Nitrification Research Articles

Efficient nitrate removal by nitrogen-doped carbon spheres electrodes with interconnected architecture in novel stirring capacitive deionization: Dual promoting effect of facile mass transfer and additional active centers

Efficient nitrate removal by nitrogen-doped carbon spheres electrodes with interconnected architecture in novel stirring capacitive deionization: Dual promoting effect of facile mass transfer and additional active centers

Nitrate removal for drinking water by FeCl3-oxidated polypyrrole- grafted activated carbon: Adsorption property and mechanism

Developing efficient nitrate removal technologies is crucial for ensuring the safety of drinking water, a polypyrrole-grafted activated carbon (PPy-AC) was synthesized via in situ chemical oxidative polymerization to enhance nitrate adsorption from water. It was showed that the PPy-AC composite featured a maximum adsorption capacity of 13.36 mg NO3−-N/g and exhibited high selectivity toward nitrate in the presence of co-existing anions. The PPy-AC composite exhibited a considerable capacity for adsorbing nitrate over a wide pH range of 3.0–9.0. The absorption performances were well-fitted by the Redlich-Peterson isotherm model, and the adsorption kinetics were well-described by the pseudo-second-order equation. Furthermore, the mass and charge balance calculations showed that 8.4% of the nitrogen atoms in the PPy-AC facilitated the adsorption of nitrate. The mechanisms of nitrate removal by the PPy-AC composite were determined through the electrostatic attraction and ion-exchange process, in which the nitrate ions are replaced by doped chloride ions, and the other N+ sites in PPy were occupied by nitrate ions. The PPy-AC is a promising material for the nitrate removal from wastewater.

Cation Substitution Strategy for Developing Perovskite Oxide with Rich Oxygen Vacancy-Mediated Charge Redistribution Enables Highly Efficient Nitrate Electroreduction to Ammonia.

The electrocatalytic nitrate (NO3-) reduction reaction (eNITRR) is a promising method for ammonia synthesis. However, its efficacy is currently limited due to poor selectivity, largely caused by the inherent complexity of the multiple-electron processes involved. To address these issues, oxygen-vacancy-rich LaFe0.9M0.1O3-δ (M = Co, Ni, and Cu) perovskite submicrofibers have been designed from the starting material LaFeO3-δ (LF) by a B-site substitution strategy and used as the eNITRR electrocatalyst. Consequently, the LaFe0.9Cu0.1O3-δ (LF0.9Cu0.1) submicrofibers with a stronger Fe-O hybridization, more oxygen vacancies, and more positive surface potential exhibit a higher ammonia yield rate of 349 ± 15 μg h-1 mg-1cat. and a Faradaic efficiency of 48 ± 2% than LF submicrofibers. The COMSOL Multiphysics simulations demonstrate that the more positive surface of LF0.9Cu0.1 submicrofibers can induce NO3- enrichment and suppress the competing hydrogen evolution reaction. By combining a variety of in situ characterizations and density functional theory calculations, the eNITRR mechanism is revealed, where the first proton-electron coupling step (*NO3 + H+ + e- → *HNO3) is the rate-determining step with a reduced energy barrier of 1.83 eV. This work highlights the positive effect of cation substitution in promoting eNITRR properties of perovskites and provides new insights into the studies of perovskite-type electrocatalytic ammonia synthesis catalysts.

Influence of seaweed extracts on the degradation and effectiveness of 3,4-dimethylpyrazole phosphate

