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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 Δkp were 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.

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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.

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* 责任作者，副教授，
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赵震(2000-)，男，山西晋城人，武汉理工大学硕士研究生，主要研究方向为废水的电离辐照处理技术..

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赵震(2000-)，男，山西晋城人，武汉理工大学硕士研究生，主要研究方向为废水的电离辐照处理技术..

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赵震(2000-)，男，山西晋城人，武汉理工大学硕士研究生，主要研究方向为废水的电离辐照处理技术..

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The components and their contents of the contamination model

, figureFileSmall=null, figureFileBig=null, tableContent=
项目组分质量浓度(mg/L)物质的量浓度(mmol/L)
目标污染物头孢噻肟钠(CTX)200.033
共存污染物乙酸乙酯1501.7
甲基异丁基酮(MIBK)1001.0
硫脲761.0
二甲苯300.33
丙酮100.17
苯并噻唑200.15
), ArticleFig(id=1234106407507783710, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1234106386938917638, language=CN, label=表1, caption=

污染模型组分及含量

, figureFileSmall=null, figureFileBig=null, tableContent=
项目组分质量浓度(mg/L)物质的量浓度(mmol/L)
目标污染物头孢噻肟钠(CTX)200.033
共存污染物乙酸乙酯1501.7
甲基异丁基酮(MIBK)1001.0
硫脲761.0
二甲苯300.33
丙酮100.17
苯并噻唑200.15
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头孢废水模型的辐照降解特性及干扰效应
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赵震 , 李王蕊 , 杨淼 , 其布日 *
中国环境科学 | 水污染与控制 2025,45(6): 3135-3142
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中国环境科学 | 水污染与控制 2025, 45(6): 3135-3142
头孢废水模型的辐照降解特性及干扰效应
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赵震 , 李王蕊, 杨淼, 其布日*
作者信息
  • 武汉理工大学化学化工与生命科学学院，湖北 武汉 430070

    • 赵震(2000-)，男，山西晋城人，武汉理工大学硕士研究生，主要研究方向为废水的电离辐照处理技术..

通讯作者:

* 责任作者，副教授，
Study on the ionizing radiation-induced degradation and the interference effect of the multi-pollutants model of cephalosporin wastewater
Zhen ZHAO , Wang-rui LI, Miao YANG, Bu-ri QI*
Affiliations
  • School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, Wuhan 430070, China
出版时间: 2025-06-20
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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.

高级氧化  /  实际废水  /  竞争反应  /  苯并噻唑  /  硫脲

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 Δkp were 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.

