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.

Nitrate recovery from groundwater and simultaneous upcycling into single-cell protein using a novel hybrid biological-inorganic system.

Nitrate pollution in groundwater is a serious problem worldwide, as its concentration in many areas exceeds the WHO-defined drinking water standard (50 mg/L). Hydrogen-oxidizing bacteria (HOB) are a group of microorganisms capable of producing single-cell protein (SCP) using hydrogen and oxygen. Furthermore, HOB can utilize various nitrogen sources, including nitrate. This study developed a novel hybrid biological-inorganic (HBI) system that coupled a new submersible water electrolysis system driven by renewable electricity with HOB fermentation for in-situ nitrate recovery from polluted groundwater and simultaneously upcycling it together with CO2 into single-cell protein. The performance of the novel HBI system was first evaluated in terms of bacterial growth and nitrate removal efficiency. With 5 V voltage applied and the initial nitrate concentration of 100 mg/L, the nitrate removal efficiency of 85.52 % and raw of 47.71 % (with a broad amino acid spectrum) were obtained. Besides, the HBI system was affected by the applied voltages and initial nitrogen concentrations. The water electrolysis with 3 and 4 V cannot provide sufficient H2 for HOB and the removal of nitrate was 57.12 % and 59.22 % at 180 h, while it reached 65.14 % and 65.42 % at 5 and 6 V, respectively. The nitrate removal efficiency reached 58.40 % and 50.72 % within 180 h with 200 and 300 mg/L initial nitrate concentrations, respectively. Moreover, a larger anion exchange membrane area promoted nitrate removal. The monitored of the determination of different forms of nitrogen indicated that around 60 % of the recovered nitrate was assimilated into cells, and 40 % was bio-converted to N2. The results demonstrate a potentially sustainable method for remediating nitrate contaminant in groundwater, upcycling waste nitrogen, CO2 sequestration and valorization of renewable electricity into food or feed.

Enhancement of ammonia synthesis via electrocatalytic reduction of low-concentration nitrate using co-doped MIL-101(Fe) nanostructured catalysts.

In the domain of electrocatalytic NO3- reduction (NO3-RR) for the treatment of low-concentration nitrate-containing domestic or industrial wastewater, the conversion of NO3- into NH4+ holds significant promise for resource recovery. Nevertheless, the central challenge in this field revolves around the development of catalysts exhibiting both high catalytic activity and selectivity. To tackle this challenge, we design a two-step hydrothermal combine with carbonization process to fabricate a cobalt-doped Fe-based MOF (MIL-101) catalyst at 800 °C temperatures. The aim was to fully leverage cobalt's demonstrated high selectivity in NO3- electroreduction and enhance activity by promoting electron transfer through the d-band of Fe. The results indicate that the synthesized catalyst inherits multiple active sites from its precursor, with the co-doping process optimized through the topological properties of the MOF. Elemental analysis and oxidation state testing were employed to scrutinize the fundamental characteristics of this catalyst type and comprehend how these features may influence its efficiency. Electrochemical analysis revealed that, even under conditions of low NO3- concentration, the Cox@MIL-Fe catalyst achieved an impressive nitrate conversion rate of 98 % at -0.9 V vs. RHE. NH4+ selectivity was notably high at 87 %, and the by-product NO2- levels remained at a minimal threshold. The Faradaic efficiency for NH4+ reached 74 %, with ammonia yield approaching 0.08 mmol h-1 cm-2. This study furnishes indispensable research data for the design of Fe-based electrocatalysts for nitrate reduction, offering profound insights into the modulation of catalysts to play a pivotal role in the electroreduction of nitrate ions.

Bioengineered FeZn/GA@Cu nanocomposite utilizing spent coffee ground extract and gum arabic: Enhanced nitrate removal via (RSM) and machine learning optimization.

