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紫外活化过硫酸盐降解二苯甲酮-4的动力学影响及降解机理与风险评价

沈一君 彭明国 徐彬焜 李志宏 杜尔登 王利平

沈一君, 彭明国, 徐彬焜, 李志宏, 杜尔登, 王利平. 紫外活化过硫酸盐降解二苯甲酮-4的动力学影响及降解机理与风险评价[J]. 环境科学研究, 2019, 32(1): 174-182. doi: 10.13198/j.issn.1001-6929.2018.07.24
引用本文: 沈一君, 彭明国, 徐彬焜, 李志宏, 杜尔登, 王利平. 紫外活化过硫酸盐降解二苯甲酮-4的动力学影响及降解机理与风险评价[J]. 环境科学研究, 2019, 32(1): 174-182. doi: 10.13198/j.issn.1001-6929.2018.07.24
SHEN Yijun, PENG Mingguo, XU Binkun, LI Zhihong, DU Erdeng, WANG Liping. Degradation of BP4 by UV-Activated Persulfate Process: Kinetic, Mechanism and Risk[J]. Research of Environmental Sciences, 2019, 32(1): 174-182. doi: 10.13198/j.issn.1001-6929.2018.07.24
Citation: SHEN Yijun, PENG Mingguo, XU Binkun, LI Zhihong, DU Erdeng, WANG Liping. Degradation of BP4 by UV-Activated Persulfate Process: Kinetic, Mechanism and Risk[J]. Research of Environmental Sciences, 2019, 32(1): 174-182. doi: 10.13198/j.issn.1001-6929.2018.07.24

紫外活化过硫酸盐降解二苯甲酮-4的动力学影响及降解机理与风险评价

doi: 10.13198/j.issn.1001-6929.2018.07.24
基金项目: 

江苏省自然科学基金项目 BK20130252

江苏省产学研前瞻性联合研究项目 BY2016029-09

国家水体污染控制与治理科技重大专项 2017X07202004

详细信息
    作者简介:

    沈一君(1994-), 女, 江苏大丰人, 15106126620@sina.cn

    通讯作者:

    杜尔登(1978-), 男, 江苏徐州人, 副教授, 博士, 主要从事水质安全保障技术研究, duerdeng@cczu.edu.cn

  • 中图分类号: X703

Degradation of BP4 by UV-Activated Persulfate Process: Kinetic, Mechanism and Risk

Funds: 

Natural Science Foundation of Jiangsu Province, China BK20130252

Prospective Joint Research Project of Jiangsu Province, China BY2016029-09

National Major Science and Technology Program for Water Pollution Control and Treatment, China 2017X07202004

  • 摘要: 活化PS(过硫酸盐)氧化工艺对于降解水中新兴微污染物具有潜在应用价值.为研究活化PS体系对BPs(二苯甲酮类)有机防晒剂的降解性能,以BP4(二苯甲酮-4)为研究对象,采用UV/PS(紫外活化过硫酸盐)工艺降解BP4,比较单一UV、单一PS和UV/PS 3种工艺对BP4的去除效果,考察各因素对UV/PS工艺去除BP4动力学的影响,同时探究BP4降解机理并进行风险评价.结果表明:BP4降解过程符合准一级反应动力学模型;最佳PS投加量为1.0 mmol/L,反应30 min后BP4去除率可达94%,增加PS投加量或降低初始c(BP4)均可促进BP4降解,无机阴离子(HCO3-和Cl-)对BP4降解均有抑制作用,酸性条件有利于BP4降解;基于HPLC-MS/MS鉴定出8种中间产物,并提出降解路径,费氏弧菌毒性试验和ECOSAR v1.10软件预测表明,UV/PS工艺降解BP4过程中生成的中间产物比母物质毒性更高.研究显示,UV/PS工艺可有效去除BP4,但其中间产物可能会造成潜在的生态风险,后续需进一步深入研究.

