Skip to main content

Advertisement

Log in

Arsenopyrite oxidative dissolution in NaCl solution at high-temperature and high-pressure conditions: kinetics, pathways, dissolution mechanism and geological implications

  • Original Paper
  • Published:
Contributions to Mineralogy and Petrology Aims and scope Submit manuscript

Abstract

Arsenopyrite (FeAsS) is one of the sulfide minerals of seafloor massive sulfide deposits. The presence of sodium chloride and high-temperature and high-pressure (HTHP) geological conditions seriously affect the process of arsenopyrite weathering. However, electrochemical oxidative dissolution has never been considered in the context of seafloors, though it has already been shown to increase dissolution significantly in terrestrial deposits. In this work, in situ electrochemical techniques and surface analysis were used to investigate the behaviors of oxidative arsenopyrite dissolution in different concentrations of NaCl at temperatures ranging from 280 to 360 °C and pressures ranging from 12.0 to 20.0 MPa. In the initial stage, arsenopyrite was oxidized to S0, As(III), and Fe(II). The S0 and As(III) were ultimately converted into SO42− and AsO43− and entered the solution. The Fe(II) was converted into α-FeOOH, γ-FeOOH, and Fe2O3 as a passivation film. The presence of Cl ions promoted the oxidative dissolution of arsenopyrite without changing its oxidation mechanism. Higher temperatures or greater pressures promoted the oxidative dissolution of arsenopyrite by enhancing charge migration and ion diffusion. Under the experimental HTHP conditions, the oxidative arsenopyrite dissolution rate constant was 8.0 × 10–5 mol∙m−2∙s−1. This work expands the understanding of the geochemical cycles of Fe, As and S and provides an experimental basis for the formation of secondary minerals from arsenopyrite weathering under the hydrothermal solution conditions of the seafloor.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  • Bard AJ, Faulkner LR (2001) Electrochemical methods: fundamentals and applications, 2nd edn. Wiley and Sons, Hoboken

    Google Scholar 

  • Bersani D, Lottici PP, Montenero A (1999) Micro-Raman investigation of iron oxide films and powders produced by Sol-Gel Syntheses. J Raman Spectrosc 30:355–360

    Article  Google Scholar 

  • Boucherit N, Hugot-Le Goff A (1992) Localized corrosion processes in iron and steels studied by in situ Raman spectroscopy. Faraday Discuss 94:137–147

    Article  Google Scholar 

  • Boucherit N, Hugot-Le Goff A, Joiret S (1992) Influence of Ni, Mo, and Cr on pitting corrosion of steels studied by Raman spectroscopy. Corrosion 48:569–578

    Article  Google Scholar 

  • Buckley AN, Walker GW (1988) The surface composition of arsenopyrite exposed to oxidising environments. Appl Surf Sci 35:227–240

    Article  Google Scholar 

  • Courtin-nomade A, Bril H, Beny JM, Kunz M, Tamura N (2010) Sulfide oxidation observed using micro-Raman spectroscopy and micro-X-ray diffraction: the importance of water/rock ratios and pH conditions. Am Miner 95(4):582–591

    Article  Google Scholar 

  • Das S, Hendry MJ (2011) Application of Raman spectroscopy to identify iron minerals commonly found in mine wastes. Chem Geol 290:101–108

    Article  Google Scholar 

  • de Faria DLA, Venaüncio Silva S, de Oliveira MT (1997) Raman microspectroscopy of some iron oxides and oxyhydroxides. J Raman Spectrosc 28:873–878

    Article  Google Scholar 

  • Deng S, Gu GH (2018) An electrochemical impedance spectroscopy study of arsenopyrite oxidation in the presence of Sulfobacillus thermosulfidooxidans. Electrochim Acta 287:106–114

    Article  Google Scholar 

  • Eom H (2013) Faraday’s law of induction. Primary theory of electromagnetics. Power Systems. Springer, Dordrecht

    Chapter  Google Scholar 

  • Fernandez MGM, Mustin C, de Donato P, Barres O, Marion P, Berthelin J (1995) Occurrences at mineral–bacterial interface during oxidation of arsenopyrite by Thiobacillus ferrooxidans. Biotechnol Bioeng 46:13–21

    Article  Google Scholar 

  • Fernandez PG, Linge HG, Wadsley MW (1996a) Oxidation of arsenopyrite (FeAsS) in acid part I: reactivity of arsenopyrite. J Appl Electrochem 26:575–583

    Article  Google Scholar 

  • Fernandez PG, Lingem HG, Willing MJ (1996b) Oxidation of arsenopyrite (FeAsS) in acid. part II. Stoichiometry and reaction scheme. J Appl Electrochem 26:585–591

