Effects of biochar on the transformation and utilization of nitrogen fertilizer in the black soil region of Northeast China.

Nitrogen (N) fertilizer is often used in production practice to effectively maintain crop productivity; however, low nitrogen use efficiency (Nue) has always been a problem. Specifically, the transformation and utilization of nitrogen fertilizer by biochar and the driving mechanisms remain unclear. We used four biochar application rates (0, 3750, 7500, and 11,250 kg·ha-1) and analyzed the effects of biochar on nitrogen fertilizer utilization, residue, and loss over three years using 15N isotope tracer technology. The results showed that (1) biochar improved the nitrogen use efficiency of maize plants, reduced total nitrogen loss, and increased the maize yield. Compared to the control treatment in the same year, the application of 7500 kg·ha-1 biochar increased the nitrogen use efficiency by 24.27 %, 27.77 %, and 35.82 %, and the yield increased by 21.1 %, 26.7 %, and 24.5 %, respectively. (2) Biochar increased the proportion of mineral nitrogen supplied by fertilizer in the mineral nitrogen pool. The application of 7500 kg·ha-1 biochar increased mineral nitrogen by 3.05 %, 3.22 %, and 3.8 %, respectively, compared to the control treatments in the same year. Biochar promoted the transformation of nitrogen in the 0-40 cm soil layer to three different soil nitrogen pools, especially the organic nitrogen pool. (3) Biochar significantly improved the soil bacterial community and increased the abundances of N transformation functional genes. The redundancy analysis (RDA) showed that the gdhA mineralization gene was the driving factor of nitrogen fertilizer transformation, contributing 43.6 % of the variance. In summary, the application of 7500 kg·ha-1 of biochar for two consecutive years was conducive to maintaining farmland soil fertility, while its use would not be recommended for more than three consecutive years.

Vermicompost and flue gas desulfurization gypsum addition to saline-alkali soil decreases nitrogen losses and enhances nitrogen storage capacity by lowering sodium concentration and alkalinity.

Saline-alkali soils have poor N storage capacity, high N loss and inadequate nutrient supply potential, which are the main limiting factors for crop yields. Vermicompost can increase organic nutrient content, improve soil structure, and enhance microbial activity and function, and the Ca2+ in flue gas desulfurization (FGD) gypsum can replace Na+ and neutralize alkalinity in saline-alkali soils though chemical improvement. This study aimed to determine if vermicompost and FGD gypsum addition could improve the N storage capacity through decreasing NH3 volatilization and 15N/NO3- leaching from saline-alkali soils. The results indicate that the combined application of vermicompost and FGD gypsum led to the displacement and leaching Na+ in the upper soil layer (0-10 cm), as well as the neutralization of HCO3- by the reaction with Ca2+. This treatment also improved soil organic matter content and macroaggregate structure. Also, these amendments significantly increased the abundance of nifH and amoA genes, while concurrently decreasing the abundance of nirK gene. The structural improvements and the lowering of Na + concentration in and alkalinity decreased cumulative NH3 volatilization, and leaching of 15N and NO3- to the deep soil layer (20-30 cm). FGD gypsum increased the 15N stocks and inorganic N stocks of saline-alkali soil, whereas vermicompost not only increased the 15N and inorganic N stocks, but also increased the total N stocks, the combination of vermicompost and FGD gypsum can not only increase the available N storage capacity, but also enhance the potential for N supply. Therefore, vermicompost and FGD gypsum decrease N loss and increase N storage capacity through structural improvement, and lowering of Na+ concentration and alkalinity, which is crucial for improving the productivity of saline-alkali soil.

Metagenomic insights into nitrogen cycling functional gene responses to nitrogen fixation and transfer in maize-peanut intercropping.

