Light-induced degradation of dimethylmercury in different natural waters.

Photo-induced degradation of dimethylmercury (DMHg) is considered to be an important source for the generation of methylmercury (MMHg). However, studies on DMHg photodegradation are scarce, and it is even debatable about whether DMHg can be degraded in natural waters. Herein, we found that both DMHg and MMHg could be photodegraded in three natural waters collected from the Yellow River Delta, while in pure water only DMHg photodegradation occurred under visible light irradiation. The effects of different environmental factors on DMHg photodegradation were investigated, and the underlying mechanisms were elucidated by density functional theory calculations and a series of control experiments. Our findings revealed that the DMHg degradation rate was higher in the tidal creek water compared to Yellow River, Yan Lake, and purified water. NO3-, NO2-, and DOM could promote the photodegradation with DOM and NO3- showing particularly strong positive effects. Different light sources were employed, and UV light was found to be more effective in DMHg photodegradation. Moreover, MMHg was detected during the photodegradation of DMHg, confirming that the photochemical demethylation of DMHg is a source of MMHg in sunlit water. This work may provide a novel mechanistic insight into the DMHg photodegradation in natural waters and enrich the study of the global biogeochemical cycle of Hg.

Electrocatalytic reduction of nitrate to ammonia by Pd/In modified Nickel foam electrode in aqueous solution.

Nitrate pollution in surface water and ground water has drawn wide attention, which has brought challenges to human health and natural ecology. Electroreduction of nitrate to NH3 in waste water was a way to turn waste into wealth, which has attracted interest of many researchers. Using Nickel foam as substrate, we prepared Pd/In bimetallic electrode (NF-Pd/In) according to a two-step electrodeposition method. There are many irregularly shaped particles in the size range of 10 nm-100 nm accumulated on the surface of prepared NF-Pd/In electrode, which could supply high specific area and more active sites for nitrate electroreduction. FESEM-EDS, XRD and XPS analysis confirmed the uniform distribution of Pd and In on the surface of prepared NF-Pd/In electrode, with a mass ratio of 4.5/1. Above 96% of 100 mg/L NO3--N was removed and 95% of NH3 selectivity was reached after 5 h of reaction under -1.6 V vs. Ag/AgCl sat. KCl when using 0.05 mol/L of Na2SO4 as electrolyte. High concentration of NaCl (0.05 mol/L) in the test solution dramatically decreased the NH3 selectivity because the produced NH3 could be further oxidized to N2 by the formed HClO from Cl-. EIS tests indicated that the prepared NF-Pd/In electrode showed much lower electrode resistance than NF due to the adsorptive property and electrocatalytic ability for nitrate removal. Density functional theory (DFT) calculations indicated that the presence of In could promote the conversion of NO3- to *NO3 during the process of nitrate electroreduction to NH3. Circulating tests demonstrated the stability of prepared NF-Pd/In electrode.

Assessing the Chemical-Free Oxidation of Trace Organic Chemicals by VUV/UV as an Alternative to Conventional UV/H2O2.

Low-pressure mercury lamps with high-purity quartz can emit both vacuum-UV (VUV, 185 nm) and UV (254 nm) and are commercially available and promising for eliminating recalcitrant organic pollutants. The feasibility of VUV/UV as a chemical-free oxidation process was verified and quantitatively assessed by the concept of H2O2 equivalence (EQH2O2), at which UV/H2O2 showed the same performance as VUV/UV for the degradation of trace organic contaminants (TOrCs). Although VUV showed superior H2O activation and oxidation performance, its performance highly varied as a function of light path length (Lp) in water, while that of UV/H2O2 proportionally decreased with decreasing H2O2 dose regardless of Lp. On increasing Lp from 1.0 to 3.0 cm, the EQH2O2 of VUV/UV decreased from 0.81 to 0.22 mM H2O2. Chloride and nitrate hardly influenced UV/H2O2, but they dramatically inhibited VUV/UV. The competitive absorbance of VUV by chloride and nitrate was verified as the main reason. The inhibitory effect was partially compensated by •OH formation from the propagation reactions of chloride or nitrate VUV photolysis, which was verified by kinetic modeling in Kintecus. In water with an Lp of 2.0 cm, the EQH2O2 of VUV/UV decreased from 0.43 to 0.17 mM (60.8% decrease) on increasing the chloride concentration from 0 to 15 mM and to 0.20 mM (53.5% decrease) at 4 mM nitrate. The results of this study provide a comprehensive understanding of VUV/UV oxidation in comparison to UV/H2O2, which underscores the suitability and efficiency of chemical-free oxidation with VUV/UV.

