宁波市饮用水源地爆发蓝藻水华时微囊藻毒素的污染分析

通过固相萃取净化,建立了超高效液相色谱-串联四极杆质谱法测定水中微囊藻毒素MC-LR和MC-RR的方法,并用该方法监测了宁波市两个饮用水源地爆发蓝藻水华时水体中的微囊藻毒素.监测结果表明,姚江水体中的微囊藻毒素污染水平低,MC-LR和MC-RR没有被检出;梅湖水库水体中MC-RR也未被检出,采取措施后,虽MC-LR有时被检出,但最高时也低于国家标准值(1.0μg/L).     

海河流域地表水中微囊藻毒素的测定

水样酸化过滤后用Oasis HLB固相萃取小柱净化富集,采用液相色谱-串联质谱法同时测定地表水中微囊藻毒素(MC-LR和MC-RR),通过优化试验条件,使方法在1.00μg/L～100μg/L范围内线性良好。MC-LR和MC-RR在水中的方法检出限为0.12 ng/L和0.2 ng/L,空白加标回收率为72.7%～88.5%,3次测定结果的RSD为9.1%～10.7%。将该方法用于6个海河流域部分重要水源地水样的监测,虽然部分水样中检测出MC-LR和MC-RR,但检出值均低于标准限值。     

杭州贴沙河微囊藻毒素污染特征及健康风险评价

在2014年9月杭州贴沙河出现蓝藻异常增殖期间,利用固相萃取-液质联用法对水体中胞外微囊藻毒素(EMC)和总微囊藻毒素(TMC)进行监测。共检出以MC-LR为主的8种微囊藻毒素(MC)单体,TMC总的质量浓度为63.9 ng/L~1 090 ng/L,其中MC-LR质量浓度为31.6 ng/L~472 ng/L,毒性等效MC-LR浓度为51.8 ng/L~862 ng/L,检出的MC-LR浓度值均低于限值标准。采用USEPA推荐模型对水体中MC污染的健康风险进行评价。各批次水样中MC-LR的非致癌健康风险指数(HI)为0.03~0.39,毒性等效MC-LR的HI介于0.04和0.72之间,均低于基准值,说明贴沙河作为饮用水水源尚无明显的健康风险。     

韶关市3座供水水库蓝藻种群及微囊藻毒素的季节变化

为了解供水水库的蓝藻种群和微囊藻毒素的季节变化,于2012年1—12月对韶关的苍村、瀑布和花山3座供水水库进行了采样分析。结果表明,3座水库为中营养型水库,监测蓝藻共9属(种),优势种为鱼腥藻和微囊藻,蓝藻最高丰度为5.67×107L-1;降水导致营养盐物质带入水库和水体不稳定性是蓝藻种群和优势种在夏秋两季季节变化和占优势的主要影响因子。3座水库ρ(微囊藻毒素)为0.1~0.9μg/L,最高值接近世界卫生组织对饮用水中MC-LR的指导性限制值(1μg/L)标准。微囊藻与微囊藻毒素呈显著正相关性(R=0.871,P0.01),表明产微囊藻毒素的蓝藻主要为微囊藻,当水库发生微囊藻水华时有发生微囊藻毒素的风险。     

响应面法优化测定水体中微囊藻毒素

针对水体中低浓度微囊藻毒素(MC-RR和MC-LR)的富集、淋洗、洗脱等前处理环节,采用单因素响应面优化法探讨微囊藻毒素前处理的最佳条件。结果表明:采用体积分数为25%的甲醇水溶液能够取得最佳淋洗效果,由One Factor设计优化得到体积分数为75%的甲醇水溶液作洗脱剂,MC-RR和MC-LR最佳回收率为89.4%和90.7%。方法在0.100 mg/L~5.00 mg/L范围内线性良好,MC-RR和MC-LR的检出限分别为0.07μg/L和0.04μg/L,实际水样加标回收率分别为80.6%和84.9%,平行测定结果的RSD分别为1.6%和2.4%。     

