Electrochemical removal of nitrate in high-salt wastewater with low-cost iron electrode modified by phosphate.

Nitrate (NO3-) is a widespread pollutant in high-salt wastewater and causes serious harm to human health. Although electrochemical removal of nitrate has been demonstrated to be a promising treatment method, the development of low-cost electro-catalysts is still challenging. In this work, a phosphate modified iron (P-Fe) cathode was prepared for electrochemical removal of nitrate in high-salt wastewater. The phosphate modification greatly improved the activity of iron, and the removal rate of nitrate on P-Fe was three times higher than that on Fe electrode. Further experiments and density functional theory (DFT) calculations demonstrated that the modification of phosphoric acid improved the stability and the activity of the zero-valent iron electrode effectively for NO3- removal. The nitrate was firstly electrochemically reduced to ammonium, and then reacted with the anodic generated hypochlorite to N2. In this study, a strategy was developed to improve the activity and stability of metal electrode for NO3- removal, which opened up a new field for the efficient reduction of NO3- removal by metal electrode materials.

Optimizing Nitrate Reduction to Ammonia via Modulating Adsorption-Desorption Dynamics with High-Entropy CuNiCoZnMn Alloy Catalysts.

NO3RR synthesis of ammonia is a complex eight-electron reaction involving multiple steps and intermediates, in which NO3- adsorption and NH3 desorption are crucial. The Cu-based high entropy quinary alloy catalyst has good surface adsorption and desorption ability for the reduction of nitric acid to ammonia. Here, the catalytic sites were coordinated by constructing CuNiCoZnMn alloys to adjust the electronic structure of the catalytic sites to facilitate the reaction of the substrate and thus optimize the whole reaction path. Based on the ternary alloy CuNiCo, the introduction of the Zn element continues to reduce the desorption energy barrier, and the introduction of the Mn element continues to enhance the initial adsorption energy so that the target product can be quickly held and released to accelerate the production of ammonia. The NH3 yield and Faraday efficiency obtained for the quinary CuNiCoZnMn alloy catalyst reached 723.7 µmol h-1 cm-2 and 96.6%, respectively, at -0.35 V vs RHE potential. The density functional theory calculations showed that the quinary CuNiCoZnMn alloy (NO3- to *NO3-) initial adsorption-free energy change and (*NH3 to NH3) NH3 desorption-free energy change are -2.50, 0.072 eV, respectively, which are significantly better than those of the ternary CuNiC and quaternary CuNiCoZn of -2.02, 0.544 eV and -1.97, 0.217 eV.

Coordination Desymmetrization of Copper Single-Atom Catalyst for Efficient Nitrate Reduction.

Coordination engineering strategy for optimizing the catalytic performance of single-atom catalysts (SACs) has been rapidly developed over the last decade. However, previous reports on copper SACs for nitrate reduction reactions (NO3RR) have mostly focused on symmetric coordination configurations such as Cu-N4 and Cu-N3. In addition, the mechanism in terms of the regulation of coordination environment and catalytic properties of SACs has not been well demonstrated. Herein, we disrupted the local symmetric structure of copper atoms by introducing unsaturated heteroatomic coordination of Cu-O and Cu-N to achieve the coordination desymmetrization of Cu-N1O2 SACs. The Cu-N1O2 SACs exhibit an efficient nitrate-to-ammonia conversion with a high FE of ~96.5 % and a yield rate of 3120 µg NH3 h-1 cm-2 at -0.60 V vs RHE. As indicated by in situ Raman spectra, the catalysts facilitate the accumulation of NO3 - and the selective adsorption of *NO2, which were further confirmed by the theoretical study of surface dipole moment and orbital hybridization. Our work illustrated the correlation between the coordination desymmetrization and the catalytic performance of copper SACs for NO3RR.

NIN-like proteins (NLPs) as crucial nitrate sensors: an overview of their roles in nitrogen signaling, symbiosis, abiotic stress, and beyond.

