二氧化氯去除水中微囊藻毒素及氧化动力学的研究
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摘要
由于内陆水体富营养化的加剧而引起的有毒有害藻类水华频繁发生,已成为国内外普遍关注的环境问题。其中,危害最严重的微囊藻水华所产生的微囊藻毒素为具有生物活性的环七肽肝毒素,是目前发现的最强的肝脏肿瘤促进剂。为此最新颁布实施的生活饮用水水质标准(GB5749-2006)中已将其列入非常规检测项目,并规定水中浓度低于1μg/L。常规工艺无法有效去除微囊藻毒素,因此急需找到新的技术控制水中微囊藻毒素的水平。本文针对这一热点问题,系统地研究了ClO_2杀灭微囊藻的效果和ClO_2去除MCs(MC-LR,MC-RR和MC-YR)的效果及氧化动力学。
     选择水华蓝藻中的3种典型藻种惠氏微囊藻和铜绿微囊藻(905#和915#),投加ClO_2进行了杀灭效果研究,结果表明:ClO_2对于微囊藻具有很好的杀灭效果。叶绿素去除率与ClO_2投加浓度、反应时间呈正相关性,与叶绿素初始浓度呈反相关性,反应温度和pH值对于叶绿素去除率影响不明显。当ClO_2投加量为2.5mg/L,温度25℃,pH=7.17时,反应15min后,惠氏微囊藻和铜绿微囊藻(905#和915#)的杀灭率分别可达到97.23%、96.2%和92.33%。通过对微囊藻毒素释放特性的研究显示,当ClO_2大于3.0mg/L时,胞内和胞外毒素都降到一个较低的水平,可以达到控制饮用水中微囊藻毒素含量的目的,保证饮用水安全。
     微囊藻毒素有多种异构体,其中以MC-LR,MC-RR和MC-YR最为普遍,研究了ClO_2去除这3种典型MCs的效果,结果表明:ClO_2对于MC-LR,MC-RR和MC-YR均具有很好的去除效果,对于100μg/L的MC-LR,MC-RR和MC-YR投加2.5mg/L ClO_2,10℃和pH6.48,反应60min时的去除率分别为94%,96.03%,94.9%。去除率与ClO_2投加剂量和反应时间呈正相关性,与MCs初始浓度呈反相关性,反应温度(5-25℃)和pH值(3.08-10.56)对于MCs去除率影响不明显。ClO_2的去除混合MCs与MC-LR,MC-RR及MC-YR的去除规律是一致的,在去除效果方面没有明显的差距。在后消毒的水样中,90min的时间2 mg/L ClO_2可以分别将10μg/L的MC-LR,MC-RR和MC-YR浓度降低至0.8,0.55和0.6μg/L;在预氧化水样中,90min的时间2 mg/L ClO_2可以分别将10μg/L的MC-LR,MC-RR和MC-YR浓度降低至0.9,0.6和0.7μg/L。
     运用孤立变数法研究了ClO_2氧化MC-LR,MC-RR和MC-YR的反应动力学,结果表明:ClO_2分别与MC-LR,MC-RR和MC-YR发生的氧化反应中,各反应物所对应的反应级数均为一级,总反应级数都为二级,反应数率常数(10℃和pH6.48)分别为k~2(MC-LR) 459.89 L/(mol·min)(R~2=0.9999),k~2(MC-RR) 583.15 L/(mol·min)(R~2=0.9998)和k~2(MC-YR) 488.43 L/(mol·min)(R~2=0.9999)。溶液pH和反应温度对各个反应速率常数的影响规律是一致的:随着pH值的升高,反应速率常数逐渐减小,10℃时在pH3.44到10.41的区间内,速率常数k~2(MC-LR)的变化范围是从5.18×10~2 L/(mol·min)到4.01×10~2 L/(mol·min) , k~2(MC-RR)变化是从6.11×10~2 L/(mol·min)到5.28×10~2 L/(mol·min) , k~2(MC-YR)变化是从5.237×10~2 L/(mol·min)到4.215×10~2 L/(mol·min);随着反应温度的升高,反应速率常数增大,活化能分别为Ea(MC-LR)64.757kJ/mol(R~2=0.9902),Ea(MC-RR)53.01kJ/mol(R~2=0.99)和Ea(MC-YR) 59.151 kJ/mol(R~2=0.99)。表明ClO_2与MC-LR,MC-RR和MC-YR在一般水处理条件下即可发生反应。在预氧化的过程中,将10μg/LMC-LR,MC-RR和MC-YR的浓度氧化降低至1.0μg/L以下,ClO_2的CT值分别为215.195,190.3和196.802 min·mg /L。在消毒的过程中,将10μg/LMC-LR,MC-RR和MC-YR的浓度氧化降低至1.0μg/L以下,ClO_2的CT值分别为156.638,137.1,和141.263 min·mg /L。
     通过液质技术初步探讨了ClO_2氧化MCs的反应机制,研究表明: ClO_2氧化MC-LR,MC-RR和MC-YR的主要氧化产物的m/z值分别为1029(995+2×17=1029) , 1072(1038+2×17=1072)和1079(1045+2×17=1079);推测的反应路径为ClO_2与MCs结构中的adda毒性基团中的共轭双键发生氧化反应,使其中一个碳碳双键(-C=C-)发生变化,双键打开,并在两个碳原子上分别加上一个OH-基团,则生成-C(OH)-C(OH)-。同时,通过LC-MS、UV光谱和TOC的测试结果表明:3个氧化反应得到的氧化产物都具有挥发性,且为有机物。
     本文研究得出ClO_2可以作为一种有效的技术去除水中的微囊藻毒素,这对蓝藻“水华”的治理和饮用水安全生产提供了科学依据,具有重要的理论意义和实际应用价值。
The enhancement of eutrophication in superficial freshwater bodies had increased of blooms of toxic cyanobacteria (blue-green algae) which had drawn attention of environmentalists worldwide. Bloom of microcystis is the most harmful, and produced microcystins which is hepatotoxic peptides and tumor-promoting agent and abundant in surface water. The analysis of microcystins is classified as uncommon item and of 1μg/L limitation in the standard of life and drinking water(GB5749-2006) which was issued and carried out recently. It is necessary to find a new method to control the level of microcystins in water because conventional water treatment processes is noffective. In this thesis, the removal of microcystis and MCs by ClO_2 were researched systematically, and the the oxidation kinetics of MCs acting with ClO_2 were studied too.
