高铁酸盐-亚硫酸盐体系氧化降解水中污染物阿特拉津

doi:10.16085/j.issn.1000-6613.2019-1989

摘要/Abstract

摘要：

针对目前日益严峻的农药污染问题，本文以阿特拉津（ATZ）为目标污染物，利用高铁酸盐活化亚硫酸盐的方式对其进行降解。探究了亚硫酸盐浓度、高铁酸盐浓度、ATZ浓度、pH以及亚硫酸盐投加方式对ATZ去除率的影响。研究结果表明，在pH为7、高铁酸盐浓度为100μmol/L、亚硫酸盐浓度为400μmol/L、ATZ的浓度为5μmol/L的条件下，10s时间内可以去除95%的ATZ。利用自由基淬灭实验对体系中的活性物质进行鉴定，结果表明，高铁酸盐-亚硫酸盐体系中起主要作用的是硫酸根自由基（SO $4 · -$ ），其对ATZ降解的贡献约占53%；其次是羟基自由基（·OH），约占36%。通过改变亚硫酸盐投加方式，减少了SO $4 · -$ 的自我消耗，提高了高铁酸盐-亚硫酸盐降解ATZ的效率。这些实验结果有助于高铁酸盐-亚硫酸盐体系的实际水处理应用。

关键词: 高铁酸盐, 亚硫酸盐, 氧化, 活化, 自由基

Abstract:

In view of the increasingly serious herbicide pollution, atrazine（ATZ）, as the target pollutant, was degraded by using ferrate to activate sulfite. The effects of sulfite concentration, ferrate concentration, ATZ concentration, pH and sulfite dosing ways on the removal of ATZ were investigated. The results show that under the conditions of pH 7, ferrate concentration of 100μmol/L, sulfite concentration of 400μmol/L, and ATZ concentration of 5μmol/L, 95% of ATZ can be removed within 10 seconds. The free radical quenching experiment was used to identify the active substances in the system. The results indicate that the main radicals in the ferrate-sulfite system are sulfate radicals (SO $4 · -$ ) and hydroxyl radicals (·OH), which accounts for 53% and 36%, respectively. By changing the sulfite dosing ways, the self-consumption of SO $4 · -$ was reduced, and the degradation of ATZ in ferrate-sulfite system was improved. These experimental results are helpful for practical water treatment applications of ferrate-sulfite systems.

Key words: ferrate, sulfite, oxidation, activation, radical

中图分类号:

X592

袁光明, 皮若冰, 吴钊成, 孙旭辉. 高铁酸盐-亚硫酸盐体系氧化降解水中污染物阿特拉津[J]. 化工进展, 2020, 39(9): 3794-3800.

Guangming YUAN, Ruobing PI, Zhaocheng WU, Xuhui SUN. Oxidative degradation of atrazine in water by ferrate-sulfite system[J]. Chemical Industry and Engineering Progress, 2020, 39(9): 3794-3800.

