Nitrate Utilization Research Articles

Directional Electron Transfer in Enzymatic Nano‐Bio Hybrids for Selective Photobiocatalytic Conversion of Nitrate

AbstractSemi‐artificial photosynthetic system (SAPS) that combines enzymes or cellular organisms with light‐absorbing semiconductors, has emerged as an attractive approach for nitrogen conversion, yet faces the challenge of reaction pathway regulation. Herein, we find that photoelectrons can transfer from the −C≡N groups at the edge of cyano‐rich carbon nitride (g‐C3N4‐CN) to nitrate reductase (NarGH), while the direct electron transfer to nitrite reductase (cd1NiR) is inhibited due to the physiological distance limit of active sites (>14 Å). By means of the directional electron transfer between g‐C3N4‐CN and extracted biological enzymes, the product of the denitrification reaction was switched from inert N2 to usable nitrite with an unprecedented selectivity of up to 95.3 %. The converted nitrite could be further utilized by anammox microbiota and dissimilatory nitrate reduction to ammonia (DNRA) microorganisms, doubling the efficiency of total nitrogen removal (96.5±2.3 %) for biological nitrogen removal and ammonia generation (12.6 mg NH4+‐N L−1 h−1), respectively. Thus, our work paves an appealing way for the sustainable treatment and utilization of nitrate for ammonia fuel production by strategically regulating the electron transfer pathway across the biotic‐abiotic interface.

Photocatalytic Synthesis of Glycine from Methanol and Nitrate.

Photocatalytic utilization of methanol and nitrate as carbon and nitrogen sources for the direct synthesis of amino acids could provide a sustainable way for the valorization of green "liquid sunlight" and nitrate waste. In this study, we develop an efficient photochemical method to synthesize glycine directly from methanol and nitrate, which cascades the C-C coupling to form glycol, nitrate reduction to NH3, and finally C-N coupling to generate glycine. Interestingly, the involved photocatalytic tandem reactions show a synergistic effect, in which the presence of nitrate is the dominant factor to enable the overall reaction and reach high synthetic efficiency. Ba2+-TiO2 nanoparticles are confirmed as a feasible and efficient catalyst system for the photosynthesis of glycine with a remarkable glycine photosynthesis rate of 870 μmol gcat -1 h-1 under optimal conditions. This work establishes a novel catalytic system for amino acid synthesis from methanol and nitrate under mild conditions. These results also allow us to further suppose the formation pathways of amino acids on the primitive earth, as an extension to proposals based on the Miller-Urey experiments.

Photocatalytic Synthesis of Glycine from Methanol and Nitrate

AbstractPhotocatalytic utilization of methanol and nitrate as carbon and nitrogen sources for the direct synthesis of amino acids could provide a sustainable way for the valorization of green “liquid sunlight” and nitrate waste. In this study, we develop an efficient photochemical method to synthesize glycine directly from methanol and nitrate, which cascades the C−C coupling to form glycol, nitrate reduction to NH3, and finally C−N coupling to generate glycine. Interestingly, the involved photocatalytic tandem reactions show a synergistic effect, in which the presence of nitrate is the dominant factor to enable the overall reaction and reach high synthetic efficiency. Ba2+−TiO2 nanoparticles are confirmed as a feasible and efficient catalyst system for the photosynthesis of glycine with a remarkable glycine photosynthesis rate of 870 μmol gcat−1 h−1 under optimal conditions. This work establishes a novel catalytic system for amino acid synthesis from methanol and nitrate under mild conditions. These results also allow us to further suppose the formation pathways of amino acids on the primitive earth, as an extension to proposals based on the Miller‐Urey experiments.