advanced oxidation processes (AOPs)  /  real wastewater  /  competitive reaction  /  benzothiazole  /  thiourea
赵震, 李王蕊, 杨淼, 其布日. 头孢废水模型的辐照降解特性及干扰效应. 中国环境科学, 2025 , 45 (6) : 3135 -3142 .
Zhen ZHAO, Wang-rui LI, Miao YANG, Bu-ri QI. Study on the ionizing radiation-induced degradation and the interference effect of the multi-pollutants model of cephalosporin wastewater[J]. China Environmental Science, 2025 , 45 (6) : 3135 -3142 .
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基于电离辐照(IR)的废水处理技术(包括γ射线和电子束辐照)因其不需要加入任何化学试剂、不易造成二次污染且经济高效而受到了广泛关注[1-3].近年来，世界各国已将IR技术大规模应用于印染、医药及冶金等各类废水.研究证实，IR技术对水中的多种抗生素(如四环素、青霉素、头孢类以及磺胺类等)有显著的降解效果，不仅能够达到较高的降解率，且抗菌活性以及生物毒性均可得到较大的改善[4-8].作为高级氧化技术(AOPs)的一种，IR主要通过产生高活性的自由基(如·OH)对污染物分子进行破坏并去除[9].但这些活性自由基没有选择性，会对水中存在的所有组分进行无差别的氧化.而实际污水组成复杂，除目标污染物分子外，还含有多种非目标组分，引发许多非目标反应，造成活性自由基的大量消耗[10-11].不仅使目标物质的降解效果远低于预期，还浪费能量，从而大大降低了处理性价比.这已成为了制约IR技术进一步推广应用的主要瓶颈.
目前已知能够干扰目标污染物辐照降解反应的组分主要包括水体中广泛存在的一些无机阴离子、金属离子、O2、溶解性有机质等[12-14].然而这些基于单因子实验的结果与真实场景中多种共存物同时作用下污染物的实际降解行为存在着较大差异[15].另一方面，如果直接使用实际废水作为实验对象，则组成过于复杂，未知信息过多，样品的均质性和稳定性也难以保证.因此，为了厘清目标污染物与各类共存物质之间的关系，确定多种共存组分同时存在对目标物质降解产生的实际干扰作用，本研究拟通过遴选实际废水(以头孢抗生素生产废水为代表)中的典型化合物，并参照实际污染浓度比例配制混合溶液构建一种多元污染模型，对模型的辐照降解特性进行考察，分析不同组分对抗生素辐照降解的干扰效应及共存组分间的交互作用，旨在为阐明复杂组成污染水体的降解行为与机理以及开发针对性的处理工艺提供参考.
1　材料与方法
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1.1　水质调查及污染模型构建
为了客观、全面地掌握头孢抗生素生产废水的实际组成，首先对国内多家制药厂的污水检测报告、药厂周边水质及制药厂废水中的各类污染物指标进行了综合调研.根据调研数据，基于实际废水中主要污染物的浓度水平，建立了由一种目标污染物CTX(头孢噻肟钠)和多种共存污染物组成的多元污染模型[16-18].其中的共存有机污染物主要来源于制药生产过程中的有机溶剂以及化工原料，例如苯并噻唑衍生物作为一种上游原料，是药物分子骨架的组成部分，因而常存在于生产废水中[19-21].此外，模型中以腐殖酸(50mg/L)作为实际废水中所含的天然有机物质(NOM)的代表，并加入天然石英砂(150mg/L)以模拟废水中的SS(悬浮颗粒物).本研究构建的多元污染模型中目标污染物与各共存物浓度如表1所示.
1.2　试剂与样品
头孢噻肟钠(CTX，CAS号：79350-37-1)(纯度>98%)、硫脲(CAS号：62-56-6)(分析纯)、苯并噻唑(CAS号：95-16-9)(纯度>98%)、腐殖酸(CAS号：1415-93-6)(纯度>90%)购自阿拉丁化学试剂有限公司，分析级乙酸乙酯、甲基异丁基甲酮(MIBK)、二甲苯、丙酮、硫酸钠、氯化钠购自国药集团化学试剂有限公司.用于配制高效液相色谱流动相的色谱级甲醇、磷酸二氢钠、磷酸氢二钠均购自上海麦克林生化科技股份有限公司.将CTX溶于去离子水中配制成不同初始浓度(10，20，50，100及200mg/L)的CTX纯水溶液(一元体系)进行辐照降解动力学研究.将不同的共存物分别与CTX混合溶于去离子水中(浓度按照表1中的比例同时提高5倍，例如CTX初始浓度为5×20=100mg/L)配制成二元混合体系，用于考察每一种共存物的单独作用.将CTX与所有共存物同时混合，按表1中的浓度配制成完整的多元污染模型.从上述完整的污染模型(即n元模型)中去除掉某一共存污染物配制成n-1元混合体系(例如由CTX、MIBK、硫脲、二甲苯、丙酮、苯并噻唑、NOM和SS组成“除去乙酸乙酯的n-1元模型”)，用于干扰效应的研究.以上溶液均避光冷藏保存.