Selective Nitrate Electroreduction to Ammonia on CNT Electrodes with Controllable Interfacial Wettability.

The development of electrocatalysts that can efficiently reduce nitrate (NO3-) to ammonia (NH3) has garnered increasing attention due to their potential to reduce carbon emissions and promote environmental protection. Intensive efforts have focused on catalyst development, but a thorough understanding of the effect of the microenvironment around the reactive sites of the catalyst is also crucial to maximize the performance of the electrocatalysts. This study explored an electrocatalytic system that utilized quaternary ammonium surfactants with a range of alkyl chain lengths to modify an electrode made of carbon nanotubes (CNT), with the goal of regulating interfacial wettability toward NO3- reduction. Trimethyltetradecylammonium bromide with a moderate alkyl chain length created a very hydrophobic interface, which led to a high selectivity in the production of NH3 (∼87%). Detailed mechanistic investigations that used operando Fourier-transform infrared (FTIR) spectroscopy and online differential electrochemical mass spectrometry (DEMS) revealed that the construction of a hydrophobic modified CNT played a synergistic role in suppressing a side reaction involving the generation of hydrogen, which would compete with the reduction of NO3-. This electrocatalytic system led to a favorable process for the reduction of NO3- to NH3 through a direct electron transfer pathway. Our findings underscore the significance of controlling the hydrophobic surface of electrocatalysts as an effective means to enhance electrochemical performance in aqueous media.

Efficient and Selective Electrochemical Nitrate Reduction to N2 Using a Flow-Through Zero-Gap Electrochemical Reactor with a Reconstructed Cu(OH)2 Cathode: Insights into the Importance of Inter-Electrode Distance.

Electrochemically converting nitrate, a widely distributed nitrogen contaminant, into harmless N2 is a feasible and environmentally friendly route to close the anthropogenic nitrogen-based cycle. However, it is currently hindered by sluggish kinetics and low N2 selectivity, as well as scarce attention to reactor configuration. Here, we report a flow-through zero-gap electrochemical reactor that shows a high performance of nitrate reduction with 100% conversion and 80.36% selectivity of desired N2 in the chlorine-free system at 100 mg-N·L-1 NO3- while maintaining a rapid reduction kinetics of 0.07676 min-1. More importantly, the mass transport and current utilization efficiency are significantly improved by shortening the inter-electrode distance, especially in the zero-gap electrocatalytic system where the current efficiency reached 50.15% at 5 mA·cm-2. Detailed characterizations demonstrated that during the electroreduction process, partial Cu(OH)2 on the cathode surface was reconstructed into stable Cu/Cu2O as the active phase for efficient nitrate reduction. In situ characterizations revealed that the highly selective *NO to *N conversion and the N-N coupling step played crucial roles during the selective reduction of NO3- to N2 in the zero-gap electrochemical system. In addition, theoretical calculations demonstrated that improving the key intermediate *N coverage could effectively facilitate the N-N coupling step, thereby promoting N2 selectivity. Moreover, the environmental and economic benefits and long-term stability shown by the treatment of real nitrate-containing wastewater make our proposed electrocatalytic system more attractive for practical applications.

Granular activated carbon assisted biocathode for effective electrotrophic denitrification in microbial fuel cells.

Granular activated carbon (GAC) has been widely used at the anode of a microbial fuel cell (MFC) to enhance anode performance due to its outstanding capacitance property. To the best of our knowledge, there haven't been any studies on GAC in the cathode for biofilm development and nitrate reduction in MFC. In this study, by adding GAC to biocathode, we investigated the impact of different GAC amounts and stirring speeds on power generation and nitrate reduction rate in MFC. The denitrification rate was found to be nearly two-times higher in MFCs with GAC (0.046 ± 0.0016 kg m-3 d-1) compared to that deprived of GAC (0.024 ± 0.0012 kg m-3 d-1). The electrotrophic denitrification has produced a maximum power density of 37.6 ± 4.8 mW m-2, which was further increased to 79.2 ± 7.4 mW m-2 with the amount of GAC in the biocathode. A comparative study performed with chemical catalyst (Pt carbon with air sparging) cathode and GAC biocathode showed that power densities produced with GAC biocathode were close to that with Pt cathode. Cyclic voltammetry analysis conducted at 10 mV s-1 between -0.9 V and +0.3 V (vs. Ag/AgCl) showed consistent reduction peaks at -0.6V (Ag/AgCl) confirming the reduction reaction in the biocathode. This demonstrates that the GAC biocathode used in this research is effective at producing power density and denitrification in MFC. Our belief that the nitrate reduction was caused by the GAC biocathode in MFC was further strengthened when SEM analysis showing bacterial aggregation and biofilm formation on the surface of GAC. The GAC biocathode system described in this research may be an excellent substitute for MFC's dual functions of current generation and nitrate reduction.