Influence of Terrigenious Inorganic Nitrogen on Marine Nitrogen Cycle Reconstruction Inferred from Sedimentary Bulk Nitrogen Isotope

This study reevaluates the application of sedimentary bulk nitrogen isotopes (δ15NTN) as proxies for reconstructing past marine nitrogen dynamics, traditionally assumed to reflect organic nitrogen (δ15NON) derived from marine productivity. Employing a novel method that utilizes persulfate oxidation to convert organic nitrogen (ON) and ammonium into nitrate, followed by nitrate reduction to nitrous oxide via denitrifying bacteria, we quantified and characterized both ON and inorganic nitrogen (IN) across diverse environments, including soils, rivers, lakes, and marine sediments. We found that IN, primarily sourced from clay-fixed ammonium via riverine and dust inputs, constitutes 30 % to 50 % of total nitrogen (TN) in marine sediments. Our findings reveal that δ15N values of IN are typically 2 ‰ to 5 ‰ lower than those of δ15NON, resulting in a − 0.5 ‰ to −2 ‰ negative shift in marine δ15NTN. This significant isotopic deviation necessitates a reevaluation of nitrogen cycle interpretations inferred from δ15NTN, especially regarding the potential underestimation of nitrate utilization in nitrate-rich regions and the overestimation of nitrogen fixation in oligotrophic oceans.

Directional Electron Transfer in Enzymatic Nano-Bio Hybrids for Selective Photobiocatalytic Conversion of Nitrate.

Semi-artificial photosynthetic system (SAPS) that combines enzymes or cellular organisms with light-absorbing semiconductors, has emerged as an attractive approach for nitrogen conversion, yet faces the challenge of reaction pathway regulation. Herein, we find that photoelectrons can transfer from the -C≡N groups at the edge of cyano-rich carbon nitride (g-C3N4-CN) to nitrate reductase (NarGH), while the direct electron transfer to nitrite reductase (cd1NiR) is inhibited due to the physiological distance limit of active sites (>14 Å). By means of the directional electron transfer between g-C3N4-CN and extracted biological enzymes, the product of the denitrification reaction was switched from inert N2 to usable nitrite with an unprecedented selectivity of up to 95.3 %. The converted nitrite could be further utilized by anammox microbiota and dissimilatory nitrate reduction to ammonia (DNRA) microorganisms, doubling the efficiency of total nitrogen removal (96.5±2.3 %) for biological nitrogen removal and ammonia generation (12.6 mg NH4 +-N L-1 h-1), respectively. Thus, our work paves an appealing way for the sustainable treatment and utilization of nitrate for ammonia fuel production by strategically regulating the electron transfer pathway across the biotic-abiotic interface.

Involvement of plasma membrane H+-ATPase in the nitrate-nutrition uptake and utilization in indica rice

Utilization of nitrogen by crops is essential for sustainable agriculture. The transport of nitrate (NO3−) across the plasma membrane is a critical gateway for N uptake and subsequent utilization. This process requires proton (H+) coupled cotransport, which is driven by proton motive force, provided by plasma membrane (PM) H+-ATPase. In this report, two indica rice varieties [Meixiangzhan 2 (MXZ) and Jifengyou 1002 (JFY)] in South China were selected and cultivated in hydroponic solution with 0.5 mM or 2.0 mM NO3− as the N source. The JFY exhibited stronger growth with higher biomass than MXZ under both 0.5 mM and 2.0 mM NO3−. PM H+-ATPase activity of JFY roots was significantly higher than that of MXZ. The higher PM H+-ATPase activity in JFY was consistent with a higher abundance of PM H+-ATPase protein and higher transcription levels of OSAs, such as OSA2, OSA7 and OSA8 in roots, OSA3, OSA7 and OSA8 in leaves. The expression of nitrate transporters (OsNRT1;1b, OsNRT2.1, OsNRT2.2, and OsNAR2.1) were also higher in roots or shoots of JFY than those in MXZ. Under 0.5 mM and 2.0 mM NO3−, the NO3− absorption and translocation rate, nitrate content, as well as nitrate reductase (NR) activity were all significantly higher in JFY, as compared to those in MXZ. Taken together, in JFY and MXZ, a higher level of PM H+-ATPase protein and higher activity coupled with greater efficiency in nitrate uptake, translocation and assimilation, suggesting the existence of a close correlation between PM H+-ATPase and nitrate utilization in indica rice. PM H+-ATPase may one of the elite genes that can contribute to nitrate use efficiency in rice.

