纳米四氧化三铁/过碳酸钠降解DDTs及降解产物
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摘要
以滴滴涕(DDTs)为降解对象,采用基于纳米Fe_3O_4/过碳酸钠的新型非均相类芬顿试剂进行处理,考察了纳米Fe_3O_4投加量、过碳酸钠投加量和初始pH值对水中DDE、DDD、o,p′-DDT和p,p′-DDT4种DDTs去除率的影响.同时,采用响应面法进行多因素实验设计,利用二次多项式和逐步回归法拟合了DDTs降解率与实验条件之间的关系,并对实验条件进行了优化.结果表明,纳米Fe_3O_4和过碳酸钠单独处理对DDTs降解率的最大值均小于60%,两者联合处理可大幅度提高DDTs降解率,表明两者对于DDTs降解存在较好的协同作用,纳米Fe_3O_4/过碳酸钠体系在碱性条件下可以有效降解水样中的DDTs.在纳米Fe_3O_4投加量为8.0 g·L~(-1)、过碳酸钠投加量为1.5 g·L~(-1)、溶液初始pH值为11的条件下,DDE、DDD、o,p′-DDT和p,p′-DDT的降解率分别为95.5%、84.3%、96.8%和87.5%,与模型预测值接近.自由基猝灭实验结果表明,羟基自由基是降解过程中主要的活性物质.GC/MS检测结果表明,DDTs脱氯生成DDE和DDD,随后DDE和DDD进一步降解生成DDMU、o,p′-TDE、DDNU、DDMS及DBP等物质.
This paper treated DDTs by a new heterogeneous Fenton reagent based on nano Fe_3O_4 and sodium percarbonate. The effects of nano Fe_3O_4 dose, sodium percarbonate dose, and the initial pH value on degradation efficiency of four DDTs, including DDE, DDD, o,p′-DDT, and p,p′-DDE in water was analyzed. The multi-factor experimental design was carried out by response surface methodology. The relationship between the degradation rate of DDTs and experimental conditions was fitted by quadratic polynomial and stepwise regression method. The experimental conditions were optimized. The results showed the maximum degradation rates of DDTs by nano Fe_3O_4 and sodium percarbonate alone were both less than 60%. The combined nano Fe_3O_4/sodium percarbonate treatment of DDTs could significantly increase the degradation rate of DDTs, indicating that they have a good synergistic effect on DDTs degradation. The combined nano Fe_3O_4/sodium percarbonate treatment process can effectively degrade DDTs in alkaline aqueous system. When the nano Fe_3O_4 dose was 8.0 g·L~(-1), the sodium percarbonate dose was 1.5 g·L~(-1), and the initial solution pH value was 11, the removal rates of four DDTs, including DDE, DDD, o,p′-DDT and p,p′-DDE, reach 95.5%, 84.3%, 96.8%, and 87.5%, respectively, which were all close to the values from verification experiment result. The free radical quenching test proved that hydroxyl radicals are the main active substances during the degrading process. GC/MS test results showed the DDTs dechlorination produces DDE and DDD, and further degradation produces DDMU, o,p′-TDE, DDNU, DDMS and DBP.
