Enhancing nitrogen and phosphorus removal in plant-biochar-pyrite stormwater bioretention systems: Impact of temperature and high-frequency heavy rainfall.

Global climate change and rapid urbanization have resulted in more frequent and intense rainfall events in urban areas, raising concerns about the effectiveness of stormwater bioretention systems. In this study, we optimized the design by constructing a multi-layer filler structure, including plant layer, biochar layer, and pyrite layer, and evaluated its performance in nitrogen (N) and phosphorus (P) removal under different temperatures (5-18 °C and 24-43 °C), rainfall intensity (47.06 mm rainfall depth), and frequency (1-5 days rainfall intervals) conditions. The findings indicate that over 775 days, the plant system consistently removed 62.3% of total nitrogen (TN) and 97.0% of total phosphorus (TP) from 103 intense rainfall events. Temperature fluctuations had minimal impact on nitrate nitrogen (NO3--N) and TP removal, with differences in removal rates of only 1.0% and 0.6%, respectively, among plant groups. Across the multi-layer structure, plant roots mitigated the impact of temperature differences on NO3--N removal, while high-frequency rainfall fluctuated the stability of NO3--N removal. Dense plant roots reinforced N and P removal by facilitating denitrification in the vadose zone (biochar) and strengthening denitrification processes. Biochar and pyrite contributed to stable microenvironments and diverse ecological functions, enhancing NO3--N and PO43- removal. In summary, the synergistic effects of the multi-layer filler structure improved and stabilized N and P removal, providing valuable insights for addressing runoff pollution in bioretention systems amidst rapid urbanization and climate change challenges.

A self-sustaining effect induced by iron sulfide generation and reuse in pyrite-woodchip mixotrophic bioretention systems: An experimental and modeling study.

Dual electron donor bioretention systems have emerged as a popular strategy to enhance dissolved nitrogen removal from stormwater runoff. Pyrite-woodchip mixotrophic bioretention systems showed a promoted and stabilized removal of dissolved nutrients under complex rainfall conditions, but the sulfate reduction process that can induce iron sulfide generation and reuse was overlooked. In this study, experiments and models were applied to investigate the effects of filler configuration and dissolved organic carbon (DOC) dissolution rate on treatment performance and iron sulfide generation in pyrite-woodchip bioretention systems. Key parameters govern that DOC dissolution and microbe-mediated processes were obtained by experiments. The water quality models that integrate one-dimensional constant flow, sorption and microbial transformation kinetics were used to predict the performance of bioretention systems. Results showed that the mixotrophic bioretention system with woodchip mixed in the vadose zone and pyrite in the saturated zone achieves a better performance in both nitrogen removal efficiency and by-product control. Comparably, woodchip and pyrite mixed in the saturated zone could encounter a high secondary pollution risk. The sensitivity coefficients of oxic/anoxic DOC dissolution rates to total nitrogen removal are 0.36 and -2.43 respectively. Iron sulfide generation was affected by DOC distribution and the competition between heterotrophic denitrifiers, autotrophic denitrifiers, and sulfate-reducing bacteria (SRB). DOC accumulation has an antagonistic effect on iron production and sulfate reduction. Extra DOC accumulation favors sulfate reduction while high DOC concentration inhibits pyrite-based denitrification and reduces Fe(III) production. The recycling of iron sulfide can improve the robustness and sustainability of bioretention systems.

Enhanced resilience in urban stormwater management through model predictive control and optimal layout schemes under extreme rainfall events.