This research focused on synthesizing an eco-friendly FeZn/GA@Cu nanocomposite using spent coffee grounds and Gum Arabic (GA). The study aimed to investigate its effectiveness as both a photocatalyst and an adsorbent, specifically for removing nitrates from aqueous solutions. The prepared nanocomposite was characterized using various analytical techniques, including XRD, TGA, FESEM with EDS, TEM, BET, FTIR, zeta potential, UV-DRS, and VSM. The RSM method, an impressive removal efficiency of 95.28 % for nitrate was projected under the specific conditions of an optimal dose of 1.82 g/L, an initial concentration of 60.00 mg/L, a pH level of 5.85, and a reaction duration of 48.90 min. It was ascertained that the peak efficiency of 98.25 % could be achieved with a carefully calibrated dose of 1.94 g/L, an initial concentration of 62.69 mg/L, a pH of 5.16, and a reaction time contained within 45.75 min. The synthesized nanocomposites have shown potential antibacterial activity against gram+ve (Staphylococcus aureus) and gram-ve (Escherichia coli) pathogens. This study suggests that the FeZn/GA@Cu nanocomposite synthesized using spent coffee grounds has potential as a photocatalyst for removing nitrate from aqueous solutions.

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.

Pd Nanoparticle Size-Dependent H* Coverage for Cu-Catalyzed Nitrate Electro-Reduction to Ammonia in Neutral Electrolyte.

Electrochemical conversion of nitrate (NO3 -) to ammonia (NH3) is an effective approach to reduce nitrate pollutants in the environment and also a promising low-temperature, low-pressure method for ammonia synthesis. However, adequate H* intermediates are highly expected for NO3 - hydrogenation, while suppressing competitive hydrogen evolution. Herein, the effect of H* coverage on the NO3RR for ammonia synthesis by Cu electrocatalysts is investigated. The H* coverage can be adjusted by changing Pd nanoparticle sizes. The optimized Pd@Cu with an average Pd size of 2.88 nm shows the best activity for NO3RR, achieving a maximum Faradaic efficiency of 97% (at -0.8 V vs RHE) and an NH3 yield of 21 mg h-1 cm- 2, from an industrial wastewater level of 500 ppm NO3 -. In situ electrochemical experiments indicate that Pd particles with 2.88 nm can promote NO3 - hydrogenation to NH3 via well-modulated coverage of adsorbed H* species. Coupling the anodic glycerol oxidation reaction, ammonium and formate are successfully obtained as value-added products in a membrane electrode assembly electrolyzer. This work provides a feasible strategy for obtaining size-dependent H* intermediates for hydrogenation.

NRT2.1 mediates the reciprocal regulation of nitrate and NO/SNO in seedling leaves of Fraxinus mandshurica and Betula platyphylla.

Nitric oxide (NO) and S-nitrosothiol (SNO) are signal molecules and the products of nitrogen metabolism. Nitrate (NO3-) is the main nitrogen source, and nitrate transporters (NRTs) are responsible for NO3- absorption or transport. However, the interactive effect between NO3-/NRT and NO/SNO in tree plants remains ambiguous. In the present study, 25 mmol L-1 NO3- and 1 mmol L-1 NO donor sodium nitroprusside (SNP) treatment that was conducted for 24 h enhanced NO/SNO and NO3- metabolism, whereas 2.5 mmol L-1 NO3- and 80 µmol L-1 N6022 (a compound that increases SNO content) treatment reduced them in seedling leaves of Fraxinus mandshurica and Betula platyphylla. Among the nine NRT family members examined, the gene expression level of NRT2.1 had a greater response to NO/SNO and NO3- treatment in the seedling leaves of F. mandshurica and B. platyphylla. Meanwhile, FmNRT2.1 mediated NO and SNO production in seedling leaves of F. mandshurica using Agrobacterium-mediated transient transformation. These findings shed light on the reciprocal regulation between NO3- and NO/SNO in seedlings of F. mandshurica and B. platyphylla, and NRT2.1 may act as a key regulatory hub.

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.

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.

Arsenic release during groundwater recharge and effects of coexisting ions in a typical inland basin with high arsenic concentration: Modeling and batch experiment.