The fixation and transfer of biological nitrogen from peanuts to maize in maize-peanut intercropping systems play a pivotal role in maintaining the soil nutrient balance. However, the mechanisms through which root interactions regulate biological nitrogen fixation and transfer remain unclear. This study employed a 15N isotope labelling method to quantify nitrogen fixation and transfer from peanuts to maize, concurrently elucidating key microorganisms and genera in the nitrogen cycle through metagenomic sequencing. The results revealed that biological nitrogen fixation in peanut was 50 mg and transfer to maize was 230 mg when the roots interacted. Moreover, root interactions significantly increased nitrogen content and the activities of protease, dehydrogenase (DHO) and nitrate reductase in the rhizosphere soil. Metagenomic analyses and structural equation modelling indicated that nrfC and nirA genes played important roles in regulating nitrogen fixation and transfer. Bradyrhizobium was affected by soil nitrogen content and DHO, indirectly influencing the efficiency of nitrogen fixation and transfer. Overall, our study identified key bacterial genera and genes associated with nitrogen fixation and transfer, thus advancing our understanding of interspecific interactions and highlighting the pivotal role of soil microorganisms and functional genes in maintaining soil ecosystem stability from a molecular ecological perspective.

Water residence time controls seasonal nitrous oxide budget in a semi-enclosed bay: Insights from an improvement estimation method.

This study developed an estimation method for the N2O budget using 15N stable isotope labeling techniques, a dual-layer model and a box model, which was used to elucidate the underlying dynamics of N2O accumulation in Zhanjiang Bay. The results showed that although the net input of N2O during the rainy season was 2.36 times higher than that during the dry season, the overall N2O concentration was only 66.6 % of that during the dry season due to the extended water residence time in the dry season. Our findings highlighted that water residence time was the key factor for the N2O emission, and a longer water residence time was unfavorable for the efflux of N2O through hydrodynamic processes and was more conducive to the production and accumulation of N2O within the bay. This research enhanced our comprehension of N2O dynamics and provided crucial insights for refining nitrogen management strategies and mitigation efforts.

Variation in Nitrogen Utilization and Nutrient Composition across Various Organs under Different Strip Logging Management Models in Moso Bamboo (Phyllostachys edulis) Forest.

The rapid restoration and renewal of the moso bamboo logging zone after strip logging has emerged as a key research area, particularly regarding whether nutrient accumulation and utilization in reserve zones can aid in the restoration and regeneration of the logging zone. In this study, a dynamic 15N isotope tracking experiment was conducted by injecting labeled urea fertilizer into bamboo culms. Logging zones and reserve zones of 6 m, 8 m, and 10 m widths were established. The conventional selective logging treatment served as a control (Con). Measurements were taken in May and October to assess the differences in nitrogen accumulation ability, utilization rates, and nutrient content across different organs in bamboo forests at different growth stages and under different treatments. Principal component analysis was conducted to evaluate and determine the importance of each indicator and strip logging treatment comprehensively. The results showed that various bamboo organs exhibited higher nitrogen accumulation and utilization rates during the peak growth period compared to the late growth period. Leaves had the highest nitrogen accumulation and utilization rates than the other organs. The average C content in various bamboo organs under different logging treatments exhibited subtle differences, irrespective of variation in logging width treatments. Bamboo culm exhibited the highest carbon accumulation. The C content in various bamboo organs was higher during the peak growth period than in the late growth period. The nitrogen content peaked in the leaves during the two growth stages and was significantly higher compared to the other organs. Most bamboo organs in the logging zones exhibited relatively higher nitrogen content than in the reserve zone and Con group. The P content was highest in bamboo leaves compared with other organs across the different strip logging treatments. Principal component analysis revealed relatively high absolute values of the coefficients for the C content, bamboo stump C content, and culm Ndff%. Log8 and Res10 zones had the highest comprehensive evaluation scores, indicating that Log8 and Res10 had the best effect on the promotion of nitrogen utilization and nutrient accumulation in various organs of moso bamboo.

15N-DNA stable isotope probing reveals niche differentiation of ammonia oxidizers in paddy soils.

