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Transformation of microcystin-LR and olefinic compounds by ferrate(VI): Oxidative cleavage of olefinic double bonds as the primary reaction pathway
Water Research ( IF 12.8 ) Pub Date : 2018-05-09 , DOI: 10.1016/j.watres.2018.05.009
Ananna Islam , Dahee Jeon , Jiwoon Ra , Jaedon Shin , Tae-Young Kim , Yunho Lee

The presence of toxic microcystins in algal-impacted surface waters is a concern for drinking water quality management. In this study, the potential of ferrate(VI) to eliminate microcystins during drinking water treatment was assessed by investigating reaction kinetics, reaction sites, transformation products, and toxicity changes for the oxidation of microcystin-LR (MC-LR) as a representative microsystin. The investigations also included several substructural model compounds of MC-LR, such as cinnamic acid and sorbic acid, to elucidate the major transformation products and pathways of MC-LR and olefinic compounds. Second-order rate constants were determined in the pH range 6–10.4 for the reaction of ferrate(VI) with MC-LR and the model compounds. The kinetic data revealed that the olefinic double bonds in the Adda and Mdha residues of MC-LR were the primary ferrate(VI) reaction sites, while the phenyl or guanidine moiety was not the reaction site. This finding was supported by detection and identification of the MC-LR transformation products of double bond cleavage, with high peak abundance in the liquid chromatography-mass spectrometry. Furthermore, the reaction of ferrate(VI) with cinnamic and sorbic acids formed the corresponding aldehydes and organic acids with near complete carbon mass balance, indicating the oxidative cleavage of the double bonds as the primary reaction pathway. A quantitative protein phosphatase 2A (PP2A) binding assay for ferrate(VI)-treated MC-LR solutions showed that the MC-LR transformation products exhibited negligible PP2A binding activity compared to that of the parent MC-LR. Oxidation experiments in a filtered river water matrix spiked with MC-LR demonstrated the efficient elimination of MC-LR during water treatment with ferrate(VI).



中文翻译:

高铁酸盐(VI)转化微囊藻毒素-LR和烯烃化合物:烯烃双键的氧化裂解为主要反应途径

受藻类影响的地表水中存在有毒微囊藻毒素是饮用水质量管理的关注点。在这项研究中,高铁酸盐(VI)在饮用水处理过程中消除微囊藻毒素的潜力通过调查反应动力学,反应部位,转化产物和毒性变化来评估微囊藻毒素-LR(MC-LR)作为代表性的微systin的氧化作用。 。研究还包括MC-LR的几种亚结构模型化合物,例如肉桂酸和山梨酸,以阐明MC-LR和烯烃化合物的主要转化产物和途径。在高铁酸盐(VI)与MC-LR和模型化合物反应的pH范围6–10.4中确定了二级速率常数。动力学数据表明,MC-LR的Adda和Mdha残基中的烯烃双键是主要的高铁酸盐(VI)反应位点,而苯基或胍基不是反应位点。液相色谱-质谱法具有高峰丰度的双键裂解MC-LR转化产物的检测和鉴定为这一发现提供了支持。此外,高铁酸盐(VI)与肉桂酸和山梨酸的反应形成了具有几乎完全碳质量平衡的相应醛和有机酸,表明双键的氧化裂解是主要反应途径。高铁酸盐(VI)处理的MC-LR溶液的定量蛋白质磷酸酶2A(PP2A)结合测定表明,与亲本MC-LR相比,MC-LR转化产物的PP2A结合活性可忽略不计。在掺有MC-LR的滤过河水基质中进行的氧化实验表明,在高铁酸盐(VI)处理水的过程中可以有效消除MC-LR。

更新日期:2018-05-09
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