1.3　辐照实验
本辐照实验采用华中科技大学应用电磁研究所的0.4MeV电子加速器完成，高压设定为400kV，电子束电流设定为2.5mA(吸收剂量1kGy/pass)，传送带速度设定为10m/min，使用FWT-60-00薄膜显色剂量片确定吸收剂量.辐照实验在室温下重复进行，样品累计吸收剂量为单次通过吸收剂量与通过次数之乘积.用注射器取5mL废水模型溶液注入真空的8cm×12cm聚乙烯样品袋中，每组实验设置2个平行样.
1.4　分析方法
采用高效液相色谱(HPLC)法测定CTX的浓度，紫外可见检测器波长设为312nm，色谱柱为Agilent 5TC-C18反向柱(250mm×4.6mm)，流动相为磷酸缓冲盐溶液(磷酸二氢钠60mg/L、磷酸氢二钠1.2g/L)和甲醇(体积比为50:50)，进样量为15 μL，流动相流速为0.8mL/min，柱温保持在40℃.COD测定采用HJ 828－2017重铬酸盐法，BOD5测定采用HJ 505－2009稀释与接种法，使用紫外可见分光光度计(UV-1800PC，上海翱艺仪器)测定样品的紫外吸光度.总有机碳(TOC)含量采用TOC分析仪(TOC-L CPN，Shimadzu)进行测定.
1.5　辐射化学参数计算
有机污染物的电离辐照降解可以利用拟一级动力学模型来描述(式1).
式中：C (mg/L)为辐照后的剩余浓度;C0 (mg/L)为辐照前的初始浓度(即在0kGy剂量下的浓度);k为剂量常数，kGy-1，能够反映辐照降解速率的快慢;D为吸收剂量，kGy.根据剂量常数可以利用式(2)和式(3)进一步算出污染物降解50%和90%所需要的吸收剂量D0.5 (kGy)和D0.9 (kGy).
在辐射化学中，通常以化合物的G表征其辐照降解效率.某一吸收剂量下CTX的G(μmol/J)可利用式4进行计算[22].
式中：D为吸收剂量，kGy;C0为辐照前污染物的初始浓度，mol/L;C为在D剂量下辐照后的剩余浓度，mol/L.
1.6　干扰效应评价
以CTX纯水溶液(无共存组分)作为对照进行IR处理，将对照组去除率(Rp)、辐射化学产额(Gp)或剂量常数(kp)与含某共存组分的二元(或多元)污染模型IR处理后的CTX去除率(Rm)、辐射化学产额(Gm)或剂量常数(km)的差值ΔRp、ΔGp或Δkp作为该共存物单独干扰效应的度量(式5~7).若差值大于0，则表示该共存组分对CTX的辐照降解有抑制作用，小于0则有促进作用.
为了考察多种共存物交互作用影响下每一种组分的作用，本研究从完整污染模型(n元模型)中去掉某种组分，配制了n-1元污染模型，并进行了IR处理.将完整污染模型的CTX去除率Rn、辐射化学产额Gn或剂量常数kn与每个n-1元污染模型的CTX去除率Rn-1、辐射化学产额Gn-1或剂量常数kn-1相减，其差值ΔRn、ΔGn或Δkn定义为该组分的去干扰效应(de-interference effect)，用来反映多种共存组分同时存在条件下的干扰效应(式8-10).
2　结果与讨论
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2.1　污染模型综合性水质指标的变化
0~5kGy辐照过程中，由图1(a)可以看到，随着吸收剂量的增加，溶液的pH值从最初的5.6逐渐降低，3kGy后趋于稳定，最终达到4左右.这通常是由于模型中的污染物发生降解，生成了小分子羧酸等物质，导致溶液呈现了酸性[6].如图1(b)所示，随着吸收剂量的增加，污染模型的COD由最初的1300mg/L逐渐降低到5kGy剂量下的1100mg/L，降低了15.4%，而BOD5在0~4kGy剂量范围内出现了明显的上升趋势.因此B/C由初始的0.15提升到了0.45，可生化性有了较大改善.但在5kGy下BOD5突然下降，导致B/C下降到了0.14.这表明在低于4kGy剂量条件下，溶液中的有机物辐解能够转化成更容易被微生物利用的产物，而在5kGy下，则生成了某种毒性较强的产物.在头孢菌素的光催化降解[23]、电化学降解[24]、γ辐射降解[6]以及其他抗生素如诺氟沙星[25]的降解相关文献中也报道了类似现象.由图1(c)可见.污染模型中CTX和苯并噻唑的特征吸收波长分别在230nm左右和215nm左右，与吸收光谱中的两处吸收峰基本吻合.经过5kGy辐照处理后，污染模型的紫外吸光度在整体上有所减弱，特别是215和230nm处的吸收峰分别降低了22.5%和18.3%.这表明辐照可以有效地破坏模型中有机分子的结构，促进其降解.污染模型经过5kGy辐照后TOC降低了13.9%(由初始的2262.0mg/L降低至1947.0mg/L)，说明辐照处理可以起到一定程度的矿化作用[26].综上，适当剂量(1~4kGy)的辐照处理能够实现污染模型水质指标的提升，但过高的吸收剂量反而会导致溶液毒性的增加.