This paper treated DDTs by a new heterogeneous Fenton reagent based on nano Fe_3O_4 and sodium percarbonate. The effects of nano Fe_3O_4 dose, sodium percarbonate dose, and the initial pH value on degradation efficiency of four DDTs, including DDE, DDD, o,p′-DDT, and p,p′-DDE in water was analyzed. The multi-factor experimental design was carried out by response surface methodology. The relationship between the degradation rate of DDTs and experimental conditions was fitted by quadratic polynomial and stepwise regression method. The experimental conditions were optimized. The results showed the maximum degradation rates of DDTs by nano Fe_3O_4 and sodium percarbonate alone were both less than 60%. The combined nano Fe_3O_4/sodium percarbonate treatment of DDTs could significantly increase the degradation rate of DDTs, indicating that they have a good synergistic effect on DDTs degradation. The combined nano Fe_3O_4/sodium percarbonate treatment process can effectively degrade DDTs in alkaline aqueous system. When the nano Fe_3O_4 dose was 8.0 g·L~(-1), the sodium percarbonate dose was 1.5 g·L~(-1), and the initial solution pH value was 11, the removal rates of four DDTs, including DDE, DDD, o,p′-DDT and p,p′-DDE, reach 95.5%, 84.3%, 96.8%, and 87.5%, respectively, which were all close to the values from verification experiment result. The free radical quenching test proved that hydroxyl radicals are the main active substances during the degrading process. GC/MS test results showed the DDTs dechlorination produces DDE and DDD, and further degradation produces DDMU, o,p′-TDE, DDNU, DDMS and DBP.
引文
Cao M,Wang L,Wang L,et al.2013.Remediation of DDTs contaminated soil in a novel Fenton-like system with zero-valent iron[J].Chemosphere,90(8):2303-2308
董华强,黄剑波,梁炽琼.2013.超声/紫外/O3/H2O2处理去除水中DDT的研究[J].安徽农业科学,41(10):4373-4375
杜尔登,张申耀,冯欣欣,等.2014.光催化降解内分泌干扰物双酚A的响应面分析与优化[J].环境工程学报,8(12):5124-5128
Enami S,Sakamoto Y,Colussi A J.2014.Fenton chemistry at aqueous interfaces[J].Proceedings of the National Academy of Sciences of the United States of America,111(2):623-628
高雪,王翠芬,刘萍,等.2015.生活用水中六六六和滴滴涕的残留分析[J].食品安全质量检测学报,6(3):987-991
黄幸然,吴旺旺,胡宝叶,等.2016.闽江水体和生物体中六六六和滴滴涕污染特征和来源解析[J].生态环境学报,25(3):482-488
Jiao Y,Wan C,Bao W,et al.2018.Facile hydrothermal synthesis of Fe3O4 @cellulose aerogel nanocomposite and its application in Fenton-like degradation of Rhodamine B[J]. Carbohydrate Polymers,189:371-378
李开环,聂志强,迭庆杞,等.2018.废弃农药厂拆除过程对周边土壤DDTs污染影响[J].中国环境科学,38(2):658-664
李绚,刘志泉,周琪浩,等.2018.高锰酸钾氧化水中沙拉沙星的动力学研究[J].中国环境科学,38(3):917-922
李慎新,钟俊波,卢燕.2008.过二硫酸钾氧化降解环境水中O-DDT的研究[J].安徽农业科学,36(30):13365-13366