Nitrogen is an essential macronutrient critical for plant growth and productivity. Plants have the capacity to uptake inorganic nitrate and ammonium, with nitrate playing a crucial role as a signaling molecule in various cellular processes. The availability of nitrate and the signaling pathways involved finely tune the processes of nitrate uptake and assimilation. NIN-like proteins (NLPs), a group of transcription factors belonging to the RWP-RK gene family, act as major nitrate sensors and are implicated in the primary nitrate response (PNR) within the nucleus of both non-leguminous and leguminous plants through their RWP-RK domains. In leguminous plants, NLPs are indispensable for the initiation and development of nitrogen-fixing nodules in symbiosis with rhizobia. Moreover, NLPs play pivotal roles in plant responses to abiotic stresses, including drought and cold. Recent studies have identified NLP homologs in oomycete pathogens, suggesting their potential involvement in pathogenesis and virulence. This review article delves into the conservation of RWP-RK genes, examining their significance and implications across different plant species. The focus lies on the role of NLPs as nitrate sensors, investigating their involvement in various processes, including rhizobial symbiosis in both leguminous and non-leguminous plants. Additionally, the multifaceted functions of NLPs in abiotic stress responses, developmental processes, and interactions with plant pathogens are explored. By comprehensively analyzing the role of NLPs in nitrate signaling and their broader implications for plant growth and development, this review sheds light on the intricate mechanisms underlying nitrogen sensing and signaling in various plant lineages.

Single-atom catalysts for electrocatalytic nitrate reduction into ammonia.

Ammonia (NH3) is a versatile and important compound with a wide range of uses, which is currently produced through the demanding Haber-Bosch process. Electrocatalytic nitrate reduction into ammonia (NRA) has recently emerged as a sustainable approach for NH3synthesis under ambient conditions. However, the NRA catalysis is a complex multistep electrochemical process with competitive hydrogen evolution reaction that usually results in poor selectivity and low yield rate for NH3synthesis. With maximum atom utilization and well-defined catalytic sites, single atom catalysts (SACs) display high activity, selectivity and stability toward various catalytic reactions. Very recently, a number of SACs have been developed as promising NRA electrocatalysts, but systematical discussion about the key factors that affect their NRA performance is not yet to be summarized to date. This review focuses on the latest breakthroughs of SACs toward NRA catalysis, including catalyst preparation, catalyst characterization and theoretical insights. Moreover, the challenges and opportunities for improving the NRA performance of SACs are discussed, with an aim to achieve further advancement in developing high-performance SACs for efficient NH3synthesis.

Improving Private Well Testing Programs: Experimental Evidence from Iowa.

Approximately 23 million U.S. households rely on private wells for drinking water. This study first summarizes drinking water behaviors and perceptions from a large-scale survey of households that rely on private wells in Iowa. Few households test as frequently as recommended by public health experts. Around 40% of households do not regularly test, treat, or avoid their drinking water, suggesting pollution exposure may be widespread among this population. Next, we utilize a randomized control trial to study how nitrate test strips and information about a free, comprehensive water quality testing program influence households' behaviors and perceptions. The intervention significantly increased testing, including high-quality follow-up testing, but had limited statistically detectable impacts on other behaviors and perceptions. Households' willingness to pay for nitrate test kits and testing information exceeds program costs, suggesting that the intervention was welfare-enhancing.

Efficient Electroreduction of Low Nitrate Concentration via Nitrate Self-Enrichment and Active Hydrogen Inducement on the Ce(IV)-Co3O4 Cathode.

Low concentrations of nitrate (NO3-) widely exist in wastewater, post-treated wastewater, and natural environments; its further disposal is a challenge but meaningful for its discharge goals. Electroreduction of NO3- is a promising method that allows to eliminate NO3- and even generate higher-value NH3. However, the massive side reaction of hydrogen evolution has raised great obstacles in the electroreduction of low concentrations of NO3-. Herein, we present an efficient electroreduction method for low or even ultralow concentrations of NO3- via NO3- self-enrichment and active hydrogen (H*) inducement on the Ce(IV)-Co3O4 cathode. The key mechanism is that the strong oxytropism of Ce(IV) in Co3O4 resulted in two changes in structures, including loose nanoporous structures with copious dual adsorption sites of Ce-Co showing strong self-enrichment of NO3- and abundant oxygen vacancies (Ovs) inducing substantial H*. Ultimately, the bifunctional role synergistically promoted the selective conversion of NH3 rather than H2. As a result, Ce(IV)-Co3O4 demonstrated a NO3- self-enrichment with a 4.3-fold up-adsorption, a 7.5-fold enhancement of NH3 Faradic efficiency, and a 93.1% diminution of energy consumption when compared to Co3O4, substantially exceeding other reported electroreduction cathodes for NO3- concentrations lower than 100 mg·L-1. This work provides an effective treatment method for low or even ultralow concentrations of NO3-.

