为了阐明复杂组成废水的辐照处理过程中多种共存污染物同时存在对目标污染物降解产生的干扰作用,根据典型抗生素废水的组成,构建了一种多元污染模型,并设计了不同条件下辐照降解实验.结果表明,电离辐照可以有效地改善头孢抗生素废水的水质,经过5kGy辐照后污染模型的COD和TOC分别降低了15.4%和13.9%.目标污染物头孢噻肟钠(CTX)纯水溶液经过5kGy辐照后降解率可达到93%以上.污染模型中的共存物质会均对CTX的辐照降解产生某种程度的干扰作用,且干扰效应的强弱与相对浓度并无明显相关性.5kGy剂量下,CTX在污染模型中的降解率比在纯水中降低了11.8%.各共存物单独存在时(二元模型)和同时存在时(多元模型)对CTX降解的干扰方式存在差异.共存物单独存在时对CTX降解影响最大的化合物是苯并噻唑、硫脲和MIBK,其干扰效应Δkp分别为0.18、0.14和0.12;而同时存在时对CTX降解干扰效应最大的化合物是硫脲、苯并噻唑和二甲苯,其去干扰效应Δkn分别为0.22、0.17和0.03.不同化合物与自由基反应的先后顺序以及各共存物间的交互作用会对CTX的降解产生显著的影响.
Abstract
In order to clarify the interference effect of multiple coexisting pollutants on the degradation of target pollutants during the irradiation treatment process of complex wastewater, a multivariate pollution model was constructed according to the composition of typical antibiotic wastewater, and radiolytic degradation experiments under different conditions were designed. The results showed that ionizing irradiation could effectively improve the water quality of cephalosporin antibiotic wastewater. After irradiation at 5kGy, the COD and TOC of the pollution model decreased by 15.4% and 13.9%, respectively. The degradation percentage of the target pollutant cefotaxime sodium (CTX) in pure aqueous solution reached more than 93%. The coexisting compounds in the pollution model all have a certain degree of interference effect on the radiolytic degradation of CTX, and there is no significant correlation between the intensity of the interference effect and the relative concentration. After irradiation at 5kGy, the degradation percentage of CTX in the pollution model was 11.8% lower than that in pure water. There were differences in the interference modes of CTX degradation when the coexisting substances existed alone (binary model) and at the same time (multivariate model). Benzothiazole, thiourea and MIBK had the greatest influence on the degradation of CTX when existing alone, of which the interference effects Δkpwere 0.18, 0.14 and 0.12, respectively; while thiourea, benzothiazole and xylene had the greatest interference effect on the degradation of CTX when existing simultaneously, the de-interference effect Δkn were 0.22、0.17 and 0.03, respectively. The sequence of the reaction between different compounds and free radicals and the interaction between the coexisting substances have a significant effect on the degradation of CTX.
关键词
苯并噻唑 /
高级氧化 /
竞争反应 /
硫脲 /
实际废水
Key words
advanced oxidation processes (AOPs) /
benzothiazole /
competitive reaction /
real wastewater /
thiourea
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
参考文献
[1] Cantwell R E, Hofmann R. Ultraviolet absorption properties of suspended particulate matter in untreated surface waters [J]. Water Research, 2011,45(3):1322-1328.
[2] Paul J, Naik D B, Bhardwaj Y K, et al. Studies on oxidative radiolysis of ibuprofen in presence of potassium persulfate [J]. Radiation Physics and Chemistry, 2014,100:38-44.
[3] Khan J A, Shah N S, Khan H M. Decomposition of atrazine by ionizing radiation: Kinetics, degradation pathways and influence of radical scavengers [J]. Separation and Purification Technology, 2015, 156:140-147.
[4] Changotra R, Rajput H, Guin J P, et al. Comparative assessment of application of ionizing radiations in degradation of amoxicillin trihydrate (AMT) in aqueous solutions [J]. Chemical Engineering Journal, 2021,421:127847.
[5] Chu L, Wang J. Degradation of antibiotics in activated sludge by ionizing radiation: Effect of adsorption affinity of antibiotics [J]. Chemical Engineering Journal, 2023,468.
[6] Chen D, Chu L, Wang J, et al. Degradation of antibiotic cephalosporin C in aqueous solution and elimination of antimicrobial activity by gamma irradiation [J]. Chemical Engineering Journal, 2019,374: 1102-1108.
[7] Tegze A, Sági G, Kovács K, et al. Degradation of fluoroquinolone antibiotics during ionizing radiation treatment and assessment of antibacterial activity, toxicity and biodegradability of the products [J]. Radiation Physics and Chemistry, 2018,147:101-105.
[8] Sági G, Bezsenyi A, Kovács K, et al. Radiolysis of sulfonamide antibiotics in aqueous solution: Degradation efficiency and assessment of antibacterial activity, toxicity and biodegradability of products [J]. Science of The Total Environment, 2018,622-623:1009-1015.
[9] Basfar A A, Khan H M, Al-Shahrani A A, et al. Radiation induced decomposition of methyl tert-butyl ether in water in presence of chloroform: Kinetic modelling [J]. Water Research, 2005,39(10): 2085-2095.
[10] Wang X S, Liu Y L, Li M, et al. Occurrence of Iodophenols in aquatic environments and the deiodination of organic iodine with Ferrate(VI) [J]. Environmental Science & Technology, 2022,56(22):16104-16114.
