间歇超声波强化ZVI/PS体系氧化降解磺胺抗生素

崔皓; 田禹; 张军

doi:10.13198/j.issn.1001-6929.2021.06.26

间歇超声波强化ZVI/PS体系氧化降解磺胺抗生素

doi: 10.13198/j.issn.1001-6929.2021.06.26

崔皓^{1, 2,},
田禹^{1, 2, ,},
张军²

1.
哈尔滨工业大学, 城市水资源与水环境国家重点实验室, 黑龙江哈尔滨 150090
2.
哈尔滨工业大学环境学院, 黑龙江哈尔滨 150090

基金项目:

国家重点研发计划项目 2019YFD1100300

国家自然科学基金项目 41877396

详细信息

作者简介:
崔皓(1992-), 男, 山东潍坊人, hitcuihao1@163.com

通讯作者:
田禹(1968-), 女, 河北唐山人, 长江学者特聘教授, 博士, 博导, 主要从事工业废水处理工艺研究, hit_tianyu@163.com

中图分类号: X703.1
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- 被引次数: 0
出版历程
- 收稿日期: 2021-04-29
- 修回日期: 2021-06-03

Degradation of Sulfonamide Antibiotics by Intermittent Ultrasound Enhanced ZVI/PS Process

CUI Hao^{1, 2
,},
TIAN Yu^{1, 2
, ,},
ZHANG Jun²

1.
State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China
2.
School of Environment, Harbin Institute of Technology, Harbin 150090, China

Funds:

National Key Research and Development Program of China 2019YFD1100300

National Natural Science Foundation of China 41877396

摘要

摘要: 磺胺抗生素(SAs)作为最早应用的一类化学合成抗菌药，其大量使用和排放对水环境造成严重污染，引起了人们对于水环境安全的高度关注. 因此，选取了水环境中检出率较高的5种特征SAs作为目标污染物，分别为磺胺甲基嘧啶(SMR)、磺胺二甲基嘧啶(SMT)、磺胺甲恶唑(SMX)、磺胺异恶唑(SIX)和磺胺噻唑(STZ). 利用高效液相色谱质谱联用仪(HPLC-MS-MS)对降解过程产生的中间产物进行检测和分析，深入研究了间歇超声波(US)强化ZVI/PS体系(简称“US-ZVI/PS体系”)降解5种SAs的效能和反应路径. 结果表明：①在US强度、pH、ZVI(零价铁)浓度和PS初始浓度分别为0.25 W/cm³、6.0、0.6 mmol/L和1.4 mmol/L条件下，30 min反应时间内，US-ZVI/PS体系对5种SAs的降解效率均超过95%. ②US-ZVI/PS体系降解5种SAs的过程均符合拟一级反应动力学，5种SAs降解速率常数大小依次为SMR(0.223)> SMT(0.215)>STZ(0.203)>SIX(0.181)> SMX(0.119). ③5种SAs的降解活性位点为苯环上邻位的3号C原子、苯氨基上的7号N原子、磺酰胺基上的8号S原子和11号N原子，US-ZVI/PS体系降解5种SAs的相同反应路径包括S—N键断裂、C—N键断裂、苯环羟基化、苯胺氧化和R取代基氧化过程，与五元环SAs相比，六元环SAs反应路径多一个N—N重排过程. 研究显示，US-ZVI/PS体系能够实现不同结构SAs的快速降解，是一种绿色、高效的高级氧化技术.
- 磺胺抗生素 /
- 超声波 /
- 零价铁 /
- 过硫酸盐 /
- 反应路径
Abstract: Sulfonamide antibiotics (SAs) are one of the first chemically synthesized antibiotics used. The widely application and discharge of SAs have caused serious pollution to the environment and aroused people's attention. Therefore, five characteristic SAs with relatively high detection rate in the water environment were selected as target pollutants, namely sulfamethazine (SMR), sulfamethazine (SMT), sulfamethoxazole (SMX), sulfaisoxazole (SIX), and sulfathiazole (STZ). High performance liquid chromatography-mass spectrometry (HPLC-MS-MS) was used to detect the intermediate products of the five SAs in the degradation process. The degradation efficiency and reaction pathways of SAs by ultrasound (US) enhanced ZVI/PS (US-ZVI/PS) process was further investigated. The results showed that: (1) Under the conditions of ultrasonic intensity, pH, ZVI and PS concentrations of 0.25 W/cm³, 6.0, 0.6 mmol/L and 1.4 mmol/L, and reaction time of 30 minutes, the degradation rates of five SAs were all above 95%. (2) The degradation process of five SAs accorded with the pseudo-first-order kinetic equation. The order of the degradation rate constant was SMR (0.223) > SMT (0.215) > STZ (0.203) > SIX (0.181)> SMX (0.119). (3) The degradation sites of the five SAs were No.3 of C atom on the benzene ring, No.7 of N atom on the phenylamino group, No.8 of S atom and No.11 of N atom on the sulfonamide group. The common degradation pathways of the five SAs included S-N bond cleavage, C-N bond cleavage, benzene ring hydroxylation, oxidation of aniline and R substituents. Compared with the five-membered ring SAs, the six-membered ring SAs had a special oxidation process. The extraction of the SO₂ group in the molecular structure led to N-N rearrangement to form new intermediates. The results showed that the US-ZVI/PS process can effectively achieve the rapid degradation of SAs with different structures. It is a green and efficient advanced oxidation technology.
- sulfonamide antibiotics /
- ultrasound /
- zero valent iron /
- persulfate /
- reaction pathways

HTML全文

图 1 US-ZVI/PS、ZVI/PS和PS体系降解SMR、SMT、SMX、SIX和STZ的效能

Figure 1. The degradation of SMR, SMT, SMX, SIX, and STZ by US-ZVI/PS, ZVI/PS and PS system