Chemoautotrophic canonical ammonia oxidizers (ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB)) and complete ammonia oxidizers (comammox Nitrospira) are accountable for ammonia oxidation, which is a fundamental process of nitrification in terrestrial ecosystems. However, the relationship between autotrophic nitrification and the active nitrifying populations during 15N-urea incubation has not been totally clarified. The 15N-labeled DNA stable isotope probing (DNA-SIP) technique was utilized in order to study the response from the soil nitrification process and the active nitrifying populations, in both acidic and neutral paddy soils, to the application of urea. The presence of C2H2 almost completely inhibited NO3--N production, indicating that autotrophic ammonia oxidation was dominant in both paddy soils. 15N-DNA-SIP technology could effectively distinguish active nitrifying populations in both soils. The active ammonia oxidation groups in both soils were significantly different, AOA (NS (Nitrososphaerales)-Alpha, NS-Gamma, NS-Beta, NS-Delta, NS-Zeta and NT (Ca. Nitrosotaleales)-Alpha), and AOB (Nitrosospira) were functionally active in the acidic paddy soil, whereas comammox Nitrospira clade A and Nitrosospira AOB were functionally active in the neutral paddy soil. This study highlights the effective discriminative effect of 15N-DNA-SIP and niche differentiation of nitrifying populations in these paddy soils. KEY POINTS: • 15N-DNA-SIP technology could effectively distinguish active ammonia oxidizers. • Comammox Nitrospira clade A plays a lesser role than canonical ammonia oxidizers. • The active groups in the acidic and neutral paddy soils were significantly different.

The impact of algal blooms on promoting in-situ N2O emissions: A case in Zhanjiang bay, China.

Under the influence of many factors, such as climate change, anthropogenic eutrophication, and the development of aquaculture, the area and frequency of algal blooms have showed an increasing trend worldwide, which has become a challenging issue at present. However, the coupled relationship between nitrous oxide (N2O) and algal blooms and the underlying mechanisms remain unclear. To address this issue, 15N isotope cultures and quantitative polymerase chain reaction (qPCR) experiments were conducted in Zhanjiang Bay during algal and non-algal bloom periods. The results showed that denitrification and nitrification-denitrification were the two processes responsible for the in-situ production of N2O during algal and non-algal bloom periods. Stable isotope rate cultivation experiments indicated that denitrification and nitrification-denitrification were promoted in the water during the algal bloom period. The in-situ production of N2O during the algal bloom period was three-fold that during the non-algal bloom period. This may be because fresh particulate organic matter (POM) from the organisms responsible for the algal bloom provides the necessary anaerobic and hypoxic environment for denitrification and nitrification-denitrification in the degradation environment. Additionally, a positive linear correlation between N2O concentrations and ammonia-oxidizing bacteria (AOB) and denitrifying bacteria (nirK and nirS) also supported the significant denitrification and nitrification-denitrification occurring in the water during the algal bloom period. However, the algal bloom changed the main process for the in-situ production of N2O, wherein it shifted from denitrification during the non-algal bloom period to nitrification-denitrification during the algal bloom period. The results of our study will improve our understanding of the processes responsible for the in-situ production of N2O during the algal bloom period, and can help formulate effective policies to mitigate N2O emissions in the bay.

Shallow wet irrigation reduces nitrogen leaching loss rate in paddy fields by microbial regulation and lowers rate of downward migration of leaching water: a 15N-tracer study.

