Simultaneous Analysis of Microcystins, Cylindrospermopsin, Anatoxin, and Nodularin in Lake Water by Liquid Chromatography-Tandem Mass Spectrometry
Abstract
Objective
To establish a method for simultaneous determination of trace levels of microcystins, cylindrospermopsin, anatoxin, and nodularin in lake water based on liquid chromatography-tandem mass spectrometry (LC-MS/MS).
Methods
After being adjusted to alkaline conditions and mixed with six internal standards, the water samples were enriched using dual HLB and ENVI-Carb cartridges. The eluates were then evaporated under nitrogen, reconstituted, and subjected to instrumental analysis. Both water and acetonitrile containing 0.1% formic acid were used as mobile phases. An ACQUITY UPLC® BEH C18 column (150 mm × 2.1 mm, 1.7 μm) was selected to separate the target cyanotoxins. Multiple reaction monitoring was applied for data acquisition, and quantification was accomplished using internal standard methods.
Results
Within certain concentration ranges, all 14 cyanotoxins examined in the study showed good linearity, with all correlation coefficients greater than 0.998. When the water volume was 100 mL, the limits of detection and quantification for the 14 cyanotoxins were 0.1-0.9 ng/L and 0.3-2.9 ng/L, respectively, and spiked recoveries and relative standard deviations were 81.7%-132.9% and 1.2%-14.9%, respectively. In the 10 lake water samples analyzed, cylindrospermopsin, anatoxin-α, and multiple microcystins were detected.
Conclusion
The method developed in the study has high-throughput capacity, as well as high sensitivity, accuracy, and reliability. The method can be applied in the simultaneous detection of microcystins, cylindrospermopsin, anatoxin, and nodularin in lake water.
Keywords: Cyanotoxins, Microcystins, Cylindrospermopsins, Liquid chromatography-tandem mass spectrometry, Lake water
Full Text:
PDFReferences
SVIRCEV Z, LALIC D, BOJADZIJA SAVIC G, et al. Global geographical and historical overview of cyanotoxin distribution and cyanobacterial poisonings. Arch Toxicol, 2019, 93(9): 2429-2481. doi: 10.1007/s00204-019-02524-4.
BURATTI F M, MANGANELLI M, VICHI S, et al. Cyanotoxins: producing organisms, occurrence, toxicity, mechanism of action and human health toxicological risk evaluation. Arch Toxicol, 2017, 91(3): 1049-1130. doi: 10.1007/s00204-016-1913-6.
ADAMSKI M, WOŁOWSKI K, KAMINSKI A, et al. Cyanotoxin cylindrospermopsin producers and the catalytic decomposition process: a review. Harmful Algae, 2020, 98: 101894. doi: 10.1016/j.hal.2020.101894.
PONIEDZIAŁEK B, RZYMSKI P, KOKOCIŃSKI M, et al. Toxic potencies of metabolite(s) of non-cylindrospermopsin producing Cylindrospermopsis raciborskii isolated from temperate zone in human white cells. Chemosphere, 2015, 120: 608-614. doi: 10.1016/j. chemosphere.2014.09.067.
GONZÁLEZ-BLANCO C, DÖRR F A, ALBUQUERQUE R, et al. Alternative isolation protocol for desulfo and zwitterionic cylindrospermopsin alkaloids and comparison of their toxicity in HepG2 cells. Molecules (Basel, Switzerland), 2020, 25(13): 3027-3045. doi: 10. 3390/molecules25133027.
CHRISTENSEN V G, KHAN E. Freshwater neurotoxins and concerns for human, animal, and ecosystem health: a review of anatoxin-α and saxitoxin. Sci Total Environ, 2020, 736: 139515. doi: 10.1016/j.scitotenv. 2020.139515.
PEARSON L, MIHALI T, MOFFITT M, et al. On the chemistry, toxicology and genetics of the cyanobacterial toxins, microcystin, nodularin, saxitoxin and cylindrospermopsin. Mar drugs, 2010, 8(5): 1650-1680. doi: 10.3390/md8051650.