    Article  Google Scholar 

  • Harmer SL, Pratt AR, Nesbitt WH, Fleet ME (2004) Sulfur species at chalcopyrite (CuFeS2) fracture surfaces. Am Mineral 89:1026–1032

    Article  Google Scholar 

  • Heinrich CA, Seward TM (1990) A spectrophotometric study of aqueous iron(II) chloride complexing from 25 to 200°C. Geochim Cosmochim Acta 54:2207–2221

    Article  Google Scholar 

  • Kwon SK, Shinoda K, Shigeru S, Waseda Y (2007) Influence of silicon on local structure and morphology of γ–FeOOH and α–FeOOH particles. Corros Sci 49:1513–1526

    Article  Google Scholar 

  • Lara RH, Ramírez-Aldaba H, Valles OP (2016) Chemical and surface analysis during evolution of arsenopyrite oxidation by Acidithiobacillus thiooxidans in the presence and absence of supplementary arsenic. Sci Total Environ 566–567:1106–1119

    Google Scholar 

  • Lasia A (2002) Electrochemical impedance spectroscopy and its applications. In: Conway BE, Bockris JO, White RE (eds) Modern aspects of electrochemistry. Modern Aspects of Electrochemistry, vol 32. Springer, Boston, MA

    Google Scholar 

  • Lazaro I, Cruz R, Gonzalez I, Monroy M (1997) Electrochemical oxidation of arsenopyrite in acidic media. Int J Miner Process 50:63–75

    Article  Google Scholar 

  • Li Q, Yang YB, Jiang T (2006) Electrochemical oxidation of arsenopyrite in acidic media. Chin J Nonferrous Met 16:1971–1975

    Google Scholar 

  • Li YQ, He Q, Chen JH (2015) Electronic and chemical structures of pyrite and arsenopyrite. Mineral Mag 79:1779–1789

    Article  Google Scholar 

  • Lin SY, Liu RQ, Bu YJ, Wang C, Wang L, Sun L, Hu YH (2018) Oxidative depression of arsenopyrite by using calcium hypochlorite and sodium humate. Minerals 8:463–477

    Article  Google Scholar 

  • Lin S, Li HP, Xu LP, Zhang YQ, Cui C (2017) A novel experimental device for electrochemical measurements in supercritical fluids up to 700°C/1000 bar and its application in the corrosion study of superalloy Inconel 740H. RSC Adv 7:33914–33920

    Article  Google Scholar 

  • Macdonald DD, Scott AC, Wentrcek P (1979) External reference electrode for use in high temperature aqueous systems. J Electrochem Soc 126:908–911

    Article  Google Scholar 

  • Macdonald JR (1985) Generalizations of “universal dielectric response” and a general distribution of activation energies model for dielectric and conducting systems. J Appl Phys 58:1971–1978

    Article  Google Scholar 

  • Majzlan J, Mazeina L, Navrotsky A (2007) Enthalpy of water adsorption and surface enthalpy of lepidocrocite (γ–FeOOH). Geochim Cosmochim Acta 71:615–623

    Article  Google Scholar 

  • McGuire MM, Jallad KN, Ben-Amotz D, Hamers RJ (2001) Chemical mapping of elemental sulfur on pyrite and arsenopyrite surfaces using near-infrared Raman imaging microscopy. Appl Surf Sci 178:105–115

    Article  Google Scholar 

  • McKibben MA, Tallant BA, del Angel JK (2008) Kinetics of inorganic arsenopyrite oxidation in acidic aqueous solutions. Appl Geochem 23:121–135

    Article  Google Scholar 

  • Mernagh TP, Trudu AG (1993) A laser Raman microprobe study of some geologically important sulphide minerals. Chem Geol 103:113–127

    Article  Google Scholar 

  • Mikhlin YL, Romanchenko AS, Asanov IP (2006) Oxidation of arsenopyrite and deposition of gold on the oxidized surfaces: A scanning probe microscopy, tunneling spectroscopy and XPS study. Geochim Cosmochim Acta 70:4874–4888

    Article  Google Scholar 

  • Mikhlin Y, Tomashevich Y (2005) Pristine and reacted surfaces of pyrrhotite and arsenopyrite as studied by X–ray absorption near–edge structure spectroscopy. Phys Chem Miner 32:19–27

    Article  Google Scholar 

  • Mycroft JR, Bancroft GM, McIntyre NS, Lorimer JW, Hill IR (1990) Detection of sulphur and polysulphides on electrochemically oxidized pyrite surfaces by X–ray photoelectron spectroscopy and Raman spectroscopy. J Electroanal Chem 292:139–152