参考文献

1	CHENG Y, HE H J, YANG C P, et al. Challenges and solutions for biofiltration of hydrophobic volatile organic compounds[J]. Biotechnology Advances, 2016, 34(6): 1091-1102.
2	BUSTER H R. Atrazine and other S-trazine herbicides in lakes and rains in Switzerland[J]. Environmental Science & Technology, 1990, 24(3): 1049-1058.
3	秦传玉, 赵勇胜, 刘娜, 等. 阿特拉津在土壤中的吸附行为[J]. 环境污染与防治, 2007, 29(3): 165-167.
3	QIN Chuanyu, ZHAO Yongsheng, LIU Na, et al. Adsorption of atrazine in soil slurry samples[J]. Environmental Pollution & Control, 2007, 29 (3): 165-167.
4	BONANSEA R I, AME M V, WUNDERLIN D A. Determination of priority pesticides in water samples combining SPE and SPME coupled to GC–MS. A case study: Suquía River basin (Argentina)[J]. Chemosphere, 2013, 90(6): 1860-1869.
5	王新颖, 孙霞, 张耀斌, 等. 腐殖酸和铁对阿特拉津光降解影响的研究[J]. 环境工程学报, 2012, 6(1): 81-86.
5	WANG Xinying, SUN Xia, ZHANG Yaobin, et al. Effects of humic acid and iron on photodegradation of atrazine[J]. Chinese Journal of Environmental Engineering, 2012, 6 (1): 81-86.
6	REILLY T J, SMALLING K L, ORLANDO J L, et al. Occurrence of boscalid and other selected fungicides in surface water and groundwater in three targeted use areas in the United States[J]. Chemosphere, 2012, 89(3): 228-234.
7	范晓旭, 宋鸽, 宋福强, 等. 阿特拉津污染水体净化技术与降解机理[J]. 环境工程, 2015, 33(9): 10-15.
7	FAN Xiaoxu, SONG Ge, SONG Fuqiang, et al. Purification technology on water polluted by atrazine and its degradation mechanisms[J]. Environmental Engineering, 2015, 33 (9): 10-15.
8	YU J P, HE H J, YANG W L, et al. Magnetic bionanoparticles of Penicillium sp. yz11-22N2 doped with Fe₃O₄ and encapsulated within PVA-SA gel beads for atrazine removal[J]. Bioresource Technology, 2018, 260: 196-203.
9	李长海, 贾冬梅, 张岩, 等. 芬顿法处理阿特拉津合成废水的优化试验[J]. 环境工程, 2017 (1): 55-58.
9	LI Changhai, JIA Dongmei, ZHANG Yan, et al. Optimization of atrazine wastewater treatment by Fenton oxidation[J]. Environmental Engineering, 2017 (1): 55-58.
10	ZHU C Y, YANG W L, HE H J, et al. Preparation, performances and mechanisms of magnetic Saccharomyces cerevisiae bionanocomposites for atrazine removal[J]. Chemosphere, 2018, 200: 380-387.
11	蔡涛, 张璐吉, 胡六江, 等. 零价铁活化过二硫酸盐氧化降解阿特拉津[J]. 应用化学, 2013, 30(1): 114-119.
11	CAI Tao, ZHANG Luji, HU Liujiang, et al. Degradation of atrazine by peroxydisulfate activated with zero-valent iron [J]. Chinese Journal of Applied Chemistry, 2013, 30 (1): 114-119.
12	OH W D, DONG Z L, LIM T T. Generation of sulfate radical through heterogeneous catalysis for organic contaminants removal: current development, challenges and prospects[J]. Applied Catalysis B: Environmental, 2016, 194: 169-201.
13	XIAO R Y, YE T T, WEI Z S, et al. Quantitative structure–activity relationship (QSAR) for the oxidation of trace organic contaminants by sulfate radical[J]. Environmental Science & Technology, 2015, 49(22): 13394-13402.
14	ANIPSITAKI G P, DIONYSIOU D D, GONZALEZ M A. Cobalt-mediated activation of peroxymonosulfate and sulfate radical attack on phenolic compounds. Implications of chloride ions[J]. Environmental Science & Technology, 2006, 40(3): 1000-1007.
15	ZHOU D N, CHEN L, LI J J, et al. Transition metal catalyzed sulfite auto-oxidation systems for oxidative decontamination in waters: a state-of-the-art minireview[J]. Chemical Engineering Journal, 2018, 346: 726-738.
16	JIANG B, LIU Y K, ZHENG J T, et al. Synergetic transformations of multiple pollutants driven by Cr()–sulfite reactions[J]. Environmental Science & Technology, 2015, 49(20): 12363-12371.
