Qualitative analysis of the most toxic and abundant microcystin variants (LR, RR, and YR) by using LCMS.IT.TOF

In S. Kim; Giang Huong Nguyen; Sung-Jo Kim; Am Jang

Journal of Industrial and Engineering Chemistry, Vol.29, 375-381, September, 2015

DOI10.1016/j.jiec.2015.04.018 Export Citation

Qualitative analysis of the most toxic and abundant microcystin variants (LR, RR, and YR) by using LCMS.IT.TOF

In S. Kim, Giang Huong Nguyen, Sung-Jo Kim, and Am Jang^{1, †}

School of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), 123 Cheomdangwagi-ro, Buk-gu, Gwangju 500-712, Republic of Korea
¹School of Civil & Architectural Engineering, Sungkyunkwan University, Jangan-gu, Suwon 440-746, Gyeonggi-do, Republic of Korea

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Contamination of microcystins (a family of heptapeptide hepatotoxins), in eutrophicated water bodies is a worldwide problem. Due to their acute and chronic poisoning of animal and human health even at a low concentration of ppb scale, the accurate analysis is required of all microcystin variants present in a sample. In this study, a sensitive and selective method for the analysis of microcystin-LR (MC-LR), microcystin-RR (MC-RR), and microcystin-YR (MC-YR) using the liquid chromatograph mass spectrometry.ion trap.time of flight (LCMS-IT-TOF) technique has been developed. A new approach to quantify and distinguish microcystin variants by using LCMS-IT-TOF, a novel hybrid mass spectrometer having the multistep tandem mass spectrometry (MSn) ability, excellent resolution, and mass accuracy, could provide highly accurate analysis for evaluation of the toxicity of microcystins in a sample. In addition, chromatographic and spectrometric conditions were optimized for high peak intensity and the fine peak separation of microcystin variants. The results obtained of multistep tandem MS spectra strongly verified the presence of the studied microcystin variants in samples, and offered the lower detection limits of 5 pg on a column for MC-RR, and 10 pg on a column for MC-LR and MC-YR under the given analytical conditions.

Keywords:Liquid chromatograph mass spectrometry-ion trap-time of flight (LCMS-IT-TOF);Microcystins (MCs);Microcystin variants;MSn fragmentation

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[1] Hitzfeld BC, Hoger SJ, Dietrich DR, Environ. Health Perspect., 108, 113 (2000)

[2] WHO, Guidelines for Drinking-water Quality-Incorporating First Addendum to Third Edition-Volume 1: Recommendations, WHO, Geneva, 2006.

[3] Bhattacharya R, Sugendran K, Dangi RS, Rao PV, Biomed. Environ. Sci., 10, 93 (1997)

[4] McElhiney J, Lawton LA, Toxicol. Appl. Pharmacol., 203, 219 (2005)

[5] Zhao Y, Xie P, Fan H, Environ. Sci. Technol., 46, 34 (2011)

[6] Abramsson-Zetterberg L, Sundh UB, Mattsson R, Mutat. Res./Genet. Toxicol. Environ. Mutagen., 699, 5 (2010)

[7] Bischoff K, Vet. Hum. Toxicol., 43, 294 (2001)

[8] Gupta N, Pant SC, Vijayaraghavan R, Rao PVL, Toxicology, 188, 285 (2003)

[9] Zegura B, Sedmak B, Filipic M, Toxicon, 41, 41 (2003)

[10] Murata H, Shoji H, Oshikata M, Harada KI, Suzuki M, Kondo F, Goto H, J. Chromatogr. A, 693, 263 (1995)

[11] Zhang X, Song L, Zhang P, He J, Liu Y, Matsuura H, Watanabe MM, Phycol. Res., 60, 20 (2012)

[12] Campas M, Szydłowska D, Trojanowicz M, Marty JL, Talanta, 72, 179 (2007)

[13] Gurbuz F, Metcalf JS, Codd GA, Karahan AG, Environ. Forensics, 13, 105 (2012)

[14] Ortea PM, Allis O, Healy BM, Lehane M, NıShuilleabhain A, Furey A, James KJ, Chemosphere, 55, 1395 (2004)

[15] Miles CO, Sandvik M, Nonga HE, Rundberget T, Wilkins AL, Rise F, Ballot A, Environ. Sci. Technol., 46, 8937 (2012)

[16] Lajeunesse A, Segura PA, Gelinas M, Hudon C, Thomas K, Quilliam MA, Gagnon C, J. Chromatogr. A, 1219, 93 (2012)

[17] Yu Y, Xu J, Liu Y, Qiao S, Chen Y, Clin. Chim. Acta, 413, 894 (2012)

[18] Babica P, Kohoutek J, Blaha L, Adamovsky O, Marsalek B, Anal. Biochem., 385, 1545 (2006)

[19] Lotierzo M, Abuknesha R, Davis F, Tothill IE, Environ. Sci. Technol., 46, 5504 (2012)

[20] Kim IS, Nguyen GH, Kim S, Lee J, Yu HW, Environ. Eng. Res., 14, 250 (2009)