The resting cyst of dinoflagellate Scrippsiella acuminata host bacterial microbiomes with more diverse trophic strategies under conditions typically observed in marine sediments.

Variation in the condition of marine sediments provides selective preservation milieus, which act as a key determinant for the abundance and distribution of dinoflagellate resting cysts in natural sediments. Microbial degradation is an understudied biological factor of potential importance in the processes. However, gaps remain in our knowledge about the fundamental information of the bacterial consortia associated with dinoflagellate resting cysts both in laboratory cultures and in the field. Here we used Scrippsiella acuminata as a representative of cyst-producing dinoflagellates to delineate the diversity and composition of bacterial microbiomes co-existing with the laboratory-cultured resting cysts, and to explore possible impacts of low temperature, darkness, and anoxia (the mock conditions commonly observed in marine sediments) on the associated bacterial consortia. Bacterial microbiome with high diversity were revealed associated with S. acuminata at resting stage. The mock conditions could significantly shift bacterial community structure and exert notably inhibitory effects on growth-promoting bacteria. Resting cysts under conditions typically observed in marine sediments fostered bacterial microbiomes with more diverse trophic strategies, characteristic of prominently enriched anaerobic chemotrophic bacteria generating energy via respiration with several different terminal electron acceptors, which yielded more acidic milieu unfavorable for the preservation of calcareous resting cysts. Our findings suggest that there is complex and dynamic interaction between dinoflagellates resting cysts and the associated bacterial consortia in natural sediments. This intrinsic interaction may influence the maintenance and/or accumulation of dinoflagellate resting cysts with potential of germination and initiation blooms in the field.

Interfacial Electronic Interactions Promoted Activation for Nitrate Electroreduction to Ammonia over Ag-modified Co3O4.

Electrocatalytic nitrate (NO3-) reduction to ammonia (NRA) offers a promising pathway for ammonia synthesis. The interfacial electronic interactions (IEIs) can regulate the physicochemical capabilities of catalysts in electrochemical applications, while the impact of IEIs on electrocatalytic NRA remains largely unexplored in current literature. In this study, the high-efficiency electrode Ag-modified Co3O4 (Ag1.5Co/CC) is prepared for NRA in neutral media, exhibiting an impressive nitrate conversion rate of 96.86%, ammonia Faradaic efficiency of 96.11%, and ammonia selectivity of ~100%. Notably, the intrinsic activity of Ag1.5Co/CC is ~81 times that of Ag nanoparticles (Ag/CC). Multiple characterizations and theoretical computations confirm the presence of IEIs between Ag and Co3O4, which stabilize the CoO6 octahedrons within Co3O4 and significantly promote the adsorption of reactants (NO3-) as well as intermediates (NO2- and NO), while suppressing the Heyrovsky step, thereby improving nitrate electroreduction efficiency. Furthermore, our findings reveal a synergistic effect between different active sites that enables tandem catalysis for NRA: NO3- reduction to NO2- predominantly occurs at Ag sites while NO2- tends to hydrogenate to ammonia at Co sites. This study offers valuable insights for the development of high-performance NRA electrocatalysts.

A Metal-Sulfur-Carbon Catalyst Mimicking the Two-Component Architecture of Nitrogenase.

The production of ammonia (NH3) from nitrogen sources involves competitive adsorption of different intermediates and multiple electron and proton transfers, presenting grand challenges in catalyst design. In nature nitrogenases reduce dinitrogen to NH3 using two component proteins, in which electrons and protons are delivered from Fe protein to the active site in MoFe protein for transfer to the bound N2. We draw inspiration from this structural enzymology, and design a two-component metal-sulfur-carbon (M-S-C) catalyst composed of sulfur-doped carbon-supported ruthenium (Ru) single atoms (SAs) and nanoparticles (NPs) for the electrochemical reduction of nitrate (NO3-) to NH3. The catalyst demonstrates a remarkable NH3 yield rate of ~37 mg L-1 h-1 and a Faradaic efficiency of ~97% for over 200 hours, outperforming those consisting solely of SAs or NPs, and even surpassing most reported electrocatalysts. Our experimental and theoretical investigations reveal the critical role of Ru SAs with the coordination of S in promoting the formation of the HONO intermediate and the subsequent reduction reaction over the NP-surface nearby. This study proves a better understanding of how M-S-Cs act as a synthetic nitrogenase mimic during ammonia synthesis, and contributes to the future mechanism-based catalyst design.

