Fast and Accurate Determination of Algal Toxins in Water using Online Preconcentration and UPLC-Orbitrap Mass Spectrometry

온라인 시료주입과 UPLC-Orbitrap 질량분석법을 이용한 수질 조류독소의 고속분석방법 개발 및 환경시료적용

  • 장제헌 (한국수자원공사 수질분석연구센터) ;
  • 김윤석 (한국수자원공사 수질분석연구센터) ;
  • 최재원 (한국수자원공사 수질분석연구센터)
  • Published : 2012.11.30

Abstract

Due to the fast response to algae bloom issue in drinking water treatment plant, very fast determination methodology for algal toxin is required. In this study, column switching technique based online preconcentration method was combined with high resolution full scan mass spectrometer to save sample preparation time and to obtain fast and accurate result. After parameter optimization of online preconcentration, 1mL filtered sample was directly injected to trap column with switching valve system. Next, target toxins are eluted by 98% acetonitrile and analysed with 150 - 1,100 amu scan range at 50,000 resolving power. Method detection limit (MDL) for microcystin-LR, the most toxic isomer, was 0.1 ng/mL and others such as microcystin-YR, microcystin-RR and nodularin were 0.08, 0.03 and 0.04 ng/mL, respectively. This is the best improved sensitivities with 1mL volume in the literature. Furthermore, due to the use of ultra pressure HPLC (UPLC), the whole method run was completed in 4 min. Real sample applications for 173 sample including 55 surface water and 118 treatment plant samples for raw and treated water could be done within 16 hours. In our calculation, this methodology is roughly 80% faster than the previous manual solid-phase extraction with LC-MS/MS method.

Keywords

References

  1. Kim, J. H., Kim, H. C., and Yun, M. A. (2009). Method for simultaneous determination of cyanotoxins in water by LCMS/ MS, Journal of Korean Society on Water Environment, 25(4), pp. 597-605. [Korean Literature]
  2. Lee, J. J., Kim, H. B., Moon, J. S., Lee, J. A., Lee, H. J., Park, H. K., Park, J. H., and Seo, J. K. (2010). Assessment of Microcystin Analysis Methods for Convenient Nonitoring, Korean Society on Water Environment (Fall), pp. 643-644. [Korean Literature]
  3. NIER. (2009). An Assessment of Warning Criteria on Algal Bloom (II), National Institute of Environmental Research, pp. 4-5. [Korean Literature]
  4. Park, H. K., Kim, H. B., Moon, J. S., Lee, J. A., Lee, H. J., Lee, J. J., Park, J. H., Seo, J. K., and Youn, S. J. (2011). Investigation of Criterion on Harmful Algae Alert System using Correlation between Cell Number and Cellular Microcystins Content of Korean Toxic Cyanobacteria, Journal of Korean Society on Water Environment, 27(4), pp. 491-498. [Korean Literature]
  5. Yu, S. J., Han, E. Y., Hwang, J. Y., Ryu, J. K., and Yoon, Y. S. (1999). Analysis of Microcystins in Daecheong Reservior using by High Performance Liquid Chromatography, Journal of Korean Society on Water Environment, 15(4), pp. 517-526. [Korean Literature]
  6. Cong, L., Chena, Q., Huang, B., Lu, B., Ren, Y., and Zhang, J. (2006). Determination of Trace Amount of Microcystins in Water Samples using Liquid Chromatography Coupled with Triple Quadrupole Mass Spectrometry, Nalytica Chimica Acta, 569 (31), pp. 157-168.
  7. Fastner, J., Flieger, I., and Neumann, U. (1998). Optimized Extraction of Microcystins from Field Samples a Comparison of Different Solvents and Procedures, Water Research, 32(10), pp. 3177-3181. https://doi.org/10.1016/S0043-1354(98)00073-6
  8. Harada, K., Matsuura, K., and Suzuki, M. (1988). Analysis and Purification of Toxic Peptides from Cyanobacteria by Reversed-phase High-performance Liquid Chromatography, Journal of Chromatography A, 448, pp. 275-283.
  9. Harada, K. I., Kiyonaga, F., Makoto, S., and Tomoyo, N. (2004). Comprehensive Analysis System using Liquid Chromatography. Mass Spectrometry for the Biosynthetic Study of Peptides Produced by Cyanobacteria, Journal of Chromatography A, 1033, pp. 107-113. https://doi.org/10.1016/j.chroma.2004.01.006
  10. Henriksen, A. S. and Olli, K. (1996). Sedimentation and Buoyancy of Aphanizomenon cf. flos-aquac (Nostocales, Cyanophyta) in a Nutrient-replete and Nutrient-depleted Coastal Area of the Baltic Sea, Hycologia, 35, pp. 94-101.
  11. Lawton, L. A., Codd, G. A., and Edwards, C. (1994). Extraction and High-performance Liquid Chromatographic Method for the Determination of Microcystins in Raw and Treated Waters, Analyst, 119, pp. 1525-1530. https://doi.org/10.1039/an9941901525
  12. Lee, H. S., Kim, K., Kim, Y. H., Do, K. S., Jeong, C. K., Lee, H. M., and Choi, S. J. (1999). On Line Trace Enrichment for the Simultaneous Determination of Microcystins in Aqueous Samples using High Performance Liquid Chromatography with Diode-array Detection, Journal of Chromatography A, 848 (1.2), pp. 179-184.
  13. Petrovic, M., Barcelo, D., and Tavazzi, S. (2002). Columnswitching System with Restricted Access Pre-column Packing for an Integrated Sample Cleanup and Liquid Chromatographic - mass Spectrometric Analysis of Alkylphenolic Compounds and Steroid Sex Hormones in Sediment, Journal of Chromatography A, 971(20), pp. 37-45.
  14. Repavich, W. M., Meisner, L. F., Sonzogni, W. C., Standridge, J. H., and Wedepohl, R. E. (1990). Cyanobacteria (blue-green algae) in Wisconsin Waters: Acute and Chronic Toxicity, Water Research, 24, pp. 225-231. https://doi.org/10.1016/0043-1354(90)90107-H
  15. Sivonen, K. (2009). Cyanobacterial Toxins. Encyclopedia of Microbiology (Third Edition), pp. 290-307.
  16. WHO. (1999). Toxic Cyanobacteria in Water, A Guide to Their Public Health Consequences, Monitoring and Management, pp. 163-164.
  17. Zweigenbaum, J. A., Beattieb, K. A., Coddb, G. K., and Heniona, J. D. (2000). Direct Analysis of Microcystins by Microbore Liquid Chromatography Electrospray Ionization Ion-trap Tandem Mass Spectrometry, Journal of Pharmaceutical and Biomedical Analysis, 23(4), pp. 723-733. https://doi.org/10.1016/S0731-7085(00)00354-X