含铝钝化剂对蔬菜-土壤系统Cd和Pb的钝化效果
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摘要
为了解含铝钝化剂对土壤重金属的钝化效果,采用土培盆栽试验方法,以还原铝粉、硫磺、氢氧化钙为主要原料,按一定质量比例制备成含铝复合重金属钝化剂产品,研究了施用几种含铝重金属钝化剂对蔬菜产量、重金属Cd和Pb含量及其土壤重金属Cd和Pb形态含量的影响,结果表明:在污染土壤常规施用化肥处理(PS+CF)的基础上,添施几种含铝的复合重金属钝化剂处理(PS+CF+Al_1、PS+CF+Al_2、PS+CF+Al_3和PS+CF+Al_4)均可在一定程度上提高蔬菜的生物产量、降低蔬菜重金属Cd和Pb含量,并提高蔬菜收获后土壤pH值、减少土壤有效态Cd和Pb的含量。其中,PS+CF+Al4处理效果相对最佳,可比PS+CF处理提高蔬菜的生物产量32.48%,降低菜体重金属Cd含量71.95%~74.69%、Pb含量63.36%~74.69%,提高土壤pH值28.72%,减少土壤中有效态Cd含量12.50%、Pb含量32.42%;X射线衍射分析结果显示,PS+CF+Al_4处理蔬菜收获后土壤的Cd和Pb主要以Cd_3(PO_4)_2、Pb(PO_2)_2、Pb_2(P_4O_(12))、Pb_3O_2SO_4等几种难溶性化合物形态存在,这进一步佐证了该复合重金属钝化剂的钝化效果。因此,含铝复合重金属钝化剂4(硫磺、还原铝粉和氢氧化钙按质量分数比2∶15∶100均匀混合而成)对蔬菜-土壤系统的Cd、Pb具有明显的钝化效果。
With zero-valent aluminum, sulfur, and calcium hydroxide as the main raw materials, a few heavy metal passivating agents have been made according to a certain weight proportion of these materials. A soil-pot trial was also conducted to investigate the effects of using these heavy metal passivating agents on the vegetable yield, contents of cadmium and plumbum in vegetables, and their available contents in soils. The results of "Pollution soil + chemical fertilizer"(i.e., treatment of "PS +CF") showed that the use of passivating agents would increase the vegetable yield and decrease the contents of Cd and Pb in vegetables, enhance the soil pH, but reduce the available contents of Cd and Pb in soils to a certain extent(i.e., treatment of "PS+CF+Al_1", "PS+CF+Al_2", "PS+CF+Al_3", and "PS+CF+Al_4"). Among them, the effects of the "PS+CF+Al4" treatment were comparatively the best; it could increase the vegetable yield by 32.48%, decrease the contents of Cd and Pb in vegetables by 71.95%~74.69% and 63.36%~74.69%, respectively, and enhance the soil pH by 28.72%, but reduce the available contents of Cd and Pb in soils by 12.50% and 32.42%, respectively. X-ray diffraction analysis showed that Cd and Pb in the "PS+CF+Al_4" soils mainly exist as Cd_3(PO_4)_2, Pb(PO_2)_2, Pb_2(P_4O_(12)), Pb_3O_2SO_4, and other insoluble forms. This is further evidence of the passivation effect of the composite passivation agent. Therefore, heavy metal passivating agents containing zero-valent aluminum(i.e., Al_4)has an obvious passivation effect on Cd and Pb in the vegetable-soil system.
With zero-valent aluminum, sulfur, and calcium hydroxide as the main raw materials, a few heavy metal passivating agents have been made according to a certain weight proportion of these materials. A soil-pot trial was also conducted to investigate the effects of using these heavy metal passivating agents on the vegetable yield, contents of cadmium and plumbum in vegetables, and their available contents in soils. The results of "Pollution soil + chemical fertilizer"(i.e., treatment of "PS +CF") showed that the use of passivating agents would increase the vegetable yield and decrease the contents of Cd and Pb in vegetables, enhance the soil pH, but reduce the available contents of Cd and Pb in soils to a certain extent(i.e., treatment of "PS+CF+Al_1", "PS+CF+Al_2", "PS+CF+Al_3", and "PS+CF+Al_4"). Among them, the effects of the "PS+CF+Al4" treatment were comparatively the best; it could increase the vegetable yield by 32.48%, decrease the contents of Cd and Pb in vegetables by 71.95%~74.69% and 63.36%~74.69%, respectively, and enhance the soil pH by 28.72%, but reduce the available contents of Cd and Pb in soils by 12.50% and 32.42%, respectively. X-ray diffraction analysis showed that Cd and Pb in the "PS+CF+Al_4" soils mainly exist as Cd_3(PO_4)_2, Pb(PO_2)_2, Pb_2(P_4O_(12)), Pb_3O_2SO_4, and other insoluble forms. This is further evidence of the passivation effect of the composite passivation agent. Therefore, heavy metal passivating agents containing zero-valent aluminum(i.e., Al_4)has an obvious passivation effect on Cd and Pb in the vegetable-soil system.