Partial substitution of nitrate by chloride in fertigation recipes allows for lower nitrate input in hydroponic lettuce crops.

The management of nitrogen (N) fertilization is of fundamental importance in hydroponics. To reduce the supply of nitrate (NO3 -) in fertigation recipes for Batavia lettuce crops grown in closed hydroponics, partial replacement of nitrate by chloride (NO3 -/Cl-) at different ratios but with the same equivalent sum was experimentally tested. The experiment included four nutritional treatments in the replenishment nutrient solution, particularly T1; 0.7 mM Cl-/19 mM NO3 -, T2; 2 mM Cl-/17.7 mM NO3 -, T3; 4 mM Cl-/15.7 mM NO3 - and T4; 6 mM Cl-/13.7 mM NO3 -. The results showed that reducing nitrate supply combined with equivalent increase in chloride application gradually reduced the gap between nitrate input and nitrogen uptake concentrations, with the smallest differences occurring in T4 treatment, which reduced the nitrate concentration in the drainage by 50%. The tested treatments led to very small variations in plant water uptake, production of fresh biomass and nutritional quality, which is justified by the proper functioning of key physiological mechanisms, such as stomatal conductance, which was followed by an increased efficiency of nitrogen use up to 25% (kg fresh biomass kg-1 N supply). The steady level of C/N ratio in the plant tissue irrespective of NO3 -/Cl- supply ratio points to sufficiency in photosynthetic products and adequacy in the supply of nitrogen, although leaf Cl- content increased up to 19.6 mg g-1 dry weight in the lowest NO3 -/Cl- treatment. Nutrient uptake concentrations were determined as follows: 13.4 (N), 1.72 (P), 10.2 (K), 3.13 (Ca), 0.86 (Mg, mmol L-1), 27.8 (Fe), 5.63 (Mn), 5.45 (Zn) and 0.72 (Cu, µmol L-1). This study suggests that replacing 30% of NO3 - supply with Cl- in fertigation recipes for hydroponic lettuce crops reduces leaf nitrate content without affecting physiological processes, growth, and quality, verifying in parallel the role of chloride as a beneficial macronutrient. Finally, a relationship between Cl- uptake and its concentration in the root zone solution was established enabling the simulation of chloride to water consumption.

The Arabidopsis thaliana ecotype Ct-1 achieves higher salt tolerance relative to Col-0 via higher tissue retention of K+ and NO3.

Agriculture is vital for global food security, and irrigation is essential for improving crop yields. However, irrigation can pose challenges such as mineral scarcity and salt accumulation in the soil, which negatively impact plant growth and crop productivity. While numerous studies have focused on enhancing plant tolerance to high salinity, research targeting various ecotypes of Arabidopsis thaliana has been relatively limited. In this study, we aimed to identify salt-tolerant ecotypes among the diverse wild types of Arabidopsis thaliana and elucidate their characteristics at the molecular level. As a result, we found that Catania-1 (Ct-1), one of the ecotypes of Arabidopsis, exhibits greater salt tolerance compared to Col-0. Specifically, Ct-1 exhibited less damage from reactive oxygen species (ROS) than Col-0, despite not accumulating antioxidants like anthocyanins. Additionally, Ct-1 accumulated more potassium ions (K+) in its shoots and roots than Col-0 under high salinity, which is crucial for water balance and preventing dehydration. In contrast, Ct-1 plants were observed to accumulate slightly lower levels of Na+ than Col-0 in both root and shoot tissues, regardless of salt treatment. These findings suggest that Ct-1 plants achieve high salinity resistance not by extruding more Na+ than Col-0, but rather by absorbing more K+ or releasing less K+. Ct-1 exhibited higher nitrate (NO3-) levels than Col-0 under high salinity conditions, which is associated with enhanced retention of K+ ions. Additionally, genes involved in NO3- transport and uptake, such as NRT1.5 and NPF2.3, showed higher transcript levels in Ct-1 compared to Col-0 when exposed to high salinity. However, Ct-1 did not demonstrate significantly greater resistance to osmotic stress compared to Col-0. These findings suggest that enhancing plant tolerance to salt stress could involve targeting the cellular processes responsible for regulating the transport of NO3- and K+. Overall, our study sheds light on the mechanisms of plant salinity tolerance, emphasizing the importance of K+ and NO3- transport in crop improvement and food security in regions facing salinity stress.