Groundwater recharge is a viable solution to groundwater overexploitation. However, the injection of recharge water may break the dissolution balance and induce the release of trace elements especially arsenic (As), which has been identified in river deltas. Only a few studies have been conducted in inland basins with high As concentration, high pH, and low Eh. Aiming to analyze As release with groundwater recharge in inland high-As regions and determine the effects of coexisting ions in recharge water, this study established PHase Equilibria Calculation (PHREEQC) models using rainwater and groundwater data from three inland sedimentary basins with slow groundwater flow in semi-arid regions. The simulations fitted with the batch experiments, achieving an R-squared (R2) of 0.98. The coexisting ions in the recharge water significantly affected As release during recharge. Ca2+ inhibited the release of total arsenic (Total-As) by increasing the surface charge of iron oxides. NO3- inhibited Total-As release by promoting the conversion of trivalent As into pentavalent As. Conversely, HCO3- facilitated As release by competing with arsenate for adsorption sites. On the basis of the modeling and batch experiment results, Total-As release with groundwater recharge was predicted. The results indicated that the high Ca2+ concentration in the recharge water inhibited the As release by 83.5 %, which can be used as a strategy to control As release during groundwater recharge in high-As inland basins.

Nitrate Inhibits Nodule Nitrogen Fixation by Accumulating Ureide in Soybean Plants.

The mechanism by which nitrate inhibits nitrogen fixation in soybean (Glycine max L.) is not fully understood. Accumulation of ureide in soybean plant tissues may regulate the nitrogen fixation capacity through a feedback pathway. In this study, unilaterally nodulated dual-root soybeans prepared by grafting were grown in sand culture. They were subjected to the removal of the nodulated side roots, and were given either nitrate supply or no supply to the non-nodulated side roots for 3 days (experiment I). Additionally, they received nitrate supply to the non-nodulated side roots for 1-14 days (experiment II). The results showed that nitrate supply increased the levels of asparagine and ureide in soybean shoots (Experiment I). In Experiment II, nodule dry weight, nodule number, nodule nitrogenase activity, and nodule urate oxidase activity decreased significantly after 3, 7, and 14 days of nitrate supply. Ureide content in the shoots and nodules increased after 1, 3, and 7 days of nitrate supply, but decreased after 14 days of nitrate supply. There was a significant positive correlation between urate oxidase activity and nitrogenase activity. Hence, we deduced that nitrate supply increased the asparagine content in soybean shoots, likely inhibiting ureide degradation, which induced the accumulation of ureide in soybean shoots and nodules, and, in turn, feedback inhibited the nodule nitrogen fixation. In addition, urate oxidase activity can be used to assess the nitrogen fixation capacity of nodules.

Assessing the Fates of Water and Nitrogen on an Open-Field Intensive Vegetable System under an Expert-N System with EU-Rotate_N Model in North China Plain.

Nitrate leaching, greenhouse gas emissions, and water loss are caused by conventional water and fertilizer management in vegetable fields. The Expert-N system is a useful tool for recommending the optimal nitrogen (N) fertilizer for vegetable cultivation. To clarify the fates of water and N in vegetable fields, an open-field vegetable cultivation experiment was conducted in Dongbeiwang, Beijing. This experiment tested two irrigation treatments (W1: conventional and W2: optimal) and three fertilizer treatments (N1: conventional, N2: optimal N rate by Expert-N system, and N3: 80% optimal N rate) on cauliflower (Brassica oleracea L.), amaranth (Amaranthus tricolor L.), and spinach (Spinacia oleracea L.). The EU-Rotate_N model was used to simulate the fates of water and N in the soil. The results indicated that the yields of amaranth and spinach showed no significant differences among all the treatments in 2000 and 2001. However, cauliflower yield under the W1N2 and W1N3 treatments obviously reduced in 2001. Compared with the W1 treatment, W2 reduced irrigation amount by 27.9-29.8%, water drainage by over 76%, increased water use efficiency by 5-17%, and irrigation water use efficiency by 29-45%. Nitrate leaching was one of the main pathways in this study, accounting for 8.4% of the total N input; compared to N1, the input of fertilizer N under the N2 and N3 treatments decreased by over 66.5%, consequently reducing gaseous N by 48-72% and increasing nitrogen use efficiency (NUE) by 17-37%. Additionally, compared with the W1 treatments, gaseous N loss under the W2 treatments was reduced by 18-26% and annual average NUEs increased by 22-29%. The highest annual average NUEs were under W2N3 (169.6 kg kg-1) in 2000 and W2N2 (188.0 kg kg-1) in 2001, respectively. We found that optimizing fertilizer management allowed subsequent crops to utilize residual N in the soil. Therefore, we suggest that the W2N3 management should be recommended to farmers to reduce water and N loss in vegetable production systems.