引文
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[13]饶品华,张文启,李永峰,等.氧化铝对水体中重金属离子吸附去除研究[J].水处理技术,2009,35(12):71-74.RAO Pin-hua,ZHANG Wen-qi,LI Yong-feng,et al.Study on simultaneous removal of multiple heavy metals from water by alumina[J].Technology of Water Treatment,2009,35(12):71-74.
[14]罗涛,黄东风,何盈,等.土壤重金属钝化剂的筛选及蔬菜降污专用肥应用效果研究[J].农业环境科学学报,2007,26(4):1390-1395.LUO Tao,HUANG Dong-feng,HE Ying,et al.Heavy metal passivetors screening and the application effect of special fertilizer for reducing heavy metal pollution in vegetable[J].Journal of Agro-Environment Science,2007,26(4):1390-1395.
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[18]Kumpiene J,Lagerkvist A,Maurice C.Stabilization of As,Cr,Cu,Pb and Zn in soil using amendments:A review[J].Waste Management,2008,28:215-225.
[19]Franco D V,Silval L M D,Jardim W F.Reduction of hexavalent chromium in soil and ground water using zero-valent iron under batch and semi-batch conditions[J].Water Air&Soil Pollution,2009,197(1/2/3/4):49-60.
[20]李天然,蒋建国,李德安,等.铁基固体材料对钒矿污染土壤的固化效果研究[J].中国环境科学,2016,36(7):2108-2114.LI Tian-ran,JIANG Jian-guo,LI De-an,et al.Solidifying effect of heavy metals in the vanadium deposit-polluted soil by iron-based solid agents[J].China Environmental Science,2016,36(7):2108-2114.
[21]纪雄辉,梁永超,鲁艳红,等.污染稻田水分管理对水稻吸收积累镉的影响及其作用机理[J].生态学报,2007,27(9):3930-3939.JI Xiong-hui,LIANG Yong-chao,LU Yan-hong,et al.The effect of water management on the mechanism and rate of uptake and accumulation of cadmium by rice growing in polluted paddy soil[J].Acta Ecologica Sinica,2007,27(9):3930-3939.
[22]吴宝麟,杨志辉,柴立元,等.磷基及铁基钝化剂对Pb、Cd、As复合污染土壤的修复效果及其工艺条件优化[J].安全与环境学报,2015,15(5):314-319.WU Bao-Lin,YANG Zhi-hui,CAI Li-yuan,et al.Remediation effects of phosphorus and ferric amendments on the soil complexly contaminated by Pb,Cd and As and the process optimization[J].Journal of Safety and Environment,2015,15(5):314-319.
[23]Kumpiene J,Ore S,Renella G,et al.Assessment of zero-valent iron for stabilization of chromium,copper and arsenic in soil[J].Environmental Pollution,2006,144(1):62-69.
[24]Tomasevic D D,Kozma G,Kerkez D V,et al.Toxic metal immobilization in contaminated sediment using bentonite and kaolinite-supported nano zero-valent iron[J].Journal of Nanoparticle Research,2014,16(8):1-15.
[25]王丹,李鑫,王代长,等.硫素对水稻根系铁锰胶膜形成及吸收镉的影响[J].环境科学,2015,36(5):1877-1887.WANG Dan,LI Xin,WANG Dai-chang,et al.Effect of sulfur on the formation and uptake of Cd in rice roots[J].Environment Science,2015,36(5):1877-1887.
[26]孙丽娟,段德超,彭程,等.硫对土壤重金属形态转化及植物有效性的影响研究进展[J].应用生态学报,2014,25(7):2141-2148.SUN Li-juan,DUAN De-chao,PENG Cheng,et al.Influence of sulfur on the speciation transformation and phyto-availability of heavy metals in soil:A review[J].Chinese Journal of Applied Ecology,2014,25(7):2141-2148.