Remote sensing estimates of global sea surface nitrate: Methodology and validation.

Information about sea surface nitrate (SSN) concentrations is crucial for estimating oceanic new productivity and for carbon cycle studies. Due to the absence of optical properties in SSN and the intricate relationships with environmental factors affecting spatiotemporal dynamics, developing a more representative and widely applicable remote sensing inversion algorithm for SSN is challenging. Most methods for the remote estimation of SSN are based on data-driven neural networks or deep learning and lack mechanistic descriptions. Since fitting functions between the SSN and sea surface temperature (SST), mixed layer depth (MLD), and chlorophyll (Chl) content have been established for the open ocean, it is important to include the remote sensing indicator photosynthetically active radiation (PAR), which is critical in nitrate biogeochemical processes. In this study, we employed an algorithm for estimating the monthly average SSN on a global 1° by 1° resolution grid; this algorithm relies on the empirical relationship between the World Ocean Atlas 2018 (WOA18) monthly interpolated climatology of nitrate in each 1°â€¯× 1° grid and the estimated monthly SST and PAR datasets from Moderate Resolution Imaging Spectroradiometer (MODIS) and MLD from the Hybrid Coordinate Ocean Model (HYCOM). These results indicated that PAR potentially affects SSN. Furthermore, validation of the SSN model with measured nitrate data from different months and locations for the years 2018-2023 yielded a high prediction accuracy (N = 12,846, R2 = 0.93, root mean square difference (RMSE) = 3.12 µmol/L, and mean absolute error (MAE) = 2.22 µmol/L). Further independent validation and sensitivity tests demonstrated the validity of the algorithm for retrieving SSN.

Improved Nitrate-to-Ammonia Electrocatalysis through Hydrogen Poisoning Effects.

Electrochemical conversion from nitrate to ammonia is a key step in sustainable ammonia production. However, it suffers from low productive efficiency or high energy consumption due to a lack of desired electrocatalysts. Here we report nickel cobalt phosphide (NiCoP) catalysts for nitrate-to-ammonia electrocatalysis that display a record-high catalytic current density of -702±7 mA cm-2, ammonia production rate of 5415±26 mmol gcat-1 h-1 and Faraday efficiency of 99.7±0.2 % at -0.3 V vs. RHE, affording the estimated energy consumption as low as 22.7 kWh kgammonia-1. Theoretical and experimental results reveal that these catalysts benefit from hydrogen poisoning effects under low overpotentials, which leave behind catalytically inert adsorbed hydrogen species (HI*) at Co-hollow sites and thereupon enable ideally reactive HII* at secondary Co-P sites. The dimerization between HI* and HII* for H2 evolution is blocked due to the catalytic inertia of HI* thereby the HII* drives nitrate hydrogenation timely. With these catalysts, the continuous ammonia production is further shown in an electrolyser with a real energy consumption of 18.9 kWh kgammonia-1.

Discovery of Benzothiazol-2-ylthiophenylpyrazole-4-carboxamides as Novel Succinate Dehydrogenase Inhibitors.

Succinate dehydrogenase (SDH) has been considered an ideal target for discovering fungicides. To develop novel SDH inhibitors, in this work, 31 novel benzothiazol-2-ylthiophenylpyrazole-4-carboxamides were designed and synthesized using active fragment exchange and a link approach as promising SDH inhibitors. The findings from the tests on antifungal activity indicated that most of the synthesized compounds displayed remarkable inhibition against the fungi tested. Compound Ig N-(2-(((5-chlorobenzo[d]thiazol-2-yl)thio)methyl)phenyl)-3-(difluoromethyl)-1-methyl-1H-yrazole-4-carboxamide, with EC50 values against four kinds of fungi tested below 10 µg/mL and against Cercospora arachidicola even below 2 µg/mL, showed superior antifungal activity than that of commercial fungicide thifluzamide, and specifically compounds Ig and Im were found to show preventative potency of 90.6% and 81.3% against Rhizoctonia solani Kühn, respectively, similar to the positive fungicide thifluzamide. The molecular simulation studies suggested that hydrophobic interactions were the main driving forces between ligands and SDH. Encouragingly, we found that compound Ig can effectively promote the wheat seedlings and the growth of Arabidopsis thaliana. Our further studies indicated that compound Ig could stimulate nitrate reductase activity in planta and increase the biomass of plants.

