Denitrification (DNF) and dissimilatory nitrate reduction
to ammonium
(DNRA) compete in reducing sediment conditions where DNF permanently
removes nitrogen (N), while DNRA retains N with the conversion of
nitrate (NO3
–) to ammonium (NH4
+). Thus, an increase in the level of DNRA can undermine
permanent N removal. We investigated the relative magnitude and controls
of these two processes at two milldam-affected riparian sites. DNRA
(5.2–37.6 μg L–1 h–1) accounted for 10–79% of total NO3
– reduction and was highest in riparian sediments with higher iron
(Fe) and sodium (Na+) in groundwater. DNF was the primary
mechanism for NO3
– reduction when Fe
and Na+ concentrations were low but when NO3
– was elevated. DNRA rates were higher for treatments
with higher dissolved organic carbon (DOC):NO3
– and Fe:NO3
– ratios, indicating the
stimulation of both heterotrophic and Fe2+ driven autotrophic
DNRA. DNF and DNRA rates and their microbial functional genes decreased
with increasing sediment depths. These findings imply that hydrologically
stagnant and persistently reducing conditions associated with relict
milldams and similar anthropogenic structures may enhance DNRA at
the expense of DNF and undermine permanent N removal in riparian zones.
Thus, the effects of such structures need to be accounted for in watershed
N management strategies.