山仔水库富营养化现状及其水华微囊藻毒素产生和分布特征研究
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摘要
山仔水库是福州第二饮用水源地,建库十余年来,水体富营养化发展趋势日益加剧。本研究一方面通过对该水库水华发生期水质的现状监测调查,分析各污染物浓度的时空分布特征、各理化水质指标之间的相关性,并评价该水库富营养化现状程度;另一方面,在优化超高效液相色谱检测微囊藻毒素(Microcystin,MC)色谱条件的基础上,对水库蓝藻水华发生期MC的产生和时空分布规律进行研究,并探讨了水库中存在的两种主要MC异构体(MC-LR、MC-RR)之间的相关性,结果表明:
     (1)按水深的垂直分布来看,水温、pH、溶解氧、化学耗氧量、硝氮和叶绿素a沿垂向分布有一定规律,而总氮、氨氮、总磷、正磷酸盐和总铁则未表现出明显的垂向空间分布上的变化趋势;通过比较表层和底层的各水质污染指标间的相关性分析发现,表层水体和底层水体各有特点,水质指标间的相关性程度存在显著差异。
     (2)利用2008年7-12月山仔水库各主要理化水质指标的监测值进行富营养现状程度的评价,结果显示,该水库目前处在中营养——中度富营养状态之间,富营养的发展趋势不容乐观。
     (3)超高效液相色谱检测微囊藻毒素(Microcystin,MC)色谱条件优化结果为:色谱柱:Acquity UPLC~(TM) BEH-C_(18)柱(1.7μm,1.0×50mm);流动相:甲醇:水(含0.1%三氟乙酸)=57:43,流速为0.3mL/min,柱温为30℃,进样量为10μL,检测含难分离杂质的环境样品时需要使用梯度洗脱程序,多数情况等度洗脱即可满足要求。
     (4)山仔水库蓝藻细胞内两种主要的MC异构体MC-LR与MC-RR的浓度、MC-(LR+RR)总浓度以及MC-(LR/RR)比值之间,沿水深垂向分布上均没有明显的规律性。MC-LR的浓度范围在0.01μg/L-11.43μg/L之间;而MC-RR的浓度普遍低于MC-LR,处于0.003μg/L-1.19μg/L之间。MC-(LR/RR)比值大小会因不同季节而引起的水温变化随之呈现一定的规律。
     (5)山仔水库蓝藻胞内MC横向分布为:水体表层MC-LR和的MC-RR浓度范围分别为0.05-11.43μg/L、0.01-1.16μg/L,表层胞内毒素多数以MC-LR为主;水体中层MC-LR和的MC-RR浓度范围分别为0.03-1.09μg/L、0.01-1.07μg/L,中层胞内毒素主导的异构体是MC-RR;水体底层MC-LR和的MC-RR浓度范围分别为0.03-1.02μg/L、0.003-1.07μg/L,其中,两种异构体总体比例较相当。此外,相关性研究结果表明,两不同结构毒素含量之间没有显著相关性。
ShanZi reservoir is the second water resource in Fuzhou. Its eutrophication development trend is getting more and more seriously during recent ten years. In this study, one hand, the present situation of water quality in ShanZi was monitored, and the spatial and temperal distribution characteristic of which ,as well as the correlations among each water pollutant index were analyzed. Moreover, the present situation of the ShanZi reservoir eutrophication level was calculated and assessmented. On the other hand, the microcystins(MCs) detection conditions of Ultra-performance liquid chromatography(UPLC) were optimized.On the base of the above research, the spatial and temperal distribution features of MCs which produced in cyanobacteria bloom were systemly surveyed,and the correlation between the two main isoform of Intra-LR and Intra-RR was analyzed. The results showed as follows:
     (1) The vertical distribution of the water quality indics including W.T.、pH、DO、COD、NO_3-N and chl.a,revealed some varying rule ,but TN、NH_4-N、TP、PO~(3-)P and Fe hadn't any rule. On account of the correlations among water pollutant index ,there was a large distinction between surface and bottom water environment.
     (2) The eutrophication level assessment result of the ShanZi reservoir was between moderate nutrition to moderate eutrophication ,based on the related water quality indics monitored data during July to December in 2008 .
     (3) The best chromatography condition of UPLC: chromatography column was Acquity UPLC~(TM)BEH-C_(18)(1.7μm,1.0×50mm );Mobile phase was Methanol: Water (0.1%TFA)=57:43;The flow of mobile phase was 0.3mL/min; Column temperature was 30℃; Detected wavelength was 238nm; Injection volume was 10μL.It needs gradient elution for detecting the environment sample which is difficult to be separated,but most of the time equal degree of elution was enough.
     (4) Among the intracell of MC-LR、MC-RR、MC-(LR+RR) and MC-(LR/RR) ,there weren't had any distinct rule on the vertical distribution of the reservoir. The intra-LR concentration range was 0.01μg/L-11.43μg/L,and 0.003μg/L-1.19μg/L for intra--RR. The vertical distribution of the propotional values of MC-(LR/RR) were rulely changed .
     (5) As to the cyanobacteria bloom in horizontal. distribution features were as follows:on the surface layer, the range content of MC-LR and MC-RR were 0.05-11.43μg/L and 0.01-1.16μg/L,respectively. MC-LR was the main isoform. In the middle layer, the range of content of MC-LR and MC-RR were 0.03-1.09μg/L and 0.01-1.07μg/L, respectively,but the main isoform of the middle layer was MC-RR. At the bottom, he range of content of MC-LR and MC-RR were 0.03-1.02μg/L and 0.003-1.07μg/L, respectively,and their two were about the same. Moreover, another conclusion was drawn that it hadn't a significant correlation between intra-LR and intra-RR.
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