     

  • 图  1  单一PS、单一UV、UV/PS工艺对BP4的降解效果随时间的变化

    Figure  1.  Comparison of BP4 degradation by UV alone, PS alone and UV/PS process

    图  2  不同PS投加量对BP4的降解效果随时间的变化

    PS投加量/(mmol/L):1—0.5;2—1.0;3—1.5;4—2.0.

    Figure  2.  BP4 degradation by the UV/PS process with different PS doses

    图  3  不同初始c(BP4)对BP4的降解效果随时间的变化

    初始c(BP4)/(mmol/L):1—0.003;2—0.006;3—0.010;4—0.013;5—0.016.

    Figure  3.  BP4 degradation by the UV/PS process with different BP4 initial molar concentration

    图  4  c(HCO3-)对BP4降解效果随时间的变化

    c(HCO3-)/(mmol/L):1—0;2—0.5;3—1.0;4—1.5;5—2.0.

    Figure  4.  Influence of HCO3- on BP4 degradation by UV/PS process

    图  5  c(Cl-)对BP4降解效果随时间的变化

    c(Cl-)/(mmol/L):1—0;2—0.5;3—1.0;4—1.5;5—2.0.

    Figure  5.  Influence of Cl- on BP4 degradation by UV/PS process

    图  6  不同pH对BP4的降解效果随时间的变化

    溶液pH:1—3;2—5;3—7;4—9;5—11.

    Figure  6.  BP4 degradation by UV/PS process at different pH

    图  7  BP4及中间产物结构式和二级质谱

    Figure  7.  Mass spectrometry of BP4 and its intermediates

    图  8  BP4在UV/PS工艺降解过程中的反应路径

    Figure  8.  Proposed degradation mechanism of BP4 degradation by UV/PS process

    图  9  UV/PS工艺降解BP4过程对费氏弧菌相对抑制率随时间的变化

    Figure  9.  Inhibition of bioluminescence during BP4 degradation by UV/PS process

    表  1  BP4及中间产物质谱参数

    Table  1.   Mass spectrometry characteristics of BP4 and its intermediates

    项目 化学式 分子量 保留时间/min 二级质谱碎片(负离子模式)
    BP4 C14H12O6S 308 6.13 210.9(100)、209.8(45)、290.6(45)、227.0(40)、181.8(30)、262.6(25)
    Pr294 C13H10O6S 294 6.59 213.0(100)、134.8(50)、214.8(20)
    Pr244 C14H12O4 244 7.93 182.0(100)、188.9(35)、226.0(25)
    Pr248 C8H8O7S 248 9.33 247.1(100)、204.7(30)、201.0(10)
    Pr220 C7H8O6S 220 10.51 219.0(100)、132.9(20)、147.9(15)
    Pr206 C6H6O6S 206 9.90 205.1(100)、189.1(25)
    Pr138-a C7H6O3 138 1.20 137.2(100)、93.1(35)
    Pr138-b C7H6O3 138 4.71 93.1(100)、137.2(65)
    Pr122 C7H6O2 122 3.48 120.9(100)、76.7(55)
      注:括号中数值为相对丰度.
    下载: 导出CSV

    表  2  利用ECOSAR v1.10软件预测BP4及其中间产物急性毒性

    Table  2.   Acute toxicity prediction of BP4 and its intermediates by ECOSAR v1.10 software

    mg/L
    项目 LC50(水蚤48 h) LC50(鱼96 h) EC50(绿藻96 h)
    BP4 1 358.4 9 336.4 7 322.2
    Pr244 193.1 308.2 101.8
    Pr248 5 229.2 61 309.0 31 671.3
    Pr220 1 180 000.0 30 263.7 1 075.1
    Pr206 2 990 000.0 61 176.4 1 558.0
    Pr294 73 282.8 128 000.0 35 951.4
    Pr138-a 159.2 692.7 776.9
    Pr138-b 52.5 156.3 235.8
    Pr122 729.6 1 300.8 622.8
      注:LC50为对水蚤和鱼半致死浓度;EC50为对绿藻半致死浓度.
    下载: 导出CSV
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  • 收稿日期:  2018-02-12
  • 修回日期:  2018-07-18
  • 刊出日期:  2019-01-25

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