2.2　CTX的电离辐照降解动力学
如图2(a)所示，随着吸收剂量的增加，CTX浓度呈指数下降.在吸收剂量为5kGy下，不同初始浓度CTX的去除率达到了92.8%~99.8%，表明电子束辐照能够有效地去除水中的CTX.Niu等[27]使用电化学法来对CTX进行降解，一定条件下降解率为86.33%;而Wang等[28]使用光催化的方法在60min对CTX的降解率为82.7%.无论是在降解率还是在效率方面，电离辐照技术对CTX的降解应用都有着巨大的潜力.CTX的ln(C/C0)与吸收剂量的关系表明，CTX的降解符合一级动力学.随着污染物初始浓度从10mg/L增加到200mg/L,k由1.15kGy-1降低到了0.49kGy-1(图2(c)). D0.5和D0.9也相应地从10mg/L浓度时的0.6kGy和2.0kGy分别提升至200mg/L浓度时的1.4kGy和4.7kGy.可见，污染物初始浓度与其辐照降解速率呈明显负相关关系.这是由于污染物初始浓度越高，在相同吸收剂量下发生反应的分子比例越小，从而导致了k的降低[29].
同时，G随着初始浓度的增高而增高，但随着吸收剂量的增加而降低(图2(b)).这是因为初始浓度越高，污染物与自由基反应的机会越多.而吸收剂量增加则会导致溶液中产生更多的降解中间产物，这些中间产物会与原污染物分子竞争活性自由基，导致单位能量去除的分子数降低[29-31].
2.3　各共存物单独存在时对CTX辐照降解的干扰效应
如图3(a)所示，辐照实验结果表明，在不同共存物存在时，CTX均能够被有效降解，其浓度随吸收剂量的增加而快速降低.经5kGy剂量辐照后，各混合溶液中CTX的降解率均达到75%以上.同时，几种共存物均会对CTX的辐照降解产生不同程度的干扰作用.无论从CTX去除率(图3(b))、降解速率常数k(图3(c))或是G(图3(d))来看，对CTX降解影响最大的共存化合物均是苯并噻唑，其次为硫脲和MIBK.而其余3种有机污染物，即丙酮、二甲苯和乙酸乙酯，在各自的二元体系中影响较弱.
乙酸乙酯作为模型中浓度最高的共存组分，其干扰效应却不是最强的;相反，浓度最小的苯并噻唑却表现出了最强的干扰效应.这表明，在本研究构建的废水模型中，干扰效应的强弱主要由共存物本身的性质，即对自由基的亲和力或消耗自由基的能力决定，而受化合物相对浓度的影响不显著.同时，由图3(b)可知，对任意一种共存物质而言，其对CTX去除率的影响程度与吸收剂量之间并无明显的相关性.但从G的改变来看，大部分共存物质(除二甲苯外)在1kGy下的干扰效应远高于其他辐照剂量下的干扰效应.当吸收剂量超过2kGy时，共存物对CTX辐射化学产额的改变并不显著.这可能是由于，当吸收剂量增加时，纯CTX溶液辐照降解的G本来就比较小(图2(b))，因此共存物作用下其改变量ΔGp也相应地比较小.换言之，吸收剂量增加本身会导致CTX降解中间产物对活性自由基的竞争作用增强，此时由共存化合物造成的干扰效应就会相对变弱.
2.4　各共存物同时存在时对CTX辐照降解的干扰效应
尽管利用上述二元混合体系可以较为简单直接地表明某一共存物对CTX降解的影响，但无法反映真实污水中多种共存物质的复杂关系.为了阐明各种共存物在复杂组成污水中对CTX降解的影响，本研究进行了多元污染模型的辐照处理实验，并在此基础上设计了n-1组分辐照实验.可以合理地推想，当某个n-1元模型曲线越接近空白组，则表明该组去掉的污染物在复杂体系中对于CTX的辐照降解干扰越强;相反，越接近完整模型则表明其对CTX降解的影响越弱.
由图4(a)可以观察到，与空白组相比，在完整的污染模型中，CTX的辐照降解受到了明显的抑制，降解率下降了11.8%.而6条n-1组分模型中，去硫脲组、去苯并噻唑组和去二甲苯组的一级动力学拟合曲线基本上位于空白组(即仅含CTX的纯水溶液，k＝0.91kGy-1)与完整的多元污染模型(k＝0.39kGy-1)之间，其余3条曲线与完整模型曲线差异较小.这表明，从污染模型中去掉硫脲、苯并噻唑或二甲苯后，CTX受到的干扰作用会明显变弱.根据1.6节中的定义，亦即硫脲、苯并噻唑和二甲苯的去干扰效应较为显著.其中，去掉硫脲组的曲线(k＝0.61kGy-1)最接近空白组，而与完整模型的曲线距离最远，其次是去掉苯并噻唑组(k＝0.56kGy-1).在5kGy吸收剂量下，完整模型中CTX的降解率为88.1%，而在去硫脲组和去苯并噻唑组中CTX降解率均提升至94%.