    Article  Google Scholar 

  • Neil C, Jun Y (2016) Promotion of arsenopyrite dissolution and secondary mineral formation and phase transformation by aqueous Fe3+. Abstracts of Papers–am Chem Soc 251:63

    Google Scholar 

  • Neil CW, Yang YJ, Schupp D, Ju Y (2014) Water chemistry impacts on arsenic mobilization from arsenopyrite dissolution and secondary mineral precipitation: implications for managed aquifer recharge. Environ Sci Technol 48:4395–4405

    Article  Google Scholar 

  • Nesbitt HW, Muir IJ (1998) Oxidation states and speciation of secondary products on pyrite and arsenopyrite reacted with mine waste waters and air. Mineral Petrol 62:123–144

    Article  Google Scholar 

  • Nesbitt HW, Muir IJ, Pratt AR (1995) Oxidation of arsenopyrite by air and airsaturated, distilled water and implications for mechanisms of oxidation. Geochim Cosmochim Acta 59:1773–1786

    Article  Google Scholar 

  • Nicol MJ, Guresin N (2003) Anodic behaviour of arsenopyrite and cathodic reduction of ferrate (VI) and oxygen in alkaline solutions. J Appl Electrochem 33:1017–1024

    Article  Google Scholar 

  • Nie X, Li X, Du C, Huang Y, Du H (2009) Characterization of corrosion products formed on the surface of carbon steel by Raman spectroscopy. J Raman Spec 40:76–79

    Article  Google Scholar 

  • Osseo–Assare K, Xue T, Ciminelli VST (1984) Solution chemistry of cyanide leaching systems. Precious Metals, Mining Extraction and Processing. AIME, Warrendale, pp 173–197

  • Papangelakis VG, Demopoulous GP (1990a) Acid pressure oxidation of arsenopyrite. Part I. Reaction Chemistry Can Metall Quart 29:1–12

    Article  Google Scholar 

  • Papangelakis VG, Demopoulous GP (1990b) Acid pressure oxidation of arsenopyrite. Part II. Reaction Kinetics Can Metall Quart 29:13–20

    Article  Google Scholar 

  • Parker GK, Woods R, Hope GA (2008) Raman investigation of chalcopyrite oxidation. Coll Surf a: Physicochem Eng Aspects 318:160–168

    Article  Google Scholar 

  • Parthasarathy H, Liu H, Dzombak DA, Karamalidis AK (2016) The effect of Na–Ca–Cl brines on the dissolution of arsenic from arsenopyrite under geologic carbon dioxide storage conditions. Chem Geol 428:1–7

    Article  Google Scholar 

  • Pearce CI, Pattrick RAD, Vaughan DJ (2006) Electrical and magnetic properties of sulfides. Rev Mineral Geochem 61:127–180

    Article  Google Scholar 

  • Pokrovski GS, Kara S, Roux J (2002) Stability and solubility of arsenopyrite, FeAsS, in crustal fluids. Geochim Cosmochim Acta 66:2361–2378

    Article  Google Scholar 

  • Ramya S, Krishna DNG, Mudali UK (2018) In–situ Raman and X–ray photoelectron spectroscopic studies on the pitting corrosion of modified 9Cr–1Mo steel in neutral chloride solution. Appl Surf Sci 428:1106–1118

    Article  Google Scholar 

  • Refait P, Genin JMR (1993) The oxidation of ferrous hydroxide in chloride–containing aqueous media and Pourbaix diagrams of green rust one. Corros Sci 34:797–819

    Article  Google Scholar 

  • Richardson S, Vaughan DJ (1989) Arsenopyrite: a spectroscopic investigation of altered surfaces. Mineral Mag 53:223–229

    Article  Google Scholar 

  • Sanchez VM, Hiskey JB (1991) Electrochemical behaviour of arsenopyrite in alkaline media. Min Metall Proc 8:1–6

    Google Scholar 

  • Sanchez VM, Hiskey JB (1998) An electrochemical study of the surface oxidation of arsenopyrite in alkaline media. Metall Mater Trans 19B:943–949

    Google Scholar 

  • Shim SH, Duffy TS (2002) Raman spectroscopy of Fe2O3 to 62 GPa. Am Mineral 87:318–326

    Article  Google Scholar 

  • Simard S, Odziemkowski M, Irish DE, Brossard L, Ménard H (2001) In situ micro–Raman spectroscopy to investigate pitting corrosion product of 1024 mild steel in phosphate and bicarbonate solutions containing chloride and sulphate ions. J Appl Electrochem 31:913–920