Fimbriimonadales performed dissimilatory nitrate reduction to ammonium (DNRA) in an anammox reactor

Bacteria belonging to the order Fimbriimonadales are frequently detected in anammox reactors. However, the principal functions of these bacteria and their potential contribution to nitrogen removal remain unclear. In this study, we aimed to systematically validate the roles of Fimbriimonadales in an anammox reactor fed with synthetic wastewater. High-throughput 16S rRNA gene sequencing analysis revealed that heterotrophic denitrifying bacteria (HDB) were the most abundant bacterial group at the initial stage of reactor operation and the abundance of Fimbriimonadales members gradually increased to reach 38.8 % (day 196). At the end of reactor operation, Fimbriimonadales decreased to 0.9 % with an increase in anammox bacteria. Correlation analysis demonstrated nitrate competition between Fimbriimonadales and HDB during reactor operation. Based on the phylogenetic analysis, the Fimbriimonadales sequences acquired from the reactor were clustered into three distinct groups, which included the sequences obtained from other anammox reactors. Metagenome-assembled genome analysis of Fimbriimonadales allowed the identification of the genes narGHI and nrfAH, responsible for dissimilatory nitrate reduction to ammonium (DNRA), and nrt and nasA, responsible for nitrate and nitrite transport. In a simulation based on mass balance equations and quantified bacterial groups, the total nitrogen concentrations in the effluent were best predicted when Fimbriimonadales was assumed to perform DNRA (R2 = 0.70 and RMSE = 18.9). Moreover, mass balance analysis demonstrated the potential contribution of DNRA in enriching anammox bacteria and promoting nitrogen removal. These results prove that Fimbriimonadales compete with HDB for nitrate utilization through DNRA in the anammox reactor under non-exogenous carbon supply conditions. Overall, our findings suggest that the DNRA pathway in Fimbriimonadales could enhance anammox enrichment and nitrogen removal by providing substrates (nitrite and/or ammonium) for anammox bacteria.

Time-course transcriptomic analysis reveals transcription factors involved in modulating nitrogen sensibility in maize

Nitrogen (N) serves both as a vital macronutrient and a signaling molecule for plants. Unveiling key regulators involved in N metabolism helps dissect the mechanisms underlying N metabolism, which is essential for developing maize with high N use efficiency. Two maize lines, B73 and Ki11, show differential chlorate and low-N tolerance. Time-course transcriptomic analysis reveals that the expression of NUGs in B73 and Ki11 have distinct responsive patterns to nitrate variation. By the coexpression networks, significant differences in the number of N response modules and regulatory networks of transcription factors (TFs) are revealed between B73 and Ki11. There are 23 unique TFs in B73 and 41 unique TFs in Ki11. MADS26 is a unique TF in the B73 N response network, with different expression level and N response pattern in B73 and Ki11. Overexpression of MADS26 enhances the sensitivity to chlorate and the utilization of nitrate in maize, at least partially explaining the differential chlorate tolerance and Low-N sensitivity between B73 and Ki11. The findings in this work provide unique insights and promising candidates for maize breeding to reduce unnecessary N overuse.

Construction waste as a filler of denitrification biofilter for nitrate utilization from wastewater: Characteristics, performance, microbial community and soilless culture

Construction waste (CW) is produced in large quantities, resulting in severe land occupation and resource depletion. This study utilized CW as fillers to construct a denitrification biofilter (DNBF-CW) for treating secondary effluent from wastewater plants. Performance and mechanism were analyzed by water quality, biomass and its distribution, physicochemical characteristics, microbial community structure, extracellular polymeric substances and protein secondary structure analysis. Results indicated that DNBF-CW achieve NO3−-N and chemical oxygen demand (COD) removal efficiencies (RE) of 97 % and 70 %. The β-sheet of DNBF-CW increased from 47 % to 58 %, accompanied by decrease in random curls from 22 % to 0. Post-use CW showed potential as soilless cultivation substrates, boosting germination rates by 42 ± 7 %. Mechanism investigations elucidated that ZX3 improved efficiency by modulating microbial community composition, with Pseudomonas reaching 37 %. This study shows the multiple use of construction waste, which presents a novel, efficient, and eco-friendly solution for water treatment.

Effect of Fe2+-activated persulfate combined with biodegradation in removing gasoline BTX from karst groundwater: A box-column experimental study.

