Mineral Systems and Thermodynamic Stability of Arsenic Minerals in the Environment

  • Marina V. CharykovaEmail author
  • Vladimir G. Krivovichev
Conference paper
Part of the Lecture Notes in Earth System Sciences book series (LNESS)


Arsenic is widely distributed in the environment. The paper presents systematized data published about the thermodynamics of some relatively common arsenic oxysalts, which are formed in the weathering zone of the arsenide and sulfide ores, and determines approaches to quantitative physicochemical modeling of their formation conditions. The interpretations are summarized on the Eh–pH diagrams, synthesized from equilibrium calculations, and reported geologic occurrences. The most recent thermodynamic data available were used for the construction of diagrams from reactions which are balanced equations of Eh–pH relationships among species which are thermodynamically stable within the ranges of oxidation potential and pH considered for each reaction. The Eh–pH diagrams of systems, containing As and Fe, Cu, Pb, Co, Ni, Ca, were calculated and constructed using the Geochemist’s Workbench (GMB 9.0) software package. Eh–pH stability relationships have been determined for some widespread arsenic oxysalts (scorodite, mimetite, erythrite, olivenite, annabergite, beudantite, conichalcite, adamite, duftite) and in order to interpret conditions of formation of these minerals and to compare their geologic stabilities of ore deposits. The understanding of mechanisms of arsenic behavior in the near-surface conditions is one of actual problems of modern mineralogy and geochemistry and it is very important for the solving of some environmental problems.


Arsenates Environmental mineralogy and geochemistry Physicochemical modeling Eh–pH diagrams 