17	LIU Z Z, YANG S J, YUAN Y N, et al. A novel heterogeneous system for sulfate radical generation through sulfite activation on a CoFe₂O₄ nanocatalyst surface[J]. Journal of Hazardous Materials, 2017, 324: 583-592.
18	XIAO Q, WANG T, YU S L, et al. Influence of UV lamp, sulfur(Ⅳ) concentration, and pH on bromate degradation in UV/sulfite systems: mechanisms and applications[J]. Water Research, 2017, 111: 288-296.
19	JIANG B, WANG X L, LIU Y K, et al. The roles of polycarboxylates in Cr(Ⅳ)/sulfite reaction system: Involvement of reactive oxygen species and intramolecular electron transfer[J]. Journal of Hazardous Materials, 2016, 304: 457-466.
20	CHEN L, PENG X Z, LIU J H, et al. Decolorization of orange Ⅱ in aqueous solution by an Fe(Ⅱ)/sulfite system: replacement of persulfate[J]. Industrial & Engineering Chemistry Research, 2012, 51(42): 13632-13638.
21	ZHOU D N, YUAN Y N, YANG S J, et al. Roles of oxysulfur radicals in the oxidation of acid orange 7 in the Fe(Ⅲ)–sulfite system[J]. Journal of Sulfur Chemistry, 2015, 36(4): 373-384.
22	ZHANG J, ZHU L, SHI Z Y, et al. Rapid removal of organic pollutants by activation sulfite with ferrate[J]. Chemosphere, 2017, 186: 576-579.
23	JIANG B, XIN S S, LIU Y J, et al. The role of thiocyanate in enhancing the process of sulfite reducing Cr() by inhibiting the formation of reactive oxygen species[J]. Journal of Hazardous Materials, 2018, 343: 1-9.
24	NETA P, HUIE R E. Free-radical chemistry of sulfite[J]. Environmental Health Perspectives, 1985, 64: 209-217.
25	WANG Z, JIANG J, PANG S Y, et al. Is sulfate radical really generated from peroxydisulfate activated by iron (Ⅱ) for environmental decontamination [J]. Environmental Science & Technology, 2018, 52(19): 11276-11284.
26	FENG M B, SHARMA V K. Enhanced oxidation of antibiotics by ferrate(Ⅵ)-sulfur(Ⅳ) system: elucidating multi-oxidant mechanism[J]. Chemical Engineering Journal, 2018, 341: 137-145.
27	XIE P C, GUO Y Z, CHEN Y Q, et al. Application of a novel advanced oxidation process using sulfite and zero-valent iron in treatment of organic pollutants[J]. Chemical Engineering Journal, 2017, 314: 240-248.
28	ZHANG L, CHEN L, XIAO M, et al. Enhanced decolorization of orange Ⅱ solutions by the Fe(Ⅱ)–sulfite system under xenon lamp irradiation[J]. Industrial & Engineering Chemistry Research, 2013, 52(30): 10089-10094.
29	JIANG Y J, GOODWILL J E, TOBIASON J E, et al. Impacts of ferrate oxidation on natural organic matter and disinfection byproduct precursors[J]. Water Research, 2016, 96: 114-125.
30	WU S H, LI H R, LI X, et al. Performances and mechanisms of efficient degradation of atrazine using peroxymonosulfate and ferrate as oxidants[J]. Chemical Engineering Journal, 2018, 353: 533-541.
31	HERRMANN H, REESE A, ZELLNER R. Time-resolved UV/VIS diode array absorption spectroscopy of SO_x^-(x=3, 4, 5) radical anions in aqueous solution[J]. Journal of Molecular Structure, 1995, 348: 183-186.
32	HAYON E, MCGARVEY J J. Flash photolysis in the vacuum ultraviolet region of sulfate, carbonate, and hydroxyl ions in aqueous solutions[J]. The Journal of Physical Chemistry, 1967, 71(5): 1472-1477.
33	YANG, JIANG J, LU X L, et al. Production of sulfate radical and hydroxyl radical by reaction of ozone with peroxymonosulfate: a novel advanced oxidation process[J]. Environmental Science & Technology, 2015, 49(12): 7330-7339.

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