Optimizing the layout of urban stormwater management systems is an effective method for mitigating the risk of urban flooding under extreme storms. However, traditional approaches that consider only economic costs or annual runoff control rates cannot dynamically respond to the uncertainties of extreme weather, making it difficult to completely avoid large accumulations of water and flooding in a short period. This study proposes an integrated method combining system layout optimization and Model Predictive Control(MPC)to enhance the system's resilience and effectiveness in flood control. An optimization framework was initially built to identify optimal system layouts, balancing annual average life cycle cost (AALCC) and resilience index. The MPC was then applied to the optimal layout selected using the Technique for Order Preference by Similarity to Ideal Solution (TOPSIS) method, aiming to alleviate inundation cost-effectively. The adaptability of MPC to varying sets of control horizons and its efficacy in managing the hydrograph and flood dynamics of urban drainage system were examined. Conducted in Yubei, Chongqing, this study revealed patterns in optimal layout fronts among various extreme design rainfalls, showing that peak position rate and return period significantly influence system resilience. The contribution of MPC to the optimal system layout was particularly notable, resulting in improved instantaneous and overall flood mitigation. The application of MPC increased the resilience index by an average of 0.0485 and offered cost savings of 0.0514 million yuan in AALCC. Besides, our findings highlighted the importance of selecting an optimal set of control horizons for MPC, which could reduce maximum flood depth from 0.43m to 0.19m and decrease conduit peak flow by up to 14% at a flood-prone downstream location.

Removal, accumulation, and micro-ecosystem impacts of typical POPs in bioretention systems with different media: A runoff infiltration study.

Bioretention systems prove effective in purifying common persistent organic pollutants (POPs) found in urban rainfall runoff. However, the response process of the microecosystem in the media becomes unclear when POPs accumulate in bioretention systems. In this study, we constructed bioretention systems and conducted simulated rainfall tests to elucidate the evolution of micro-ecosystems within the media under typical POPs pollution. The results showed all POPs in runoff were effectively removed by surface adsorption in different media, with load reduction rates of >85 % for PCBs and OCPs and > 80 % for PAHs. Bioretention soil media (BSM) + water treatment residuals (WTR) media exhibited greater stability in response to POPs contamination compared to BSM and pure soil (PS) media. POPs contamination significantly impacted the microecology of the media, reducing the number of microbial species by >52.6 % and reducing diversity by >27.6 % at the peak of their accumulation. Enzyme activities were significantly inhibited, with reductions ranging from 44.42 % to 60.33 %. Meanwhile, in terms of ecological functions, the metabolism of exogenous carbon sources significantly increased (p < 0.05), while nitrogen and sulfur cycling processes were suppressed. Microbial diversity and enzyme activities showed some recovery during the dissipation of POPs but did not reach the level observed before the experiment. Dominant bacterial species and abundance changed significantly during the experiment. Proteobacteria were suppressed, but remained the dominant phylum (all relative abundances >41 %). Bacteroidota, Firmicutes, and Actinobacteria adapted well to the contamination. Pseudomonas, a typical POPs-degrading bacterium, displayed a positive correlation between its relative abundance and POPs levels (mean > 10 %). Additionally, POPs and media properties, including TN and pH, are crucial factors that collectively shape the microbial community. This study provides new insights into the impacts of POPs contamination on the microbial community of the media, which can improve media design and operation efficiency.

Investigation of pollutants accumulation in the submerged zone for pyrite-based bioretention facilities under continuous rainfall events.

Submerged zone in bioretention facilities for stormwater treatment has been approved to be an effective structure amendment to improve denitrification capability. However, the role and influence of water quality changes in the submerged zone under natural continuous random rainfall patterns are still not clear, especially when the rainfall is less than the pore water in the submerged zone. In this study, continuous rainfall events with different rainfall volume (light rain-light rain-heavy rain) were designed in a lab-scale woodchip mulched pyrite bioretention facility to test the effects of rainfall pattern. The results exhibited that light rain events significantly affected the pollutant removal performance of bioretention for the next rainfall. Different effects were observed during the long-term operation. In the 5th month, light rain reduced the ammonia removal efficiency of subsequent rainstorm events by 8.70%, while in the 12th month, when nitrate leakage occurred, light rain led to a 40.24% reduction in the next heavy rain event's nitrate removal efficiency. Additionally, light rain would also affect the concentration of by-products in the next rainfall. Following a light rain, the concentration of sulfate in the subsequent light rainfall can increase by 24.4 mg/L, and by 11.92 mg/L in a heavy rain. The water quality in the submerged zone and media characteristics analysis suggested that nitrogen conversion capacity of the substrate and microbes, such as Nitrospira (2.86%) and Thiobacillus (35.71%), as well as the in-situ accumulation of pollutants under light rain played important roles. This study clarifies the relationship between successive rainfall events and provides a more comprehensive understanding of bioretention facilities. This is beneficial for field study of bioretention facilities in the face of complex rainfall events.