李纪华,薛韫坤,何坚.2012.过碳酸钠降解水相中罗丹明B的实验研究[J].环境工程,30(S2):176-178
Ma J,Xia X,Ma Y,et al. 2018. Stability of dissolved percarbonate and its implications for groundwater remediation [J]. Chemosphere,205:41-44
马楠.2012.西溪湿地国家公园地表水中有机氯农药残留特征及风险评价[J].江苏农业科学,40(6):363-365
潘丽冰.2018.基于过硫酸盐高级氧化法降解DDT的研究[D].济南:山东大学.42-45
彭远锋.2016.微波强化过碳酸钠氧化降解邻苯二甲酸二丁酯的研究[D].广州:广东工业大学.28-43
Qin W,Fang G,Wang Y,et al.2016.Efficient transformation of DDT by peroxymonosulfate activated with cobalt in aqueous systems: Kinetics,products,and reactive species identification[J].Chemosphere,148:68-76
钱卉.2008.过碳酸钠降解菊酯类农药的研究[D].南京:南京师范大学.26-36
田依林,李明玉,马同森,等.2003.Fenton试剂氧化水中芳香族化合物的机理[J].污染防治技术,16(1):12-15
Wang Y,Lin X,Shao Z,et al.2017.Comparison of Fenton,UV-Fenton and nano-Fe3O4,catalyzed UV-Fenton in degradation of pH loroglucinol under neutral and alkaline conditions: role of complexation of Fe3+,with hydroxyl group in pH loroglucinol[J].Chemical Engineering Journal,313:938-945
王占杰.2008.有机氯化物滴滴涕降解研究[D].北京:北京化工大学.17-22
Xie Z,Wang C,Yin L.2017.Nickel-assisted iron oxide catalysts for the enhanced degradation of refractory DDT in heterogeneous Fenton-like system[J].Journal of Catalysis,353:11-18
肖喆,霍守亮,昝逢宇,等.2017.纳米Fe3O4催化非均相Fenton体系降解含酚废水的研究[J].工业水处理,37(12):82-86
Yan P,Sui Q,Lyu S,et al. 2018. Elucidation of the oxidation mechanisms and pathways of sulfamethoxazole degradation under Fe(II) activated percarbonate treatment[J]. Science of the Total Environment,s 640-641:973-980
杨乐.2016.纳米Fe3O4类Fenton工艺深度处理焦化废水效能及参数优化[D].哈尔滨:哈尔滨工业大学.3-7
张帆,张进明,肖梅,等.2017.响应面法优化催化臭氧氧化处理邻苯二甲酸二甲酯废水的研究[J].环境污染与防治,39(10):1092-1096.
Zhao H,Chen Y,Peng Q,et al.2017.Catalytic activity of MOF(2Fe/Co)/carbon aerogel for improving H2O2 and ·OH generation in solar photo-electro-Fenton process[J].Applied Catalysis B Environmental,203:127-137
朱峥嵘,石崇,朱颖一,等.2018.响应面法优化纳米Fe3O4/CaO2处理含PAEs废水的研究[J].安全与环境工程,25(3):78-85
Zhu C,Fang G,Dionysiou D D,et al.2016.Efficient transformation of DDTs with persulfate activation by zero-valent iron nanoparticles:A mechanistic study[J].Journal of Hazardous Materials,316:232-241
赵娜娜,黄启飞,王琪,等.2007.滴滴涕在我国典型POPs污染场地中的空问分布研究[J].环境科学学报,27(10):1669-1674
赵启红.2007.过碳酸钠对有机磷农药的降解研究[D].南京:南京师范大学.34-36
张俊鹏,祁士华,胡英,等.2012.岩溶地下河水体中有机氯农药研究[J].科技通报,28(4):54-57
董华强,黄剑波,梁炽琼.2013.超声/紫外/O3/H2O2处理去除水中DDT的研究[J].安徽农业科学,41(10):4373-4375
杜尔登,张申耀,冯欣欣,等.2014.光催化降解内分泌干扰物双酚A的响应面分析与优化[J].环境工程学报,8(12):5124-5128
Enami S,Sakamoto Y,Colussi A J.2014.Fenton chemistry at aqueous interfaces[J].Proceedings of the National Academy of Sciences of the United States of America,111(2):623-628
高雪,王翠芬,刘萍,等.2015.生活用水中六六六和滴滴涕的残留分析[J].食品安全质量检测学报,6(3):987-991
黄幸然,吴旺旺,胡宝叶,等.2016.闽江水体和生物体中六六六和滴滴涕污染特征和来源解析[J].生态环境学报,25(3):482-488
