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The long-term efficacy of stormwater treatment systems requires continuous pollutant removal without substantial re-release. Hence, the division of incoming pollutants between temporary and permanent removal pathways is fundamental. This is pertinent to nitrogen, a critical water body pollutant, which on a broad level may be assimilated by plants or microbes and temporarily stored, or transformed by bacteria to gaseous forms and permanently lost via denitrification. Biofiltration systems have demonstrated effective removal of nitrogen from urban stormwater runoff, but to date studies have been limited to a 'black-box' approach. The lack of understanding on internal nitrogen processes constrains future design and threatens the reliability of long-term system performance. While nitrogen processes have been thoroughly studied in other environments, including wastewater treatment wetlands, biofiltration systems differ fundamentally in design and the composition and hydrology of stormwater inflows, with intermittent inundation and prolonged dry periods. Two mesocosm experiments were conducted to investigate biofilter nitrogen processes using the stable isotope tracer 15NO3(-) (nitrate) over the course of one inflow event. The immediate partitioning of 15NO3(-) between biotic assimilation and denitrification were investigated for a range of different inflow concentrations and plant species. Assimilation was the primary fate for NO3(-) under typical stormwater concentrations (∼1-2 mg N/L), contributing an average 89-99% of 15NO3(-) processing in biofilter columns containing the most effective plant species, while only 0-3% was denitrified and 0-8% remained in the pore water. Denitrification played a greater role for columns containing less effective species, processing up to 8% of 15NO3(-), and increased further with nitrate loading. This study uniquely applied isotope tracing to biofiltration systems and revealed the dominance of assimilation in stormwater biofilters. The findings raise important questions about nitrogen release upon plant senescence, seasonally and in the long term, which have implications on the management and design of biofiltration systems.

Our understanding of the effects of pharmaceuticals on key biogeochemical processes and biofilm assemblage composition in surface waters is limited despite the prevalence of ng/L to µg/L concentrations of these compounds. We examined the effects of 3 commonly-prescribed pharmaceuticals: ciprofloxacin (140 ng/L), diphenhydramine (300 ng/L), and fluoxetine (20 ng/L); both individually and as a mixture, on key ecosystem processes at environmentally-realistic concentrations. We used mesocosms to expose naturally-occurring biofilm communities and artificial benthic substrates to these pharmaceuticals and measured the effects of exposure on biofilm, seston, and sediment communities. Established biofilm functions were unaffected by pharmaceutical treatments. However, successional biofilms experienced 42 to 81% reductions in primary production and 59 to 83% reductions in community respiration. Denitrification in sediment communities was reduced by 41 to 73% in shaded conditions, but was not affected when left in ambient light. Diatom assemblage structure was unaffected by pharmaceuticals in successional biofilms, whereas the composition of established biofilm assemblages changed with exposure to treatments that contained ciprofloxacin, diphenhydramine, and all 3 pharmaceuticals. Our study adds to a growing body of evidence indicating that chronic exposure to sub-lethal concentrations of pharmaceuticals may substantially alter key ecosystem processes and communities. [ABSTRACT FROM AUTHOR]

Abstract: Wetlands are often biogeochemical hotspots, and they can remove excess N via denitrification and assimilatory uptake. Wetlands are also susceptible to plant invasions, but the effect of invasive plants on denitrification in freshwater wetland sediments is not well‐studied. Two distinct mechanisms suggest the potential for invasive plants to alter denitrification. First, invasive plants often produce more biomass than non‐invasive species, thus potentially providing additional carbon (C) for denitrifiers. Second, some invasive wetland plants funnel more oxygen into the root zone than non‐invasive plants, potentially stimulating coupled nitrification–denitrification. Using the push–pull isotope pairing technique, we measured denitrification and coupled nitrification–denitrification in the sediments beneath monoculture plots of Phragmites australis and Typha domingensis, and beneath unvegetated sediments, in an urban wetland in Melbourne, Australia. We also measured pore water nutrient concentrations and calculated the diffusive flux of nutrients from the sediments into the overlying water column. We hypothesised that plots containing P. australis would have the highest denitrification and coupled nitrification–denitrification rates, followed by plots containing T. domingensis, with the lowest rates in the unvegetated plots, as a result of higher C and oxygen availability. Instead, we found that denitrification and coupled nitrification–denitrification rates were highly variable, with no difference among plot type. However, we did find that diffusive flux of ammonium from the sediments into the water column was lower in the vegetated plots than in the unvegetated plots, suggesting that vegetation enhances wetland N retention via plant assimilatory uptake. [ABSTRACT FROM AUTHOR]

