RESUMO
In this work we investigated the behaviour of pure HgS during extraction with dilute HCl to establish its extractability in 1 and 6 M HCl at the concentration level close to those occurring in natural sediments and soils. We found that neither cinnabar nor metacinnabar were soluble in 1 M HCl, whereas both were partially extracted by 6 M HCl. Metacinnabar precipitated in the laboratory was most prone to dissolution in 6 M HCl (up to 90%), followed by crystalline (commercial) metacinnabar (up to 70%) and cinnabar (up to 15%). Solubility of HgS in 6 M HCl was found to be dependent on its concentration, and an exponential relationship between quantity of HgS added to 20 mL of 6 M HCl (the range of 0.1-10 mg was used) and the solubility in 6 M HCl was established. For higher concentrations of HgS (10 mg in 20 mL of acid), a similarly low solubility of cinnabar was obtained as found in the literature. A study of dissolution kinetics of HgS in 6 M HCl indicated that it was a fairly slow process. Unexpected oxidation of HgS in water or 1 M HCl was found for extractions performed in Teflon vials previously used for the digestion of residual undissolved HgS by aqua regia. We presumed that the Teflon material could preserve some oxidising gases (presumably Cl(2)) developed during digestion with aqua regia which can then oxidise HgS during extraction with water or 1 M HCl. Regarding the extraction of Hg from natural sediments, we concluded that 6 M HCl could not be used to extract reactive Hg and predict bioavailability of mercury in sediments containing HgS and that experiments with model compounds should not be done at a concentration level several orders of magnitude higher than in natural samples.
RESUMO
The extractability of metacinnabar and cinnabar, alone or in the presence of some sediment components, with various concentrations of HNO3 (1, 4, 6, and 14 M) was studied. Both forms of HgS (0.2-0.3 mg HgS in 10-20 mL of acid) were insoluble in all HNO3 concentrations as pure compounds. The presence of FeCl3 enhanced solubility of both cinnabar and metacinnabar, especially when concentrated HNO3 was used for the extraction. As the same effect was not obtained in the presence of FeOOH, we concluded that chloride and not Fe3+ was responsible for HgS dissolution. In fact, addition of very low chloride concentration to concentrated HNO3 provoked partial (Cl>10(-4) M) or even total dissolution (Cl>10(-2) M) of HgS. In dilute HNO3 (4-6 M) cinnabar was much less affected by chloride addition than metacinnabar. Extraction of HgS by concentrated HNO3 in the presence of sediment of various salinities demonstrated that the amount of dissolved HgS increased with the increase of the sediment salinity (from freshwater to estuarine and marine sediment), confirming that chloride enhances dissolution of HgS. Removal of chloride by washing the sediment with Milli-Q water significantly reduced dissolution of added HgS during extraction by concentrated HNO3. These results demonstrate that conclusions based on the extraction schemes using concentrated HNO3 as single extractant or as the first extractant in the sequential extraction procedures can be biased. A verification of artifactual oxidation of HgS, when using more concentrated HNO3 as extractant, would help to verify reliability of the applied extraction procedure.