Nitrate electro-bioremediation and water disinfection for rural areas.

Nitrate-contaminated groundwater is a pressing issue in rural areas, where up to 40 % of the population lacks access to safely managed drinking water services. The high costs and complexity of centralised treatment in these regions exacerbate this problem. To address this challenge, the present study proposes electro-bioremediation as a more accessible decentralised alternative. Specifically, the main focus of this study is developing and evaluating a compact reactor designed to accomplish simultaneous nitrate removal and groundwater disinfection. Significantly, this study has established a new benchmark for nitrate reduction rate within bioelectrochemical reactors, achieving the maximum reported rate of 5.0 ± 0.3 kg NO3- m-3NCC d-1 at an HRTcat of 0.7 h. Furthermore, thein-situ generation of free chlorine was effective for water disinfection, resulting in a residual concentration of up to 4.4 ± 1.1 mg Cl2 L-1 in the effluent at the same HRTcat of 0.7 h. These achievements enabled the treated water to meet the drinking water standards for nitrogen compounds (nitrate, nitrite, and nitrous oxide) as well as pathogens content (T. coliforms, E. coli, and Enterococcus). In conclusion, this study demonstrates the potential of the electro-bioremediation of nitrate-contaminated groundwater as a decentralised water treatment system in rural areas with a competitive operational cost of 1.05 ± 0.16 € m-3.

Electrochemical production of hydroxylamine from nitrate on metal electrodes: A comparative study of selectivity and efficiency.

Despite the great potential of electrochemical nitrate reduction as a hydroxylamine production method, this strategy has not been sufficiently examined, and the effects of electrode material type on the selectivity and efficiency of this reduction remain underexplored. To bridge this gap, the present study evaluated six metals (Ag, Cu, Ni, Sn, Ti, and Zn) as cathode materials for the electrochemical reduction of nitrate to hydroxylamine, showing that the selectivity of hydroxylamine production was maximal for Sn, while the corresponding faradaic and energy utilization efficiencies were maximal for Ti. Although all tested materials favored nitrate reduction over hydrogen evolution, the disparity in the onset potentials of these reactions did not adequately explain the variations in nitrate removal efficiency, which was found to be influenced by material resistance and charge-transfer properties. The rate constants of elementary nitrate reduction steps determined from the time-dependent concentrations of nitrate and its reduction products (nitrous acid, hydroxylamine, and ammonium) were used to calculate the selectivity and efficiency of hydroxylamine production for each electrode. In turn, these selectivities and efficiencies were correlated with the density functional theory-computed adsorption energies of a key hydroxylamine precursor on different electrodes to afford a volcano-type plot with Ti and Sn at its pinnacle. Thus, this study introduces valuable descriptors and methods for the further screening of electrocatalysts for hydroxylamine generation and the establishment of more environmentally friendly hydroxylamine production techniques utilizing sustainable electricity.

Electrochemical Reduction of Flue Gas Denitrification Wastewater to Ammonia Using a Dual-Defective Cu2O@Cu Heterojunction Electrode.

Wet flue gas denitrification offers a new route to convert industrial nitrogen oxides (NOx) into highly concentrated nitrate wastewater, from which the nitrogen resource can be recovered to ammonia (NH3) via electrochemical nitrate reduction reactions (NITRRs). Low-cost, scalable, and efficient cathodic materials need to be developed to enhance the NH3 production rate. Here, in situ electrodeposition was adopted to fabricate a foamy Cu-based heterojunction electrode containing both Cu-defects and oxygen vacancy loaded Cu2O (OVs-Cu2O), which achieved an NH3 yield rate of 3.59 mmol h-1 cm-2, NH3 Faradaic efficiency of 99.5%, and NH3 selectivity of 100%. Characterizations and theoretical calculations unveiled that the Cu-defects and OVs-Cu2O heterojunction boosted the H* yield, suppressed the hydrogen evolution reaction (HER), and served as dual reaction sites to coherently match the tandem reactions kinetics of NO3-to-NO2 and NO2-to-NH3. An integrated system was further built to combine wet flue gas denitrification and desulfurization, simultaneously converting NO and SO2 to produce the (NH4)2SO4 fertilizer. This study offers new insights into the application of low-cost Cu-based cathode for electrochemically driven wet denitrification wastewater valorization.