• Both denitrification and DNRA decreased due to drying of sediments, but DNRA decreased more than denitrification. • Rates of both denitrification and DNRA increased with increasing temperature in slurries. • The relative increase in DNRA was more than denitrification with increasing temperature. Constructed wetlands are increasingly used within urban areas to reduce pollutant runoff, including nitrogen. These environments are exposed to frequent wetting and drying events, and also increasing temperatures due to the heat island effect and seasonal variation. In this study, we have investigated the role of drying and rewetting of sediments and temperature on the partitioning of two nitrate reduction pathways: denitrification (DNF) and dissimilatory nitrate reduction to ammonium (DNRA) in four constructed urban stormwater wetlands in Melbourne, Australia. Our results suggest that both DNF and DNRA decreased due to drying of sediments, but DNRA decreased to a greater extent. Rates of DNRA from the drying-rewetting treatment decreased 5–90% compared to the control. Moreover, a concomitant increase in NH 4 + fluxes and a slight change in sediment oxygen demand (SOD) suggest that oxic conditions arising from sediment drying was responsible for the decreased rates of DNF and DNRA. Rates of both DNF and DNRA increased with increasing temperature in slurries. The DNF:DNRA ratio suggests that the relative increase in DNRA was more than DNF with increasing temperature. The mean activation energy of DNF ranged from 41 ± 1 to 64 ± 4 kJ mol−1 and the corresponding temperature coefficient (Q 10) values ranged from 1.3 to 2.4. In comparison, the mean activation energy of DNRA was higher and ranged from 50 ± 8 to 107 ± 14 kJ mol−1 with the corresponding Q 10 values ranging from 1.2 to 3.4. Overall, our results suggest that drying and re-wetting of sediments decreases nitrate reduction and increases nitrogen retention, whereas increased temperature enhances the recycling of bioavailable nitrogen in wet sediments in constructed urban stormwater wetlands. [ABSTRACT FROM AUTHOR]

Abstract Denitrification (DNF) and dissimilatory nitrate reduction to ammonium (DNRA) are two competing nitrate reduction pathways that remove or recycle nitrogen, respectively. However, factors controlling the partitioning between these two pathways are manifold and our understanding of these factors is critical for the management of N loads in constructed wetlands. An important factor that controls DNRA in an aquatic ecosystem is the electron donor, commonly organic carbon (OC) or alternatively ferrous iron and sulfide. In this study, we investigated the role of natural organic carbon (NOC) and acetate at different OC/NO 3 − ratios and ferrous iron on the partitioning between DNF and DNRA using the 15N-tracer method in slurries from four constructed stormwater urban wetlands in Melbourne, Australia. The carbon and nitrate experiments revealed that DNF dominated at all OC/NO 3 − ratios. The higher DNF and DNRA rates observed after the addition of NOC indicates that nitrate reduction was enhanced more by NOC than acetate. Moreover, addition of NOC in slurries stimulated DNRA more than DNF. Interestingly, slurries amended with Fe2+ showed that Fe2+ had significant control on the balance between DNF and DNRA. From two out of four wetlands, a significant increase in DNRA rates (p <.05) at the cost of DNF in the presence of available Fe2+ suggests DNRA is coupled to Fe2+ oxidation. Rates of DNRA increased 1.5–3.5 times in the Fe2+ treatment compared to the control. Overall, our study provides direct evidence that DNRA is linked to Fe2+ oxidation in some wetland sediments and highlights the role of Fe2+ in controlling the partitioning between removal (DNF) and recycling (DNRA) of bioavailable N in stormwater urban constructed wetlands. In our study we also measured anammox and found that it was always <0.05% of total nitrate reduction in these sediments. Graphical abstract Unlabelled Image Highlights • Natural organic carbon (NOC) and ferrous iron showed significant effect on the partitioning between DNF and DNRA. • Nitrate reduction was stimulated more by the addition of NOC than acetate. • NOC enhanced DNRA more than denitrification. • Fe2+ had a significant control on the balance between denitrification and DNRA. • There was a link between DNRA and Fe2+ oxidation in Fe2+ amended slurries. [ABSTRACT FROM AUTHOR]

Abstract: The Yarra River Estuary is a salt wedge estuary prone to hypoxia in the bottom waters during low flow periods. Rates of denitrification and dissimilatory nitrate reduction to ammonium (DNRA) were quantified using 15N in relation to oxygen, nitrate and available reductants. Denitrification was the dominant nitrate reduction pathway under all oxygen conditions, however, DNRA increased from <1% under hypoxic conditions (<50μmolL−1 O2) to ∼18% of total nitrate reduction under oxygen saturation in the water column in intact core incubations. Microprofiles of nitrate reduction pathways in intact cores using diffusive equilibrium in thin layer (DET) gels showed significant rates of DNRA only occurred under oxic conditions in the presence of Fe2+. Cores incubated anoxically, developed free sulfide within the porewater, had very low concentrations of Fe2+ and low rates of DNRA. Slurry incubations with varying concentrations of NO3 − showed that denitrifying bacteria had a higher affinity than nitrate ammonifying bacteria with K m values of 49 and 86μmolL−1 for denitrification and DNRA, respectively, however, this could not explain the change in the rates of DNRA relative to denitrification observed. Further slurry incubations to investigate the relationship between DNRA and Fe2+ oxidation were inconclusive and complicated by very high backgrounds of sorbed (HCl extractable) Fe2+. Addition of Fe2+ to the slurry did not stimulate denitrification compared to a control (no Fe2+ addition), however, there was a significant decrease in the Fe2+ concentration over the period where DNRA occurred in the Fe2+ addition treatment, and no significant decrease in the control treatment. The ratio of DNRA to Fe2+ consumption was 15±6 and 7±3 for the Fe2+ and control treatments, respectively. We suggest reduced rates of DNRA under anoxic conditions can be explained by the binding of Fe2+ with free sulfides and the formation of FeS removing available Fe2+ for DNRA. [Copyright &y& Elsevier]