Simultaneous Removal of TCE and Cr(Ⅵ) in Groundwater by Using Bentonite-supported Nanoscale Fe/Ni
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摘要: 纳米零价铁原位注射修复地下水污染是近年发展的新技术，以往研究多侧重于单一目标污染物的去除效果及作用机理，但是地下水多种污染物共存问题不容忽视。本文针对典型污染物三氯乙烯TCE和六价铬Cr（Ⅵ），运用合成的活性高、稳定性强的膨润土负载纳米铁镍（B-Fe/Ni）开展修复实验，研究B-Fe/Ni对TCE和Cr（Ⅵ）共存复合污染的修复效果及其作用机制。通过一步法合成B-Fe/Ni，对TCE和不同浓度Cr（Ⅵ）混合污染的去除进行试验研究，对反应前后的样品B-Fe/Ni进行表征，并跟踪反应过程中TCE和Cr（Ⅵ）的浓度变化。结果表明：B-Fe/Ni同步去除水中TCE和Cr（Ⅵ）快速高效，50 mg/L Cr（Ⅵ）在2 h内能被B-Fe/Ni（1 g/L）完全去除而不受共存TCE（0.1 mmol/L）的影响，然而TCE降解速率会随共存Cr（Ⅵ）的浓度（0、10、30、50 mg/L）增大而降低。经透射电镜-电子能谱及X射线光电子能谱表征验证，这是由于B-Fe/Ni与Cr（Ⅵ）快速反应，生成部分Fe-Cr共沉淀会覆盖B-Fe/Ni表面的活性位点，抑制了TCE的降解，但通过分析TCE降解产物可知，B-Fe/Ni同样能对TCE完全脱氯。因此，B-Fe/Ni适用于地下水复合污染修复，实际应用时需考虑多种污染物共存的相互影响，选择适宜试剂用量和注射方式，这对纳米零价铁修复技术的发展具有重要理论意义和应用参考价值。Abstract:
BACKGROUND The injection of nanoscale zero valent iron particles (nZVI) into groundwater has been recently developed as an in-situ groundwater remediation technology. Most researches focused on how to remove a single type pollutant and the related mechanism. However, cases on the coexisting multiple pollutants in groundwater should not be ignored. OBJECTIVES To synthesize the bentonite-supported nanoscale Fe/Ni bimetals(B-Fe/Ni), in order to remove typical pollutants of trichloroethylene (TCE) and hexavalent chromium[Cr(Ⅵ)] which exhibit high reactivity and are more stable to remediate contaminated water. Also, to assess the performance of B-Fe/Ni on the removal of coexisting TCE and Cr(Ⅵ) and to determine the reaction mechanism. METHODS B-Fe/Ni was synthesized by one-step method and the batch experiments were conducted on the removal of TCE coexisted with different concentration of Cr(Ⅵ) by B-Fe/Ni. The samples of B-Fe/Ni were characterized before and after the reaction, and the contents of TCE and Cr(Ⅵ) were also monitored. RESULTS B-Fe/Ni can efficiently remediate Cr(Ⅵ) and TCE in water. B-Fe/Ni (1 g/L) could completely remove Cr(Ⅵ) (50 mg/L) in 2 h in the presence of coexisting TCE (0.1 mmol/L). However, the degradation rate of TCE by B-Fe/Ni was decreased with increased initial concentration of Cr(Ⅵ) (0, 10, 30, 50 mg/L). According to TEM-EDS and XPS for B-Fe/Ni before and after reaction, it is shown that Fe-Cr co-precipitation from the fast interaction of B-Fe/Ni with Cr(Ⅵ) occupied the reactive sites on the surface of B-Fe/Ni, mitigating the degradation of TCE. According to the final products of TCE degradation, it is shown that TCE was completely dechlorinated. CONCLUSIONS B-Fe/Ni is suitable for the remediation of groundwater combined pollution. In practical applications, it is necessary to consider the mutual influence of multiple pollutants and select the appropriate reagent dosage and injection method. The proposed method has important theoretical significance and application for the development of ZVI repair technology. -
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图 4 B-Fe/Ni的X射线光电子能谱表征谱图：反应前(a)的Fe谱；降解TCE后(b)的Fe谱；去除TCE和Cr(Ⅵ)后(c)的Fe谱；(d) Cr谱
Figure 4.
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[1] Lefevre E, Bossa N, Wiesner M R, et al.A review of the environmental implications of in situ remediation by nanoscale zero valent iron (nZVI):Behavior, transport and impacts on microbial communities[J].Science of the Total Environment, 2016, 565:889-901. doi: 10.1016/j.scitotenv.2016.02.003
[2] Gillham R W, O'hannesin S F.Enhanced degradation of halogenated aliphatics by zero-valent iron[J].Ground Water, 1994, 32(6):958-967. doi: 10.1111/gwat.1994.32.issue-6
[3] Magdalena S, Patryk O, Yong S O.Review on nano zer-ovalent iron (nZVI):From synthesis to environmental applications[J].Chemical Engineering Journal, 2016, 287:618-632. doi: 10.1016/j.cej.2015.11.046
[4] Zou Y D, Wang X X, Ayub K, et al.Environmental remediation and application of nanoscale zero valent iron and its composites for the removal of heavy metal ions:A review[J].Environmental Science and Technology, 2016, 50:7290-7304. doi: 10.1021/acs.est.6b01897
[5] Zhao X, Liu W, Cai Z Q, et al.An overview of preparation and applications of stabilized zero-valent iron nanoparticles for soil and groundwater remediation[J].Water Research, 2016, 100:235-266.