Closing Dichloramine Decomposition Nitrogen and Oxygen Mass Balances: Relative Importance of End-Products from the Reactive Nitrogen Species Pathway.

In drinking water chloramination, monochloramine autodecomposition occurs in the presence of excess free ammonia through dichloramine, the decay of which was implicated in N-nitrosodimethylamine (NDMA) formation by (i) dichloramine hydrolysis to nitroxyl which reacts with itself to nitrous oxide (N2O), (ii) nitroxyl reaction with dissolved oxygen (DO) to peroxynitrite or mono/dichloramine to nitrogen gas (N2), and (iii) peroxynitrite reaction with total dimethylamine (TOTDMA) to NDMA or decomposition to nitrite/nitrate. Here, the yields of nitrogen and oxygen-containing end-products were quantified at pH 9 from NHCl2 decomposition at 200, 400, or 800 µeq Cl2·L-1 with and without 10 µM-N TOTDMA under ambient DO (∼500 µM-O) and, to limit peroxynitrite formation, low DO (≤40 µM-O). Without TOTDMA, the sum of free ammonia, monochloramine, dichloramine, N2, N2O, nitrite, and nitrate indicated nitrogen recoveries ±95% confidence intervals were not significantly different under ambient (90 ± 6%) and low (93 ± 7%) DO. With TOTDMA, nitrogen recoveries were less under ambient (82 ± 5%) than low (97 ± 7%) DO. Oxygen recoveries under ambient DO were 88-97%, and the so-called unidentified product of dichloramine decomposition formed at about three-fold greater concentration under ambient compared to low DO, like NDMA, consistent with a DO limitation. Unidentified product formation stemmed from peroxynitrite decomposition products reacting with mono/dichloramine. For a 2:2:1 nitrogen/oxygen/chlorine atom ratio and its estimated molar absorptivity, unidentified product inclusion with uncertainty may close oxygen recoveries and increase nitrogen recoveries to 98% (ambient DO) and 100% (low DO).

Conversion of biobased substances into biochar to enhances nutrient adsorption and retention capacity.

Reducing the environmental issues brought on by nutrients especially nitrogen pollution and loss is important. Owing to its unique composition and physico-chemical characteristics, biomass-derived biochar exhibits varying degrees of adsorption and interception for all types of soil nutrients. Thus, a novel way to improve nutrient absorption in the soil is to include biomass derived biochar into it. Various biomass-derived biochar from locally available biobased substances was synthesized through low-cost portable charring kiln. It has been quantified the influence of four biobased substances and three pyrolysis temperature on different morphomineralogical characteristics of biochar for utilizing as low-cost sorbent to manage nutrient adsorption and retention capacity. The morphomineralogical characteristics were principally manipulated by feedstocks rather than pyrolysis temperature. Higher porosity and surface area of biomass-derived biochar illustrated its soil structural modification and nutrient retention capacity along with their utilization for adsorbents. With increase in pyrolysis temperature, the adsorption capacity of biochar for NH4+-N and NO3--N was gradually weakened and gradually enhanced respectively. The adsorption process of ammonia nitrogen and nitrate nitrogen conformed to the Langmuir model and the fitted KL value was less than 1 indicating that the adsorption process was uniform monolayer adsorption and the adsorption of biochar was favorable adsorption. With increase in biochar application rate the leaching of NO3--N decreased having higher at 2.5 t ha-1 application rate followed by 5 t ha-1 and lower at 7.5 t ha-1. In packed soil column, the NH4+-N in leachate was maximum in T7 (18.6), followed by T4 (17.9), T13 (17.3) and minimum in T10 (17.2) at same application rate of manures and biochar. Finally, results also revealed that packed soil column performed better as compared with intact soil column to retain soil nutrient and hence, leaching potential of nutrient was less in packed column than intact soil column. In conclusion, biomass-derived biochar can enhance the amount of nutrient that is absorbed into the soil while decreasing the loss of nutrient from the soil in the form of ammonia and nitrate. To sum up, biomass-derived biochar can increase the adsorption amount of the nitrogen and reduce the loss of ammonia nitrogen and nitrate nitrogen in the soil, thus retaining the nitrogen.

Nitrate Radicals Suppress Biogenic New Particle Formation from Monoterpene Oxidation.

