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随着药品和医疗行业的快速发展,人类和动物对抗生素的消耗量逐渐增加。抗生素可以有效治愈多种疾病,避免病情恶化[1]。常用的抗生素按照其化学结构及性质分类,包括磺胺类(sulfonamides,SAs)、四环素类(tetracyclines,TCs)、氟喹诺酮类(quinolones,QNs)、大环内酯类(macrolides,MCs)、β-内酰胺类(β-lactams,β-Ls)和氨基糖苷类(aminoglycosides,AGs)等[2]。其中,磺胺类抗生素的使用占比较高[3],磺胺嘧啶(sulfadiazine,SDZ)是一种典型的磺胺类抗生素,其制备成本较低且具有广泛的应用有效性,抗菌性强且易吸收,在人用药及兽药中被广泛使用。甲氧苄啶(trimethoprim,TMP)作为一种磺胺增效剂,常与磺胺类抗生素联用以获得更强的抗菌活性。环丙沙星(ciprofloxacin,CIP)和恩诺沙星(enrofloxacin,EFA)作为氟奎诺酮类抗菌药物,也被广泛使用。各类抗生素的广泛使用及其对生物降解的高抗性导致含有抗生素的医疗废水、生活废水无法得到有效地去除,进而在环境中不断积累。有研究表明,在陆生、水生环境,甚至直接饮用水中都已频繁检测到抗生素残留[4-5]。因此,迫切需要开发高效、环保的水处理技术,对现有的和日常输出的含抗生素废水进行有效处理。
高级氧化工艺(advanced oxidation processes,AOPs)可以产生多种具有较高氧化电位的活性氧物质,被认为是目前处理不可生物降解和难生物降解有机化合物的最有效技术[6]。在AOPs中,高活性物质既可以通过能量注入直接解离水分子产生,也可以通过不同的方式激活氧化剂生成。由于水分子的直接解离需要较高的能量消耗,而氧化剂活化方式的AOPs过程具有操作简单、能耗低的优点,从而受到广泛关注。氧化剂活化方式中常用的氧化剂有过氧化氢(H2O2)[7]、臭氧(O3)[8]、过硫酸盐(persulfate,PS)[9]、高碘酸盐(periodate,PI)[10-11]。与H2O2、O3和PS相比,PI具有更好的热稳定性,并且易于运输和储存,因此,近年来通过活化PI处理有机废水的研究备受关注[12-14]。
PI活化过程可生成多种高活性物质,包括高碘酸根自由基(IO3·、IO4·)、羟基自由基(·OH)、超氧根阴离子自由基(·O2−)、O(3P)原子、单线态氧(1O2)、电子(e−)和空穴(h+)等,其在有机物降解过程中均有一定的作用。目前已经开发并应用的PI活化方法或试剂包括冷冻[15]、超声[16]、紫外线(UV)照射[17-19]、羟胺[20]、碱[21]、金属离子[22]、非均相金属催化剂[23-26]等。TiO2作用一种广泛使用的催化剂,因其化学稳定性强、毒性小、成本效益高而被广泛研究、应用。已有研究证实,紫外光协同TiO2活化PI可以有效提高多种水体中难降解有机物的处理效果[27]。而太阳光作为可再生能源,也被用于活化PI降解水体有机污染物[28]。ZHANG等[27]使用紫外光活化PI和TiO2,用于处理水体中的有机污染物,150 min时的降解率可达88%;GUO等[29]在模拟太阳光照射下活化PI,用于降解烷基咪唑基离子液体,结果在120 min内对1-己基-2,3-二甲基咪唑溴化铵的去除率达到了99%;HUANG等[30]采用氙灯模拟太阳光活化PI,对甲氧苄啶进行降解,结果显示,初始质量浓度为20 mg·L−1的甲氧苄啶在4 mol·L−1PI的添加条件下,50 min后的降解率可达92%。
基于模拟太阳光对PI的活化作用和TiO2的促进作用,本研究建立模拟太阳光活化PI水处理体系,并在该体系中引入TiO2,系统地研究了该联合体系中典型抗生素的降解效果及过程。采用氙灯为模拟太阳(simulated solar, SS)光源,建立模拟太阳光活化PI(PI/SS)系统,首先以SDZ为目标物,考察了TiO2添加前后体系中SDZ降解效果的变化以及相应的降解过程,并通过H2O2质量浓度测定和猝灭剂添加影响实验,初步探究模拟太阳光下TiO2活化PI降解SDZ作用机理。最后,通过考察TMP、CIP和EFA等典型抗生素溶液在PI/TiO2/SS体系中的降解效果验证了该协同过程的有效性。
模拟太阳光下高碘酸钠/TiO2协同降解水体抗生素
Synergetic degradation of antibiotics in water by periodate/TiO2 under stimulated solar irradiation
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摘要: 为了拓宽抗生素废水高效降解的方法,研究采用氙灯作为模拟太阳光源(Simulated sunlight,SS)活化高碘酸盐(Periodate,PI),建立用于抗生素降解的水处理体系,并通过在其中引入TiO2(PI/TiO2/SS),提升作用效果。研究首先以磺胺嘧啶(sulfadiazine,SDZ)为代表,分析了PI/TiO2/SS系统中影响其降解的关键参数,包括TiO2含量、PI含量、SDZ质量浓度和溶液初始pH等。结果表明,在0.3 mmol·L−1 PI和0.05 g·L−1 TiO2的条件下,处理30 min后SDZ的去除率可达95.13%,且PI含量越高、TiO2用量越大以及SDZ初始质量浓度越低时,降解率越高;在较宽的溶液pH范围内,PI/TiO2/SS体系均能实现SDZ的高效降解;反应过程中SDZ溶液的UV-Vis光谱和COD去除分析结果证明了PI/TiO2/SS体系协同作用。通过溶液中H2O2质量浓度的测定以及淬灭剂实验揭示了PI/TiO2/SS体系中·O2−>IO3·和·OH>h+对SDZ的降解作用。