Environmental contextThe chemical speciation of mercury (Hg) largely controls its biogeochemical cycling and exposure to biota. Here, we investigate the thermodynamic stabilities of complexes formed between inorganic divalent Hg (HgII) and 15 biogeochemically relevant low-molecular-mass (LMM) thiol ligands. This information is critical for accurate modelling of the chemical speciation of HgII and to clarify the role of HgII–LMM thiol complexes in the cycling of Hg in the environment.
AbstractInorganic divalent mercury (HgII) has a very high affinity for reduced sulfur functional groups. Reports from laboratory experiments suggest that HgII complexes with specific low-molecular-mass (LMM) thiol (RSH) ligands control rates of HgII transformation reactions. Because of methodological limitations for precise determination of the highly stable HgII complexes with LMM thiol ligands, constants reported in the literature remain inconsistent. This uncertainty impedes accurate modelling of the chemical speciation of HgII and the possibility to elucidate the role of HgII complexes with LMM thiols for Hg transformation reactions. Here, we report values of thermodynamic stability constants for 15 monodentate, two-coordinated HgII complexes, Hg(SR)2, formed with biogeochemically relevant LMM thiol ligands. The constants were determined by a two-step ligand-exchange procedure where the specific Hg(SR)2 complexes were quantified by liquid chromatography–inductively coupled plasma mass spectrometry. Thermodynamic stability constants (log β2) determined for the Hg(SR)2 complexes ranged from 34.6, N-cysteinylglycine, to 42.1, 3-mercaptopropionic acid, for the general reaction Hg2++2RS– ⇌ Hg(SR)2. Density functional theory (DFT) calculations showed that electron-donating carboxyl and carbonyl groups have a stabilising effect on the HgII–LMM thiol complexes, whereas electron-withdrawing protonated primary amino groups have a destabilising effect. Experimental results and DFT calculations demonstrated that the presence of such functional groups in the vicinity of the RSH group caused significant differences in the stability of Hg(SR)2 complexes. These differences are expected to be important for the chemical speciation of HgII and its transformation reactions in environments where a multitude of LMM thiol compounds are present.
How easy is CO2 fixation by M–C bond containing complexes (M = Cu, Ni, Co, Rh, Ir)?
