Water, Air, and Soil Pollution

, Volume 80, Issue 1–4, pp 1053–1056 | Cite as

Solubility of cinnabar (red HgS) and implications for mercury speciation in sulfidic waters

  • K. Paquette
  • G. Helz
Part Xa Aquatic Cycling of Mercury in Biota and Sediments


New experiments have been conducted to determine the speciation of dissolved mercury (Hg) over wide pH (1–12) and sulfide concentration ranges (0.5–30 mM) and in the presence of elemental sulfur (S0) or Hg0, conditions that encompass those of near-bottom and pore waters of sediments. Samples containing synthetic red mercuric sulfide (HgS, cinnabar), buffer solution, aliquots of bisulfide (HS−1) solution, and, in special cases, S0 or Hg0 were prepared anaerobically and allowed to equilibrate for several months. Filtered samples were analyzed for pH, total sulfide (ΣS2−), and total mercury [Hg]tot. Plots of [Hg]tot values vs. pH at varying ΣS2− verified the formation of three previously known mercury-sulfide complexes (HgS2Hnn−2) and revealed that a new Hg2SOH+ complex is important at low pH and low ΣS2−. Our constants for ionic strength (I) 0.7 and 250 C are as follows: K1=10−5.76(+0.71, −1.02) for HgScinn+H2S ↔ HgS2H20; K2=10−4.82(+0.72, −1.10) for HgScinn+HS ↔ HgS2H; K3=10−13.41(+0.76, −0.93) for HgScinn+HS ↔ HgS22−+H+; K4=10−8.36(+0.71, −0.93) for 2HgScinn+H++H2O ↔ Hg2SOH++H2S. With decreasing pH, below 1, Hg solubility decreased sharply, indicating the formation of a new solid phase, inferred to be corderoite (Hg3S2Cl2). From our solubility data, we calculated the free energy of formation (ΔGfo) of Hg3S2Cl2 to be −396 (+3, −11) kJ/mol. In experiments where excess S0(s) was present, a new mercury-polysulfide dimer was identified; its formation constant is K5=10−1.99(+0.69, −1.27) for 2HgScinn+2HS + nS0 ↔ Hg3S4IISnoH22−. Data from experiments where Hg0(aq) was added confirmed the reversibility of HgS dissolution. An application of our mercury-sulfide speciation model to a natural anoxic basin, Saanich Inlet, British Columbia, is discussed.


Sulfide Mercury Free Energy Ionic Strength Pore Water 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Foord, E. E. and Berendsen, P.: 1974,Amer. Mineral. 59, 652–655.Google Scholar
  2. Lu, X., Johnson, W. K., Wong, C. S.: 1986,Mar. Pollut. Bull. 17, No. 6, 263–267.Google Scholar
  3. Schwarzenbach, G. and Widmer, M.: 1963,Helv. Chim. Acta. 46, 2613–2628.Google Scholar
  4. Williamson, M. A. and Rimstidt, J. D.: 1992,Geochim. et Cosmochim. Acta. 56, 3867–3880.Google Scholar

Copyright information

© Kluwer Academic Publishers 1995

Authors and Affiliations

  • K. Paquette
    • 1
  • G. Helz
    • 1
  1. 1.Department of Chemistry and BiochemistryUniv. Of MarylandCollege ParkUSA

Personalised recommendations