[11] Bao Q, Dong J, Dong Z, et al. A review on ionizing radiation-based technologies for the remediation of contaminated groundwaters and soils [J]. C, hemical Engineering Journal, 2022,446:136964.
[12] Nie J, Zou J, Yan S, et al. Photosensitized Transformation of Peroxymonosulfate in Dissolved Organic Matter Solutions under Simulated Solar Irradiation [J]. Environmental Science & Technology, 2022,56(3):1963-1972.
[13] Song W, Yan S, Cooper W J, et al. Hydroxyl radical oxidation of cylindrospermopsin (cyanobacterial toxin) and its role in the photochemical transformation [J]. Environmental Science & Technology, 2012,46(22):12608-12615.
[14] 王建龙,初里冰.电离辐照技术在废水处理中的研究进展[J]. 环境工程学报, 2017,11(2):653-672.Wang Jianlong, Chu Libing. Research progress of ionizing irradiation technology on wastewater treatment [J]. Chinese Journal of Environmental Engineering, 2017,11(2):653-672.
[15] Wang S, Wang J. Oxidative removal of carbamazepine by peroxymonosulfate (PMS) combined to ionizing radiation: Degradation, mineralization and biological toxicity [J]. Science of The Total Environment, 2019,658:1367-1374.
[16] 王在峰,张水燕,张厚勇,等.头孢菌素制药行业水污染物特征成分谱解析[J]. 环境污染与防治, 2015,37(4):30-34,41.Wang Zaifeng, Zhang Shuiyan, Zhang Houyong, et al. Characteristic water pollutants composition analysis for cephalosporin pharmaceutical industry [J]. Environmental Pollution & control, 2015,37(4):30-34,41.
[17] 白辉.抗生素制药生产废水中特征有机污染物的分层同步检测方法及处理工艺去除效率研究[D]. 济南:山东大学, 2012.Bai Hui. Study on the layered synchronous detection method and treatment process removal efficiency of characteristic organic pollutants in antibiotic pharmaceutical production wastewater [D]. Jinan: ShanDong University, 2012.
[18] Xue J, Lei D, Zhao X, et al. Antibiotic residue and toxicity assessment of wastewater during the pharmaceutical production processes [J]. Chemosphere, 2022,291:132837.
[19] Islam M K, Baek A R, Sung B, et al. Synthesis, Characterization, and Anticancer Activity of Benzothiazole Aniline Derivatives and Their Platinum (II) Complexes as New Chemotherapy Agents [J]. 2021, 14(8):832.
[20] Negru G, Ghinet A, Bîcu E. 7-Chloroquinolinehydrazones as First- in-Class Anticancer Experimental Drugs in the NCI-60Screen among Different Investigated Series of Aryl, Quinoline, Pyridine, Benzothiazole and Imidazolehydrazones [J]. 2023,16(5):691.
[21] Moodley R, Mashaba C, Rakodi G H, et al. New quinoline– urea–benzothiazole hybrids as promising antitubercular agents: synthesis, in vitro antitubercular activity, cytotoxicity studies, and in silico ADME profiling [J]. 2022,15(5):576.
[22] Burton M. An introduction to radiation chemistry [J]. Journal of Chemical Education, 1951,28(8):404.
[23] Wang X H, Lin A Y C. Phototransformation of cephalosporin antibiotics in an aqueous environment results in higher toxicity [J]. Environmental Science & Technology, 2012,46(22):12417-12426.
[24] Yang B, Zuo J, Li P, et al. Effective ultrasound electrochemical degradation of biological toxicity and refractory cephalosporin pharmaceutical wastewater [J]. Chemical Engineering Journal, 2016, 287:30-37.
[25] Shah N S, Khan J A, Sayed M, et al. Solar light driven degradation of norfloxacin using as-synthesized Bi3+ and Fe2+ co-doped ZnO with the addition of HSO5−: Toxicities and degradation pathways investigation [J]. Chemical Engineering Journal, 2018,351:841-855.
[26] Wang S, Wang J. Carbamazepine degradation by gamma irradiation coupled to biological treatment [J]. Journal of Hazardous Materials, 2017,321:639-646.
[27] Niu Y, Yin Y, Xu R, et al. Electrocatalytic oxidation of low concentration cefotaxime sodium wastewater using Ti/SnO2–RuO2 electrode: Feasibility analysis and degradation mechanism [J]. Chemosphere, 2022,297:134146.
[28] Wang X, Li Z, Zhang Y, et al. Enhanced photocatalytic antibacterial and degradation performance by p-n-p type CoFe2O4/CoFe2S4/ MgBi2O6 photocatalyst under visible light irradiation [J]. Chemical Engineering Journal, 2022,429:132270.
[29] Changotra R, Guin J P, Khader S A, et al. Electron beam induced degradation of ofloxacin in aqueous solution: Kinetics, removal mechanism and cytotoxicity assessment [J]. Chemical Engineering Journal, 2019,356:973-984.
[30] Changotra R, Guin J P, Varshney L, et al. Assessment of reaction intermediates of gamma radiation-induced degradation of ofloxacin in aqueous solution [J]. Chemosphere, 2018,208:606-613.
[31] Huang D, Wang Z, Zhang J, et al. Gamma radiolytic degradation of 3,4-dichloroaniline in aqueous solution [J]. Separation and Purification Technology, 2016,170:264-271.
基金
环境模拟与污染控制国家重点联合实验室专项经费资助项目(24K26ESPCT)
PDF(1394 KB)
京公网安备 11010802030352号 
