Biochars can remove potentially toxic elements, such
as inorganic
mercury [Hg(II)] from contaminated waters. However, their performance
in complex water matrices is rarely investigated, and the combined
roles of natural organic matter (NOM) and ionic composition in the
removal of Hg(II) by biochar remain unclear. Here, we investigate
the influence of NOM and major ions such as chloride (Cl
–
), nitrate (NO
3
–
), calcium (Ca
2+
), and sodium (Na
+
) on Hg(II) removal by a wood-based
biochar (SWP700). Multiple sorption sites containing sulfur (S) were
located within the porous SWP700. In the absence of NOM, Hg(II) removal
was driven by these sites. Ca
2+
bridging was important
in enhancing removal of negatively charged Hg(II)-chloro complexes.
In the presence of NOM, formation of soluble Hg-NOM complexes (as
seen from speciation calculations), which have limited access to biochar
pores, suppressed Hg(II) removal, but Cl
–
and Ca
2+
could still facilitate it. The ability of Ca
2+
to aggregate NOM, including Hg-NOM complexes, promoted Hg(II) removal
from the dissolved fraction (<0.45 μm). Hg(II) removal in
the presence of Cl
–
followed a stepwise mechanism.
Weakly bound oxygen functional groups in NOM were outcompeted by Cl
–
, forming smaller-sized Hg(II)-chloro complexes, which
could access additional intraparticle sorption sites. Therein, Cl
–
was outcompeted by S, which finally immobilized Hg(II)
in SWP700 as confirmed by extended X-ray absorption fine structure
spectroscopy. We conclude that in NOM containing oxic waters, with
relatively high molar ratios of Cl
–
: NOM and Ca
2+
: NOM, Hg(II) removal can still be effective with SWP700.