China consumes 35% of the world's fertilizer every year; however, most of the nitrogen fertilizers, which are essential for rice cultivation, are not used effectively. In this study, factors affecting the nitrogen leaching loss rate were studied in typical soil and rice varieties in South China. The effects of various irrigation measures on rice growth and nitrogen leaching loss were investigated by conducting experiments with eight groups. These groups included traditional irrigation (TI) and shallow wet irrigation (SWI). The TI is a common irrigation method for farmers in South China, maintaining a water layer of 5-8 cm depth. For SWI, after establishing a shallow water layer usually maintaining at 1-2 cm, paddy is irrigated when the field water level falls to a certain depth, then this process is then repeat as necessary. The nitrogen distribution characteristics were determined using 15N isotope tracing. In addition, the effects of nitrification, denitrification, and microbial composition on soil nitrogen transformation at different depths were studied by microbial functional gene quantification and high-throughput sequencing. The results revealed that in the SWI groups, the total nitrogen leaching loss rate reduced by 0.3-0.8% and the nitrogen use efficiency (NUE) increased by 2.18-4.43% compared with those in the TI groups. After the 15N-labeled nitrogen fertilizer was applied, the main pathways of nitrogen were found to be related to plant absorption and nitrogen residues. Furthermore, paddy soil ammonia-oxidizing archaea were more effective than ammonia-oxidizing bacteria for soil ammonia oxidation by SWI groups. The SWI measures increased the relative abundance of Firmicutes in paddy soil, enhancing the ability of rice to fix nitrogen to produce ammonium nitrogen, thus reducing the dependence of rice on chemical fertilizers. Moreover, SWI enhanced the relative abundance of nirS and nosZ genes within surface soil bacteria, thereby promoting denitrification in the surface soil of paddy fields. SWI also promoted ammonia oxidation and denitrification by increasing the abundance and activity of Proteobacteria, Nitrospirae, and Bacteroidetes. Collectively, SWI effectively reduced the nitrogen leaching loss rate and increase NUE.

A study on the simultaneous determination of nitrogen content and 15N isotope abundance in plants using peak height intensities at m/z 28 and 29.

A method for simultaneous determination of nitrogen content and 15N isotope abundance in plants was established by Elemental analysis-gas isotope ratio mass spectrometry. Taking poplar leaves and l-glutamic acid as standards, nitrogen content was determined using the standard curve established by weighted least squares regression between the mass of nitrogen element and the total peak height intensity at m/z 28 and 29. Then the 15N isotope abundance was calculated with the peak height intensity at m/z 28 and 29. Through the comparison of several sets of experiments, the impact of mass discrimination effect, tin capsule consumables, isotope memory effect, and the quality of nitrogen on the results were assessed. The results showed that with a weight of 1/x2, the standard curve has a coefficient of determination (R2) of 0.9996. Compared to the traditional Kjeldahl method, the measured nitrogen content deviated less than 0.2 %, and the standard deviation (SD) was less than 0.2 %. Compared to the sodium hypobromite method, the 15N isotopic abundances differed less than 0.2 atom%15N, and the SD was less than 0.2 atom% 15N. The established method offers the advantages of being fast, simple, accurate, and high throughput, providing a novel approach for the simultaneous determination of nitrogen content and 15N isotope abundance in plant samples.

Aridity creates global thresholds in soil nitrogen retention and availability.

Identifying tipping points in the relationship between aridity and gross nitrogen (N) cycling rates could show critical vulnerabilities of terrestrial ecosystems to climate change. Yet, the global pattern of gross N cycling response to aridity across terrestrial ecosystems remains unknown. Here, we collected 14,144 observations from 451 15 N-labeled studies and used segmented regression to identify the global threshold responses of soil gross N cycling rates and soil process-related variables to aridity index (AI), which decreases as aridity increases. We found on a global scale that increasing aridity reduced soil gross nitrate consumption but increased soil nitrification capacity, mainly due to reduced soil microbial biomass carbon (MBC) and N (MBN) and increased soil pH. Threshold response of gross N production and retention to aridity was observed across terrestrial ecosystems. In croplands, gross nitrification and extractable nitrate were inhibited with increasing aridity below the threshold AI ~0.8-0.9 due to inhibited ammonia-oxidizing archaea and bacteria, while the opposite was favored above this threshold. In grasslands, gross N mineralization and immobilization decreased with increasing aridity below the threshold AI ~0.5 due to decreased MBN, but the opposite was true above this threshold. In forests, increased aridity stimulated nitrate immobilization below the threshold AI ~1.0 due to increased soil C/N ratio, but inhibited ammonium immobilization above the threshold AI ~1.3 due to decreased soil total N and increased MBC/MBN ratio. Soil dissimilatory nitrate reduction to ammonium decreased with increasing aridity globally and in forests when the threshold AI ~1.4 was passed. Overall, we suggest that any projected increase in aridity in response to climate change is likely to reduce plant N availability in arid regions while enhancing it in humid regions, affecting the provision of ecosystem services and functions.