In-situ chemical oxidation with persulfate (PS-ISCO) is a preferred approach for the remediation of fuel-contaminated groundwater. Persulfate (PS) can be activated by various methods to produce stronger sulfate radicals for more efficient ISCO. Despite karst aquifers being widespread, there are few reports on PS-ISCO combined with Fe2+-activated PS. To better understand the effects of Fe2+-activated PS for the remediation of gasoline-contaminated aquifers in karst areas, a box-column experiment was conducted under flow conditions, using karst groundwater and limestone particles to simulate an aquifer. Gasoline was used as the source of hydrocarbon contaminants. Dissolved oxygen and nitrate were added to enhance bioremediation (EBR) and ferrous sulfate was used to activate PS. The effect of Fe2+-activated PS combined with biodegradation was compared during the periods of EBR + ISCO and ISCO alone, using the mass flow method for data analysis. The results showed that the initial dissolution of benzene, toluene, and xylene (BTX) from gasoline injection was rapid and variable, with a decaying trend at an average pseudo-first-order degradation rate constant of 0.032 d-1. Enhanced aerobic biodegradation and denitrification played a significant role in limestone-filled environments, with dissolved oxygen and nitrate utilization ratios of 59 ~ 72% and 12-70%, respectively. The efficiency of EBR + ISCO was the best method for BTX removal, compared with EBR or ISCO alone. The pseudo-first-order degradation rate constants of BTX reached 0.022-0.039, 0.034-0.070, and 0.027-0.036 d-1, during the periods of EBR alone, EBR + ISCO, and ISCO alone, respectively. The EBR + ISCO had a higher BTX removal ratio range of 71.0 ~ 84.3% than the ISCO alone with 30.1 ~ 45.1%. The presence of Fe2+-activated PS could increase the degradation rate of BTX with a range of 0.060 ~ 0.070 d-1, otherwise, with a range of 0.034-0.052 d-1. However, Fe2+-activated PS also consumed about 3 times the mass of PS, caused a further decrease in pH with a range of 6.8-7.6, increased 3-4 times the Ca2+ and 1.6-1.8 times the HCO3- levels, and decreased the BTX removal ratio of ISCO + EBR, compared to the case without Fe2+ activation. In addition, the accumulation of ferric hydroxides within a short distance indicated that the range of PS activated by Fe2+ may be limited. Based on this study, it is suggested that the effect of Fe2+-activated PS should be evaluated in the remediation of non-carbonate rock aquifers.

Nitrate and nitrite utilization during denitrifying phosphorus removal: Electron acceptor preference and feasible process combinations

Denitrifying phosphorus removal (DPR), which is dominated by denitrifying polyphosphate-accumulating organisms (DPAOs), is a promising process for nitrogen and phosphorus removal. Denitrifying glycogen-accumulating organisms (DGAOs) and DPAOs typically coexist in the DPR sludge, complicating the study of DPAOs’ denitrification capacity. In this study, two reactors were fed with nitrate and nitrite during the anoxic phase to cultivate nitrate-DPR and nitrite-DPR sludge. Both reactors yielded high and low DGAO abundance sludges, enabling the evaluation of the denitrification capacity of DPAOs. For the nitrate-DPR sludge, the nitrite reduction rate was 1.63 times higher than the nitrate reduction rate when DPAOs were the primary denitrifiers. For the nitrite-DPR sludge, the reduction rate of nitrite was more than three times that of nitrate, irrespective of DGAO abundance. These findings indicated that DPAOs preferred nitrite to nitrate and were well suited to reduce nitrite rather than reduce nitrate to supply nitrite.

Functional regimes define the response of the soil microbiome to environmental change.