Solid-liquid redistribution and degradation of antibiotics during hydrothermal treatment of sewage sludge: Interaction between biopolymers and antibiotics.

Waste activated sludge serves an important reservoir for antibiotics within wastewater treatment plants, and understanding the occurrence and evolution of antibiotics during sludge treatment is crucial to mitigate the potential risks of subsequent resource utilization of sludge. This study explores the degradation and transformation mechanisms of three typical antibiotics, oxytetracycline (OTC), ofloxacin (OFL), and azithromycin (AZI) during sludge hydrothermal treatment (HT), and investigates the influence of biopolymers transformation on the fate of these antibiotics. The findings indicate that HT induces a shift of antibiotics from solid-phase adsorption to liquid-phase dissolution in the initial temperature range of 25-90 °C, underscoring this phase's critical role in preparing antibiotics for subsequent degradation phases. Proteins (PN) and humic acids emerge as crucial for antibiotic binding, facilitating their redistribution within sludge. Specifically, the binding capacity sequence of biopolymers to antibiotics is as follows: OFL>OTC>AZI, highlighting that OFL-biopolymers display stronger electrostatic attraction, more available adsorption sites, and more stable binding strength. Furthermore, antibiotic degradation mainly occurs above 90 °C, with AZI being the most temperature-sensitive, degrading 92.97% at 180 °C, followed by OTC (91.26%) and OFL (52.51%). Concurrently, the degradation products of biopolymers compete for active sites to form novel amino acid-antibiotic conjugates, which inhibits the further degradation of antibiotics. These findings illuminate the effects of biopolymers evolution on intricate dynamics of antibiotics fate in sludge HT and are helpful to optimize the sludge HT process for effective antibiotics abatement.

Promoting oxygen vacancies utility for tetracycline degradation via peroxymonosulfate activation by reduced Mg-doped Co3O4: Kinetics and key role of electron transfer pathway.

Developing cobalt-based catalysts with a high abundance of oxygen vacancies (Vo) and exceptional Vo utility efficiency for the prompt removal of stubborn contaminants through peroxymonosulfate (PMS) activation poses a significant challenge. Herein, we reported the synthesis of the reduced Mg-doped Co3O4 nanosheets, i.e. Mg-doped Co3O4-r, via Mg doping and followed by NaBH4 reduction, aiming to degrade tetracycline (TC). Various characterization results illustrated that NaBH4 reduction imparted higher Vo utility efficiency to Mg-doped Co3O4-r, along with an ample presence of reduced Co2+ species and an increased surface area, thereby substantially elevating PMS activation capability. Notably, Mg-doped Co3O4-r achieved more than 97.9% degradation of 20 mg/L TC within 10 min, showing an over 8-fold increase in reaction rate relative to the Mg-doped Co3O4 (kobs: 0.3285 min-1 vs 0.0399 min-1). The high removal efficiency of TC was sustained across a broad pH range of 3-11, even in the presence of common anions and humic acid. Radical quenching trials, EPR outcomes, and electrochemical analysis indicated that neither radicals nor 1O2 were the primary active species. Instead, electron transfer pathway played a dominant role in TC degradation. The Mg-doped Co3O4-r displayed excellent recyclability and versatility. Even after the fifth cycle, it maintained an impressive 83.0% removal of TC. Furthermore, it exhibited rapid degradation capabilities for various pollutants, including levofloxacin, pefloxacin, ciprofloxacin, malachite green, and rhodamine B. The TC degradation pathway was proposed based on LC-MS determination of its degradation intermediates. This study showcases an innovative strategy for the rational design of an efficient cobalt-based activator, leveraging electron transfer pathways through PMS activation to degrade antibiotics effectively.

Multi-media interaction improves the efficiency and stability of the bioretention system for stormwater runoff treatment.