[27]李东坡,武志杰.化学肥料的土壤生态环境效应[J].应用生态学报,2008,19(5):1158-1165.LI Dong-po,WU Zhi-jie.Impact of chemical fertilizers application on soil ecological environment[J].Chinese Journal of Applied Ecology,2008,19(5):1158-1165.
[2]环境保护部,国土资源部.全国土壤污染状况调查公报[EB/OL].[2014-4-17].http://www.mlr.gov.cn/xwdt/jrxw/201404/t20140417_1312998.htm Ministry of Environmental Protection,Ministry of Land and Resources.National soil pollution survey bulletin[EB/OL].[2014-4-17].http://www.mlr.gov.cn/xwdt/jrxw/201404/t20140417_1312998.htm
[3]马铁铮,马友华,徐露露,等.农田土壤重金属污染的农业生态修复技术[J].农业资源与环境学报,2013,30(5):39-43.MA Tie-zheng,MA You-hua,XU Lu-lu,et al.Agro-ecological remediation technologies on heavy metal contamination in cropland soils[J].Journal of Agricultural Resources and Environment,2013,30(5):39-43.
[4]曾希柏,李莲芳,梅旭荣.中国蔬菜土壤重金属含量及来源分析[J].中国农业科学,2007,40(11):2507-2517.ZENG Xi-bai,LI Lian-fang,MEI Xu-rong.Heavy metal content in soils of vegetable-growing lands in China and source analysis[J].Scientia Agricultura Sinica,2007,40(11):2507-2517.
[5]庞文品,秦樊鑫,吕亚超,等.贵州兴仁煤矿区农田土壤重金属化学形态及风险评估[J].应用生态学报,2016,27(5):1468-1478.PANG Wen-pin,QIN Fan-xin,L譈Ya-chao,et al.Chemical speciations of heavy metals and their risk assessment in agricultural soils in a coal mining area from Xingren County,Guizhou Province,China[J].Chinese Journal of Applied Ecology,2016,27(5):1468-1478.
[6]李剑睿,徐应明,林大松,等.农田重金属污染原位钝化修复研究进展[J].生态环境学报,2014,23(4):721-728.LI Jian-rui,XU Ying-ming,LIN DA-song,et al.In situ immobilization remediation of heavy metals in contaminated soils:A review[J].Ecology and Environmental Sciences,2014,23(4):721-728.
[7]王立群,罗磊,马义兵,等.重金属污染土壤原位钝化修复研究进展[J].应用生态学报,2009,20(5):1214-1222.WANG Li-qun,LUO Lei,MA Yi-bing,et al.In situ immobilization remediation of heavy metals-contaminated soils:A review[J].Chinese Journal of Applied Ecology,2009,20(5):1214-1222.
[8]韩伟江.零价铁和酸洗零价铝处理重金属废水的实验研究[D].广州:广东工业大学,2015.HAN Wei-jiang.Experimental studies of heavy metal wastewater treated by zero valent iron and acid-washed zero-valent aluminum[D].Guangzhou:Guangdong University of Technology,2015.
[9]Lin C J,Wang S L,Huang P M,et al.Chromate reduction by zero-valent Al metal as catalyzed by polyoxometalate[J].Water Research,2009,43:5015-5022
[10]Liu W P,Zhang H H,Cao B P,et al.Oxidative removal of bisphenol A using zero valent aluminum-acid system[J].Water Research,2011,45(4):1872-1878.
[11]Lien H L,Zhang W X.Enhanced dehalogenation of halogenated methanes by bimetallic Cu/Al[J].Chemosphere,2002,49:371-378
[12]孙志勇,成文,方战强.纳米氧化铝吸附溶液中Cr(Ⅵ)的研究[J].华南师范大学学报(自然科学版),2014,46(2):79-85.SUN Zhi-yong,CHENG Wen,FANG Zhan-qiang.Adsorption of hexavalent chromium by nano-alumina particle[J].Journal of South China China Normal University(Natural Science Edition),2014,46(2):79-85.
[13]饶品华,张文启,李永峰,等.氧化铝对水体中重金属离子吸附去除研究[J].水处理技术,2009,35(12):71-74.RAO Pin-hua,ZHANG Wen-qi,LI Yong-feng,et al.Study on simultaneous removal of multiple heavy metals from water by alumina[J].Technology of Water Treatment,2009,35(12):71-74.
