Nickel sulfide formation at low temperature: initial precipitates, solubility and transformation products

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doi:10.1071/EN10076

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Nickel sulfide formation at low temperature: initial precipitates, solubility and transformation products

Richard T. Wilkin ^A ^B and David A. Rogers ^A

^A US Environmental Protection Agency, National Risk Management Research Laboratory, Ground Water and Ecosystems Restoration Division, 919 Kerr Research Drive, Ada, OK 74820, USA.
^B Corresponding author. Email: wilkin.rick@epa.gov

Environmental Chemistry 7(6) 514-523 http://dx.doi.org/10.1071/EN10076
Submitted: 15 July 2010 Accepted: 24 September 2010 Published: 21 December 2010





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Environmental context. Remediation technologies often rely on manipulation of redox conditions or natural redox processes to favour microbial sulfate-reduction and mineral sulfide formation for treatment of inorganic contaminants in groundwater, including nickel. However, few data are available on the structural properties, solubility and mineral transformation processes involving nickel sulfides. These data are needed in order to constrain the long term performance of groundwater remediation efforts.

Abstract. The formation of nickel sulfides has been examined experimentally over the temperature range from 25 to 60°C. At all conditions studied, hexagonal (α-NiS) was the initial precipitate from solution containing Ni²⁺ and dissolved sulfide. Freshly precipitated nickel sulfide possesses significant residual Ni–O coordination as revealed by X-ray absorption spectroscopy. With progressive aging, residual Ni–O coordination is replaced by Ni–S coordination. The formation of millerite (β-NiS, rhombohedral) was not detected in any of the synthesis experiments. In the presence of elemental sulfur, hexagonal NiS converted to polydymite (Ni₃S₄) and vaesite (NiS₂). Thus, conversion of nickel monosulfide to thiospinel and disulfide structures appears to be redox dependent, analogous to aging and transformation processes of iron sulfides. In the absence of elemental sulfur or with only hydrogen sulfide or bisulfide present, transformation of hexagonal NiS was not observed after 1680 h at 60°C. Low-pH solubility experiments yielded a solubility product for hexagonal NiS of log K_s0 = –2.69 ± 0.26. Solubility data at pH > 3 suggest that Ni–bisulfide complexation is important in controlling the solubility of Ni in sulfidic solutions.

Additional keywords: groundwater, remediation, X-ray absorption spectroscopy.

References

[1] K. G. Scheckel, R. G. Ford, R. T. Wilkin, Nickel, in Monitored Natural Attenuation of Inorganic Contaminants in Ground Water – Volume 2: Assessment for Non-radionuclides Including Arsenic, Cadmium, Chromium, Copper, Lead, Nickel, Nitrate, Perchlorate, and Selenium, EPA600/R-07/139 (Eds R. Ford, R. Wilkin, R. Puls) 2007, pp. 21–31 (US Environmental Protection Agency: Cincinnati, OH).

[2] T. Thoenen, Pitfalls in the use of solubility limits for radioactive waste disposal: the case of nickel in sulfidic groundwaters. Nucl. Technol. 1999, 126, 75..

[3] S. G. Benner, D. W. Blowes, W. D. Gould, R. B. Herbert, C. J. Ptacek, Geochemistry of a permeable reactive barrier for metals and acid mine drainage. Environ. Sci. Technol. 1999, 33, 2793..

[4] R. D. Ludwig, R. G. McGregor, D. W. Blowes, S. G. Benner, K. Mountjoy, A permeable reactive barrier for treatment of heavy metals. Ground Water 2002, 40, 59.
| CrossRef | CAS | PubMed |

[5] M. B. J. Lindsay, C. J. Ptacek, D. W. Blowes, W. D. Gould, Zerovalent iron and organic carbon mixtures for remediation of acid mine drainage: batch experiments. Appl. Geochem. 2008, 23, 2214.
| CrossRef | CAS |

[6] G. Kullerud, R. A. Yund, The Ni–S system and related minerals. J. Petrol. 1962, 3, 126..

[7] D. J. Vaughan, J. R. Craig, in Geochemistry of Hydrothermal Ore Deposits, 3rd edn (Ed. H. L. Barnes) 1997, pp. 367–434 (Wiley: New York).

[8] T. Carlsson, U. Vuorinen, The reliability of solubility data: Results from a limited literature survey focusing on Ni, Pd and Np, VTT Tiedotteita-Meddelanden-Research Notes 1928 1998 (Technical Research Centre of Finland: Espoo, Finland).

[9] W. Hummel, E. Curti, Nickel aqueous speciation and solubility at ambient conditions: a thermodynamic elegy. Monatsh. Chem. 2003, 134, 941.
| CrossRef | CAS |

[10] J. P. Gramp, J. M. Bigham, K. Sasaki, O. H. Tuovinen, Formation of Ni- and Zn-sulfides in cultures of sulfate-reducing bacteria. Geomicrobiol. J. 2007, 24, 609.
| CrossRef | CAS |

[11] B. Ravel, M. Newville, Athena, Artemis, Hephaestus: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 2005, 12, 537.
| CrossRef | CAS | PubMed |

[12] J. J. Rehr, Recent developments in multiple-scattering calculations of XAFS and XANES. Jpn. J. Appl. Phys. 1993, 32, 8..