Bioretention systems are one of the most widely used stormwater control measures for urban runoff treatment. However, stable and effective dissolved nutrient treatment by bioretention systems is often challenged by complicated stormwater conditions. In this study, pyrite-only (PO), pyrite-biochar (PB), pyrite-woodchip (PW), and pyrite-woodchip-biochar mixed (M) bioretention systems were established to study the feasibility of improving both stability and efficiency in bioretention system via multi-media interaction. PB, PW, and M all showed enhanced dissolved nitrogen and/or phosphorus removal compared to PO, with M demonstrating the highest efficiency and stability under different antecedent drying durations (ADD), pollutant levels, and prolonged precipitation depth. The total dissolved nitrogen and dissolved phosphorus removal in M ranged between 64%-86% and 80%-95%, respectively, with limited organic matter and iron leaching. Pore water, microbial community, and material analysis collectively indicate that pyrite, woodchip, and biochar synergistically facilitated multiple nutrient treatment processes and protected each other against by-product leaching. Pyrite-woodchip interaction greatly increased nitrate removal by facilitating mixotrophic denitrification, while biochar further enhanced ammonium adsorption and expanded the denitrification area. The Fe3+ generated by pyrite aerobic oxidation was adsorbed on the biochar surface and potentially formed a Fe-biochar composite layer, which not only reduced Fe3+-induced pyrite excessive oxidation but also potentially increased organic matter adsorption. Fe (oxyhydr)oxides intermediate product formed by pyrite oxidation, in return, controlled the phosphorus and organic matter leaching from biochar and woodchip. Overall, this study demonstrates that multi-media interaction may enable bioretention systems to achieve stable and effective urban runoff treatment.

Smaller Aerobic Granules Significantly Reduce N2O Production by Ammonia-Oxidizing Bacteria: Evidences from Biochemical and Isotopic Analyses.

The mitigation of nitrous oxide (N2O) is of primary significance to offset carbon footprints in aerobic granular sludge (AGS) systems. However, a significant knowledge gap still exists regarding the N2O production mechanism and its pathway contribution. To address this issue, the impact of varying granule sizes, dissolved oxygen (DO), and nitrite (NO2-) levels on N2O production by ammonia-oxidizing bacteria (AOB) during nitrification in AGS systems was comprehensively investigated. Biochemical and isotopic experiments revealed that increasing DO or decreasing NO2- levels reduced N2O emission factors (by 13.8 or 19.5%) and production rates (by 0.08 or 0.35 mg/g VSS/h) via weakening the role of the AOB denitrification pathway since increasing DO competed for more electrons required for AOB denitrification. Smaller granules (0.5 mm) preferred to diminish N2O production via enhancing the role of NH2OH pathway (i.e., 59.4-100% in the absence of NO2-), while larger granules (2.0 mm) induced conspicuously higher N2O production via the AOB denitrification pathway (approximately 100% at higher NO2- levels). Nitrifying AGS systems with a unified size of 0.5 mm achieved 42% N2O footprint reduction compared with the system with mixed sizes (0.5-2.0 mm) under optimal conditions (DO = 3.0 mg-O2/L and NO2- = 0 mg-N/L).

Nitrite improved nitrification efficiency and enriched ammonia-oxidizing archaea and bacteria in the simultaneous nitrification and denitrification process.

Simultaneous nitrification and denitrification (SND) is effective and energy-saving for wastewater treatment. As an inevitable intermediate product in the SND process, nitrite affects the efficiency of ammonia oxidation and the composition of nitrifiers. To investigate the impact of nitrite on ammonia oxidation efficiency, two reactors performing SND were respectively operated without nitrite (R1 as control) and with 20 mg N/L nitrite addition (R2 as experimental). The total nitrogen removal efficiency was 74.5% in R1 while 99.0% in R2. With nitrite addition (i.e., 20 mg N/L), the ammonia removal rate in R2 increased to 4.5 times of that in R1. The ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB) contributed to respective around 46.9% and 41.8% ammonia removal in R2 based on the results of experiments with specific inhibitors. The number of respective AOA and AOB ammonia monooxygenase gene (amoA) copies increased by 280 and 30 times due to nitrite addition, according to the qPCR results. The high-throughput sequencing results illustrated the increase of dominant AOB species from 0.40% in R1 to 1.59% in R2 and the phylogenetic tree analysis revealed a close link to Nitrosospira multiformis. These results indicated that the ammonia removal efficiency was improved and AOA/AOB were enriched by nitrite addition. The specific nitrite reductases in AOA and AOB boosted the adaptation of nitrite addition. This study demonstrated the positive impacts of nitrite addition on the ammonia removal efficiency and rate in the SND process.