The metabolic activity of soil microbiomes plays a central role in carbon and nitrogen cycling. Given the changing climate, it is important to understand how the metabolism of natural communities responds to environmental change. However, the ecological, spatial, and chemical complexity of soils makes understanding the mechanisms governing the response of these communities to perturbations challenging. Here, we overcome this complexity by using dynamic measurements of metabolism in microcosms and modeling to reveal regimes where a few key mechanisms govern the response of soils to environmental change. We sample soils along a natural pH gradient, construct >1500 microcosms to perturb the pH, and quantify the dynamics of respiratory nitrate utilization, a key process in the nitrogen cycle. Despite the complexity of the soil microbiome, a minimal mathematical model with two variables, the quantity of active biomass in the community and the availability of a growth-limiting nutrient, quantifies observed nitrate utilization dynamics across soils and pH perturbations. Across environmental perturbations, changes in these two variables give rise to three functional regimes each with qualitatively distinct dynamics of nitrate utilization over time: a regime where acidic perturbations induce cell death that limits metabolic activity, a nutrient-limiting regime where nitrate uptake is performed by dominant taxa that utilize nutrients released from the soil matrix, and a resurgent growth regime in basic conditions, where excess nutrients enable growth of initially rare taxa. The underlying mechanism of each regime is predicted by our interpretable model and tested via amendment experiments, nutrient measurements, and sequencing. Further, our data suggest that the long-term history of environmental variation in the wild influences the transitions between functional regimes. Therefore, quantitative measurements and a mathematical model reveal the existence of qualitative regimes that capture the mechanisms and dynamics of a community responding to environmental change.

The growth and nutrient removal properties of heterotrophic microalgae Chlorella sorokiniana in simulated wastewater containing volatile fatty acids

To reduce the high cost of organic carbon sources in waste resource utilization in the cultivation of microalgae, volatile fatty acids (VFAs) derived from activated sludge were used as the sole carbon source to culture Chlorella sorokiniana under the heterotrophic cultivation. The addition of VFAs in the heterotrophic condition enhanced the total nitrogen (TN) and phosphorus (TP) removal of C. sorokiniana, which proved the advantageous microalgae in using VFAs in the heterotrophic culture after screening in the previous study. To discover the possible mechanism of nitrogen and phosphorus adsorption in heterotrophic conditions by microalgae, the effect of different ratios of VFAs (acetic acid (AA): propionic acid (PA): butyric acid (BA)) on the nutrient removal and growth properties of C. sorokiniana was studied. In the 8:1:1 group, the highest efficiency (77.19%) of VFAs assimilation, the highest biomass (0.80 g L−1) and lipid content (31.35%) were achieved, with the highest TN and TP removal efficiencies of 97.44 % and 91.02 %, respectively. Moreover, an aerobic denitrifying bacterium, Pseudomonas, was determined to be the dominant genus under this heterotrophic condition. This suggested that besides nitrate uptake and utilization by C. sorokiniana under the heterotrophy, the conduct of the denitrification process was also the main reason for obtaining high nitrogen removal efficiency.

Physiological and morphological plasticity in response to nitrogen availability of a yeast widely distributed in the open ocean.

Yeasts are prevalent in the open ocean, yet we have limited understanding of their ecophysiological adaptations, including their response to nitrogen availability, which can have a major role in determining the ecological potential of other planktonic microbes. In this study, we characterized the nitrogen uptake capabilities and growth responses of marine-occurring yeasts. Yeast isolates from the North Atlantic Ocean were screened for growth on diverse nitrogen substrates, and across a concentration gradient of three environmentally relevant nitrogen substrates: nitrate, ammonium, and urea. Three strains grew with enriched nitrate while two did not, demonstrating that nitrate utilization is present but not universal in marine yeasts, consistent with existing knowledge of nonmarine yeast strains. Naganishia diffluens MBA_F0213 modified the key functional trait of cell size in response to nitrogen concentration, suggesting yeast cell morphology changes along chemical gradients in the marine environment. Meta-analysis of the reference DNA barcode in public databases revealed that the genus Naganishia has a global ocean distribution, strengthening the environmental applicability of the culture-based observations. This study provides novel quantitative understanding of the ecophysiological and morphological responses of marine-derived yeasts to variable nitrogen availability in vitro, providing insight into the functional ecology of yeasts within pelagic open ocean environments.