3,4-Dimethylpyrazole phosphate (DMPP) is acknowledged as one of the most efficient nitrification inhibitors (NIs); however, researchers have suggested that its effectiveness needs to be further improved. The authors combined the biostimulant seaweed extract (SE) with DMPP and conducted an indoor incubation experiment to initially investigate the impact of the influence of SE on the degradation and effectiveness of DMPP. Meanwhile, a method for the extraction and determination of DMPP was developed. DMPP performed better, with a longer effective time in loess than black soil, and SE showed a delayed effect on DMPP degradation of DMPP at the beginning of the incubation and then accelerated the degradation process. This was attributed to the adsorption effect of SE on DMPP, consequently reducing its effectiveness. The SE delayed the hydrolysis of urea in various soils; however, no significant impact on urease activity was observed (P < 0.05) (P < 0.05). Furthermore, it also increased potential nitrification rate (PNR) from 10 to 21 days and promoting the rapid transformation of NH4+-N in black soil. The SE reduced PNR within 21 days and inhibited nitrification in loess. In addition, the SE appeared to mitigate the adverse effects of excessive nitrogen on microorganisms The combination of DMPP and SE was not conducive to the inhibition of soil nitrification, and this formulation in field applications requires further investigation.

Effect of the inoculation of Phanerochaete chrysosporium on nitrogen migration and organic matter conversion during electrolytic manganese residue composting

Composting has made it practicable to dispose electrolytic manganese residues (EMR) in a less toxic way, nevertheless, the decomposition and the loss of nitrogen is a critical issue. This study aimed to investigate the role of Phanerochaete chrysosporium (PC) inoculation on nitrogen migration and promotion of decomposing organic matter (OM), as well as the effect on bacterial community structure during EMR composting. The results exhibited that nitrogen loss tallied with the first-order kinetic model. PC inoculation increased the relative microbial abundance of Firmicutes, which improved the efficiency of nitrogen nitrification and OM degradation, and increased the germination index and total nitrogen content by 13.8% and 2.95 g/kg, respectively. Moreover, aromatic benzenes replaced heteropolysaccharides, alcohols and ethers as the main components of OM in fertilizer, leading up to a more stable humus structure. This study provides a rationale and a novel perspective on the resource and nutrient conservation of EMR-contaminated soils.

Irrigation management is a key farmer practice for a more efficient nitrate use: a case study in an intensive open field endive crop

Irrigation management is a key farmer practice for a more efficient nitrate use: a case study in an intensive open field endive crop

High-valent cobalt active sites derived from electrochemical activation of metal-organic frameworks for efficient nitrate reduction to ammonia

Metal-organic frameworks (MOFs) exhibited great potential in the electrocatalytic reduction of nitrate to ammonia (eNO3RR), but the structural transformation and the identification of the active sites in the electrochemical process have rarely been reported. Herein, a series of MOFs have been fabricated for eNO3RR. The Co-based MOF (Co-TPA) is selected as a representative for exploration through in-situ and ex-situ techniques to reveal the structural evolution during eNO3RR. The structural transformation from the Co-TPA to electrochemically activated catalyst (Co-TPA-E) is verified, and it is found that the in-situ formed high-valent Co species (CoOOH) are the active sites for eNO3RR. Moreover, the formation of the high-valence CoOOH species can be further facilitated by introducing highly electronegative Cu ions into the Co-TPA-E, resulting in excellent catalytic activity with an NH3 yield rate of 1.12 mmol h−1 cm−2 at − 0.326 V vs. RHE and a maximum Faradaic efficiency of 99.62 %.

Efficient nitrogen removal from municipal wastewater by an autotrophic-heterotrophic coupled anammox system: The up-regulation of key functional genes

The metabolic pathways based on key functional genes were innovatively revealed in the autotrophic-heterotrophic coupled anammox system for real municipal wastewater treatment. The nitrogen removal performance of the system was stabilized at 88.40 ± 3.39 % during the treatment of real municipal wastewater. The relative abundances of the nitrification functional genes ammonia oxidase (amoA/B/C), hydroxylamine oxidoreductase (hao), and nitrite oxidoreductases (nxrA/B) were increased by 1.2–2.4 times, and these three nitrification functional genes were mostly contributed by Nitrospira that dominated the efficient nitrification of the system. The relative abundance of anammox bacteria Candidatus Brocadia augmented from 0.35 % to 0.75 %, accompanied with the increased expression of hydrazine synthase (hzs) and hydrazine dehydrogenase (hdh), resulting in the major role of anammox (81.24 %) for nitrogen removal. The expression enhancement of the functional genes nitrite reductase (narG/H, napA/B) that promoted partial denitrification (PD) of the system weakened the adverse effects of the sharp decline in the population of PD microbe Thauera (from 5.7 % to 2.2 %). The metabolic module analysis indicated that the carbon metabolism pathways of the system mainly included CO2 fixation and organic carbon metabolism, and the stable enrichment of autotrophic bacteria ensured stable CO2 fixation. Furthermore, the enhanced expression of the glucokinases (glk, GCK, HK, ppgk) and the abundant pyruvate kinase (PK) achieved stable hydrolysis ability of organic carbon metabolism function of the system. This study offers research basics to practical application of the mainstream anammox process.