2017年夏季巢湖水华期间浮游植物与蓝藻毒素的时空变化特征

蓝藻水华暴发过程中水华物种的演替及其与蓝藻毒素的关系，对于湖泊的风险评估具有重大意义。于2017年水华暴发较为严重的夏季（6-8月）对巢湖水体的理化参数、浮游植物和蓝藻毒素进行了调查和分析。结果表明：夏季巢湖基本上处于富营养-超富营养的状态。24个样本共鉴定出浮游植物7门72属117种，以绿藻门、蓝藻门和硅藻门为主。浮游植物的群落组成和细胞密度存在明显的时空差异性，其中6月浮游植物平均细胞密度为1.35×10⁸ cells/L，优势种属主要为微囊藻（Microcystis spp.，优势度为0.397）、水华长孢藻（Dolichospermum flos-aquae，优势度为0.195）和水华束丝藻（Aphanizomenon flos-aquae，优势度为0.181）；7月浮游植物平均细胞密度为1.31×10⁸ cells/L，优势种属主要为微囊藻（优势度为0.741）和黏伪鱼腥藻（Pseudanabaena mucicola，优势度为0.072）；8月浮游植物平均细胞密度为1.01×10⁸ cells/L，优势种属主要为微囊藻（优势度为0.646）。11种蓝藻毒素在夏季巢湖水体中均有不同程度的检出，其中以微囊藻毒素MC-LR、MC-RR和MC-YR为主，最高检出浓度分别为0.115、0.107、0.018 μg/L。此外，分析了拟柱孢藻毒素浓度与水华束丝藻细胞密度的关系，显示两者之间存在非常显著的正相关性（P<0.01），表明水华束丝藻可能是其最主要的产毒蓝藻。11种蓝藻毒素的浓度均未超过饮用水安全标准的规定，但其潜在的安全风险依然需要密切注意。     

UPLC-MS/MS测定地表水中总微囊藻毒素的快速前处理方法探究

为方便地表水中总微囊藻毒素(TMCs)的预警监测,探究提取MC-LR、MC-RR、MC-YR的不同快速前处理方法,建立同时测定3种TMCs的煮沸-过滤-UPLC-MS/MS法。该方法在0.006μg/L~50.0μg/L范围内线性良好,方法检出限为0.006μg/L~0.010μg/L,实际水样3个质量浓度水平的加标回收率为88.6%~108%,6次测定结果的RSD为2.6%~9.4%。     

淡水水体中微囊藻毒素的监测技术

随着水体富营养化的日益加剧 ,有毒蓝藻水华在世界范围内频繁发生。有毒蓝藻产生的毒素对人类和动物有潜在的危害 ,迫切要求对水体中特别是饮用水源中的蓝藻毒素进行监测。微囊藻毒素是蓝藻产生的一类环状七肽 ,可以抑制蛋白磷酸酶 1和 2 A。微量微囊藻毒素还促进肿瘤的发生。简要介绍了近年来发展起来的几类微囊藻毒素监测技术 ,以期引起有关部门的重视     

太湖梅梁湾水源水中微囊藻毒素浓度的变化

对太湖梅梁湾水源水中的总藻毒素TMC[(TMC-LR) (TMC-RR)]和胞外藻毒素EMC[(EMC-LR) (EMC-RR)]进行了跟踪检测.结果表明,水体中TMC-RR、TMC-LR、EMC-RR、EMC-LR质量浓度平均分别为1.819 μg/L、1.090 μg/L、0.491 μg/L和0.077 μg/L,无锡市的主要水源地水质已受到微囊藻毒素的污染.提出,应加强水源地水体中微囊藻毒素浓度的监测,确保饮用水的安全.     