Mitigating Intraphase Catalytic-Domain Transfer via CO2 Laser for Enhanced Nitrate-to-Ammonia Electroconversion and Zn-Nitrate Battery Behavior.

Developing sustainable energy solutions is critical for addressing the dual challenges of energy demand and environmental impact. In this study, a zinc-nitrate (Zn-NO3-) battery system was designed for the simultaneous production of ammonia (NH3) via the electrocatalytic NO3- reduction reaction (NO3RR) and electricity generation. Continuous wave CO2 laser irradiation yielded precisely controlled CoFe2O4@nitrogen-doped carbon (CoFe2O4@NC) hollow nanocubes from CoFe Prussian blue analogs (CoFe-PBA) as the integral electrocatalyst for NO3RR in 1.0-M KOH, achieving a remarkable NH3 production rate of 10.9 mgh-1cm-2 at -0.47 V versus RHE with exceptional stability. In-situ and ex-situ methods revealed that the CoFe2O4@NC surface transformed into high-valent Fe/CoOOH active-species, optimizing the adsorption energy of NO3RR (*NO2 and *NO species) intermediates. Furthermore, DFT calculations validated the possible NO3RR pathway on CoFe2O4@NC starting with NO3- conversion to *NO2 intermediates, followed by reduction to *NO. Subsequent protonation forms the *NH and *NH2 species, leading to NH3 formation via final protonation. The Zn-NO3- battery utilizing the CoFe2O4@NC cathode exhibits dual functionality by generating electricity with a stable open-circuit voltage of 1.38-V versus Zn/Zn2+ and producing NH3. This study inspires the simple design of low-cost catalysts for NO3RR-to-NH3 conversion and positions the Zn-NO3- battery as a promising technology for industrial applications.

Ruthenium Anchored Laser-Induced Graphene as Binder-Free and Free-Standing Electrode for Selective Electrosynthesis of Ammonia from Nitrate.

Developing effective electrocatalysts for the nitrate reduction reaction (NO3RR) is a promising alternative to conventional industrial ammonia (NH3) synthesis. Herein, starting from a flexible laser-induced graphene (LIG) film with hierarchical and interconnected macroporous architecture, a binder-free and free-standing Ru-modified LIG electrode (Ru-LIG) is fabricated for electrocatalytic NO3RR via a facile electrodeposition method. The relationship between the laser-scribing parameters and the NO3RR performance of Ru-LIG electrodes is studied in-depth. At -0.59 VRHE, the Ru-LIG electrode exhibited the optimal and stable NO3RR performance (NH3 yield rate of 655.9 µg cm-2 h-1 with NH3 Faradaic efficiency of up to 93.7%) under a laser defocus setting of +2 mm and an applied laser power of 4.8 W, outperforming most of the reported NO3RR electrodes operated under similar conditions. The optimized laser-scribing parameters promoted the surface properties of LIG with increased graphitization degree and decreased charge-transfer resistance, leading to synergistically improved Ru electrodeposition with more exposed NO3RR active sites. This work not only provides a new insight to enhance the electrocatalytic NO3RR performance of LIG-based electrodes via the coordination with metal electrocatalysts as well as identification of the critical laser-scribing parameters but also will inspire the rational design of future advanced laser-induced electrocatalysts for NO3RR.

