Ultra-trace levels analysis of microcystins and nodularin in surface water by on-line solid-phase extraction with high-performance liquid chromatography tandem mass spectrometry.

An on-line solid phase extraction coupled with high-performance liquid chromatography in tandem with mass spectrometry (on-line SPE/HPLC/MS-MS) method for the determination of five microcystins and nodularin in surface waters at submicrogram per liter concentrations has been optimized. Maximum recoveries were achieved by carefully optimizing the extraction sample volume, loading solvent, wash solvent, and pH of the sample. The developed method was also validated according to both UNI EN ISO IEC 17025 and UNICHIM guidelines. Specifically, ten analytical runs were performed at three different concentration levels using a reference mix solution containing the six analytes. The method was applied for monitoring the concentrations of microcystins and nodularin in real surface water during a sampling campaign of 9 months in which the ELISA method was used as standard official method. The results of the two methods were compared showing good agreement when the highest concentration values of MCs were found. Graphical abstract An on-line SPE/HPLC/MS-MS method for the determination of five microcystins and nodularin in surface waters at sub µg L(-1) was optimized and compared with ELISA assay method for real samples.

Management of a toxic cyanobacterium bloom (Planktothrix rubescens) affecting an Italian drinking water basin: a case study.

An extraordinary bloom of Planktothrix rubescens, which can produce microcystins (MCs), was observed in early 2009 in the Occhito basin, used even as a source of drinking water in Southern Italy. Several activities, coordinated by a task force, were implemented to assess and manage the risk associated to drinking water contaminated by cyanobacteria. Main actions were: evaluation of analytical protocols for screening and confirmatory purpose, monitoring the drinking water supply chain, training of operators, a dedicated web site for risk communication. ELISA assay was considered suitable for health authorities as screening method for MCs and to optimize frequency of sampling according to alert levels, and as internal control for the water supplier. A liquid chromatography-tandem mass spectrometric method able to quantify 9 MCs was optimized with the aim of supporting health authorities in a comprehensive risk evaluation based on the relative toxicity of different congeners. Short, medium, and long-term corrective actions were implemented to mitigate the health risk. Preoxidation with chlorine dioxide followed by flocculation and settling have been shown to be effective in removing MCs in the water treatment plant. Over two years, despite the high levels of cyanobacteria (up to 160 × 10(6) cells/L) and MCs (28.4 µg/L) initially reached in surface waters, the drinking water distribution was never limited.