Oxidation Characteristics of the Reactivity Between Pyrite and Aqueous Arsenate

  • Yongling Liu
  • Songhai WuEmail author
  • Shaoyi Jia
  • Zongsheng Liang
  • Xu Han
Research Article


Natural pyrites contain high levels of adsorbed and structurally incorporated arsenic (As), which may simultaneously result in the release of As and affect the oxidation process of pyrite. However, the oxidation and electrochemical behaviors of As on the oxidation reactivity of pyrites are still not clear. In this study, pyrite was prepared by a hydrothermal method and applied to study the oxidation mechanism between pyrite and aqueous arsenate. Analyses of X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy demonstrate that the as-prepared sample is an octahedron-like pyrite with high purity and crystallinity. The interaction between As(V) and pyrite as well as the electrochemical behaviors of pyrite oxidation in the presence of aqueous arsenate were investigated under acidic conditions by an ion analysis method, cyclic voltammetry (CV), Tafel, and electrochemical impedance spectroscopy (EIS). The results of the chemical reaction indicate that electrons are transferred from S22− to dissolved oxygen with the formation of SO42− in the initial As(V) concentration range of 0–0.3 mmol/L. In the initial As(V) concentration range of 0.4–1.2 mmol/L, electrons are transferred from S22− to As(V) with the formation of elemental S0 and As(III). The CV, the Tafel plot and EIS analyses indicate that aqueous arsenate in an electrolyte promotes oxidation reactivity and passivation of the pyrite electrode. Moreover, the electron transfer rate increases with increasing aqueous arsenate concentration in the electrolyte.


Pyrite Aqueous arsenate Pyrite electrode Oxidation reactivity Electrochemistry 



This work was financially supported by the National Key Research and Development Program of China (No. 2017YFC0211500) and the National Natural Science Foundation of China (Nos. 51878449; 21806121; 51508384).