Heterostructured Co-Doped-Cu2O/Cu Synergistically Promotes Water Dissociation for Improved Electrochemical Nitrate Reduction to Ammonia.

Electrochemical nitrate reduction reaction (NO3RR) has recently emerged as a promising approach for sustainable ammonia synthesis and wastewater treatment, while the activity and selectivity for ammonia production have remained low. Herein, rational design and controllable synthesis of heterostructured Co-doped Cu2O/Cu nanoparticles embedded in carbon framework (Co-Cu2O/Cu@C) is reported for NO3RR. The Co-Cu2O/Cu@C exhibits a high ammonia yield rate of 37.86 mg h-1 mg-1 cat. with 98.1% Faraday efficiency, which is higher than those obtained for most of the Cu-based catalysts under similar conditions. Density functional theory calculations indicated that the strong electronic interactions at Cu/Co-Cu2O interface facilitate the N species deoxygenation process and doping of Co promotes water dissociation to generate *H for the N species hydrogenation process, leading to enhanced NO3RR performance. This work provides a new design strategy toward high-performance catalysts toward NO3RR for ammonia generation.

Arrhenius equation construction and nitrate source identification of denitrification at the Lake Taihu sediment - water interface with 15 N isotope.

Total nitrogen in Taihu Lake, China has gradually decreased since 2015 while the total phosphorus concentration has exhibited an increasing trend, indicating an asynchronous change. The dominant nitrogen removal process in freshwater ecosystems is denitrification which primarily occurs at the sediment-water interface. In this study, 15 N isotope incubation experiments were attempted to analyze the effect of water temperature on denitrification, to construct the regional denitrification Arrhenius equations considering water temperature, and to identify the nitrate source of denitrification in Lake Taihu sediments. The results indicated that the potential N2 production rates and denitrification rates generally decreased in the west to east direction, which was significantly positively correlated with the nitrate concentration of overlying water by Pearson correlation coefficient analysis (P < 0.05). In addition, when the water temperature was lower than 30 °C, the rates of the potential N2 production and denitrification were higher with an increase in water temperature, but when the water temperature was overhigh, denitrification was inhibited. The ratio of the total denitrification rate of nitrate from the water column in the sediment to the total denitrification rate during the incubation experiment was above 0.5 at each sampling site. This indicated that the denitrification in the Lake Taihu sediment primarily occurred at the expense of nitrate from the water column. The research results of Arrhenius equation construction and nitrate source identification of denitization can be applied to improve the accuracy of water quality model of Taihu Lake, which is of great significance to improve Taihu Lake water quality, and can act as a reference for the water environment treatment of other shallow eutrophic lakes in China and abroad.

Delineation of the complex microbial nitrogen-transformation network in an anammox-driven full-scale wastewater treatment plant.