Insights into the transport and bio-degradation of dissolved inorganic nitrogen in the biochar-pyrite amended stormwater biofilter using dynamic modeling.

The stormwater biofilter is a prevailing green infrastructure for urban stormwater management, but it is less effective in dissolved nitrogen removal, especially for nitrate. The mechanism that governs the nitrate leaching and performance stability of stormwater biofilters is poorly understood. In this study, a water quality model was developed to predict the ammonium and nitrate dynamics in a biochar-pyrite amended stormwater biofilter. The transport of dissolved nitrogen species was described by advection-dispersion models. The kinetics of adsorption and pyrite-based autotrophic denitrification are included in the model and simulated with a steady-state saturated flow. The model was calibrated and validated using eleven storm events. The modeling results reveal that the contribution of pyrite-based autotrophic denitrification to nitrate leaching alleviation improves with the increased drying duration. The nitrate removal efficiency was affected by a series of design parameters. Pyrite filling rate has a minor effect on nitrate removal promotion. Service area ratio and submerged zone depth are the key parameters to prevent nitrate leaching, as they influence the emergence and discharge time of nitrate breakthrough. The high inflow volume (high service area ratio) and small submerged zone can lead to earlier and increased discharge of peak nitrate otherwise the peak nitrate could be retained in the submerged zone and denitrified during the drying period. The developed mechanistic model provides a useful tool to evaluate the treatment ability of stormwater biofilters under varying conditions and offers a guideline for biofilter design optimization.

Microbial community dynamics and metagenomics reveal the potential role of unconventional functional microorganisms in nitrogen and phosphorus removal biofilm system.

The conventional functional microorganisms for nitrogen and phosphorus removal, such as Nitrosomonas, Nitrobacter, Nitrospira and Candidatus Accumulibacter, were hotspots in past research. However, the role of diverse unconventional functional microorganisms was neglected. In this study, a biofilm system was developed to explore the potential role of unconventional functional microorganisms in nutrients removal. According to the results of microbial community dynamics and metagenomics, complete ammonia oxidizing (comammox) bacteria was 20 times more abundant than ammonia-oxidizing bacteria (AOB) at day 121 and its abundance of amoA gene was almost the same as AOB. Although Nitrospira dominated the nitrite-oxidizing bacteria (NOB), diverse unconventional nxrB-containing microorganisms, particularly Chloroflexi, also significantly contributed to the nitrite oxidation. Binning analysis showed that Myxococcota-affiliated Haliangium had the necessary genes owns by phosphorus-accumulating organisms (PAO) and was likely to be the primary PAO since its abundance (6.38 %) was much higher than other conventional PAO (0.70 %). Comparing metagenome-assembled genomes of comammox bacteria with AOB and ammonia-oxidizing archaea (AOA), it possessed potential metabolic versatility in hydrogen and phosphorus, which may be the primary reason for the positive effect of the alternating anaerobic and aerobic conditions on the enrichment of comammox bacteria. Collectively, our findings broaden the understanding on the microbial mechanism of nitrogen and phosphorus removal in biofilm system.

Insights into simultaneous nitrogen and phosphorus removal in biofilm: The overlooked comammox Nitrospira and the positive role of glycogen-accumulating organisms.