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图 2 US-ZVI/PS体系氧化降解5种特征磺胺抗生素的拟一级动力学曲线

Figure 2. The pseudo-first order fitting curves of five SAs degradation by US-ZVI/PS system

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图 3 US-ZVI/PS体系降解5种SAs的反应路径

Figure 3. The degradation pathways of SAs by US-ZVI/PS system

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表 1 5种典型SAs的性质

Table 1. The properties of five typical SAs

化合物名称	CAS号	分子式	摩尔质量/(g/mol)	解离常数	分子结构
磺胺甲基嘧啶(SMR)	127-79-7	C₁₁H₁₂N₄O₂S	264	pK_a1=2.2、 pK_a2=6.8
磺胺二甲嘧啶(SMT)	57-68-1	C₁₂H₁₄N₄O₂S	278	pK_a1=2.3、 pK_a2=7.4
磺胺甲恶唑(SMX)	723-46-6	C₁₀H₁₁N₃O₃S	253	pK_a1=1.7、 pK_a2=5.6
磺胺异恶唑(SIX)	127-69-5	C₁₁H₁₃N₃O₃S	267	pK_a1=1.5、 pK_a2=5.0
磺胺噻唑(STZ)	72-14-0	C₉H₉N₃O₂S₂	255	pK_a1=2.0、 pK_a2=7.1

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表 2 SMR降解的中间产物的分子结构式和质谱碎片离子分布

Table 2. The structure of intermediate products of SMR and the MS/MS fragments

中间产物名称	物质结构	分子式	一级质谱质子化离子 ([M+H]⁺)	二级质谱碎片离子 (m/z)
SMR		C₁₁H₁₂N₄O₂S	265	156、110、172
SMR 294		C₁₁H₁₀N₄O₄S	295	197、123
SMR 280		C₁₁H₁₂N₄O₃S	281	254、236
SMR 200		C₁₁H₁₂N₄	201	201、159
SMR 173		C₆H₇NO₃S	174	110、92
SMR 150		C₄H₆O₆	151	106、75
SMR 139		C₅H₅N₃O₂	140	95、59
SMR 123		C₆H₅NO₂	124	78

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表 3 SMT降解中间产物的分子结构式和质谱碎片离子分布

Table 3. The structure of intermediate products of SMT and the MS/MS fragments

中间产物名称	物质结构	分子式	一级质谱质子化离子 ([M+H] ⁺)	二级质谱碎片离子 (m/z)
SMT		C₁₂H₁₄N₄O₂S	279	156、108、85
SMT 310		C₁₂H₁₄N₄O₄S	311	156、91
SMT 308		C₁₂H₁₂N₄O₄S	309	150、122、95
SMT 214		C₁₂H₁₄N₄	215	156、95
SMT 214		C₇H₁₀N₄O₂S	215	157、119
SMT 188		C₆H₈N₂O₃S	189	157、95
SMT 183		C₆H₅N₃O₄	184	118、94
SMT 173		C₆H₇NO₃S	174	110、92
SMT 139		C₆H₅NO₃	140	94
SMT 119		C₃H₉N₃O₂	120	104

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表 4 SMX降解中间产物的分子结构式和质谱碎片离子分布

Table 4. The structure of intermediate products of SMX and the MS/MS fragments

中间产物名称	物质结构	分子式	一级质谱质子化离子 ([M+H]⁺)	二级质谱碎片离子 (m/z)
SMX		C₁₀H₁₁N₃O₃S	254	156、100
SMX 287		C₁₀H₁₃N₃O₅S	288	132、94
SMX 283		C₁₀H₉N₃O₅S	284	156、113、61
SMX 269		C₁₀H₁₁N₃O₄S	270	109、98
SMX 146		C₄H₆N₂O₄	147	90、73
SMX 139		C₆H₅NO₃	140	103、85、57
SMX 132		C₄H₈N₂O₃	133	71
SMX 100		C₄H₈N₂O	101	57
SMX 98		C₄H₆N₂O	99	84、68

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表 5 SIX降解中间产物的分子结构式和质谱碎片离子分布

Table 5. The structure of intermediate products of SIX and the MS/MS fragments

中间产物名称	物质结构	分子式	一级质谱质子化离子 ([M+H]⁺)	二级质谱碎片离子 (m/z)
SIX		C₁₁H₁₃N₃O₃S	268	156、96、80
SIX 297		C₁₁H₁₁N₃O₅S	298	252、112、96
SIX 227		C₉H₁₃N₃O₄	228	166、92
SIX 200		C₇H₈N₂O₃S	201	173、117
SIX 173		C₆H₇NO₃S	174	110、92
SIX 112		C₅H₈N₂O	113	93、80、65
SIX 97		C₅H₇NO	98	68
SIX 93		C₆H₇N	94	77

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表 6 STZ降解中间产物的分子结构式和质谱碎片离子分布

Table 6. The structure of intermediate products of STZ and the MS/MS fragments

中间产物名称	物质结构	分子式	一级质谱质子化离子 ([M+H]⁺)	二级质谱碎片离子 (m/z)
STZ		C₉H₉N₃O₂S₂	256	156、108、92
STZ 289		C₉H₁₁N₃O₄S₂	290	156、108、92
STZ 285		C₉H₇N₃O₄S₂	286	241、162、69
STZ 218		C₇H₁₀N₂O₂S₂	219	156、113、61
STZ 173		C₆H₇NO₃S	174	110、92
STZ 139		C₆H₅NO₃	140	110、81、54
STZ 134		C₃H₆N₂O₂S	135	101、86
STZ 100		C₃H₄N₂S	101	74、59

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