[13] J. J. Rehr, R. C. Albers, S. I. Zabinksky, High-order multiple-scattering calculations of X-ray absorption fine structure. Phys. Rev. Lett. 1992, 69, 3397.
| CrossRef | CAS | PubMed |

[14] W. Lotmar, W. Feitknecht, Über Änderungen der Ionenabstande in Hydroxyschichtengittern. Zeit. Kristal. 1936, 93A, 368..

[15] J. Trahan, R. G. Goodrich, S. F. Watkins, X-ray diffraction measurements on metallic and semiconducting hexagonal NiS. Phys. Rev. 1970, B2, 2859..

[16] P. Lundqvist, X-ray studies on the binary system Ni–S. Ark. Kemi Mineral. Geol. 1947, 24A, 12..

[17] G. Nowack, D. Schwarzenbach, T. Hahn, Charge densities in CoS₂ and NiS₂. Acta Crystallogr. 1991, B47, 650..

[18] H. Wang, A. Pring, Y. Ngothai, B. O’Neill, The kinetics of the α→β transition in synthetic nickel monosulfide. Am. Min. 2006, 91, 171.
| CrossRef | CAS |

[19] H. Sowa, H. Ahsbahs, W. Schmitz, X-ray diffraction studies of millerite NiS under non-ambient conditions. Phys. Chem. Miner. 2004, 31, 321.
| CrossRef | CAS |

[20] N. Štrbac, D. Živkovic, I. Mihajlović, B. Boyanov, Z. Živkovic, Mechanism and kinetics of the oxidation of synthetic α-NiS. J. Serbian Chem. Soc. 2008, 73, 211.
| CrossRef |

[21] M. A. A. Schoonen, Mechanisms of sedimentary pyrite formation, in Sulfur Biogeochemistry: Past and Present (Eds J. P. Amend, K. J. Edwards, T. W. Lyons) 2004, pp. 117–134 (Geological Society of America: Boulder, CO).

[22] M. A. A. Schoonen, H. L. Barnes, Reactions forming pyrite and marcasite from solution. II. Via FeS precursors below 100°C. Geochim. Cosmochim. Acta 1991, 55, 1505.
| CrossRef | CAS |

[23] J. W. Morse, G. W. Luther, Chemical influences on trace metal sulfide interactions in anoxic basins. Geochim. Cosmochim. Acta 1999, 63, 3373.
| CrossRef | CAS |

[24] D. Rickard, G. W. Luther III, Metal sulfide complexes and clusters, in Sulfide Mineralogy and Geochemistry: Reviews in Mineralogy and Geochemistry, Vol. 61 (Ed. D. J. Vaughan) 2006 (Mineralogical Society of America: Chantilly, VA).

[25] A. M. Scheidegger, G. M. Lamble, D. L. Sparks, Investigation of Ni sorption on pyrophyllite: an XAFS study. Environ. Sci. Technol. 1996, 30, 548.
| CrossRef | CAS |

[26] C. M. Bethke, Geochemical Reaction Modeling 1996 (Oxford University Press: New York).

[27] A. Thiel, H. Gessner, Über Nickelsulfid und Kobaltsulfid. I. Die scheinbare Anomalie im Verhalten des Nickelsulfids gegen Säure. Zeit. Anorg. Chem. 1914, 86, 1.
| CrossRef | CAS |

[28] D. D. Wagman, W. H. Evans, V. B. Parker, R. H. Schumm, I. Halow, S. M. Bailey, K. L. Churney, R. L. Nuttal, The NBS tables of chemical thermodynamic properties. Selected values for inorganic C1 and C2 organic substances in SI units. J. Phys. Chem. Ref. Data 1982, 11, 1..

[29] D. J. Vaughan, J. R. Craig, Mineral Chemistry of Metal Sulfides 1978 (Cambridge University Press: Cambridge, UK).

[30] R. A. Robie, B. S. Hemingway, Thermodynamic properties of minerals and related substances at 298.15 K and 1 bar (10⁵ pascals) pressure and at higher temperatures, in US Geological Survey Bulletin report 2131 1995 (US Geological Survey: Denver, CO).

[31] R. Al-Farawati, C. M. G. van den Berg, Metal-sulfide complexation in seawater. Mar. Chem. 1999, 63, 331.
| CrossRef | CAS |

[32] D. Dyrssen, Sulfide complexation in surface seawater. Mar. Chem. 1988, 24, 143.
| CrossRef | CAS |

[33] G. W. Luther, D. T. Rickard, S. Theberge, A. Oldroyd, Determination of metal (bi)sulfide stability constants of Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺ by voltammetric methods. Environ. Sci. Technol. 1996, 30, 671.
| CrossRef | CAS |

[34] S. Huang, E. Lopez-Capel, D. A. C. Manning, D. Rickard, The composition of nanoparticulate nickel sulfide. Chem. Geol. 2010, 277, 207..

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