Enhancement of nutrient removal in an activated sludge process using aerobic granular sludge augmentation strategy with ammonium-based aeration control

To enhance nutrient removal from low-strength municipal wastewater in a continuous-flow activated sludge (CFAS) process using aerobic granular sludge (AGS) augmentation strategy, a pilot-scale demonstration was configured with a mainstream reactor (anaerobic/aerobic process) and a sidestream sequencing batch reactor for AGS production. The aeration of the mainstream reactor was controlled based on dissolved oxygen (DO) and ammonium concentrations during Phases I and II–III, respectively. During Phase III, an anoxic zone was created in the mainstream aerobic tank. Throughout the demonstration period, excellent sludge settleability in the mainstream reactor (SVI30 ≤ 80 mL g−1) under long sludge retention time conditions (≥12 d) allowed the maintenance of a high mixed liquor suspended solids concentration (≥3000 mg L−1). The total nitrogen (TN) removal ratio improved significantly during Phases II and III (49.3 ± 4.1% and 50.1 ± 10.2%, respectively) compared to Phase I (43.2 ± 5.5%). Low DO concentration (< 0.5 mg L−1) by the ammonium-based aeration tended to increase the simultaneous nitrification and denitrification efficiency (> 40%), enhancing TN removal (> 50%). The reduction of DO and nitrate concentrations in the returning sludge liquor can stabilize phosphorus removal (approximately 80% of the 25th percentile). In addition, the aeration efficiency during Phase III decreased by 26–29% compared to Phase I. These results suggest that the introduction of ammonium-based aeration control to the CFAS using the AGS augmentation strategy could contribute to superior sewerage treatment, including nutrient removal and a low carbon footprint.

Engineering oxygen vacancies in perovskite oxides by in-situ electrochemical activation for highly efficient nitrate reduction

Perovskite oxides have emerged as a new category of catalysts for NO3RR, yet their low intrinsic catalytic activity results in unsatisfactory performance. Oxygen vacancy engineering has recently been found to be effective for improving the NO3RR performance of perovskite oxides. Herein, a novel and efficient strategy of electrochemical activation for in-situ oxygen vacancies (OVs) creation in perovskite oxide La0.9FeO3-δ was reported. The results showed that the NO3−-N removal rate increased 2.6-fold on activated La0.9FeO3-δ in comparison to pristine La0.9FeO3-δ. The enhanced NO3RR performance was attributed to the presence of more OVs, which served to increase the adsorption energy of NO3− while also promoting atomic H* formation for NO3−-N hydrogenation. Furthermore, a continuous experiment lasting 240 h found the activated La0.9FeO3-δ exhibited extremely high stability. Additionally, we demonstrated that the electrochemical activation method was applicable to other typical perovskite oxides, such as LaCoO3, indicating its generalizability. This study provides a simple and scalable approach for the preparation of a high-performance perovskite oxide-type electrocatalysts for NO3RR.