  1. 1.
    Macpherson HA, Stoldt CR (2012) Iron pyrite nanocubes: size and shape considerations for photovoltaic application. ACS Nano 6:8940–8949CrossRefGoogle Scholar
  2. 2.
    An XL, Huang FG, Ren HT et al (2017) Oxidative dissolution of amorphous FeS and speciation of secondary Fe minerals: effects of pH and As(III) concentration. Chem Geol 462:44–54CrossRefGoogle Scholar
  3. 3.
    Abraitis PK, Pattrick RAD, Vaughan DJ (2004) Variations in the compositional, textural and electrical properties of natural pyrite: a review. Int J Miner Process 74:41–59CrossRefGoogle Scholar
  4. 4.
    Schoonen MAA, Harrington AD, Laffers R et al (2010) Role of hydrogen peroxide and hydroxyl radical in pyrite oxidation by molecular oxygen. Geochim Cosmochim Acta 74(17):4971–4987CrossRefGoogle Scholar
  5. 5.
    Zhang P, Yuan SH, Liao P (2016) Mechanisms of hydroxyl radical production from abiotic oxidation of pyrite under acidic conditions. Geochim Cosmochim Acta 172:444–457CrossRefGoogle Scholar
  6. 6.
    Kim EJ, Batchelor B (2009) Macroscopic and X-ray photoelectron spectroscopic investigation of interactions of arsenic with synthesized pyrite. Environ Sci Technol 43(8):2899–2904CrossRefGoogle Scholar
  7. 7.
    Bostick BC, Fendorf S (2003) Arsenite sorption on troilite (FeS) and pyrite (FeS2). Geochim Cosmochim Acta 67(5):909–921CrossRefGoogle Scholar
  8. 8.
    Bostick BC, Chen C, Fendorf S (2004) Arsenite retention mechanisms within estuarine sediments of pescadero, CA. Environ Sci Technol 38(12):3299–3304CrossRefGoogle Scholar
  9. 9.
    Sun F, Dempsey BA, Osseo-Asare KA (2012) As(V) and As(III) reactions on pristine pyrite and on surface-oxidized pyrite. J Colloid Interf Sci 388(1):170–175CrossRefGoogle Scholar
  10. 10.
    Qiu G, Gao T, Hong J et al (2017) Mechanisms of arsenic-containing pyrite oxidation by aqueous arsenate under anoxic conditions. Geochim Cosmochim Acta 217:306–319CrossRefGoogle Scholar
  11. 11.
    Chernyshova IV (2004) Pyrite oxidation mechanism in aqueous solutions: an in situ FTIR study. Russ J Electrochem 40(1):69–77CrossRefGoogle Scholar
  12. 12.
    Lin HK, Say WC (1999) Study of pyrite oxidation by cyclic voltammetric, impedance spectroscopic and potential step techniques. J Appl Electrochem 29(8):987–994CrossRefGoogle Scholar
  13. 13.
    Sanchez VM, Hiskey JB (1991) Electrochemical behavior of arsenopyrite in alkaline media. Miner Metall Proc 8:1–6Google Scholar
  14. 14.
    Renock D, Voorhis J (2017) Electrochemical investigation of arsenic redox processes on pyrite. Environ Sci Technol 51(7):3733–3741CrossRefGoogle Scholar
  15. 15.
    Le Pape P, Blanchard M, Brest J et al (2017) Arsenic incorporation in pyrite at ambient temperature at both tetrahedral S−I and octahedral FeII sites: evidence from EXAFS−DFT analysis. Environ Sci Technol 51(1):150–158CrossRefGoogle Scholar
  16. 16.
    Peiffer S, Behrends T, Hellige K et al (2015) Pyrite formation and mineral transformation pathways upon sulfidation of ferric hydroxides depend on mineral type and sulfide concentration. Chem Geol 400:44–55CrossRefGoogle Scholar
  17. 17.
    Han YS, Jeong HY, Demond AH et al (2011) X-ray absorption and photoelectron spectroscopic study of the association of As(III) with nanoparticulate FeS and FeS-coated sand. Water Res 45(17):5727–5735CrossRefGoogle Scholar
  18. 18.
    Zhang SL, Jia SY, Yu B et al (2016) Sulfidization of As(V)-containing schwertmannite and its impact on arsenic mobilization. Chem Geol 420:270–279CrossRefGoogle Scholar
  19. 19.
    Ouyang YT, Liu Y, Zhu RL et al (2015) Pyrite oxidation inhibition by organosilane coatings for acid mine drainage control. Miner Eng 72:57–64CrossRefGoogle Scholar
  20. 20.
    Renock D, Gallegos T, Utsunomiya S et al (2009) Chemical and structural characterization of As immobilization by nanoparticles of mackinawite (FeSm). Chem Geol 268(1–2):116–125CrossRefGoogle Scholar
  21. 21.
    Nesbitt HW, Muir IJ (1998) Oxidation states and speciation of secondary products on pyrite and arsenopyrite reacted with mine waste waters and air. Miner Petrol 62(1):123–144CrossRefGoogle Scholar
  22. 22.
    Qiu GH, Gao TY, Hong J et al (2018) Mechanisms of interaction between arsenian pyrite and aqueous arsenite under anoxic and oxic conditions. Geochim Cosmochim Acta 228(1):205–219CrossRefGoogle Scholar
  23. 23.
    Lehner S, Savage K (2008) The effect of As Co, and Ni impurities on pyrite oxidation kinetics: batch and flow-through reactor experiments with synthetic pyrite. Geochim Cosmochim Acta 72(7):1788–1800CrossRefGoogle Scholar
  24. 24.
    Cruz R, Méndez BA, Monroy M et al (2001) Cyclic voltammetry applied to evaluate reactivity in sulfide mining residues. Appl Geochem 16(14):1631–1640CrossRefGoogle Scholar
  25. 25.
    Giannetti BF, Bonilla SH, Zinola CF et al (2001) A study of the main oxidation products of natural pyrite by voltammetric and photoelectrochemical responses. Hydrometallurgy 60(1):41–53CrossRefGoogle Scholar
  26. 26.
    Gu G, Sun X, Hu K et al (2012) Electrochemical oxidation behavior of pyrite bioleaching by Acidthiobacillus ferrooxidans. Trans Nonferr Metal Soc 22(5):1250–1254CrossRefGoogle Scholar
  27. 27.
    Cristina C, Paul C, Mircea P (2014) Characterization of pyrite reactivity by cyclic voltammetry. Rev Chim (Bucharest) 65(2):215–218Google Scholar
  28. 28.
    Almeida C, Giannetti B (2002) Comparative study of electrochemical and thermal oxidation of pyrite. J Solid State Electr 6(2):111–118CrossRefGoogle Scholar
  29. 29.
    Yang HY, Yang L, Wei XJ (2001) Mechanism on bio-oxidation of arsenopyrite with Thiobacillus ferrooxidans strain SH-T. Chinese J Nonferr Metal 11(2):323–327 (in Chinese) MathSciNetGoogle Scholar
  30. 30.
    Zhang F, Zhao L, Chen H et al (2008) Corrosion resistance of superhydrophobic layered double hydroxide films on aluminum. Angew Chem In Ed 47(13):2466–2469CrossRefGoogle Scholar
  31. 31.
    Wang Z, Xie X, Xiao S et al (2010) Adsorption behavior of glucose on pyrite surface investigated by TG, FTIR and XRD analyses. Hydrometallurgy 102(1–4):87–90CrossRefGoogle Scholar
  32. 32.
    Liu Y, Dang Z, Wu PX et al (2011) Influence of ferric iron on the electrochemical behavior of pyrite. Ionics 17(2):169–176CrossRefGoogle Scholar
  33. 33.
    Lehner S, Ciobanu M, Savage K et al (2008) Electrochemical impedance spectroscopy of synthetic pyrite doped with As Co, and Ni. J Electrochem Soc 155(5):P61–P70CrossRefGoogle Scholar

Copyright information

© Tianjin University and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Yongling Liu
    • 1
  • Songhai Wu
    • 1
    Email author
  • Shaoyi Jia
    • 1
  • Zongsheng Liang
    • 1
  • Xu Han
    • 2
  1. 1.School of Chemical Engineering and TechnologyTianjin UniversityTianjinChina
  2. 2.Key Lab of Indoor Air Environment Quality Control, School of Environmental Science and EngineeringTianjin UniversityTianjinChina

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