水中3种微囊藻毒素的高效液相色谱测定方法优化

对天然水体中3种痕量微囊藻毒素（MC-RR、MC-YR、MC-LR）的淋洗、洗脱、液相色谱测定等环节进行单因素不同水平考察,结果表明：以体积分数为45%的甲醇水溶液（含0.1%的TFA）为固相萃取淋洗剂、10 mL甲醇（含01%TFA）为固相萃取洗脱剂,体积分数为70%的甲醇水溶液（含0.1%TFA）为液相色谱流动相,可在6 min内有效分离MC-RR、MC-YR、MC-LR。将优化后的方法用于实际加标水样的测定,MC-RR、MC-YR、MC-LR的方法检出限分别为0.064 μg/L、0.098 μg/L、0.095 μg/L,加标回收率为87.0%~116%,RSD为10.2%~18.8%。     

固相萃取-高效液相色谱法测定武汉东湖水体中微囊藻毒素

建立了固相萃取-高效液相色谱法(SPE-HPLC)测定东湖水样中微囊藻毒素(MC)的方法,考察了不同流动相、淋洗液和洗脱液对MC-RR和MC-LR测定的影响。结果表明,MC-RR和MC-LR的方法检出限分别为0.0789μg/L和0.0234μg/L,其线性定量范围分别为0.1～10.0mg/L和0.06～10.0mg/L;样品测定回收率为78.4%～97.4%,RSD小于6.3%。该法灵敏度高,快速准确,用于实际水样测定的结果令人满意。     

中国北方山区水库与引黄水库富营养化特征

于2012年10月—2013年8月对中国北方地区2种典型水库:山区水库(卧虎山、锦绣川)和引黄水库(鹊山、玉清)进行了采样调查,对其水质特征和富营养化现状进行分析研究。结果表明:2类水库水质的最大差异在于山区水库的氮含量显著高于引黄水库,这主要与水源、氮素来源和水库的进水方式有关。山区水库中SD与藻类生物量、TP关系密切;而引黄水库中,影响SD的环境因素较复杂,除藻类生物量和氮、磷外,碱度和水温也与SD密切相关。全年水平上,卧虎山水库营养状态指数显著高于其他水库,属中-富营养水体,锦绣川水库、鹊山水库和玉清水库均属中营养水平。时间上,同类型水库的营养状态指数季节变化基本一致。参与营养状态计算的4个因子中,Chla和TN对营养状态指数的贡献最大,表明这两者是引起2类水库营养状态加重的重要原因。典型的水源及进水方式、流域人类活动类型和强度是影响山区水库和引黄水库营养状态的主要外部因素。     

Management of toxic cyanobacteria for drinking water production of Ain Zada Dam

Blooms of toxic cyanobacteria in Algerian reservoirs represent a potential health problem, mainly from drinking water that supplies the local population of Ain Zada (Bordj Bou Arreridj). The objective of this study is to monitor, detect, and identify the existence of cyanobacteria and microcystins during blooming times. Samples were taken in 2013 from eight stations. The results show that three potentially toxic cyanobacterial genera with the species Planktothrix agardhii were dominant. Cyanobacterial biomass, phycocyanin (PC) concentrations, and microcystin (MC) concentrations were high in the surface layer and at 14 m depth; these values were also high in the treated water. On 11 May 2013, MC concentrations were 6.3 μg/L in MC-LR equivalent in the drinking water. This study shows for the first time the presence of cyanotoxins in raw and treated waters, highlighting that regular monitoring of cyanobacteria and cyanotoxins must be undertaken to avoid potential health problems.     

