High catalytic hydrolysis of microcystins on pyrite surface

  • Yanfen Fang
  • Xinqiang Cao
  • Weiyong Feng
  • Wei Zhou
  • David Johnson
  • Yingping HuangEmail author
Original Paper


Eutrophication of water bodies is a phenomenon during which toxic microcystins from cyanobacteria are released into water. Natural minerals in soils and sediments are able to catalyze the degradation of microcystins. Here we studied the hydrolytic removal of microcystins on the surface of pyrite (FeS2). The surface structure of pyrite was analyzed by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and Fourier transformed infrared. The surface acidity of pyrite was measured by in situ diffuse reflectance infrared Fourier transform spectroscopy during pyridine adsorption/desorption. The concentration of d-alanine, d-glutamic acid, l-arginine and l-leucine were determined in pyrite/microcystin aqueous solution by high-performance liquid chromatography. Hydrolysis at the pyrite–microcystin interface was monitored by attenuated total reflection Fourier transformed infrared spectroscopy. Results show that sulfion and iron are layered, wherein the sulfion is above the surface, which provides active sites for the hydrolysis of microcystins. The hydrolysis rate of microcystins was up to 100% at 60 °C after 24 h in the presence of pyrite, based on the yield of l-arginine. Surface Lewis (≡Fe) and Brönsted acid (≡SH) sites of pyrite possibly bond to the carbonyl oxygen of peptide bonds, leading to highly efficient hydrolysis of microcystins.


Pyrite Hydrolysis Microcystins Amino acid Acid catalysis 



This work is founded by the National Natural Science Foundation of China (21577078, 21677086, 21407092 and 21972073), the Natural Science Foundation for Innovation Group of Hubei Province, China (2015CFA021), and the Three Gorges University Master's Thesis Training Fund (2019SSPY154).

Supplementary material

10311_2019_948_MOESM1_ESM.doc (1.5 mb)
Supplementary file1 (DOC 1487 kb)


  1. Bertrand C, Witczak L, Sabadie J et al (2003) Flazasulfuron: alcoholysis, chemical hydrolysis, and degradation on various minerals. J Agric Food Chem 51:7717–7721. CrossRefGoogle Scholar
  2. Brigante M, Zanini G, Avena M (2010) Effect of humic acids on the adsorption of paraquat by goethite. J Hazard Mater 184:241–247. CrossRefGoogle Scholar
  3. Borda M, Elsetinow A, Strongin D et al (2003) A mechanism for the production of hydroxyl radical at surface defect sites on pyrite. Geochim Cosmochim Ac 67:935–939. CrossRefGoogle Scholar
  4. Barrow GM (1956) The nature of hydrogen bonded ion-pairs: the reaction of pyridine and carboxylic acids in chloroform. J Am Chem Soc 78:5802–5806. CrossRefGoogle Scholar
  5. Fang Y, Zhou W, Tang C et al (2018) Brönsted catalyzed hydrolysis of microcystin-LR by siderite. Enviro Sci Technol 52:6426–6437. CrossRefGoogle Scholar
  6. Miao C, Ren Y, Chen M et al (2016) Microcystin-LR promotes migration and invasion of colorectal cancer through matrix metalloproteinase-13 up-regulation. Mol Carcinogen 55:514–524. CrossRefGoogle Scholar
  7. Tan J, Yang L, Kang Q et al (2011) In situ ATR-FTIR and UV–visible spectroscopy study of photocatalytic oxidation of ethanol over TiO2 nanotubes. Anal Lett 44(6):1114–1125. CrossRefGoogle Scholar
  8. Wei J, Furrer G, Kaufmann S et al (2001) Influence of clay minerals on the hydrolysis of carbamate pesticides. Environ Sci Technol 35:2226–2232. CrossRefGoogle Scholar
  9. Xian H, Zhu J, Tan W et al (2018) The mechanism of defect induced hydroxylation on pyrite surfaces and implications for hydroxyl radical generation in prebiotic chemistry. Geochim Cosmochim Acta 244:163–172. CrossRefGoogle Scholar
  10. Yoo J, Lee C, Wang B et al (2001) Investigation of catalytic property in the t-butylation of 1,2-dihydroxybenzene using FT-IR and XPS study. Res Chem Intermed 27:561–570. CrossRefGoogle Scholar
  11. Zhou W, Fang Y, Zhang Y et al (2017) Mechanism of photochemical degradation of MC-LR by pyrite. Environ Sci 38:3762–3768. CrossRefGoogle Scholar

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© Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.College of Biology and PharmacyChina Three Gorges UniversityYichangChina
  2. 2.Engineering Research Center of Eco-Environment in Three Gorges Reservoir Region, Ministry of EducationChina Three Gorges UniversityYichangChina

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