawy M,Nasser A E.Heavy metal immobilization in contaminated soils using phosphogypsum and rice straw compost[J].Land Degradation&Development,2015,26(8):819-824.
[4]Sana E,Shafaqat A,Shamaila N,et al.Citric acid assisted phytoremediation of cadmium by Brassicanapus L[J].Ecotoxicology and Environmental Safety,2014,106(2014):164-172.
[5]高瑞丽,朱俊,汤帆,等.水稻秸秆生物炭对镉、铅复合污染土壤中重金属形态转化的短期影响[J].环境科学学报,2016,36(1):251-256.
[6]Houben D,Evrard L,Sonnet P.Benefical effects of biochar application to contaiminated soils on the bioavailability of Cd,Pb and Zn and the biomass production of papeseed[J].Biomass and Bioenergy,2013,57:196-204.
[7]Akeem A O,Mustafa G.Uptake of Ni2+and rhodamine B by nano-hydroxyapatite/alginate composite beads:Batch and continuous-flow systems[J].Toxicological and Environmental Chemistry,2016,98(2):189-203.
[8]Mobasherpour E,Salahi M,Pazouki.Comparative of the removal of Pb2+,Cd2+and Ni2+by nano crystallite hydroxyapatite from aqueous solutions:Adsorption isotherm study[J].Arabian Journal of Chemistry,2010(5):439-446.
[9]Smiciklas I,Dimovic S,Plecas I,et al.Removal of CO2-from aqueous solutions by hydroxyapatite[J].Water Research,2006,40(12):2267-2274.
[10]崔红标,田超,周静,等.纳米羟基磷灰石对重金属污染土壤Cu/Cd形态分布及土壤酶活性影响[J].农业环境科学学报,2011,30(5):874-880.
[11]Doan H D,Lohi A,Dang V B H,et al.Removal of Zn2+and Ni2+by adsorption in a fixed bed of wheat straw[J].Process Safety and Environment Protection,2008,86(4):259-267.
[12]Wei W,Cui J.Effects of low molecular weight organic acids on the immobilization of aqueous Pb2+using phosphate rockband different crystallized hydroxyapatite[J].Chemosphere,2014,105:14-23.
[13]Smiciklas I,Onjia A,Raicevic S,et al.Factors influencing the removal of divalent cations by hydroxyapatite[J].Journal of Hazard Materials,2008,152(2):876-884.
[14]Fernane F,Mecherri M O,Sharrock P,et al.Sorption of cadmium and copper ions on natural and synthetic hydroxyapatite particles[J].Materials Characterization,2008,59(5):554-559.
[15]Mehrnaz A,Sharifah M,Ismail Y,et al.Immobilization of Pb,Cd,and Zn in a contaminated soil using eggshell and banana stem amendments:Metal leachability and a sequential extraction study[J].Environmental Science and Pollution Research,2015,22(1):223-230.
[16]陈杰华,王玉军,王汉卫,等.基于TCLP法研究纳米羟基磷灰石对污染土壤重金属的固定[J].农业环境科学学报,2009,28(4):645-648.
[17]刘文霞,郭华武,李博,等.铅与丁草胺的交互作用对油麦菜生长和抗氧化酶活性的影响[J].环境科学学报,2011,31(10):2282-2289.
[18]王维,仓龙,俞元春,等.纳米羟基磷灰石对土壤镉化学形态和水稻镉吸收的影响[J].广东农业科学,2014(9):83-87.
[19]Cui H B,Zhou J,Zhao Q G,et al.Fractions of Cu,Cd,and enzyme activities in a contaminated soil as affected by applications of micro-and nanohydroxyapatite[J].Journal of Soils and Sediments,2013,4(13):742-752.
[20]Zhang L D,Fang M.Nanomaterials in pollution trace detection and environmental improvement[J].Nano Today,2010,5(2):128-142.
[21]He M,Shi H,Zhao X Y,et al.Immobilization of Pb and Cd in contaminated soil using nanocrystallite hydroxyapatite[J].Procedia Environmental Sciences,2013(8):657-665.