Simultaneous nitrogen and phosphorus removal (SNPR) biofilm system is an effective wastewater treatment process. However, the understanding on the mechanism of functional microorganisms driving SNPR is still limited, especially the role of complete ammonia oxidation (comammox) Nitrospira and glycogen-accumulating organisms (GAO). In this study, a sequencing batch biofilm reactor (SBBR) performing SNPR was operated for 249 d. Based on the 16S rRNA gene, comammox amoA amplicon sequencing, metagenomics and batch experiment, we found that comammox Nitrospira was the main ammonia-oxidizing microorganisms (AOM) and provided nitrite for anaerobic ammonia oxidation (anammox) bacteria (AnAOB). Besides, GAO was dominated by the bacteria of genus Defluviicoccus and played a primary role in reducing nitrate rather than nitrite. Fluorescent in situ hybridization (FISH) analysis confirmed that Nitrospira was enriched in the inner layer of the biofilm. Thus, we put forward a novel insight into the mechanism of SNPR biofilm system. Comammox Nitrospira was responsible for nitrite and nitrate production in the inner biofilm, and AnAOB consumed the produced nitrite during the anammox process. While GAO reduced nitrate to nitrite and polyphosphate-accumulating organisms (PAO) converted nitrite to dinitrogen via denitrifying phosphorus removal in the outer biofilm. These findings provide a new understanding in SNPR biofilm system.

Interface engineering-induced perovskite/spinel LaCoO3/Co3O4 heterostructured nanocomposites for efficient peroxymonosulfate activation to degrade levofloxacin.

Conventional perovskite oxides (ABO3) tend to suffer from their inactive surfaces and limited active sites that reduce their catalytic activity and stability, while interface engineering is a facile modulating technique to boost the catalyst's inherent activity by constructing heterogeneous interfaces. In this study, perovskite/spinel LaCoO3/Co3O4 nanocomposites with heterogeneous interfaces were synthesized via sol-gel and in-situ gradient etching methods to activate peroxymonosulfate (PMS) for degrading levofloxacin (LEV). LaCoO3 on the surface was etched into spinel Co3O4, and LaCoO3/Co3O4 nanocomposites with two crystal structures of perovskite and spinel were successfully formed. The surface-modified LaCoO3/Co3O4 exhibited superior catalytic performance with a reaction rate constant more than 2 times that of the original LaCoO3, as well as excellent pH adaptability (3-11) and reusability (more than 6 recyclings) for LEV degradation. Besides, multiple characterization techniques were carried out to find that LaCoO3/Co3O4 possessed a larger specific surface area and richer oxygen vacancies after surface modification, which provided more active sites and accelerated mass transfer rate. The mechanism of reactive oxygen species involved in the reaction system was proposed that LaCoO3/Co3O4 not only reacted with PMS directly to produce SO4•- and •OH but also its surface hydroxyl group helped to form the [≡Co(Ⅲ)OOSO3]+ reactive complex with PMS to produce O2•- and 1O2. In addition, electrochemical experiments demonstrated that the surface electronic structure of LaCoO3/Co3O4 was effectively regulated, exhibiting a faster electron transfer rate and facilitating the redox process. By detecting and identifying degradation intermediates, three degradation pathways for LEV were proposed. Our work provided profound insights into the design of efficient and long-lasting catalysts for advanced oxidation processes.

Pretreatment of septic tank wastewater by packed anaerobic baffled reactor: Pollutant degradation and microbial community succession in different compartments.

Anaerobic baffled reactor (ABR) is widely used in rural sewage treatment due to its unique structure, strong impact load resistance, and low energy consumption. However, there is a lack of research on pollutant degradation patterns and microbial community succession patterns in each compartment of ABR. In this study, a packed anaerobic baffled reactor (PABR) was constructed. The effects of T and HRT on the pollutant removal performance of PABR were investigated, and the pollutant degradation and microbial community succession in different compartments of PABR were studied. The results show that the removal rates of COD, NH4+-N, and TN of PABR can reach 85.54 ± 1.08%, 16.94 ± 1.01%, and 5.64 ± 1.18% respectively, and PABR has a good pollutant removal effect. With the extension of HRT, the COD removal rate of PABR increases steadily, and the NH4+-N and TN removal rate of PABR increases to a certain extent. The recommended HRT is 72 h. T has a significant impact on the COD removal effect of PABR. The increase of T in a certain range is conducive to the removal of pollutants by PABR. The COD removal rate of PABR decreases gradually along the flow direction, and the removal of organic matter is mainly concentrated in the first compartment. PABR has good removal capacity for CODss and better nitrogen removal capacity compared with traditional ABR. The richness and diversity of the microbial community in PABR increased gradually along the flow direction. The bacterial species in each compartment were similar but the proportion was different, showing the characteristics of multi-stage and separated phase operation. This study provides a new reference for the application of ABR in rural sewage treatment.