Microbial-driven nitrogen removal is a crucial step in modern full-scale wastewater treatment plants (WWTPs), and the complexity of nitrogen transformation is integral to the various wastewater treatment processes. A full understanding of the overall nitrogen cycling networks in WWTPs is therefore a prerequisite for the further enhancement and optimization of wastewater treatment processes. In this study, metagenomics and metatranscriptomics were used to elucidate the microbial nitrogen removal processes in an ammonium-enriched full-scale WWTP, which was configured as an anaerobic-anoxic-anaerobic-oxic system for efficient nitrogen removal (99.63%) on a duck breeding farm. A typical simultaneous nitrification-anammox-denitrification (SNAD) process was established in each tank of this WWTP. Ammonia was oxidized by ammonia-oxidizing bacteria (AOB), archaea (AOA), and nitrite-oxidizing bacteria (NOB), and the produced nitrite and nitrate were further reduced to dinitrogen gas (N2) by anammox and denitrifying bacteria. Visible red anammox biofilms were formed successfully on the sponge carriers submerged in the anoxic tank, and the nitrogen removal rate by anammox reaction was 4.85 times higher than that by denitrification based on 15N isotope labeling and analysis. This supports the significant accumulation of anammox bacteria on the carriers responsible for efficient nitrogen removal. Two distinct anammox bacteria, named "Ca. Brocadia sp. PF01" and "Ca. Jettenia sp. PF02", were identified from the biofilm in this investigation. By recovering their genomic features and their metabolic capabilities, our results indicate that the highly active core anammox process found in PF01, suggests extending its niche within the plant. With the possible contribution of the dissimilatory nitrate reduction to ammonium (DNRA) reaction, enriching PF02 within the biofilm may also be warranted. Collectively, this study highlights the effective design strategies of a full-scale WWTP with enrichment of anammox bacteria on the carrier materials for nitrogen removal and therefore the biochemical reaction mechanisms of the contributing members.

Removal efficacy and mechanism of nitrogen and phosphorus by biological aluminum-based P-inactivation agent (BA-PIA).

In this study, aluminum-based P-inactivation agent (Al-PIA) was used as a high-efficiency microbial carrier, and the biological Al-PIA (BA-PIA) was prepared by artificial aeration. Laboratory static experiments were conducted to study the effect of BA-PIA on reducing nitrogen and phosphorus contents in water. Physicochemical characterization and isotope tracing method were applied to analyze the removal mechanism of nitrogen and phosphorus. High-throughput techniques were used to analyze the characteristic bacterial genus in the BA-PIA system. The nitrogen and phosphorus removal experiment was conducted for 30 days, and the removal rates of NH4+-N, TN and TP by BA-PIA were 81.87%, 66.08% and 87.97%, respectively. The nitrogen removal pathways of BA-PIA were as follows: the nitrification reaction accounted for 59.0% (of which denitrification reaction accounted for 56.4%), microbial assimilation accounted for 18.1%, and the unreacted part accounted for 22.9%. The characteristic bacteria in the BA-PIA system were Streptomyces, Nocardioides, Saccharopolyspora, Nitrosomonas, and Marinobacter. The loading of microorganisms only changed the surface physical properties of Al-PIA (such as specific surface area, pore volume and pore size), without changing its surface chemical properties. The removal mechanism of nitrogen by BA-PIA is the conversion of NH4+-N into NO2--N and NO3--N by nitrifying bacteria, which are then reduced to nitrogen-containing gas by aerobic denitrifying bacteria. The phosphorus removal mechanism is that metal compounds (such as Al) on the surface of BA-PIA fix phosphorus through chemisorption processes, such as ligand exchange. Therefore, BA-PIA overcomes the deficiency of Al-PIA with only phosphorus removal ability, and has better application prospects.

Simple and sensitive spectrophotometric method for estimating the nitrogen-fixing capacity of bacterial cultures.

Biological nitrogen fixation (BNF) is a process through which a group of microorganisms called diazotrophs convert unassimilable atmospheric nitrogen into ammonia. In aqueous media, ammonia yields ammonium ions that can be assimilated by microorganisms and plants. To reduce the application of nitrogen fertilizers and their environmental effects, an alternative approach toward sustainable agriculture is the induction of artificial associations between diazotrophs and plants. This has led to increased interest in the search for microorganisms capable of supplying nitrogen to crops. This article presents a simple, economical, and sensitive spectrophotometric method for estimating the BNF capacity of bacteria cultured in a liquid NFb medium, based on the variation of absorbance caused by the change in color of bromothymol blue in the culture medium. The structure and color of this indicator are modified by pH shifts, which depend on the concentration of fixed ammonium ions.•The nitrogen concentration (estimated from the ammonium in the culture medium) showed a positive correlation (R 2 = 0.984) with the absorbance measured at 610 nm. The regression equation obtained through the origin was y = 0.009682140x, where y is the absorbance and x is the nitrogen concentration in the culture medium.•The methods used at present to measure the efficiency of BNF require expensive equipment, which may not be affordable for many laboratories or companies working in this field.•This technique can be used for pure bacterial strains and microbial consortia from soil or commercial products.