[14]罗涛,黄东风,何盈,等.土壤重金属钝化剂的筛选及蔬菜降污专用肥应用效果研究[J].农业环境科学学报,2007,26(4):1390-1395.LUO Tao,HUANG Dong-feng,HE Ying,et al.Heavy metal passivetors screening and the application effect of special fertilizer for reducing heavy metal pollution in vegetable[J].Journal of Agro-Environment Science,2007,26(4):1390-1395.
[15]中国土壤学会.土壤农业化学分析方法[M].北京:中国农业科技出版社,2000.Chinese Soil Society.Analytical methods of soil agricultural chemistry[M].Beijing:China Agricultural Science and Technology Press,2000.
[16]国家质量监督检验检疫总局,国家标准化管理委员会.GB/T23739—2009土壤质量有效态铅和镉的测定原子吸收法[S].北京:中国标准出版社,2009.General Administration of Quality Supervision,Inspection and Quarantine,National Standardization Management Committee.GB/T 23739—2009 Soil quality-Analysis of available lead and cadmium contents in soils-Atomic absorption spectrometry[S].Beijing:China Standard Press,2009.
[17]Hartley W,Edwards R,Leppn W.Arsenic and heavy metal mobility in iron oxide-amended contaminated soils as evaluated by short-and longterm leaching tests[J].Environmental Pollution,2004,131:495-504.
[18]Kumpiene J,Lagerkvist A,Maurice C.Stabilization of As,Cr,Cu,Pb and Zn in soil using amendments:A review[J].Waste Management,2008,28:215-225.
[19]Franco D V,Silval L M D,Jardim W F.Reduction of hexavalent chromium in soil and ground water using zero-valent iron under batch and semi-batch conditions[J].Water Air&Soil Pollution,2009,197(1/2/3/4):49-60.
[20]李天然,蒋建国,李德安,等.铁基固体材料对钒矿污染土壤的固化效果研究[J].中国环境科学,2016,36(7):2108-2114.LI Tian-ran,JIANG Jian-guo,LI De-an,et al.Solidifying effect of heavy metals in the vanadium deposit-polluted soil by iron-based solid agents[J].China Environmental Science,2016,36(7):2108-2114.
[21]纪雄辉,梁永超,鲁艳红,等.污染稻田水分管理对水稻吸收积累镉的影响及其作用机理[J].生态学报,2007,27(9):3930-3939.JI Xiong-hui,LIANG Yong-chao,LU Yan-hong,et al.The effect of water management on the mechanism and rate of uptake and accumulation of cadmium by rice growing in polluted paddy soil[J].Acta Ecologica Sinica,2007,27(9):3930-3939.
[22]吴宝麟,杨志辉,柴立元,等.磷基及铁基钝化剂对Pb、Cd、As复合污染土壤的修复效果及其工艺条件优化[J].安全与环境学报,2015,15(5):314-319.WU Bao-Lin,YANG Zhi-hui,CAI Li-yuan,et al.Remediation effects of phosphorus and ferric amendments on the soil complexly contaminated by Pb,Cd and As and the process optimization[J].Journal of Safety and Environment,2015,15(5):314-319.
[23]Kumpiene J,Ore S,Renella G,et al.Assessment of zero-valent iron for stabilization of chromium,copper and arsenic in soil[J].Environmental Pollution,2006,144(1):62-69.
[24]Tomasevic D D,Kozma G,Kerkez D V,et al.Toxic metal immobilization in contaminated sediment using bentonite and kaolinite-supported nano zero-valent iron[J].Journal of Nanoparticle Research,2014,16(8):1-15.
[25]王丹,李鑫,王代长,等.硫素对水稻根系铁锰胶膜形成及吸收镉的影响[J].环境科学,2015,36(5):1877-1887.WANG Dan,LI Xin,WANG Dai-chang,et al.Effect of sulfur on the formation and uptake of Cd in rice roots[J].Environment Science,2015,36(5):1877-1887.
[26]孙丽娟,段德超,彭程,等.硫对土壤重金属形态转化及植物有效性的影响研究进展[J].应用生态学报,2014,25(7):2141-2148.SUN Li-juan,DUAN De-chao,PENG Cheng,et al.Influence of sulfur on the speciation transformation and phyto-availability of heavy metals in soil:A review[J].Chinese Journal of Applied Ecology,2014,25(7):2141-2148.
[27]李东坡,武志杰.化学肥料的土壤生态环境效应[J].应用生态学报,2008,19(5):1158-1165.LI Dong-po,WU Zhi-jie.Impact of chemical fertilizers application on soil ecological environment[J].Chinese Journal of Applied Ecology,2008,19(5):1158-1165.