Nanosized titanium dioxide (TiO2) is a naturally existing
nanoscale semiconducting mineral, and its co-occurrence with microbes
may elicit differential environmental effects. In this study, the
impacts of TiO2 nanoparticles (NPs) on the reductive dissolution
of As(V) and Fe(III) from flooded arsenic-enriched soils were examined
under intermittent illumination and dark conditions. The amendment
with TiO2 NPs under intermittent illumination resulted
in the highest As/Fe reduction among all amendments. In the amendment
with TiO2 NPs, the maximum concentrations of Fe(II) derived
from intermittent illumination and dark treatments were nearly 2.1-
and 1.7-fold higher than the soils amended with acetate alone under
dark conditions (36.5 ± 4.5 mg/L), respectively, and nearly 1.6-
and 1.2-fold higher than the increased As(III) concentrations (8175.2
± 125.5 μg/L) detected under the same conditions. However,
the removal of total organic carbon derived from the amendment with
acetate-TiO2 NPs under intermittent illumination was only
0.8 times that of the amendment with acetate alone under dark conditions.
Because TiO2 NPs are highly responsive to sunlight, more
photoelectrons supplied from intermittently illuminated soils were
separated synchronously by accompanying them with the capture of photoholes
by humic/fulvic acids; thereafter, the photoelectrons participated
in As(V)/Fe(III) reduction. In addition, the electrical conductivities
of TiO2 NPs-supplemented soil particles were nearly 1.6-fold
higher than that of nonsupplemented samples, thereby enabling a long-distance
electron transfer. Moreover, the amendment with TiO2 NPs
with intermittent illumination resulted in an increase to the abundances
of several metal-reducing bacteria in the soil microbial community,
e.g., Bacillus, Thermincola, Pseudomonas, and Clostridium, correspondingly boosting the involved
microbial degradation of organic substrates to supply more bioelectrons
for As(V)/Fe(III) reduction. The findings have an important implication
on the understanding of the role of nanosized minerals in the biogeochemical
cycling of metal pollutants.