A long term study elucidates the relationship between media amendment and pollutant treatment in the stormwater bioretention system: Stability or efficiency?

Media amendment has been more and more frequently tested in stormwater bioretention systems for enhanced runoff pollutant treatment. However, few studies systematically evaluated the amended system over a long time span, which hindered the further optimization of the proposed amended media. In this study, biochar-pyrite system (PB), conventional sand system (SB), and biochar-woodchip system (WB) were established and operated for 26 months. Media amendment greatly enhanced the dissolved nutrient removal, the highest total dissolved nitrogen removal in PB and WB were 65.6±3.6% and 68.2±2.5%, respectively. Compared with PB, WB could maintain excellent nitrogen removal under long-term operation. In contrast, PB demonstrated stable and more effective total dissolved phosphorus removal during all stages (73.1±3.1%-80.3±4.1%). A high content of phosphorus and organic matter was leached in WB especially at initial operation, while the initial pollutant leaching in PB and SB is much lower, about one-third of WB. Microbial and metabolic function analysis indicated that the microbial community in the bioretention system is complicated and stable. Media amendment enhanced microbial diversity and the relative abundance of functional genera related to nitrogen (Nitrospira, Thauera, Denitratisoma, etc.), sulfur (Thiobacillus, Geobacter, Desulfovibrio, etc.), and carbon cycles (cellulomonas, saccharimonadales, and SBR1031, etc.), which well explained the enhanced pollutant removal and by-product leaching in different systems. Overall, the current study indicates that although media amendment is conducive to enhanced dissolved nutrient removal in bioretention systems, it can hardly maintain both stability and efficiency from initial set-up to long-term operation. In practical application, catchment characteristics, prioritized pollutants, meteorological factors, etc. should all be considered before choosing suitable amended media and its design factors, thereby maximising the stability and efficiency of the bioretention system.

Assessing Intermediate Formation and Electron Competition during Thiosulfate-Driven Denitrification: An Experimental and Modeling Study.

There is increasing interest in thiosulfate-driven denitrification for low C/N wastewater treatment, but the denitrification performance varies with the thiosulfate oxidation pathways. Models have been developed to predict the products of denitrification, but few consider thiosulfate reduction to elemental sulfur (S0), an undesirable reaction that can intensify electron competition with denitrifying enzymes. In this study, the model using indirect coupling of electrons (ICE) was developed to predict S0 formation and electron competition during thiosulfate-driven denitrification. Kinetic data were obtained from sulfur-oxidizing bacteria (SOB) dominated by the branched pathway and were used to calibrate and validate the model. Electron competition was investigated under different operating conditions. Modeling results reveal that electrons produced in the first step of thiosulfate oxidation typically prioritize thiosulfate reduction, then nitrate reduction, and finally nitrite reduction. However, the electron consumption rate for S0 formation decreases sharply with the decline of thiosulfate concentration. Thus, a continuous feeding strategy was effective in alleviating the competition between thiosulfate reduction and denitrifying enzymes. Electron competition leads to nitrite accumulation, which could be a reliable substrate for anammox. The model was further evaluated with anammox integration. Results suggested that the branched pathway and continuous supply of thiosulfate are favorable to create a symbiotic relationship between SOB and anammox.

Corncob-pyrite bioretention system for enhanced dissolved nutrient treatment: Carbon source release and mixotrophic denitrification.