Applying the 15N labelling technique to material derived from a landfill simulation experiment to understand nitrogen cycle processes under aerobic and anaerobic conditions.

Reactive nitrogen (N) species, such as ammonium (NH4+), nitrate (NO3) and gaseous nitrous oxide (N2O), are released into the environment during the degradation of municipal solid waste (MSW), causing persistent environmental problems. Landfill remediation measures, such as in-situ aeration, may accelerate the degradation of organic compounds and reduce the discharge of ammonium via leachate. Nonetheless, the actual amount of N in the waste material remains relatively constant and a coherent explanation for the decline in leachate ammonium concentrations is still lacking. Hence, the present study aimed to elucidate the dynamics of N and its transformation processes during waste degradation. To this end, the gross rates of organic N mineralization and nitrification were measured using 15N pool dilution in waste material derived from a landfill simulation reactor (LSR) experiment. The results revealed a high potential for N mineralization and nitrification, the latter of which declined with the diminishing amount of extractable ammonium (after aeration). The analysis of the concentration and isotopic composition of N2O formed confirmed incomplete denitrification as the main source for N2O. Moreover, the natural abundance of 15N was investigated in various waste N pools to verify the conclusions drawn from the 15N tracing experiment. δ15N values of total waste N increased during aeration, indicating that nitrification is the major driver for N losses from aerated waste. The application of stable isotopes thereby allowed unprecedented insights into the complex N dynamics in decomposing landfill waste, of their response to aeration and their effect on hydrological versus gaseous loss pathways.

Sulfate-Enabled Nitrate Synthesis from Nitrogen Electrooxidation on a Rhodium Electrocatalyst.

The electrocatalytic nitrogen oxidation reaction (NOR) to generate nitrate is gaining increasing attention as an alternative approach to the conventional industrial manufacture. But, current progress in NOR is limited by the difficulties in activation and conversion of the strong N≡N bond (941 kJ mol-1 ). Herein, we designed to utilize sulfate to enhance NOR performance over an Rh electrocatalyst. After the addition of sulfate, the inert Rh nanoparticles exhibited superior NOR performance with a nitrate yield of 168.0 µmol gcat -1 h-1 . The 15 N isotope-labeling experiment confirmed the produced nitrate from nitrogen electrooxidation. A series of electrochemical in situ characterizations and theoretical calculation unveiled that sulfate promoted nitrogen adsorption and decreased the reaction energy barrier, and in situ formed sulfate radicals reduced the activation energy of the potential-determining step, thus accelerating NOR.

Using isotope pool dilution to understand how organic carbon additions affect N2 O consumption in diverse soils.