[6] Su Y, Adeleye A S, Huang Y X, et al.Simultaneous removal of cadmium and nitrate in aqueous media by nanoscale zerovalent iron (nZVI) and Au doped nZVI particles[J].Water Research, 2014, 63:102-111. doi: 10.1016/j.watres.2014.06.008
[7] Qian D X, Su Y M, Huang Y X, et al.Simultaneous molybdate (Mo(Ⅵ)) recovery and hazardous ions immobilization via nanoscale zerovalent iron[J].Journal of Hazardous Materials, 2018, 344:698-706. doi: 10.1016/j.jhazmat.2017.10.036
[8] Fu F, Han W, Huang C, et al.Removal of Cr(Ⅵ) from wastewater by supported nanoscale zero-valent iron on granular activated carbon[J].Desalination and Water Treatment, 2013, 51(13-15):2680-2686. doi: 10.1080/19443994.2012.749328
[9] Pang Z, Yan M, Jia X, et al.Debromination of deca-bromodiphenyl ether by organo-montmorillonite-supported nanoscale zero-valent iron:Preparation, characterization and influence factors[J].Journal of Environmental Sciences-China, 2014, 26(2):483-491. doi: 10.1016/S1001-0742(13)60419-2
[10] Choi H, Souhail R A, Shirish A, et al.Synthesis of reactive nano-Fe/Pd bimetallic system-impregnated activated carbon for the simultaneous adsorption and dechlorination of PCBs[J].Chemistry Materials, 2008, 20:3649-3655. doi: 10.1021/cm8003613
[11] Lin C H, Shinh Y H, MacFarlane J, et al.Amphiphilic compounds enhance the dechlorination of pentachloro-phenol with Ni/Fe bimetallic nanoparticles[J].Chemical Engineering Journal, 2015, 262:59-67. doi: 10.1016/j.cej.2014.09.038
[12] Zhao D, Cheng J, Cheng J W.One-step synthesis of ben-tonite-supported nanoscale Fe/Ni bimetals for rapid degradation of methyl orange in water[J].Environmental Chemistry Letters, 2014, 12:461-466. doi: 10.1007/s10311-014-0473-3
[13] Wang S H, Han Y T, Cao X, et al.Enhanced degradation of trichloroethylene using bentonite-supported nanoscale Fe/Ni and humic acids[J].Environmental Chemistry Letters, 2016, 14:237-242. doi: 10.1007/s10311-015-0548-9
[14] Weng X L, Cai W L, Lan R F, et al.Simultaneous remo-val of amoxicillin, ampicillin and penicillin by clay supported Fe/Ni bimetallic nanoparticles[J].Environmental Pollution, 2018, 236:562-569. doi: 10.1016/j.envpol.2018.01.100
[15] 樊文井, 成岳, 余淑贞, 等.流变相法制备包覆型CMC-Fe0及降解水中TCE的研究[J].环境科学, 2015, 36(6):2161-2167. http://d.old.wanfangdata.com.cn/Periodical/hjkx201506039
Fan W J, Cheng Y, Yu S Z, et al.Preparation of coated CMC-Fe0 using rheological phase reaction method and research on degradation of TCE in water[J].Environmental Science, 2015, 36(6):2161-2167. http://d.old.wanfangdata.com.cn/Periodical/hjkx201506039
[16] Rajajayavel S R C, Ghoshal S.Enhanced reductive dech-lorination of trichloroethylene by sulfidated nanoscale zerovalent iron[J].Water Research, 2015, 78:144-153. doi: 10.1016/j.watres.2015.04.009
[17] Gu M B, Farooq U, Lu S G, et al.Degradation of trich-loroethylene in aqueous solution by rGO supported nZVI catalyst under several oxic environments[J].Journal of Hazardous Materials, 2018, 349:35-44. doi: 10.1016/j.jhazmat.2018.01.037
[18] 王谦, 李延, 孙平, 等.含铬废水处理技术及研究进展[J].环境科学与技术, 2013, 36(A2):150-156. http://d.old.wanfangdata.com.cn/Periodical/gyysyfs201005002
Wang Q, Li Y, Sun P, et al.The treatment technology and research progress of hexavalent chromium-containing wastewater[J].Environmental Science & Technology, 2013, 36(A2):150-156. http://d.old.wanfangdata.com.cn/Periodical/gyysyfs201005002
[19] Fu F L, Ma J, Xie L P, et al.Chromium removal using resin supported nanoscale zero-valent iron[J].Journal of Environmental Management, 2013, 128:822-827. doi: 10.1016/j.jenvman.2013.06.044
[20] 张保科, 王蕾, 马生凤.电感耦合等离子体质谱法测定含气天然矿泉水中的铬[J].岩矿测试, 2013, 32(4):568-571. doi: 10.3969/j.issn.0254-5357.2013.04.008 http://www.ykcs.ac.cn/article/id/f4ece52c-7679-4883-a2ff-e57adb9b0536