     Removal of three typical microcystis including M. aeruginosa(905#和915#)and M. wesenbergii in aqueous solution by ClO_2 were investigated systematically, and the results were showed as follow, ClO_2 could effectively remove M. aeruginosa and M. wesenbergii. The removal efficiency of chlorophyll was in positive correlation to ClO_2 dosage and the reaction time and in negative correlation to initial concentration chlorophyll, whereas it was affected by temperature and pH value slightly. The removal ratios of M. wesenbergii and M. aeruginosa(905#和915#)could reach to their maximum as approximately 97.23%、96.2%和92.33% respectively under the conditions as follows: the ClO_2 dosage 2.5mg/L, reaction time15 min, and pH 7.17. The study of the mechanism of intracellular microcystins release showed that ClO_2 dosage 3.0mg/L, intracellular and extracellular microcystins had fallen to a very little level.Therefor, ClO_2 is a suitable oxidant for the degradation of microcystins in drinking water treatment processes.
     MC-LR, MC-RR and MC-YR were very typical among congeners of MCs, removal efficiency of them by ClO_2 was studied. Experimental results indicated that MCs were removed by ClO_2 effectively, at pH 6.48 and 10℃, dosage ClO_2 is 2.5 mg/L, and the initial concentration of MC-LR, MC-RR and MC-YR are 100μg·L-1,respectively, the removal efficiency are 94%, 96.03% and 94.9%. The efficiency of removal was in positive correlation to ClO_2 dosage and reaction time and in negative correlation to initial concentration of MC-LR, whereas it was affected by temperature(5-25℃) and pH (3.08-10.56) value slightly. The removal of mixed MCs by ClO_2 had no obvious difference with that of MC-LR, MC-RR and MC-YR. MC-LR, MC-RR and MC-YR were decreased from 10μg/L of to 0.9, 0.6和0.7μg/L by 2 mg/L ClO_2 in preoxidation process in 90min, respectively, and 0.8, 0.55和0.6μg/L in disinfection processes.
     The oxidation kinetics of MC-LR, MC-RR and MC-YR was investigated in detail using chlorine dioxide according to the method of the law of isolated parameter. Experimental results indicated that the oxidation process was second order overall and first order with respect to reactants in three actions of ClO_2 oxidation MC-LR, MC-RR and MC-YR. At pH 6.48 and 10℃, the rate constant k as follow, k~2(MC-LR) 459.89 L/(mol·min)(R~2 = 0.9999) , k~2(MC-RR) 583.15 L/(mol·min)(R~2=0.9998) and k~2(MC-YR) 488.43 L/(mol·min)(R~2=0.9999), in the three reaction, the rate constant k of the actions could be increased through increasing temperature and decreasing pH value and ranged from 5.18×10~2 L/(mol·min) to 4.01×10~2 L/(mol·min) for MC-LR, 6.11×10~2 L/(mol·min) to 5.28×10~2 L/(mol·min) for MC-RR and 5.237×10~2 L/(mol·min) to 4.215×10~2 L/(mol·min) for MC-YR at 10℃. Activation energy of degradation by ClO_2 was 64.757kJ/mol for MC-LR, 53.01 kJ·mol-1 for MC-RR and 59.151 kJ/mol for MC-YR, it would be concluded that ClO_2 could remove MC-LR, MC-RR and MC-YR effectively on the condition of traditional water treatment. Study on removal efficiency of MC-LR, MC-RR and MC-YR by ClO_2 in preoxidation process and disinfection processes was carried out too, and the results was as follow, values of chlorine dioxide expose(CT) required for oxidation of MC-LR, MC-RR and MC-YR from 10μg/L to below 1.0μg/L process was 215.195,190.3 and 196.802 min·mg /L in preoxidation process and 156.638,137.1 and 141.263 min·mg /L in disinfection processes, respectively.
     Reaction mechanism of ClO_2 oxidation MCs were performed, analysis on structure and character of the products of ClO_2 oxidation MCs (MC-LR, MC-RR and MC-YR) by methods of UV(UV spectrophotometer), TOC (total organic carbon) and HPLC-MS was to make sure the possible path of reaction. The reaction products of MC-LR and ClO_2 were characterized by LC-MS and the main oxidation product which has m/z value of 1029(995+2×17=1029) could be determined, m/z value of 1072(1038+2×17=1072) for MC-RR and m/z value of 1079(1045+2×17=1079) for MC-YR. Results indicated that ClO_2 act with the the diene group of adda in MCs and change the structure of double bond between carbon and carbon in adda, the group of OH- were added the two carbon atoms to make the -C(OH)-C(OH)-. Products in the three action are all volatilizable and organics.
     Therefore, oxidation of ClO_2 could be taken as an effective technology for removing MCs from drinking water resources in traditional drinking water supplies in case of cyanobacterial toxin risk and the product was unharmful, this could be taken as basis of control of toxic cyanobacteria blooms and safe drinking water and has great theoretical and practical value .
引文
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