Homonuclear dual-atom catalysts embedded on N-doped graphene for highly efficient nitrate reduction to ammonia: From theoretical prediction to experimental validation

Electrocatalytic reduction of nitrate (NO3−) to ammonia (NRA) is emerging as an attractive strategy to attain valuable NH3 synthesis and harmful NO3− removal, but developing efficient electrocatalysts remains challenging. Herein, taking homonuclear dual metal catalysts (DACs) embedded on N-doped graphene as the example, we proposed a three-step strategy to theoretically evaluate their NRA catalytic performance by means of density functional theory (DFT) computations, which enables us to rapidly identify Cu2@N3−6 as the most promising NRA catalyst with a low limiting potential (−0.14 V). More importantly, such theoretical prediction was further validated by our proof-of-concept experiment: the NH3 yield rate of ∼18.2 mg h−1 cm−2 at − 0.8 V vs RHE and the Faradaic efficiency of 97.4% were achieved. Our studies may offer a feasible avenue to rapidly and precisely achieve efficient NRA catalysts by using theoretical prediction as a guideline for experimentalists to avoid the traditional “trial and error method”.

Boosted N2 Activation through 4f–2p–3d Orbital Hybridization for Efficient Nitrate Electrosynthesis

AbstractThe electrochemical N2 oxidation reaction (NOR) has emerged as a promising approach for achieving high selectivity in nitric acid (HNO3) production. However, the sluggish N2 activation process in NOR due to the high cleavage energy barrier of the N≡N bond remains a challenge. Herein, a novel orbital hybridization strategy for tuning the NOR performance through the construction of cerium (Ce) 4f–O 2p–Co 3d network in Ce‐doped Co3O4 (Ce–Co3O4) is proposed. The Ce–Co3O4 catalyst exhibits an enhanced HNO3 yield of 24.76 µg h−1 mgcat−1 and a promoted Faradaic efficiency of 31.93% in 0.1 m Na2SO4 electrolyte under ambient conditions compared to those of the pure Co3O4 (13.75 µg h−1 mgcat−1 and 23.43%). Density functional theory caculations demonstrate the strong 4f–2p–3d orbital hybridization and electron transfer in Ce–Co3O4. Moreover, a series of in situ techniques provide direct evidence of stronger adsorption peaks for Co─N bond and the key intermediate *NO formed after N2 activation on the surface of Ce–Co3O4. This work provides a promising route for the preparation of efficient NOR catalysts and sheds light on the mechanism of N2 activation through orbital hybridization.

Effects of different aeration strategies and ammonia-nitrogen loads on nitrification performance and microbial community succession of mangrove constructed wetlands for saline wastewater treatment

In highly salinized environments, nitrification is the process that limits the rate of nitrogen transformation and removal. Therefore, this study concentrated on the impacts of different aeration strategies and NH4+–N loads on the nitrification performance of mangrove constructed wetlands (CWs), as well as investigating the succession mechanism of ammonia-oxidizing microorganisms (AOMs). The results showed that both the CW with continuous aeration (CA-CW) and intermittent aeration (IA-CW) achieved a nitrification efficiency of more than 98% under an NH4+–N loading of 1.25–4.7 g/(m2·d). However, the total nitrogen removal rates of IA-CW under low and high ammonia-nitrogen loads (LAL, 20.09 ± 4.4% and HAL, 8.77 ± 1.35%, respectively) were higher than those of CA-CW (16.11 ± 4.7% and 3.32 ± 2.3%, respectively), especially under HAL (p < 0.05). Pearson correlation analysis showed that under different operating conditions, the differential secretion of Kandelia candel rhizosphere organic matter had a certain regulatory effect on nitrification and denitrification groups such as Candidatus Nitrocosmicus, Nitrancea, Truepera, Pontibacter, Halomonas, and Sulfurovum in the wetland root layer. The quantitative polymerase chain reaction revealed that the NH4+–N load rate was the primary factor driving the succession of the AOMs, with different aeration strategies exacerbating this process. Overall, this study revealed that the dominant AOMs in mangrove CWs could be significantly altered by regulating the aeration modes and pollution loads to adjust the rhizosphere organic matter in situ, thereby resulting in more efficient nitrification.