Estimating Yield Response Functions to Nitrogen for Annual Crops in Iran

Nitrate is a crucial element for crop growth, and its optimal application is essential for maximizing agricultural yield. In Iranian agriculture, there is a substantial gap between recommended nitrate usage and what farmers actually apply. In this study, our primary objective is to determine the most effective utilization of nitrate for crop cultivation. Simultaneously, we aim to analyze the factors that contribute to the disparity between optimal and current nitrate application practices. Furthermore, our research explores the impact of these differences on regional variations in crop yields. This is achieved using a quadratic yield response function model based on unbalanced panel data spanning the years 2000 to 2016, which includes a total of 14 crop activities and encompasses 31 administrative regions. The results show that rice exhibits the highest nitrogen usage, while rain-fed wheat demonstrates the lowest utilization at the optimal point. Depending on whether random- or fixed-effects estimation is found to be the most suitable specification, average yields corresponding to the optimal level of nitrogen use are calculated by region, or the average across all regions. In Iran, the top-performing regions for cereals like rain-fed wheat and irrigated barley can achieve yields of 1.33 and 3 t/ha, respectively. These yields represent a 31% and a 9% increase from the levels observed in 2016. The outcomes derived from the estimated yield response function will be integrated into comprehensive agricultural, economic, and environmental optimization models. These integrated models will facilitate the assessment of various fertilizer policies on fertilizer use, land allocation, farm-household incomes, and environmental externalities, such as nitrate leaching and nitrate balance. This study holds substantial scientific promise, given its exploration of the policy implications surrounding fertilizer usage, making it crucial not only for Iran, but also for many developing nations grappling with inefficient and unsustainable agricultural practices. It represents the first of its kind in the literature, providing estimations of optimal nitrogen use and crop yield points across all regions in Iran. This is achieved through advanced visualization using GIS maps.

The trihelix transcription factor MdSIP1-2 interacts with MdNIR1 promoter to regulate nitrate utilization in apple

Nitrate is not only the main nitrogen (N) source for plant growth and development, but also an important signaling molecule for plants to cope with the changing environment. To adapt to N fluctuations in the environment, plants have established sophisticated regulatory networks. Although some nitrate signaling regulatory genes have been determined, whether the trihelix transcription factors (TFs) regulate N metabolism remains unclear. Here, an apple trihelix TF-encoding gene 6B-INTERACTING PROTEIN1–2 (SIP1–2) was identified, which is inducible upon nitrate treatment. Under N deficiency condition, the MdSIP1–2-OE transgenic apple calli and Arabidopsis repressed the expression of genes involved in N transport and metabolism, and repressed the activity of both nitrate reductase and nitrite reductase, leading to decreased N content and biomass. These results indicated that MdSIP1–2 inhibited the utilization of nitrate, and MdSIP1–2 may play a negative regulatory role in nitrate signal transduction in plant. In vivo and in vitro experiments showed that MdSIP1–2 directly bound to the GT1 motif of the MdNIR1 promoter to repress its transcription. Taken together, these results revealed that the trihelix TF family gene MdSIP1–2 plays a crucial role in regulating nitrate transport and metabolism, and providing new insights for plants to adapt to N fluctuation in environment.

A nitrogen isoscape of phytoplankton in the western North Pacific created with a marine nitrogen isotope model

The nitrogen isotopic composition (δ15N) of phytoplankton varies substantially in the ocean reflecting biogeochemical processes such as N2 fixation, denitrification, and nitrate assimilation by phytoplankton. The δ15N values of zooplankton or fish inherit the values of the phytoplankton on which they feed. Combining δ15N values of marine organisms with a map of δ15N values (i.e., a nitrogen isoscape) of phytoplankton can reveal the habitat of marine organisms. Remarkable progress has been made in reconstructing time-series of δ15N values of migratory fish from various tissues, such as otoliths, fish scales, vertebrae, and eye lenses. However, there are no accurate nitrogen isoscapes of phytoplankton due to observational heterogeneity, preventing improvement in the accuracy of estimating migratory routes using the fish δ15N values. Here we present a nitrogen isoscape of phytoplankton in the western North Pacific created with a nitrogen isotope model. The simulated phytoplankton is relatively depleted in 15N at the subtropical site (annual average δ15N value of phytoplankton of 0.6‰), where N2 fixation occurs, and at the subarctic site (2.1‰), where nitrate assimilation by phytoplankton is low due to iron limitation. The simulated phytoplankton is enriched in 15N at the Kuroshio–Oyashio transition site (3.9‰), where nitrate utilization is high, and in the region around the Bering Strait site (6.7‰), where partial nitrification and benthic denitrification occur. The simulated δ15N distributions of nitrate, phytoplankton, and particulate organic nitrogen are consistent with δ15N observations in the western North Pacific. The seamless nitrogen isoscapes created in this study can be used to improve our understanding of the habitat of marine organisms or fish migration in the western North Pacific.

