Bioconversion of elemental mercury
(Hg0) into immobile, nontoxic, and less bioavailable species
is of vital environmental significance. Here, we investigated bioconversion
of Hg0 in a sulfate-reducing membrane biofilm reactor (MBfR).
The MBfR achieved effective Hg0 removal by sulfate bioreduction.
16 S rDNA sequencing and metagenomic sequencing revealed that diverse
groups of mercury-oxidizing/sulfate-reducing bacteria (Desulfobulbus, Desulfuromonas, Desulfomicrobium, etc.) utilized
Hg0 as the initial electron donor and sulfate as the terminal
electron acceptor to form the overall redox. These microorganisms
coupled Hg0 bio-oxidation to sulfate bioreduction.
Analysis on mercury speciation in biofilm by sequential extraction
processes (SEPs) and inductively coupled mass spectrometry (ICP-MS)
and by mercury temperature programmed desorption (Hg-TPD) showed that
mercury sulfide (HgS) and humic acid-bound mercury (HA-Hg) were two
major products of Hg0 bio-oxidation. With HgS and HA-Hg
comprehensively characterized by X-ray diffraction (XRD), excitation-emission
matrix spectra (EEM), scanning electron microscopy-energy disperse
spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS), and
Fourier transform infrared spectroscopy (FTIR), it was proposed that
biologically oxidized mercury (Hg2+) further reacted with
biogenic sulfides to form cubically crystallized metacinnabar (β-HgS)
extracellular particles. Hg2+ was also complexed with functional
groups −SH, −OH, −NH–, and
−COO– in humic acids from extracellular polymeric
substances (EPS) to form HA-Hg. HA-Hg may further react with biogenic
sulfides to form HgS. Bioconversion of Hg0 into HgS was
therefore achieved and can be a feasible biotechnique for flue gas
demercuration.