Occurrence, distribution and bioaccumulation of antibiotics in the Haihe River in China

The occurrence, distribution and bioaccumulation of 22 antibiotics, including eight fluoroquinolones (FQs), nine sulfonamides (SAs) and five macrolides (MLs), in the Haihe River were investigated. Surface water, sediment and fish samples were analyzed by HPLC-MS/MS. Ofloxacin, sulfamethoxazole, sulfadiazine, erythromycin and roxithromycin were found in all surface water samples. SAs were the predominant antibiotics in surface water samples in the mainstream of Haihe River, with the maximum concentration of 201 ng L(-1) for sulfamethoxazole. Compared with Haihe River, higher concentrations of antibiotics were found in the surface water samples in the Dagu and Chentaizi Drainage Rivers. The antibiotics pollution in the mainstream of Haihe River may derive from its tributaries, whereas the wastewater from fish ponds was not the main source of FQs, SAs and MLs in the river water. In sediment samples, FQs were the most frequently detected antibiotics and their concentrations were much higher than SAs and MLs. The high concentrations and detection frequencies of FQs in sediments indicate that sediments are an important reservoir for FQs as they are strongly adsorbed onto sediments. Ciprofloxacin and erythromycin exhibited potential bioaccumulation in crucian carp, with mean bioaccumulation factors of 3262 L kg(-1) and 4492 L kg(-1), respectively.     

Identification of microcystins contamination in surface water samples from the Three Gorges Reservoir, China

Physicochemical and biological parameters related to water quality and microcystins (MCs) contamination in aquatic environment of the Three Gorges Reservoir were investigated in August 2004 and January 2005. A solid-phase extraction method and an HPLC equipped with photodiode array were used for MC-LR detection. A quantitative analysis showed the total MC-LR concentrations of water samples ranged from non-detectable to 0.57 μg L?1 among the seven sampling sites. The highest MC-LR concentration was found at sampling site G (Wushan), which was followed by F (Kaixian), E (Wanzhou), D (Fuling), C (Cuntan), and A (Daxigou). The correlation analysis showed the MC-LR concentration was positively correlated with chlorophyll-a concentration. This result suggests that MC concentration in water can be indirectly estimated by analyzing the chlorophyll-a concentration. Overall, the results of this study suggest that more importance should be placed on monitoring of MC contamination and water quality in the Three Gorges Reservoir to ensure drinking water safety and reduce the potential exposure of people to these health hazards.     

Association between biotic and abiotic parameters and the occurrence of cyanobacteria in a Brazilian reservoir

The water reservoir of Vargem das Flores, Brazil, has been subject to eutrophication problems. The occurrence of cyanobacterial blooms in this water body has raised concerns regarding the presence of toxic metabolites. In order to understand the factors that promote the proliferation and distribution of cyanobacteria in the reservoir, physicochemical parameters, species composition, and toxicity of the reservoir water column were analyzed at monthly intervals over a 3-year period (2004-2007) using a range of analytical techniques. The results showed that cyanobacteria were absent in the dry period, returning after the onset of stratification. A succession pattern was observed within this group. The Aphanocapsa genus was dominant in the last rainy period of the study (October 2006 to March 2007). However toxicity was only detected when the genera Microcystis and Sphaerocavum were present (October 2005). The principal components analysis showed negative correlation between cyanobacteria and orthophosphate. The change of dominant cyanobacteria along the 3 years of study and the final prevalence of nontoxic genera in the reservoir is an evidence of water quality improvement in response to the management techniques implemented in the reservoir basin.     

基于实测光谱的海河悬浮物浓度反演研究

悬浮物浓度是评价水质优劣的重要指标之一。以天津滨海新区海河为研究区域,进行光谱数据测量和水体样本采集,并在实验室进行水质参数提取,得到归一化光谱反射率和光谱一阶微分数据。然后对光谱测量数据和悬浮物浓度实测值进行相关性分析,发现896 nm归一化光谱反射率和光谱反射率比值(R_(896)/R_(546))与悬浮物浓度相关性较好。最后,分别建立单波段、波段比值和一阶微分函数拟合模型,进行对比分析。结果表明,基于R_(896)/R_(546)的二次多项式模型拟合效果最好,方差齐性检验(F)值也是最高的,可用于该地区水体的悬浮物浓度反演和预测。