Jiao Y,Wan C,Bao W,et al.2018.Facile hydrothermal synthesis of Fe3O4 @cellulose aerogel nanocomposite and its application in Fenton-like degradation of Rhodamine B[J]. Carbohydrate Polymers,189:371-378
李开环,聂志强,迭庆杞,等.2018.废弃农药厂拆除过程对周边土壤DDTs污染影响[J].中国环境科学,38(2):658-664
李绚,刘志泉,周琪浩,等.2018.高锰酸钾氧化水中沙拉沙星的动力学研究[J].中国环境科学,38(3):917-922
李慎新,钟俊波,卢燕.2008.过二硫酸钾氧化降解环境水中O-DDT的研究[J].安徽农业科学,36(30):13365-13366
李纪华,薛韫坤,何坚.2012.过碳酸钠降解水相中罗丹明B的实验研究[J].环境工程,30(S2):176-178
Ma J,Xia X,Ma Y,et al. 2018. Stability of dissolved percarbonate and its implications for groundwater remediation [J]. Chemosphere,205:41-44
马楠.2012.西溪湿地国家公园地表水中有机氯农药残留特征及风险评价[J].江苏农业科学,40(6):363-365
潘丽冰.2018.基于过硫酸盐高级氧化法降解DDT的研究[D].济南:山东大学.42-45
彭远锋.2016.微波强化过碳酸钠氧化降解邻苯二甲酸二丁酯的研究[D].广州:广东工业大学.28-43
Qin W,Fang G,Wang Y,et al.2016.Efficient transformation of DDT by peroxymonosulfate activated with cobalt in aqueous systems: Kinetics,products,and reactive species identification[J].Chemosphere,148:68-76
钱卉.2008.过碳酸钠降解菊酯类农药的研究[D].南京:南京师范大学.26-36
田依林,李明玉,马同森,等.2003.Fenton试剂氧化水中芳香族化合物的机理[J].污染防治技术,16(1):12-15
Wang Y,Lin X,Shao Z,et al.2017.Comparison of Fenton,UV-Fenton and nano-Fe3O4,catalyzed UV-Fenton in degradation of pH loroglucinol under neutral and alkaline conditions: role of complexation of Fe3+,with hydroxyl group in pH loroglucinol[J].Chemical Engineering Journal,313:938-945
王占杰.2008.有机氯化物滴滴涕降解研究[D].北京:北京化工大学.17-22
Xie Z,Wang C,Yin L.2017.Nickel-assisted iron oxide catalysts for the enhanced degradation of refractory DDT in heterogeneous Fenton-like system[J].Journal of Catalysis,353:11-18
肖喆,霍守亮,昝逢宇,等.2017.纳米Fe3O4催化非均相Fenton体系降解含酚废水的研究[J].工业水处理,37(12):82-86
Yan P,Sui Q,Lyu S,et al. 2018. Elucidation of the oxidation mechanisms and pathways of sulfamethoxazole degradation under Fe(II) activated percarbonate treatment[J]. Science of the Total Environment,s 640-641:973-980
杨乐.2016.纳米Fe3O4类Fenton工艺深度处理焦化废水效能及参数优化[D].哈尔滨:哈尔滨工业大学.3-7
张帆,张进明,肖梅,等.2017.响应面法优化催化臭氧氧化处理邻苯二甲酸二甲酯废水的研究[J].环境污染与防治,39(10):1092-1096.
Zhao H,Chen Y,Peng Q,et al.2017.Catalytic activity of MOF(2Fe/Co)/carbon aerogel for improving H2O2 and ·OH generation in solar photo-electro-Fenton process[J].Applied Catalysis B Environmental,203:127-137
朱峥嵘,石崇,朱颖一,等.2018.响应面法优化纳米Fe3O4/CaO2处理含PAEs废水的研究[J].安全与环境工程,25(3):78-85
Zhu C,Fang G,Dionysiou D D,et al.2016.Efficient transformation of DDTs with persulfate activation by zero-valent iron nanoparticles:A mechanistic study[J].Journal of Hazardous Materials,316:232-241
赵娜娜,黄启飞,王琪,等.2007.滴滴涕在我国典型POPs污染场地中的空问分布研究[J].环境科学学报,27(10):1669-1674
赵启红.2007.过碳酸钠对有机磷农药的降解研究[D].南京:南京师范大学.34-36
张俊鹏,祁士华,胡英,等.2012.岩溶地下河水体中有机氯农药研究[J].科技通报,28(4):54-57