Degradation of organochlorine pesticides in water by persulfate catalyzed by ball-milled and sulfidated-zero valent iron
YAO Mengdong1,, YUE Junjie1, XU Xuejing2, ZHANG Peng2,,, SHANG Xiaofu3, WANG Cuiping2, SUN Hongwen2 1.School of Environmental Science and Safety Engineering, Tianjin University of Technology, Tianjin 300384, China 2.MOE Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Engineering Center of Environmental Diagnosis and Contamination Remediation, College of Environmental Science and Engineering, Nankai University, Tianjin 300350, China 3.Tianjin Huankelijia Environmental Remediation Technology Co. Ltd., Tianjin 300191, China
Abstract:To explore the effects of preparation parameters of sulfidated-zero valent iron (S-mZVI) and environmental factors such as pH, humic acid, $ {\rm{HC}}{{\rm{O}}^ -_3} $ and $ {\rm{N}}{{\rm{O}^ -_3}} $ on the removal of organochlorine pesticides (OPPs) by the S-mZVI/sodium persulfate (S-mZVI/PS) system, the S-mZVI with different S/Fe molar ratios was prepared by the ball-milling technology, and then was used to activate PS for the degradation of 4,4′-DCBP and β-HCH. The results showed that the presence of S could not only achieve mZVI sulfidation during the ball-milling process, but also improved the ball-milling efficiency of mZVI. The morphology of mZVI was mainly in the form of aggregate scales, while the ball milled S-mZVI became dispersed into irregular spherical particles, and the larger the S/Fe molar ratio, the smoother the surface and the closer the spherical morphology of the particles. Compared with mZVI/PS system, S-mZVI/PS system had greater catalytic degradation activities for 4,4′-DCBP and β-HCH, and their degradation efficiency and corrosion rate of mZVI increased with the increasing of S/Fe molar ratios. At the S/Fe molar ratio of 0.10 and PS/Fe dosage ratio of 1/2, the greatest degradation of 4, 4’-DCBP and β-HCH in the S-mZVI/PS system was achieved and their final degradation rates in 120 min were 92.4% and 93.0%, respectively. Moreover, with the increase of initial pH, the degradation efficiencies of 4,4′-DCBP and β-HCH decreased gradually, but there were slight differences in their final degradation rates at various pHs. The degradation efficiencies of 4,4′-DCBP and β-HCH decreased in the presences of humic acid and $ {\rm{HC}}{{\rm{O}}^ -_3} $, and the stronger inhibition effects the higher concentrations. However, the presence and concentration of $ {\rm{N}}{{\rm{O}}^ -_3} $ had no effect on the degradation of 4 4′-DCBP and β-HCH in S-mZVI/PS system. Therefore, sulfur-modified ZVI can significantly improve the PS activation efficiency and the degradation rates of OPPs, which has good applicability for the remediation of OPPs-polluted water. Key words:sulfidated zero valent iron/ persulfate/ organochlorine pesticides/ degradation/ environmental factors.
图1S-mZVI在不同S/Fe摩尔比下SEM图、S-mZVI (S/Fe=0.10)的SEM图谱、EDS图谱、元素能谱 Figure1.SEM images of S-mZVI with various S/Fe molar ratios and SEM image of S-mZVI with S/Fe = 0.10 and the corresponding EDS spectra and EDS mapping
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1.School of Environmental Science and Safety Engineering, Tianjin University of Technology, Tianjin 300384, China 2.MOE Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Engineering Center of Environmental Diagnosis and Contamination Remediation, College of Environmental Science and Engineering, Nankai University, Tianjin 300350, China 3.Tianjin Huankelijia Environmental Remediation Technology Co. Ltd., Tianjin 300191, China Received Date: 2020-03-08 Accepted Date: 2021-06-01 Available Online: 2021-09-15 Keywords:sulfidated zero valent iron/ persulfate/ organochlorine pesticides/ degradation/ environmental factors Abstract:To explore the effects of preparation parameters of sulfidated-zero valent iron (S-mZVI) and environmental factors such as pH, humic acid, $ {\rm{HC}}{{\rm{O}}^ -_3} $ and $ {\rm{N}}{{\rm{O}^ -_3}} $ on the removal of organochlorine pesticides (OPPs) by the S-mZVI/sodium persulfate (S-mZVI/PS) system, the S-mZVI with different S/Fe molar ratios was prepared by the ball-milling technology, and then was used to activate PS for the degradation of 4,4′-DCBP and β-HCH. The results showed that the presence of S could not only achieve mZVI sulfidation during the ball-milling process, but also improved the ball-milling efficiency of mZVI. The morphology of mZVI was mainly in the form of aggregate scales, while the ball milled S-mZVI became dispersed into irregular spherical particles, and the larger the S/Fe molar ratio, the smoother the surface and the closer the spherical morphology of the particles. Compared with mZVI/PS system, S-mZVI/PS system had greater catalytic degradation activities for 4,4′-DCBP and β-HCH, and their degradation efficiency and corrosion rate of mZVI increased with the increasing of S/Fe molar ratios. At the S/Fe molar ratio of 0.10 and PS/Fe dosage ratio of 1/2, the greatest degradation of 4, 4’-DCBP and β-HCH in the S-mZVI/PS system was achieved and their final degradation rates in 120 min were 92.4% and 93.0%, respectively. Moreover, with the increase of initial pH, the degradation efficiencies of 4,4′-DCBP and β-HCH decreased gradually, but there were slight differences in their final degradation rates at various pHs. The degradation efficiencies of 4,4′-DCBP and β-HCH decreased in the presences of humic acid and $ {\rm{HC}}{{\rm{O}}^ -_3} $, and the stronger inhibition effects the higher concentrations. However, the presence and concentration of $ {\rm{N}}{{\rm{O}}^ -_3} $ had no effect on the degradation of 4 4′-DCBP and β-HCH in S-mZVI/PS system. Therefore, sulfur-modified ZVI can significantly improve the PS activation efficiency and the degradation rates of OPPs, which has good applicability for the remediation of OPPs-polluted water.
将0.224 g mZVI(S-mZVI)加入40 mL EPA瓶中，再加入40 mL 100 mmol·L?1的过硫酸钠溶液和200 μL 2 g·L?1的目标物母液，使目标物浓度达到10 mg·L?1。OCPs需利用丙酮助溶，且为避免共溶剂效应加入丙酮的量不超过0.5%。随后立即置于恒温气浴振荡箱中(25 ℃，150 r·min?1)避光反应，反应期间定时取样检测4,4′-DCBP和β-HCH的浓度；为探究硫化改性对mZVI的腐蚀速率的影响，采用邻菲啰啉法测定反应期间溶液中总铁离子和Fe2+的浓度。
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