此外,对比考察了TiO2添加前后甲氧苄啶(Trimethoprim,TMP)、环丙沙星(Ciprofloxacin,CIP)和恩诺沙星(Enrofloxacin,EFA)溶液降解效果的变化,在一定程度上证明了PI/TiO2/SS体系针对抗生素废水处理的普适性。Abstract: In order to broaden the efficient degradation method of antibiotics in wastewater, the xenon lamp was used as the simulated sunlight (SS) source to activate the periodate (PI), and the water treatment system for antibiotics degradation was set up accordingly. The TiO2 was introduced to the system to improve the degradation effect. At first, sulfadiazine (SDZ) was taken as a representative, the key parameters in PI/TiO2/SS system affecting SDZ degradation were analyzed, which included TiO2 content, PI content, SDZ concentration and initial pH values of the solutions. The results showed that the SDZ degradation rate could reach 95.13% after 30 min treatment at 0.3 mmol·L−1 PI and 0.05 g·L−1 TiO2. The higher PI content, the higher TiO2 dosage, and the lower the SDZ concentration, the higher the degradation rate. The efficient degradation of SDZ in the PI/TiO2/SS system could be achieved in a wide range of solution pH. The UV-Vis spectra and COD removal analysis of SDZ solution during the reaction process proved the synergetic degradation effect of PI/TiO2/SS system. The action rule of ·O2− > IO3· and ·OH > h+ in the PI/TiO2/SS system for the SDZ degradation was revealed through the experiments of the H2O2 concentration detection and quenching experiments. In addition, the study investigated and compared the degradation of trimethoprene (TMP), ciprofloxacin (CIP) and enrofloxacin (EFA) solutions before and after TiO2 addition, which proved the universality of PI/TiO2/SS system for the treatment of antibiotic wastewater to some extent.
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Key words:
- simulated sunlight /
- TiO2 /
- periodate activation /
- antibiotic degradation /
- mechanism analysis
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表 1 正交实验设计
Table 1. Orthogonal experimental design
因素 水平 (A )TiO2/(g·L−1) (B) PI/(mmol·L−1) (C) pH 1 0.05 0.1 5 2 0.10 0.2 7 3 0.15 0.3 9 表 2 正交实验结果
Table 2. Orthogonal experimental results
序号 影响因子 A B C 降解率/% 1 0.05 0.1 5 57.72 2 0.05 0.2 7 82.71 3 0.05 0.3 9 94.97 4 0.10 0.1 7 60.1 5 0.10 0.2 9 83.4 6 0.10 0.3 5 94.1 7 0.15 0.1 9 61.75 8 0.15 0.2 5 83.88 9 0.15 0.3 7 95.46 K1 235.40 179.57 235.70 K2 237.60 249.99 238.27 K3 241.09 284.53 240.12 k1 78.47 59.86 78.57 k2 79.20 83.33 79.42 k3 80.36 94.84 80.04 R 1.90 34.99 1.47 -
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