    Article  Google Scholar 

  • Stefánsson A, Lemke KH, Seward TM (2019) Iron(III) chloride complexation in hydrothermal solutions: a combined spectrophotometric and density functional theory study. Chem Geol 524:77–87

    Article  Google Scholar 

  • Steudel R (1996) Mechanism for the formation of elemental sulfur from aqueous sulfide in chemical and microbiological desulfurization processes. Ind Eng Chem Res 35:1417–1423

    Article  Google Scholar 

  • Toner BM, Rouxel O, Santelli CM, Edwards KJ (2008) Sea–floor weathering of hydrothermal chimney sulfides at the East Pacific Rise 9 degrees N: chemical speciation and isotopic signature of Iron using X–ray absorption spectroscopy and laser–ablation MC–ICP–MS. Gastroenterol Jpn 4:234–235

    Google Scholar 

  • Toniazzo V, Lazaro I, Humbert B (1999) Bioleaching of pyrite by Thiobacillus ferrooxidans: fixed grains electrode to study superficial oxidized compounds. Earth Planet Sci Lett 328:535–540

    Google Scholar 

  • Tyukova EE, Voroshin SV (2004) Stability of arsenopyrite at temperatures below 300°C. Dokl Earth Sci 399:1240–1244

    Google Scholar 

  • Walker FP, Schreiber ME, Rimstidt JD (2006) Kinetics of arsenopyrite oxidative dissolution by oxygen. Geochim Cosmochim Acta 70:1668–1676

    Article  Google Scholar 

  • Wang SF, Jiao BB, Zhang MM, Guo QJ, Wang X, Jia YF (2018) Arsenic release and speciation during the oxidative dissolution of arsenopyrite by O2 in the absence and presence of EDTA. J Hazard Mater 346:184–190

    Article  Google Scholar 

  • Wang Y, Han X, Petersen S, Frische M, Qiu Z, Li H, Wu Z, Cui R (2017) Mineralogy and trace element geochemistry of sulfide minerals from the Wocan Hydrothermal Field on the slow–spreading Carlsberg Ridge, Indian Ocean. Ore Geol Rev 84:1–19

    Article  Google Scholar 

  • Yu YM, Zhu YX, Gao ZM (2004a) Stability of arsenopyrite and As(III) in low–temperature acidic solutions. Sci China Ser D 47:427–436

    Article  Google Scholar 

  • Yu Y, Zhu Y, Gao Z, Gammons CH, Li D (2007) Rates of arsenopyrite oxidation by oxygen and Fe(III) at pH 1.8–12.6 and 15–45°C. Environ Sci Technol 41:6460–6464

    Article  Google Scholar 

  • Yu Y, Zhu Y, Williams-Jones AE, Gao Z, Di D (2004b) A kinetic study of the oxidation of arsenopyrite in acidic solutions: implications for the environment. Appl Geochem 19:435–444

    Article  Google Scholar 

  • Zhang H, Li X, Du C, Qi H, Huang Y (2009) Raman and IR spectroscopy study of corrosion products on the surface of the hot–dip galvanized steel with alkaline mud adhesion. J Raman Spec 40:656–660

    Article  Google Scholar 

  • Zhang X, Xiao K, Dong CF, Wu JS, Li XG, Huan YZ (2011) In situ Raman spectroscopy study of corrosion products on the surface of carbon steel in solution containing Cl and SO42–. Eng Fail Anal 18:1981–1989

    Article  Google Scholar 

  • Zheng K, Li HP, Wang S, Feng XN, Wang LY, Liu QY (2020a) Arsenopyrite weathering in sodium chloride solution: Arsenic geochemical evolution and environmental effects. J Hazard Mater 392:122502

    Article  Google Scholar 

  • Zheng K, Li HP, Wang S, Wang LY, Liu QY (2020b) Block and malleable arsenopyrite hot–pressure sintering: applied implications. J Mater Res Technol 9:8997–9003

    Article  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (U1812402), the National Natural Science Foundation of China (41873074), and the National Major Scientific Instruments and Equipment’s Development Project of National Natural Science Foundation of China (41827802).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Heping Li.

Ethics declarations

Conflict of interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Additional information

Communicated by Gordon Moore.

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 5397 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, Q., Zheng, K., Wang, S. et al. Arsenopyrite oxidative dissolution in NaCl solution at high-temperature and high-pressure conditions: kinetics, pathways, dissolution mechanism and geological implications. Contrib Mineral Petrol 177, 66 (2022). https://doi.org/10.1007/s00410-022-01929-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00410-022-01929-2

Keywords

Navigation