Nitrous oxide (N2 O) is a formidable greenhouse gas with a warming potential ~300× greater than CO2 . However, its emissions to the atmosphere have gone largely unchecked because the microbial and environmental controls governing N2 O emissions have proven difficult to manage. The microbial process N2 O consumption is the only know biotic pathway to remove N2 O from soil pores and therefore reduce N2 O emissions. Consequently, manipulating soils to increase N2 O consumption by organic carbon (OC) additions has steadily gained interest. However, the response of N2 O emissions to different OC additions are inconsistent, and it is unclear if lower N2 O emissions are due to increased consumption, decreased production, or both. Simplified and systematic studies are needed to evaluate the efficacy of different OC additions on N2 O consumption. We aimed to manipulate N2 O consumption by amending soils with OC compounds (succinate, acetate, propionate) more directly available to denitrifiers. We hypothesized that N2 O consumption is OC-limited and predicted these denitrifier-targeted additions would lead to enhanced N2 O consumption and increased nosZ gene abundance. We incubated diverse soils in the laboratory and performed a 15 N2 O isotope pool dilution assay to disentangle microbial N2 O emissions from consumption using laser-based spectroscopy. We found that amending soils with OC increased gross N2 O consumption in six of eight soils tested. Furthermore, three of eight soils showed Increased N2 O Consumption and Decreased N2 O Emissions (ICDE), a phenomenon we introduce in this study as an N2 O management ideal. All three ICDE soils had low soil OC content, suggesting ICDE is a response to relaxed C-limitation wherein C additions promote soil anoxia, consequently stimulating the reduction of N2 O via denitrification. We suggest, generally, OC additions to low OC soils will reduce N2 O emissions via ICDE. Future studies should prioritize methodical assessment of different, specific, OC-additions to determine which additions show ICDE in different soils.

Copper single-atom catalyst as a high-performance electrocatalyst for nitrate-ammonium conversion.

Electrocatalytic nitrate reduction reaction (NO3RR), as a promising alternative to the Haber-Bosh process, provides new opportunities for ammonia (NH3) production from the environmental and energy viewpoint. However, the NH3 yield rate and selectivity for NO3RR are still limited due to the lack of efficient electrocatalysts. Herein, we demonstrate an active and selective copper single-atom catalyst (Cu-N-C) for nitrate reduction to NH3. The complete conversion of nitrate (50 mg L-1 NO-3-N) was achieved at -1.5 V vs. SCE with a high NH3 yield rate (9.23 mg h-1 mg-1cat.) and selectivity (94%). Remarkably, Cu-N-C dramatically inhibited the formation of toxic nitrite and double-nitrogen products due to the enhanced nitrite adsorption and restrained N-N coupling that led to nitrate deep reduction to NH3. The remaining nitrate (0.06 mg L-1) and nitrite (1 mg L-1) fully meet the drinking-water standards. Density functional theory simulations reveal that the single-site nature of Cu-N-C facilitated the reduction of HNO*3 to NO*2 and NH*2 to NH3, thus leading to the selective nitrate reduction to NH3.

Effects of macrophytes and environmental factors on sediment denitrification in a subtropical reservoir.

Sediment denitrification plays an important role in nitrogen removal in aquatic systems. However, the importance in nitrogen removal in reservoirs, with a focus on seasonal differences of conditions such as macrophyte beds and environmental factors, is less well understood. This study examined sediment denitrification rate (Dn), and their potential controlling factors were determined in both macrophyte beds and deeper waters in the subtropical reservoir. The mean Dn in the reservoir annually was 18.0 ± 6.3 (mean ± S.E.) mmol N m-2 d-1, with significant seasonal variation (p < 0.01), i.e. 43.2 ± 12.8, 6.7 ± 6.3, and 4.0 ± 2.2 mmol N m-2 d-1 in winter, spring and summer respectively. There were no statistical differences in Dn between shallow waters with macrophyte beds and deeper waters without macrophyte beds, although macrophyte beds had higher denitrification rates in summer. The Dn rates were significantly correlated with temperature, conductivity, dissolved oxygen, pH, nitrate-nitrogen concentration (NO3--N) (p < 0.01) and turbidity (p < 0.05). Linear regression models demonstrated environmental variables explained between 36% and 76% of the variation in Dn. The correlation with NO3--N concentrations suggests that it may be a limited factor for Dn. Annual nitrogen removal of the reservoir by a combination of sediment and water denitrification was totally estimated to be 370 t N with an annual removal efficiency of approximately 11%. Nitrogen removal was much higher in winter than other seasons, with about 305 t N removed, accounting for 12% of the total nitrogen inputs. Therefore, denitrification appears to play a minor role throughout much of the year, but in winter months when nitrate accumulates, it may play a more major role.