On the Variability of Equatorial Pacific Nitrate and Iron Utilization

The tropical Pacific is one of the largest ocean regions on Earth where the trace element iron limits new primary production and therefore the efficiency of carbon export to the deep sea. Although there is a long history of marine biogeochemical research in the tropical Pacific, recent advancements using GEOTRACES key parameters such as iron and nitrate isotopes (nitrate δ15N and δ18O) make this a good time to review the current understanding of tropical Pacific nitrate dynamics—how both regional subsurface nitrate characteristics and surface ocean nitrate utilization change with time. While this article provides a comprehensive overview of the biological, chemical, and physical processes shaping equatorial Pacific subsurface-to-surface nutrients, it principally explores the findings from the first nitrate isotope time series in iron-limited high nutrient, low chlorophyll waters. Results indicate that the preferential recycling of bioavailable iron within the euphotic zone is required to explain even the lowest observed nitrate utilization in the eastern equatorial Pacific (EEP). Furthermore, because seasonal-to-interannual nitrate utilization variability in the EEP cannot be driven by changes in iron supply, this work argues that iron recycling (and therefore bioavailable iron) is modulated by upwelling rate changes, creating a predicted and recently observed spectrum of iron limitation in the iron-limited EEP surface waters. In other words, upper ocean physics overwhelmingly dominates seasonal-to-interannual nitrate utilization in the iron-​limited EEP. This new understanding of nitrate utilization in iron-limited waters helps to explain long-term changes in past equatorial Pacific nitrate utilization obtained via sedimentary proxy records and potentially complicates the efficacy of future iron fertilization of the equatorial Pacific.

Utilisation of carbon dioxide and nitrate for urea electrosynthesis with a Cu-based metal-organic framework.

It is important and challenging to utilise CO2 and NO3- as a feedstock for electrosynthesis of urea. Herein, we reported a stable 2D metal-organic framework (MOF) Cu-HATNA, possessing planar CuO4 active sites, as an efficient electrocatalyst for coupling CO2 and NO3- into urea, achieving a high yield rate of 1.46 g h-1 gcat-1 with a current density of 44.2 mA cm-1 at -0.6 V vs. RHE. This performance surpasses most of the previously reported catalysts, revealing the great prospects of MOFs in sustainable urea synthesis.

Awakening soil microbial utilization of nitrate by carbon regulation to lower nitrogen pollution

Soil microbial immobilization of nitrate (NO3−-N, INO3) and its role in mitigating NO3−-N pollution in agricultural ecosystems globally is often neglected because of the tenet that microbes preferentially use ammonium over NO3−-N. Soil INO3 driven by heterotrophic microorganisms is often carbon (C)-limited, and may therefore be stimulated by C sources with high C/nitrogen (N) ratios. Here, using 15NO3−-N labelling coupled with acetylene inhibition, quantitative PCR and Illumina high-throughput sequencing approaches, we demonstrated that INO3 was stimulated from zero to a substantial level by crop residue amendment without any environmental risk; the degree of stimulation depending on residue quality and soil type. The stimulation was predicted well by C mineralization of the added residue. Soil with a lower initial nutrient status had reduced INO3 efficiency due to stronger C constraint and lower return on energy investment. Fast-growing bacterial r-strategists were identified as the key driver of INO3. We estimate that, globally, residue amendment could cause a total NO3−-N loss reduction of about 33.6 Tg N yr−1 through INO3 stimulation. We suggest that soil INO3 driven by addition of exogenous C is an overlooked process that can help curb NO3−-N accumulation in soil and its subsequent release to the environment, the “nitrate time bomb”.