  1. Alpers CN, Jambor JL, Nordstrom DK (eds) (2000) Sulfate minerals: crystallography, geochemistry, and environmental significance. Rev Miner Geochem 40:1–602Google Scholar
  2. Amend JP, Saltikov C, Lu GS, Hernandez J (2014) Microbial arsenic metabolism and reaction energetics. Rev Miner Geochem 79:391–433Google Scholar
  3. Bethke CM, Yeakel S (2011) The geochemist’s workbench, release 9.0, GWB essentials guide. Aqueous Solutions, LLC, University of Illinois, ChampaignGoogle Scholar
  4. Bigham JM, Schwertmann U, Traina SJ, Winland RL, Wolf M (1996) Schwertmannite and the chemical modeling of iron in acid sulfate waters. Geochim Cosmochim Acta 60:2111–2121Google Scholar
  5. Bluteau M-C, Demopoulos GP (2007) The incongruent dissolution of scorodite: solubility, kinetics and mechanism. Hydrometall 87:163–177Google Scholar
  6. Bowell RJ, Craw D (2014) The management of arsenic in the mining industry. Rev Miner Geochem 79:507–532Google Scholar
  7. Bowell RJ, Alpers CN, Jamieson HE, Nordstrom DK, Majzlan J (2014) The environmental geochemistry of arsenic: an overview. Rev Mineral Geochem 79:1–16Google Scholar
  8. Bruneel O, Personné J-C, Casiot C, Leblanc M, Elbaz-Poulichet F, Mahler BJ, Le Flèche A, Grimont PAD (2003) Mediation of arsenic oxidation by Thiomonas sp. in acid-mine drainage (Carnoulès, France). J Appl Microbiol 95:492–499Google Scholar
  9. Charykova MV, Krivovichev VG, Depmeir W (2009) Thermodynamics of arsenates, selenites, and sulfates in the oxidation zone of sulfide ores: I. Thermodynamic constants at ambient conditions. Zapiski RMO (Proc Russ Miner Soc) 137(6):105–117(in Russian) [(2010) Geol Ore Dep 52:689–700 (Engl. Transl)]Google Scholar
  10. Charykova MV, Krivovichev VG, Yakovenko OS, Depmeier W (2011) Thermodynamics of arsenates, selenites, and sulfates in the oxidation zone of sulfide ores: III. Eh–pH diagrams for the Me–As–H2O systems (Me = Co, Ni, Fe, Cu, Zn, Pb) at 25 °C. Zapiski RMO (Proc Russ Miner Soc) 139(3):1–14 (in Russian) [(2011) Geol Ore Dep 53:501–513 (Engl. Transl)]Google Scholar
  11. Cherry JA, Shaikh AU, Tallman DE, Nicholson RV (1979) Arsenic species as an indicator of redox conditions in groundwater. J Hydrol 43:373–392Google Scholar
  12. Christy AG (2015) Anomalous mineralogical diversity in the periodic table, and its causes. Mineral Mag 79:33–49Google Scholar
  13. Cornell RM, Schwertmann U (2003) The iron oxides: structure, properties, reactions, occurrences and uses, 2nd edn. Wiley, KGaA Weinheim GermanyGoogle Scholar
  14. Craw D, Falconer D, Yongson JH (2003) Environmental arsenopyrite stability and dissolution: theory, experiment, and field observations. Chem Geol 179:71–82Google Scholar
  15. Dove PM, Rimstidt JD (1985) The solubility and stability of scorodite, FeAsO4·2H2O. Am Miner 70:838–844Google Scholar
  16. Grzyb KR (1995) NOAEM (natural organic anion equilibrium model): a data analysis algorithm for estimating functional properties of dissolved organic matter in aqueous environments: part I. Ionic component speciation and metal association. Org Geochem 23:379–390Google Scholar
  17. Hålenius U, Hatert F, Pasero M, Mills SJ (2018) New minerals and nomenclature modifications approved in 2018. Newsletter 32. Miner Mag 82:1225–1232Google Scholar
  18. Hawthorne FC (2002) The use of end-member charge-arrangements in defining new mineral species and heterovalent substitutions in complex minerals. Can Miner 40:699–710Google Scholar
  19. Hatert F, Burke EAJ (2008) The IMA-CNMNC dominant-constituent rule revised and extended. Can Miner 46:717–728Google Scholar
  20. Huber C, Filella M, Town RM (2002) Computer modelling of trace metal ion speciation: practical implementation of a linear continuous function for complexation by natural organic matter. Comput Geosci 28:587–596Google Scholar
  21. Krause E, Ettel VA (1988) Solubility and stability of scorodite, FeAsO4:2H2O: new data and further discussion. Am Miner 73:850–854Google Scholar
  22. Krivovichev VG, Charykova MV (2013a) Classification of mineral systems. St.-Petersburg University Press, St. Petersburg (in Russian)Google Scholar
  23. Krivovichev VG, Charykova MV (2013b) Number of minerals of various chemical elements: statistics 2012 (a new approach to an old problem). Zapiski RMO (Proc Russ Miner Soc) 142(4):36–42 (in Russian, English translation: Geol Ore Deposits (2014) 56:553–559)Google Scholar
  24. Krivovichev VG, Charykova MV, Krivovichev SV (2018) The concept of mineral systems and its application to the study of mineral diversity and evolution. Eur J Mineral 30:219–230Google Scholar