Zhang B K, Wang L, Ma S F.Quantification of Cr in natural sparkling mineral waters by inductively coupled plasma-mass spectrometry[J].Rock and Mineral Analysis, 2013, 32(4):568-571. doi: 10.3969/j.issn.0254-5357.2013.04.008 http://www.ykcs.ac.cn/article/id/f4ece52c-7679-4883-a2ff-e57adb9b0536
[21] Mayer K U, Blowes D W, Frind E O.Reactive transport modeling of an in situ reactive barrier for the treatment of hexavalent chromium and trichloroethylene in groundwater[J].Water Resources Research, 2001, 37(12):3091-3103. doi: 10.1029/2001WR000234
[22] 李志雄, 韩奕彤, 徐永强, 等.动态光散射技术原位表征天然有机质存在下纳米零价铁的团聚效应[J].岩矿测试, 2016, 35(6):634-641. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2016.06.010
Li Z X, Han Y T, Xu Y Q, et al.In situ measurement of aggregation effect of nanoscale zero-valent iron in the presence of natural organic matter based on the dynamic light scattering technique[J].Rock and Mineral Analysis, 2016, 35(6):634-641. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2016.06.010
[23] 李晨桦, 陈家玮.膨润土负载纳米铁去除地下水中六价铬研究[J].现代地质, 2012, 26(5):932-938. doi: 10.3969/j.issn.1000-8527.2012.05.012
Li C H, Chen J W.A study on bentonite-supported nano iron for removal of Cr(Ⅵ) in groundwater[J].Geoscience, 2012, 26(5):932-938. doi: 10.3969/j.issn.1000-8527.2012.05.012
[24] Lina S, Zhang X, Chen Z L.Removal of chromium(Ⅵ) from wastewater using bentonite-supported nanoscale zero-valent iron[J].Water Research, 2011, 45:886-892. doi: 10.1016/j.watres.2010.09.025
[25] Chen J W, Xiu Z M, Lowry G V, et al.Effect of natural organic matter on toxicity and reactivity of nano-scale zerovalent iron[J].Water Research, 2011, 45(5):1995-2001. doi: 10.1016/j.watres.2010.11.036
[26] Li Y, Li X Q, Han D H, et al.New insights into the role of Ni loading on the surface structure and the reactivity of nZVI toward tetrabromo-and tetrachlorobisphenol A[J].Chemical Engineering Journal, 2017, 311:173-182. doi: 10.1016/j.cej.2016.11.084
[27] Sahu R S, Bindumadhavan K, Doong R.Boron-doped reduced graphene oxide-based bimetallic Ni/Fe nanohybrids for the rapid dechlorination of trichloroethylene[J].Environmental Science-Nano, 2017, 4(3):565-576. doi: 10.1039/C6EN00575F
[28] 黄潇月, 王伟, 凌岚, 等.纳米零价铁与重金属的反应:"核-壳"结构在重金去除中的作用[J].化学学报, 2017, 75(6):529-537. http://d.old.wanfangdata.com.cn/Periodical/hxxb201706002
Huang X Y, Wang W, Ling L, et al.Heavy metal-nZVI reactions:The core-shell structure and applications for heavy metal treatment[J].Acta Chimica Sinica, 2017, 75(6):529-537. http://d.old.wanfangdata.com.cn/Periodical/hxxb201706002
[29] Fu R B, Yang Y P, Xu Z, et al.The removal of chromium(Ⅵ) and lead(Ⅱ) from groundwater using sepiolite-supported nanoscale zero-valent iron (S-NZVI)[J].Chemosphere, 2015, 138(3):726-734.
[30] 李云琴, 许俊鸽, 周海瑞, 等.包覆型纳米铁的制备及其降解三氯乙烯的性能研究[J].环境学报, 2014, 34(12):2985-2990. http://d.old.wanfangdata.com.cn/Periodical/hjkxxb201412004
Li Y Q, Xu J G, Zhou H R, et al.Preparation and application of encapsulated nanoscale zero-valent iron in the degradation of trichloroethene[J].Acta Scientiae Circumstantiae, 2014, 34(12):2985-2990. http://d.old.wanfangdata.com.cn/Periodical/hjkxxb201412004
[31] 黄园英, 王倩, 韩子金, 等.利用扫描电镜技术研究纳米Ni-Fe颗粒对四氯化碳快速脱氯的机理[J].岩矿测试, 2015, 34(3):342-352. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2015.03.015
Huang Y Y, Wang Q, Han Z J, et al.Kinetics and mechanism of carbon tetrachloride rapid reduction by nanoscale Ni-Fe particles using scanning electron microscope[J].Rock and Mineral Analysis, 2015, 34(3):342-352. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2015.03.015
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