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Monolithic solid-phase extraction for the rapid on-line monitoring of microcystins in surface waters

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Abstract

We describe the development and optimization of a sensitive and selective screening method for the measurement of trace levels of microcystins in surface waters. Several sample preparation techniques were compared, including solid-phase microextraction (SPME), particle-based solid-phase extraction (SPE), and monolith-based SPE. A flow-injection (FI) based approach employing a reversed-phase monolithic SPE column was found to be optimal. Quantification was performed by directly interfacing the FI-based SPE system to an electrospray ionization-mass spectrometer (ESI-MS). To more safely simulate peptidyl toxins such as the microcystins, a model peptide (i.e., angiotensin II) was used for method optimization. Sample loading flow rate and volume, eluent composition, and elution flow rate were optimized. Sample throughput was six samples per hour, a detection limit of 1.31 ng angiotensin II was demonstrated for a linear dynamic range from 1–1,000 ng and 3.4% relative standard deviation (n = 4, 100 ng sample). Sample volumes up to 1,000 ml of surface water could be loaded onto the monolithic SPE disk without exceeding the sorbent’s capacity. Unlike conventional particle-based SPE methods, the monolithic SPE disk does not need to be replaced between samples and could be used indefinitely. The FI-based SPE-ESI-MS method was successfully applied to the determination of microcystin-LR, the most common of the microcystins, in environmental samples and was demonstrated for the direct monitoring of chlorinated drinking water, with trends tracked over a period of eight months.

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Acknowledgements

We thank Professor Colleen McDermott (University of Wisconsin–Oshkosh) for generously providing the samples of cyanobacteria. This work was supported by the UWM Center for Water Security. Presented in part at the 57th Pittsburgh Conference on Analytical Chemistry & Applied Spectroscopy, Orlando, FL (March 2004).

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  1. Jessica L. Ammerman

    Present address: SEAL Analytical, Inc., Mequon Technology Center, 10520-C North Baehr Road, Mequon, WI, 53092, USA

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  1. Department of Chemistry and Biochemistry, University of Wisconsin–Milwaukee, 3210 North Cramer Street, Milwaukee, WI, 53211, USA

    Jessica L. Ammerman & Joseph H. Aldstadt III

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  1. Jessica L. Ammerman
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Correspondence to Joseph H. Aldstadt III.

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Ammerman, J.L., Aldstadt, J.H. Monolithic solid-phase extraction for the rapid on-line monitoring of microcystins in surface waters. Microchim Acta 164, 185–196 (2009). https://doi.org/10.1007/s00604-008-0056-8

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