Iron
minerals are widespread in earth’s surface water and
soil. Recent studies have revealed that under sunlight irradiation,
iron minerals are photoactive on producing reactive oxygen species
(ROS), a group of key species in regulating elemental cycling, microbe
inactivation, and pollutant degradation. In nature, iron minerals
exhibit varying crystallinity under different hydrogeological conditions.
While crystallinity is a known key parameter determining the overall
activity of iron minerals, the impact of iron mineral crystallinity
on photochemical ROS production remains unknown. Here, we assessed
the photochemical ROS production from ferrihydrites with different
degrees of crystallinity. All examined ferrihydrites demonstrated
photoactivity under irradiation, resulting in the generation of hydrogen
peroxide (H2O2) and hydroxyl radical (•OH). The photochemical ROS production from ferrihydrites increased
with decreasing ferrihydrite crystallinity. The crystallinity-dependent
photochemical •OH production was primarily attributed
to conduction band reduction reactions, with the reduction of O2 by conduction band electrons being the rate-limiting key
process. Conversely, the crystallinity of iron minerals had a negligible
influence on photon-to-electron conversion efficiency or surface Fenton-like
activity. The difference in ROS productions led to a discrepant degradation
efficiency of organic pollutants on iron mineral surfaces. Our study
provides valuable insights into the crystallinity-dependent ROS productions
from iron minerals in natural systems, emphasizing the significance
of iron mineral photochemistry in natural sites with abundant lower-crystallinity
iron minerals such as wetland water and surface soils.