New perspective on effect of β-cyclodextrin on nitrification-denitrification and denitrification phosphorus removal in biogenic manganese oxides driven moving bed biofilm reactor: Performance evaluation, microbial community and process

Effect of β-cyclodextrin (β-CD) on simultaneous removal of NH4+-N, NO3–-N, COD, and phosphorus (P) in biogenic manganese oxides (BioMnOx) driven moving bed biofilm reactor (MBBR) was investigated. 58.64% and 86.32%, 79.65% and 98.39%, 62.45% and 97.30%, and 24.80% and 95.90% of TN and COD were removed in phases I-IV, indicating that simultaneous nitrification and denitrification (SND) efficiencies were 75.44%, 83.91%, 72.71%, and 35.83%, respectively. Composition and fluorescence spectral characteristics of extracellular polymeric substance (EPS) were evaluated including the removal kinetics of TN and COD. Metabolic activity of Mn2+, decolorization performance of BioMnOx, and reactive oxygen species (ROS) characteristics were determined in biofilm. Furthermore, intermediate Mn3+ and BioMnOx concentration were analyzed. Finally, the removal process of nitrogen (N) and P was proposed based on characterizations of elemental characterization, electrochemistry, and microbial community. This study provides new insights into the N and P removal mediated by BioMnOx and β-CD.

Start-up of solid-phase denitrification process for treatment of nitrate-rich water in recirculating mariculture system: Carbon source selection and nitrate removal mechanism

Efficient nitrate removal from recirculating mariculture system (RMS) water is of significance since high concentration of nitrate would cause chronic health effects on aquatic organisms and eutrophication. Solid-phase denitrification (SPD) is a safer and more sustainable approach than conventional heterotrophic denitrification by dosing liquid carbon sources. Thus, its application for treating nitrate-rich RMS water was investigated in this study. Poly 3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV) was identified with the best nitrate removal among four kinds of carbon sources. PHBV-filled reactors started with mariculture, municipal and mixing sludges (at the ratio of 1:1) and fed with 200 mg L-1 nitrate-rich RMS water all achieved over 81% nitrate removals with a HRT of 4 days. The dissolved organic carbon concentrations of the reactors were in the range of 3–9 mg L-1. Arcobacter, Halomonas, and Psedomonas were dominant genera responsible for nitrate removal in different reactors. Metagenomic analyses indicate that both denitrification and assimilatory nitrate reduction (ANR) are the main contributors to nitrate removals. Metagenomic results illustrated nirB/D cooperated with nasA may perform ANR pathway, which transformed nitrate to ammonia for biosynthesis. These results indicate that SPD could be a safer alternative for treating nitrate-rich RMS water, and provide new insights into nitrogen metabolism pathways in SPD process.

A novel hypothermic strain, Pseudomonas reactans WL20-3 with high nitrate removal from actual sewage, and its synergistic resistance mechanism for efficient nitrate removal at 4 °C

Nitrate can be well removed by bacteria at 25–30 °C. However, nitrate removal almost ceases at temperatures lower than 5 °C. In this study, a novel hypothermic strain, Pseudomonas reactans WL20-3 exhibited an excellent aerobic nitrate removal ability at 4 °C. It had high capability for the removal of nitrate, total dissolved nitrogen (TDN), and dissolved organic carbon (DOC) at 4 °C, achieving removal efficiencies of 100%, 87.91%, and 97.48%, respectively. The transcriptome analysis revealed all genes involved in the nitrate removal pathway were significantly up-regulated. Additionally, the up-regulation of ABC transporter genes and down-regulation of respiratory chain genes cooperated with the nitrate metabolism pathway to resist low-temperature stress. In actual sewage, inoculated with WL20-3, the nitrate removal efficiency was found to be 70.70%. Overall, these findings demonstrated the impressive capacity of the novel strain WL20-3 to remove nitrate and provided novel insights into the synergistic resistance mechanism of WL20-3 at low temperature.