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 developed 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.

Quantifying HONO Production from Nitrate Photolysis in a Polluted Atmosphere.

The photolysis of particulate nitrate (pNO3-) has been suggested to be an important source of nitrous acid (HONO) in the troposphere. However, determining the photolysis rate constant of pNO3- (jpNO3-) suffers from high uncertainty. Prior laboratory measurements of jpNO3- using aerosol filters have been complicated by the "shadow effect"─a phenomenon of light extinction within aerosol layers that potentially skews these measurements. We developed a method to correct the shadow effect on the photolysis rate constant of pNO3- for HONO production (jpNO3- â†’ HONO) using aerosol filters with identical chemical compositions but different aerosol loadings. We applied the method to quantify jpNO3- â†’ HONO over the North China Plain (NCP) during the winter haze period. After correcting for the shadow effect, the normalized average jpNO3- â†’ HONO at 5 °C increased from 5.89 × 10-6 s-1 to 1.72 × 10-5 s-1. The jpNO3- â†’ HONO decreased with increasing pH and nitrate proportions in PM2.5 and had no correlation with nitrate concentrations. A parametrization for jpNO3- â†’ HONO was developed for model simulation of HONO production in NCP and similar environments.

Orthogonal signal correction assisted multivariate regression approach for the estimation of uranium and acidity in PUREX process streams.

A direct UV-Visible absorbance spectrophotometric method was developed for the simultaneous determination of uranium and nitric acid concentration in the PUREX process samples. The simulated system consisted of uranium and nitric acid in concentration range corresponding to reprocessing of spent nuclear fuel discharged from nuclear reactor was prepared. The absorbance of these samples was measured in the range of 400-470 nm at a scan speed of 100 nm/s and resultant spectra were recorded. The changes in wavelength maxima of U(VI) absorption spectrum at different nitric acid concentration was utilized to determine the concentration of uranium and nitric acid in the sample by orthogonal signal correction assisted principal component regression. After the principle component regression the RMSEP for test data (Uranium: 3-21 g/L and acidity: 2-12 M) were 0.7 g/L and 0.4 M respectively. This method is superior to conventional method being followed for routine analysis of plant control samples in view of minimizing the generation of radioactive analytical waste consisting other corrosive reagents and reducing radiation exposure to operators during analysis. This method is amenable for online monitoring also.

Utilization of Lead Nitrate to Enhance the Impact of Hydroxamic Acids on the Hydrophobic Aggregation and Flotation Behavior of Cassiterite.

Lead nitrate (LN) is frequently employed as an activator in the flotation of cassiterite using hydroxamic acids as the collectors. This study investigated the effect of LN on the hydrophobic aggregation of cassiterite when benzohydroxamic acid (BHA), hexyl hydroxamate (HHA), and octyl hydroxamate (OHA) were used as the collectors through micro-flotation, focused beam reflectance measurement (FBRM) and a particle video microscope (PVM), zeta potential, and the extended DLVO theory. Micro-flotation tests confirmed that LN activated the flotation of cassiterite using the hydroxamic acids as collectors. Focused beam reflectance measurement (FBRM) and a particle video microscope (PVM) were used to capture in situ data on the changes in size distribution and morphology of cassiterite aggregates during stirring. The FBRM and PVM image results indicated that the addition of LN could promote the formation of hydrophobic aggregates of fine cassiterite, when BHA or HHA was used as the collector, and reduce the dosage of OHA needed to induce the formation of hydrophobic aggregates of cassiterite. The extended DLVO theory interaction energies indicated that the presence of LN could decrease the electrostatic interaction energies (Vedl) and increase the hydrophobic interaction energies (Vhy) between cassiterite particles, resulting in the disappearance of the high energy barriers that existed between the particles in the absence of LN. Thus, cassiterite particles could aggregate in the presence of LN when BHA, HHA, or a low concentration of OHA was used as the collector.