Variation of nitrate sources affected by precipitation with different intensities in groundwater in the piedmont plain area of alluvial-pluvial fan.

A substantial reservoir of nitrogen (N) in soil poses a threat to the quality and safety of shallow groundwater, especially under extreme precipitation that hastens nitrogen leaching into groundwater. However, the specific impact of varying precipitation intensities on the concentration and sources of nitrate (NO3-) in groundwater across diverse hydrogeological zones and land uses remains unclear. This study aims to elucidate the fluctuations in NO3- concentration, sources, and controlling factors in shallow groundwater under different intensities of precipitation (extreme heavy precipitation and continuous heavy precipitation) in a typical alluvial-pluvial fan of the North China Plain by using stable isotopes (δ2H-H2O, δ18O-H2O, δ15N-NO3-, δ18O-NO3-), hydrochemical analyses and the SIAR model. Affected by extreme heavy precipitation the depleted isotopes of δ2H-H2O and δ18O-H2O in groundwater of the entire area suggested the rapid recharge of fast flow by precipitation. The enriched isotopes of δ2H-H2O and δ18O-H2O of north part in alluvial fan after continuous heavy precipitation showed the recharge of translatory flow of soil water. NO3-concentrations increased to 78.9 mg/L after extreme heavy precipitation and increased to 105.3 mg/L after continuous heavy precipitation when compared to those in normal year (56.8 mg/L) of north part of the alluvial fan. However, NO3- concentrations had slight variation after continuous heavy precipitation of south part of the fan due to the deep vadose zone. The contribution ratio of sources of NO3- in groundwater by using SIAR analysis revealed manure & sewage (MS) as the primary NO3- source (accounting for 59.7-78.1%) before extreme heavy precipitation, chemical fertilizer (CF) making a minor contribution (6.9-17.3%). Different precipitation events and land use types lead to changes in NO3- sources. Affected by extreme heavy precipitation, the contribution of MS decreased while CF increased, particularly in vegetables (26.2-28.1%) and farmland (29.2-34.7%). After continuous heavy precipitation, MS increased again, particularly in vegetables (50.0%) and farmlands (20.4-66.4%), with CF either increasing or remaining steady. This indicated that continuous heavy precipitation accelerated the leaching of nitrogen (organic manure application) stored in deep soil to groundwater and it has a larger influence on the increasing of NO3- concentrations of groundwater than extreme heavy precipitation which carried nitrogen (chemical fertilizer application) in shallow soil to groundwater by fast flow. These findings underscore the importance of considering soil chemical N stores and their implications for groundwater contamination mitigation under future extreme climate scenarios, particularly in agricultural management practices.

Nitrogen removal pathways in lake restoration using microalgal-bacterial granular sludge: Unraveling influence of organics and carbon to nitrogen ratio.

This study investigated the performance of microalgal-bacterial granular sludge (MBGS) in the restoration of Qingling Lake and Huangjia Lake, focusing on nitrogen removal under varying water quality conditions. Significant color changes in MBGS and differences in granule characteristics were observed, with Qingling Lake demonstrating superior removal efficiencies for ammonia nitrogen, nitrate nitrogen, and total nitrogen compared to Huangjia Lake. Stoichiometric analysis revealed that when the chemical oxygen demand (COD) and carbon-to-nitrogen (C/N) ratios were less than 20 mg/L and 20, respectively, assimilatory nitrate reduction was positively correlated with both, whereas denitrification was negatively correlated. Gene function analysis showed that Qingling Lake had a more active microbial community supporting efficient nitrogen metabolism. The findings highlighted the enormous potential of MBGS in lake restoration, demonstrating its ability to adapt to different COD concentrations and C/N ratios by altering its nitrogen removal pathways.

Sources, fate and influencing factors of nitrate in farmland drainage ditches of the irrigation area.