Recent Advances in Electrocatalysts for Efficient Nitrate Reduction to Ammonia

AbstractAmmonia as an irreplaceable chemical has been widely demanded to keep the sustainable development of the modern society. However, its industrial production consumes huge energy and releases extraordinary green‐house gases, leading to various environmental issues. To achieve the green production of ammonia is a great challenge that has been extensively pursued recently. In the review, a most promising strategy, electrochemical nitrate reduction reaction (e‐NO3RR) for the purpose is comprehensively investigated to give a full understanding of its development and mechanism and provide guidance for future directions. Particularly, the development of electrocatalysts is focused to realize the high ammonia yield rate and Faraday efficiency for industrial applications. The recent‐developed catalysts, including noble metallic materials, alloys, metal compounds, single‐metal‐atom catalysts, and metal‐free materials, are systematically discussed to review the effects of various factors on the catalytic performance in e‐NO3RR. Accordingly, the strategies, including defects engineering, coordination environment modulating, surface controlling, and hybridization, are carefully discussed to improve the catalytic performance, such as the intrinsic activity and selectivity. Finally, perspectives and challenges are given out. This review shall provide insightful guidance on the development of advanced catalytic systems for the production of green ammonia efficiently in the industry.

Atomically Mo-Doped SnO2-x for efficient nitrate electroreduction to ammonia

Electrochemical NO3–-to-NH3 reduction (NO3RR) emerges as an appealing strategy to alleviate contaminated NO3– and generate valuable NH3 simultaneously. However, substantial research efforts are still needed to advance the development of efficient NO3RR catalysts. Herein, atomically Mo-doped SnO2-x with enriched O-vacancies (Mo-SnO2-x) is reported as a high-efficiency NO3RR catalyst, delivering the highest NH3-Faradaic efficiency of 95.5% with a corresponding NH3 yield rate of 5.3 mg h−1 cm−2 at −0.7 V (RHE). Experimental and theoretical investigations reveal that d-p coupled Mo-Sn pairs constructed on Mo-SnO2-x can synergistically enhance the electron transfer efficiency, activate the NO3– and reduce the protonation barrier of rate-determining step (*NO→*NOH), thereby drastically boosting the NO3RR kinetics and energetics.

Renewable energy driven electroreduction nitrate to ammonia and in-situ ammonia recovery via a flow-through coupled device

Green ammonia production from wastewater via electrochemical nitrate reduction contributes substantially to the realization of carbon neutrality. Nonetheless, the current electrochemical technology is largely limited by the lack of suitable device for efficient and continuous electroreduction nitrate into ammonia and in-situ ammonia recovery. Here, we report a flow-through coupled device composed of a compact electrocatalytic cell for efficient nitrate reduction and a unit to separate the produced ammonia without any pH adjustment and additional energy-input from the circulating nitrate-containing wastewater. Using an efficient and selective Cl-modified Cu foam electrode, nearly 100% NO3− electroreduction efficiency and over 82.5% NH3 Faradaic efficiency was realized for a wide range of nitrate-containing wastewater from 50 to 200 mg NO3−-N L−1. Moreover, this flow-through coupled device can continuingly operate at a large current of 800 mA over 100 h with a sustained NH3 yield rate of 420 μg h−1 cm−2 for nitrate-containing wastewater treatment (50 mg NO3−-N L−1). When driven by solar energy, the flow-through coupled device can also exhibit exceptional real wastewater treatment performance, delivering great potential for practical application. This work paves a new avenue for clean energy production and environmental sustainability as well as carbon neutrality.

Pyrite and sulfur-coupled autotrophic denitrification system for efficient nitrate and phosphate removal

The inefficiency of nitrogen removal in pyrite autotrophic denitrification (PAD) and the low efficiency of PO43−-P removal in sulfur autotrophic denitrification (SAD) limit their potential for engineering applications. This study examined the use of pyrite and sulfur coupled autotrophic denitrification (PSAD) in batch and column experiments to remove NO3−-N and PO43−-P from sewage. The effluent concentration of NO3−-N was 0.32 ± 0.11 mg/L, with an average Total nitrogen (TN) removal efficiency of 99.14%. The highest PO43−-P removal efficiency was 100% on day 18. There was a significant correlation between pH and the efficiency of PO43−-P removal. Thiobacillus, Thiomonas and Thermomonas were found to be dominant at the bacterial genus level in PSAD. Additionally, the abundance of Thermomonas in the PSAD was greater than that observed in the SAD reactor. This result indirectly indicates that the PSAD system has more advantages in reducing N2O.