OHTA T, SUEOKA E, IIDA N, et al. Nodularin, a potent inhibitor of protein phosphatases 1 and 2A, is a new environmental carcinogen in male F344 rat liver. Cancer Res, 1994, 54(24): 6402-6406.
TESTAI E, SCARDALA S, VICHI S, et al. Risk to human health associated with the environmental occurrence of cyanobacterial neurotoxic alkaloids anatoxins and saxitoxins. Crit Rev Toxicol, 2016, 46(5): 385-419. doi: 10.3109/10408444.2015.1137865.
U. S. Environmental Protection Agency. Drinking water health advisory for the cyanobacterial cylindrospermopsin. US Environ Prot Agency, Off Water (D. C. EPA-820R15), 2015.
LOFTIN K A, DIETZE J E, MEYER M T, et al. Total cylindrospermopsins, microcystins/nodularins, and saxitoxins data for the 2007 United States Environmental Protection Agency National Lake Assessment: U. S. Geological Survey Data Series 929, 9 p. , 2016. doi:10.3133/ds929.
LI Z Y, YU J W, YANG M, et al. Cyanobacterial population and harmful metabolites dynamics during a bloom in Yanghe Reservoir, North China. Harmful Algae, 2010, 9(5): 481-488. doi: 10.1016/j.hal.2010.03.003.
WANG J L, ZHANG J S, HU Z Y, et al. Simultaneous rapid determination of 12 microcystins in surface water with ultra performance liquid chromatography-tandem mass spectrometry. Chin J Public Health, 2021, 37(6): 1023-1026. doi: 10.11847/zgggws1126674.
JIANG L, ZHANG D. Simultaneous determination of nine cyanotoxins in water by highperformance liquid chromatography-tandem mass spectrometry. Water Wastewater Eng, 2013, 49(6): 37-41. doi: 10.3969/j. issn.1002-8471.2013.06.008.
WANG S Q, TAO S Y, SONG L R, et al. Comparation study on the determination of anatoxins by high performanceliquid chromatography-photodiode array detector and ultra performanceliquid chromatography-tandem mass spectrometry. J Food Saf Qual, 2020, 11(12): 3982-3991. doi: 10.19812/j.cnki.jfsq11-5956/ts.2020.12.045.
KIKUCHI S, KUBO T, KAYA K. Cylindrospermopsin determination using 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid (HEPES) as the internal standard. Anal Chim Acta, 2007, 583(1): 124-127. doi: 10. 1016/j.aca.2006.10.007.
TRAN N H, LI Y, REINHARD M, et al. A sensitive and accurate method for simultaneous analysis of algal toxins in freshwater using UPLC-MS/MS and 15N-microcystins as isotopically labelled internal standards. Sci Total Environ, 2020, 738: 139727. doi: 10.1016/j.scitotenv.2020. 139727.
ZERVOU S K, CHRISTOPHORIDIS C, KALOUDIS T, et al. New SPE-LC-MS/MS method for simultaneous determination of multi-class cyanobacterial and algal toxins. J Hazard Mater, 2017, 323(Pt A): 56-66. doi: 10.1016/j.jhazmat.2016.07.020.
U. S. Environmental Protection Agency. Health effects support document for the cyanobacterial toxin microcystins. US Environ Prot Agency, Off Water (D. C. EPA-820R15102), 2015. https://www.epa.gov/sites/default/files/2017-06/documents/microcystins-support-report-2015.pdf
DÍEZ-QUIJADA L, PRIETO A I, GUZMÁN-GUILLÉN R, et al. Occurrence and toxicity of microcystin congeners other than MC-LR and MC-RR: a review. Food Chem Toxicol, 2019, 125: 106-132. doi: https://doi.org/10.1016/j.fct.2018.12.042.
Refbacks
- There are currently no refbacks.