  25. Langmuir D, Mahoney J, Rowson J (2006) Solubility products of amorphous ferric arsenate and crystalline scorodite (FeAsO4·2H2O) and their application to arsenic behavior in buried mine tailings. Geochim Cosmochim Acta 70:2942–2956Google Scholar
  26. Lei Z, Chen X, Wang J, Zhang J, Huang Y, Lu Z, Du F (2017) Guite, IMA 2017–080. CNMNC Newsletter No. 40. Miner Mag 81:1581Google Scholar
  27. Mitchell VL (2014) Health risks associated with chronic exposures to arsenic in the environment. Rev Miner Geochem 79:435–449Google Scholar
  28. Morin G, Calas G (2006) Arsenic in soils, mine tailings and former industrial sites. Elements 2:97–101Google Scholar
  29. Magalhaes MKF, Pedrosa de Jesus JD, Williams PA (1988) The chemistry of formation of some secondary arsenate minerals of Cu(II), Zn(II) and Pb(II). Miner Mag 52:679–690Google Scholar
  30. Majzlan J, Drahota P, Filippi M, Grevel K-D, Kahl W-A, Plasil J, Boerio-Goates J, Woodfield BF (2012) Thermodynamic properties of scorodite and parascorodite (FeAsO4·2H2O), kaňkite (FeAsO4·3.5H2O), and FeAsO4. Hydrometall 117–118:47–56Google Scholar
  31. Majzlan J, Števko M, Dachs E, Benisek A, Plášil J, Sejkora J (2017) Thermodynamics, stability, crystal structure, and phase relations among euchroite, Cu2(AsO4)(OH)·3H2O, and related minerals. Eur J Miner 29:5–16Google Scholar
  32. Mandarino JA, Nickel EH, Cesbron F (1984) Rules of procedure of the commission on new minerals and mineral names, international mineralogical association. Can Miner 22:367–368Google Scholar
  33. Nickel EH, Grice JD (1998) The IMA commission on new minerals and mineral names: procedures and guidelines on mineral nomenclature. Can Miner 36:913–926Google Scholar
  34. Nickel EH, Mandarino JA (1987) Procedures involving the IMA commission on new minerals and mineral names, and guidelines on mineral nomenclature (excerpt). Can Miner 25:353–377Google Scholar
  35. Nordstrom DK, Campbell KM (2014) Modeling low-temperature geochemical processes. In: Drever JI (ed) Surface and groundwater, weathering and soils (treatise on geochemistry), vol 7, pp 27–68. Elsevier Pergamon, AmsterdamGoogle Scholar
  36. Nordstrom DK, Majzlan J, Königsberger E (2014) Thermodynamic properties for arsenic minerals and aqueous species. Rev Miner Geochem 79:217–255Google Scholar
  37. O’Day PA (2006) Chemistry and mineralogy of arsenic. Elements 2:77–83Google Scholar
  38. Pasero M (2018) The New IMA list of minerals.
  39. Peng L, Chen Z (2011) Arsenic Eh–pH diagrams at 25C and 1 bar. Environ Earth Sci 62:1673–1683Google Scholar
  40. Perdue EM, Reuter JH, Parrish RS (1984) A statistical model of proton binding by humus. Geochim Cosmochim Acta 48:1257–1263Google Scholar
  41. Plant JA, Bone J, Voulvoulis N, Kinniburgh DG., Smedley PL, Fordyce FM, Klinck B (2014) Arsenic and selenium. In: Holland HD; Turekain KK (eds) Environmental geochemistry (treatise on geochemistry), vol 11, pp 13–57. Elsevier Pergamon, AmsterdamGoogle Scholar
  42. Robins RG (1987) Solubility and stability of scorodite, FeAsO4:2H2O: discussion. Am Miner 72:842–844Google Scholar
  43. Susetyo W, Dobbs JC, Carreha LA, Azarraga LV, Grimm DM (1990) Development of a statistical model for metal-humic interactions. Anal Chem 62:1215–1221Google Scholar
  44. Tipping E, Hurley MA (1992) A unifying model of cation binding by humic substances. Geochim Cosmochim Acta 56:3627–3641Google Scholar
  45. Tournassat C, Charlet L, Bosbach D, Manceau A (2002) Arsenic(III) oxidation by birnessite and precipitation of manganese (II) arsenate. Environ Sci Technol 36:493–500Google Scholar
  46. Williams M (2001) Arsenic in mine waters and international study. Env Geol 40:267–278Google Scholar
  47. Wood SA (1996) The role of humic substance in the transport and fixation of metals of economic interest (Au, Pt, Pd, U, V). Ore Geology Rev 11:1–31Google Scholar
  48. Yan X-P, Kerich R, Hendry MJ (2000) Distribution of arsenic (III), arsenic (V) and total inorganic in porewaters from a thick till and clay-rich aquitard sequence, Saskatchewan, Canada. Geochim Cosmochim Acta 62:2637–2648Google Scholar
  49. Zhu Y, Merkel BJ (2001) The dissolution and solubility, FeAsO4:2H2O evaluation and simulation with PHREEQC2. Wiss Mitt Inst Fur Geologie TU Bergakedemie Freiberg, Germany 18:1–12Google Scholar

Copyright information

© Springer Nature Switzerland AG 2020

Authors and Affiliations

  • Marina V. Charykova
    • 1
    Email author
  • Vladimir G. Krivovichev
    • 1
  1. 1.Saint Petersburg UniversitySaint PetersburgRussia

Personalised recommendations