由图4(b)可知，与二元体系实验结果类似，在n-1元混合体系中，同一物质的去干扰效应与吸收剂量的大小并无明显的相关性，不同共存物间的差异则较为显著，表明化合物种类对去干扰效应的强弱起决定作用.从剂量常数方面来看(图4(c))，硫脲和苯并噻唑为去干扰效应最强的两个化合物.对比图4(b)和图(c)还可以发现，去二甲苯组在1kGy剂量下的ΔRn高于其他几组，但在更大剂量条件下ΔRn有所减小，因此整体上来看，其Δkn值并不高，也即二甲苯对CTX的去干扰效应并不大.类似地，对于去MIBK组而言，在1~2kGy下的ΔRn与去硫脲组基本持平，但3kGy以后开始减小，导致其在剂量常数Δkn上反映出的去干扰效应非常微弱.上述现象的发生可能与多元混合体系中的各个共存物质的降解顺序有关.在较低吸收剂量下，部分物质(如二甲苯和MIBK)优先与自由基反应并发生降解，导致其在较高剂量下对CTX的去干扰效应减弱.
值得注意的是，某些化合物在多元体系辐照实验中表现出的去干扰效应与二元体系中表现出的干扰效应规律并不完全一致.例如，MIBK虽然在与CTX组成的二元混合体系中产生了较强的干扰作用(图3(c))，但在多元体系下的干扰效应远小于其他共存化合物.这表明多个组分共存时对CTX降解的干扰方式与单一组分对CTX干扰方式不同.在多元体系中，各共存化合物的交互作用(包括各个物质的降解产物间的交互作用)会对CTX的降解产生显著的影响.从图4(d)来看，以G值表达的去干扰效应与剂量的关系与二元体系中的规律有所不同.乙酸乙酯、MIBK和硫脲在1kGy下的去干扰效应并没有明显强于其他剂量，而二甲苯却在1kGy下表现出了比其他剂量强得多的去干扰效应.这可能与各共存组分间的交互作用以及干扰作用产生的先后顺序有关.
3　结论
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3.1　电子束辐照可以有效地降解头孢抗生素废水中的有机污染物.适当剂量的辐照能够提高抗生素废水的可生化性，4kGy辐照后B/C提高了200%，但过高的吸收剂量反而会使其毒性显著增加.
3.2　目标污染物CTX的降解满足一级动力学，且随着污染物浓度的增加，k值降低，G值升高.同时，污染模型中的大多数共存物质由于对活性自由基的竞争反应，均会对CTX的辐照降解产生某种程度的干扰作用.干扰效应的强弱与相对浓度并无明显相关性.
3.3　在5kGy辐照剂量下，CTX在污染模型中的降解率比在纯水中降低了11.8%.各共存化合物单独存在时(二元混合体系)和同时存在时(多元污染模型)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.而在多元污染模型中对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.
3.4　同一种物质的干扰效应和去干扰效应并没有随吸收剂量的增大而呈现规律性的增强或减弱，但在多元混合体系中，一些化合物(如二甲苯和MIBK)在较低剂量下对干扰效应的贡献显著高于其他化合物，而当剂量升高时，其优势逐渐消失.这可能与不同化合物与自由基反应并发生降解的先后顺序有关.各共存化合物的交互作用(包括各个物质的降解产物间的交互作用)会对CTX的降解产生显著的影响.
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  • 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)
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2025年第45卷第6期
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  • 接收时间：2024-11-06
  • 首发时间：2026-02-27
  • 出版时间：2025-06-20
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  • 收稿日期：2024-11-06
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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)
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    武汉理工大学化学化工与生命科学学院，湖北 武汉 430070

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