Global irrigation areas face the contradictory challenges of controlling nitrate inputs and ensuring food-safe production. To prevent and control nitrate pollution in irrigation areas, the study using the Yellow River basin (Ningxia section) of China as a case study, employed nitrogen and oxygen dual isotope tracing and extensive field investigations to analyze the sources, fate, and influencing factors of nitrate in agricultural drainage ditches. The results of source tracing of nitrate showed that annual proportions of nitrate sources entering the Yellow River in the ditches are as follows: for manure & sewage, fertilizer, and natural sources, the ratios are 33%, 35%, and 32% overall. The results of nitrate fate showed that nitrates derived from nitrate fertilizer exhibit a lower residual rate in drainage ditches (ecological ditches) compared to ammonium fertilizer, which can undergo self-ecological restoration within one year. The results of influencing factors showed that crops with high water and nutrient requirements, such as vegetables, the nitrate pollution and environmental harm resulting from "exploitative cultivation" are five times more than normal cultivation practices in dryland and paddy fields, especially winter irrigation without crop interception exacerbates the leaching of nitrate from the soil. Therefore, nitrate management in irrigation areas should focus on preventing and controlling "exploitative cultivation" and losses during winter irrigation, while appropriately adjusting the application ratio of ammonium nitrogen fertilizers. The results of the study can guide strategies to mitigate nitrate pollution in irrigated areas such as livestock farming, fertilizer application, irrigation management, ditch optimization, and crop cultivation.

Surface crystallized supramolecular to achieve highly dispersed ultrafine nano-palladium in-situ deposition to promote thermal/electrocatalytic reduction.

To promote the greening and economization of industrial production, the development of advanced catalyst manufacturing technology with high activity and low cost is an indispensable part. In this study, nitrogen-doped hollow carbon spheres (NHCSs) were used as anchors to construct a supramolecular coating formed by the self-assembly of boron clusters and ß-cyclodextrin by surface crystallization strategy, with the help of the weak reducing agent characteristics of boron clusters, highly dispersed ultra-small nano-palladium particles were in-situ embedded on the surface of NHCSs. The deoxygenation hydrogenation of nitroaromatics and the reduction of nitrate to ammonia were used as the representatives of thermal catalytic reduction and electrocatalytic reduction respectively. The excellent properties of the constructed Pd/NHCSs were proved by the probe reaction. In the catalytic hydrogenation of nitroaromatics to aminoaromatics, the reaction kinetic rate and activation energy are at the leading level. At the same time, the constructed Pd/NHCSs can also electrocatalytically reduce nitrate to high value-added ammonia with high activity and selectivity, and the behavior of Pd/NHCSs high selectivity driving nitrate conversion was revealed by density functional theory and in situ attenuated total reflection Fourier transform infrared (ATRFTIR) technique. These results all reflect the feasibility and superiority of in-situ anchoring ultra-small nano-metals as catalysts by surface crystallization to build a supramolecular cladding with reducing properties, which is an effective way to construct high-activity and low-cost advanced catalysts.

Far-UVC 222 nm Treatment: Effects of Nitrate/Nitrite on Disinfection Byproduct Formation Potential.

Irradiation at far ultraviolet C (far-UVC) 222 nm by krypton chloride (KrCl*) excilamps can enhance microbial disinfection and micropollutant photolysis/oxidation. However, nitrate/nitrite, which absorbs strongly at 222 nm, may affect the formation of disinfection byproducts (DBPs). Herein, we evaluated model organic matter and real water samples and observed a substantial increase in the formation potential for trichloronitromethane (chloropicrin) (TCNM-FP), a nitrogenous DBP, by nitrate or nitrite after irradiation at 222 nm. At a disinfection dose of 100 mJ·cm-2, TCNM-FP of humic acids and fulvic acids increased from ∼0.4 to 25 and 43 µg·L-1, respectively, by the presence of 10 mg-N·L-1 nitrate. For the effect of nitrate concentration, the TCNM-FP peak was observed at 5-10 mg-N·L-1. Stronger fluence caused a greater increase of TCNM-FP. Similarly, the increase of TCNM-FP was also observed for wastewater and drinking water samples containing nitrate. Pretreatment using ozonation and coagulation, flocculation, and filtration or the addition of H2O2 can effectively control TCNM-FP. The formation potential of other DBPs was minorly affected by irradiation at 222 nm regardless of whether nitrate/nitrite was present. Overall, far-UVC 222 nm treatment poses the risk of increasing TCNM-FP of waters containing nitrate or nitrite at environmentally relevant concentrations and the mitigation strategies merit further research.