Solid biomass waste amendment and substrates modification in bioretention systems have been increasingly used to achieve effective dissolved nutrients pollution control in stormwater runoff. However, the risk of excess chemical oxygen demand (COD) leaching from organic carbon sources is often overlooked on most occasions. Pyrite is an efficient electron donor for autotrophic denitrification, but little is known about the efficacy of autotrophic-heterotrophic synergistic effect between additional carbon source and pyrite in bioretention. Here, four bioretention columns (i.e., corncob column (C), pyrite column (P), the corncob-pyrite layered column (L-CP), and the corncob-pyrite mixed column (M-CP)) were designed and filled with soil, quartz sand, and modified media to reveal the synergistic effects. The results showed that the corncob-pyrite layered bioretention could maintain low COD effluent concentration with high stability and efficiency in treating dissolved nutrients. When the influent nitrogen and phosphorus concentrations were 8.46 mg/L and 0.94 mg/L, the average removal rates of ammonia nitrogen, total inorganic nitrogen, and phosphate were 83.6%, 70.52%, and 76.35%, respectively. The scouring experiment showed that placing the corncob in the mulch layer was beneficial to the sustained release of dissolved organic carbon (DOC). Erosion pits were found in the SEM images of used pyrite, indicating that autotrophic denitrifying bacteria in the bioretention could react with pyrite as an electron donor. The relative abundance of Thiobacillus in the submerged zone of the corncob-pyrite layered bioretention reached 38.39%, indicating that the carbon source in the mulch layer increased the relative abundance of Thiobacillus. Coexisting heterotrophic and autotrophic denitrification in this bioretention created a more abundant microbial community structure in the submerged zone. Overall, the corncob-pyrite layered bioretention is highly promising for stormwater runoff treatment, with effective pollution removal and minimal COD emission.

Extracellular DNA plays a key role in the structural stability of sulfide-based denitrifying biofilms.

Sulfide-based biofilm processes are increasingly used for wastewater denitrification, yet little is known about the extracellular polymeric substance (EPS) composition of sulfide-oxidizing biofilms. This can have an important impact on biofilm mechanical strength and stability. In this research, the properties and roles of EPS components in biofilm stability were investigated. Weak biofilm stability characterized by high roughness and numerous "needle" structures was visualized by optical coherence tomography (OCT) and microscopy. A high abundance of extracellular DNA (eDNA) and a low protein to polysaccharide ratio were found in the biofilm. The roles of eDNA, protein and polysaccharide in biofilm cohesion and adhesion were identified through enzyme treatment and atomic force microscopy (AFM). The enzymatic hydrolysis of eDNA increased the elastic modulus of biofilms by 57 times and reduced the adhesion energy by 96%. The hydrolysis of proteins led to an increase of elastic modulus by 27 times and a loss of adhesion energy by 95.5%. The enzymatic hydrolysis of polysaccharides caused minimal changes in elastic modulus and adhesion energy. These results suggest that eDNA was the key EPS component for biofilm cohesion and adhesion, possibly because it provided special binding sites and can form strong cross-linking with magnesium or other multivalent cations. This study provided new insights into the role of eDNA in biofilm stability and shed light on the development of sulfide-based denitrifying biofilms.

New insight into ammonium oxidation processes and mechanisms mediated by manganese oxide in constructed wetlands.

Manganese oxide (MnOx) mediated ammonium (NH4+) oxidation in wetlands is receiving increased interest; however, the biochemical mechanisms of this process are vague due to only few studies have focused on terrestrial ecosystems. In this study, three subsurface flow constructed wetlands (CWs), high/low content of Mn-sand CW (HMn-CW/LMn-CW) and quartz sand CW (C-CWs), were set up to explore the extent of ammonium nitrogen (NH4+-N) removal and underlying mechanisms. According to the surface characteristics of Mn-sand, MnOx nanospheres were loaded as birnessite on the sand, while changes of the Mn/N contents indicated involvement of Mn-sand in NH4+-N removal. During the 120-day operation, higher extent of NH4+-N removal with decreased nitrous oxide (N2O) emission was achieved in the HMn-CW (76%) than in the LMn-CW (73%) and C-CW (67%). According to the distribution of nitrogen compounds and Mn2+, Mn-sand in the HMn-CW delayed oxidation of NH4+ and production of nitrate and nitrite. High abundance of Zooloea and Psychrobacter was observed in the Mn-sand layer of HMn-CW, corresponding to a higher observed NH4+-N removal. NH4+ oxidation to hydroxylamine and then to nitrite was enhanced in HMn-CW due to ammonia monooxygenase genes being promoted. The decrease of N2O emission was closely related to the genus TM7a, verified by Pearson correlation analysis. Our findings expand the knowledge of MnOx-mediated NH4+ oxidation in wetlands and support the potential application of manganese oxide for effective nitrogen removal in CWs.