典型PPCPs对藻源有机物组分等的影响及其对超滤膜相应污染的机理研究

In response to the complex problem of membrane fouling in algal treatment by ultrafiltration, this research investigates the typical trace contaminants of pharmaceuticals and personal care products (PPCPs, Diclofenac, Naproxen and Carbamazepine) in natural water on the influence of Microcystic aeruginosa algogenic organic matter (AOM) and associated membrane fouling mechanism. By exploring how the PPCPs in water body lead to the changes of extracellular organic matter (EOM) and intracellularly organic matter (IOM) components and physiological and ecological characteristics, the diversity and regularity of AOM effects under different PPCPs treatments are revealed; by observing the ultrafiltration flux characteristics of IOM and EOM and organic removals, the membrane fouling mechanisms of EOM and IOM under influence of different PPACs treatments are clarified separately; and combined with the relationships between organic components and fouling indexes (FIs) and fouling resistance (FR) using high performance size exclusion chromatography (HPSEC) combined with peak-fitting prediction and fluorescence excitation-emission matrix spectroscopy coupled with parallel factor analysis (EEM-PARAFAC), the membrane fouling behaviors and mechanisms of AOM under influence of PPCPs treatments are analyzed systematically. This research has important academic value and realistic significance for the development of ultrafiltration membrane technology, membrane fouling control and high-algal water treatment with typical PPCPs.

针对超滤膜处理含藻水中膜污染的复杂性问题，本课题旨在研究水体中普遍存在的典型痕量污染物药品和个人护理用品（PPCPs，双氯芬酸、萘普生、卡马西平）对同一环境下水华藻铜绿微囊藻细胞分泌物的影响及进一步导致超滤膜污染的机理。探索水体中典型PPCPs如何会促使铜绿微囊藻藻源有机物各组分和生理特征产生变化，揭示PPCPs对藻源有机物（胞内和胞外有机物）产生影响效应的差异性和规律性；通过观察不同PPCPs影响条件下胞内和胞外有机物的超滤膜过滤特性和去除效果，探明PPCPs分别对胞内和胞外有机物组分等影响导致膜污染的机制；最后，通过高效凝胶色谱-分峰拟合和三维荧光光谱-平行因子分析方法分析有机物组分与膜污染指数和污染阻力之间的关系，综合阐释不同PPCPs影响条件下藻源有机物对膜污染的行为归趋和机理。本课题对于超滤膜技术的发展和膜污染的控制以及含典型PPCPs高藻水的处理具有重要的学术价值和现实意义。

针对超滤膜处理含藻水膜污染的复杂性问题，本课题研究了水体中普遍存在的典型痕量污染物药品和个人护理用品（PPCPs，双氯芬酸、萘普生和卡马西平）对同一环境下水华藻铜绿微囊藻藻细胞分泌物的影响及进一步导致的超滤膜污染机理。研究结果表明：水体中双氯芬酸、萘普生和卡马西平的存在及浓度的不同对铜绿微囊藻的生长和有机物特征影响是不同的。低浓度的卡马西平促进了藻细胞的生长，提高了胞内和胞外有机物中总有机碳的含量，而高浓度的卡马西平则抑制了胞外有机物总有机碳的释放，对水体的水质影响较小；双氯芬酸纳则在低浓度时对藻细胞产生明显的抑制效应。萘普生在1µg/L时藻细胞生长被显著抑制，然而，随着萘普生浓度的增大，藻细胞呈现先增长后抑制的现象。超滤膜实验结果表明：水体中低浓度的卡马西平（0.25µg/L）显著缓解了胞内和胞外有机物引起的膜污染，降低了膜的总阻力和可逆阻力，但当卡马西平浓度>0.25µg/L时，却加剧了胞内和胞外有机物引发的总阻力和可逆阻力。而双氯芬酸钠则在低浓度（0.25µg/L）时加剧了胞外有机物对超滤膜的污染，随着双氯芬酸浓度的增加，膜污染相比于藻细胞无任何浓度处理条件下显著缓解。胞内有机物膜通量的结果显示，双氯芬酸的存在在水体中无论是何种浓度处理，均显著加剧了胞内有机物对超滤膜的污染。不同PPCPs及浓度处理下的EOM和IOM的膜污染机理分析表明：滤饼层的形成仍然为胞内和胞外有机物对超滤膜污染的主要污染机制，但水体中药品和个人护理品的存在及浓度的不同会使得胞内和胞外有机物引发的膜污染机制发生了明显改变，如高浓度卡马西平（>1µg/L）浓度处理下膜通量的下降由滤饼层引发的膜污染更加严重，而水体中高浓度的双氯芬酸钠则使得胞外有机物由滤饼层引起的膜污染有所减轻。以上研究结果对于超滤膜技术在含藻水的处理，藻类的爆发以及膜污染的控制有重要的学术意义。