To
advance the scientific understanding of bacteria-driven mercury
(Hg) transformation processes in natural environments, thermodynamics
and kinetics of divalent mercury Hg(II) chemical speciation need to
be understood. Based on Hg L
III
-edge extended X-ray absorption
fine structure (EXAFS) spectroscopic information, combined with competitive
ligand exchange (CLE) experiments, we determined Hg(II) structures
and thermodynamic constants for Hg(II) complexes formed with thiol
functional groups in bacterial cell membranes of two extensively studied
Hg(II) methylating bacteria:
Geobacter sulfurreducens
PCA and
Desulfovibrio desulfuricans
ND132. The
Hg EXAFS data suggest that 5% of the total number of membranethiol
functionalities (Mem-RS
tot
= 380 ± 50 μmol g
–1
C) are situated closely enough to be involved in
a 2-coordinated Hg(Mem-RS)
2
structure in
Geobacter
. The remaining 95% of Mem-RSH is involved in mixed-ligation Hg(II)-complexes,
combining either with low molecular mass (LMM) thiols like Cys, Hg(Cys)(Mem-RS),
or with neighboring O/N membrane functionalities, Hg(Mem-RSRO). We
report log
K
values for the formation of the structures
Hg(Mem-RS)
2
, Hg(Cys)(Mem-RS), and Hg(Mem-RSRO) to be 39.1
± 0.2, 38.1 ± 0.1, and 25.6 ± 0.1, respectively, for
Geobacter
and 39.2 ± 0.2, 38.2 ± 0.1, and 25.7
± 0.1, respectively, for ND132. Combined with results obtained
from previous studies using the same methodology to determine chemical
speciation of Hg(II) in the presence of natural organic matter (NOM;
Suwannee River DOM) and 15 LMM thiols, an internally consistent thermodynamic
data set is created, which we recommend to be used in studies of Hg
transformation processes in bacterium–NOM–LMM thiol
systems.