Highly oxygenated organic molecules (HOMs) are a major source of new particles that affect the Earth's climate. HOM production from the oxidation of volatile organic compounds (VOCs) occurs during both the day and night and can lead to new particle formation (NPF). However, NPF involving organic vapors has been reported much more often during the daytime than during nighttime. Here, we show that the nitrate radicals (NO3), which arise predominantly at night, inhibit NPF during the oxidation of monoterpenes based on three lines of observational evidence: NPF experiments in the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN (European Organization for Nuclear Research), radical chemistry experiments using an oxidation flow reactor, and field observations in a wetland that occasionally exhibits nocturnal NPF. Nitrooxy-peroxy radicals formed from NO3 chemistry suppress the production of ultralow-volatility organic compounds (ULVOCs) responsible for biogenic NPF, which are covalently bound peroxy radical (RO2) dimer association products. The ULVOC yield of α-pinene in the presence of NO3 is one-fifth of that resulting from ozone chemistry alone. Even trace amounts of NO3 radicals, at sub-parts per trillion level, suppress the NPF rate by a factor of 4. Ambient observations further confirm that when NO3 chemistry is involved, monoterpene NPF is completely turned off. Our results explain the frequent absence of nocturnal biogenic NPF in monoterpene (α-pinene)-rich environments.

Influence of Oxygen Vacancy-Induced Coordination Change on Pd/CeO2 for NO Reduction.

The byproduct formation in environmental catalysis is strongly influenced by the chemical state and coordination of catalysts. Herein, two Pd/CeO2 catalysts (PdCe-350 and PdCe-800) with varying oxygen vacancies (Ov) and coordination numbers (CN) of Pd were prepared to investigate the mechanism of N2O and NH3 formation during NO reduction by CO. PdCe-350 exhibits a higher density of Ov and Pd sites with higher CN, leading to an enhanced metal-support interaction by electron transformation from the support to Pd. Consequently, PdCe-350 displayed increased levels of byproduct formation. In situ spectroscopies under dry and wet conditions revealed that at low temperatures, the N2O formation strongly correlated with the Ov density through the decomposition of chelating nitro species on PdCe-350. Conversely, at high temperatures, it was linked to the reactivity of Pd species, primarily facilitated by monodentate nitrates on PdCe-800. In terms of NH3 formation, its occurrence was closely associated with the activation of H2O and C3H6, since a water-gas shift or hydrocarbon reforming could provide hydrogen. Both bridging and monodentate nitrates showed activity in NH3 formation, while hyponitrites were identified as key intermediates for both catalysts. The insights provide a fundamental understanding of the intricate relationship among the local coordination of Pd, surface Ov, and byproduct distribution.

Electrochemical nitrate reduction over bimetallic Pd-Sn nanocatalysts with tunable selectivity toward benign nitrogen.

Nitrate is recognized as a highly impactful water contaminant among various pollutants in water. To address the ever-growing demand for water purification, this work investigates the bimetallic palladium (Pd) and tin (Sn) catalysts, which are electrochemically deposited on stainless steel mesh support (Pd-Sn/SS) for the selective conversion of harmful nitrate (NO3-) into benign nitrogen (N2) gas. Results indicate that the bimetallic composition in Pd-Sn/SS electrodes substantially influenced the reaction route for nitrate reduction as well as the performance of nitrate transformation and nitrogen selectivity. It is found that the electrode prepared from Pd:Sn = 1:1 (mole ratio) demonstrates an outstanding nitrate conversion of 95%, nitrogen selectivity of 88%, and nitrogen yield of 82%, which outperform many reported values in the literature. The electrochemically synthesized bimetallic electrode proposed herein enables a new insight for promoting the reactivity and selectivity of nitrate reduction in water.

Revealing discrepancies and drivers in the impact of lomefloxacin on groundwater denitrification throughout microbial community growth and succession.

The coexistence of antibiotics and nitrates has raised great concern about antibiotic's impact on denitrification. However, conflicting results in these studies are very puzzling, possibly due to differences in microbial succession stages. This study investigated the effects of the high-priority urgent antibiotic, lomefloxacin (LOM), on groundwater denitrification throughout microbial growth and succession. The results demonstrated that LOM's impact on denitrification varied significantly across three successional stages, with the most pronounced effects exhibited in the initial stage (53.8% promotion at 100 ng/L-LOM, 84.6% inhibition at 100 µg/L-LOM), followed by the decline stage (13.3-18.2% inhibition), while no effect in the stable stage. Hence, a distinct pattern encompassing susceptibility, insusceptibility, and sub-susceptibility in LOM's impact on denitrification was discovered. Microbial metabolism and environment variation drove the pattern, with bacterial numbers and antibiotic resistance as primary influencers (22.5% and 15.3%, p < 0.01), followed by carbon metabolism and microbial community (5.0% and 3.68%, p < 0.01). The structural equation model confirmed results reliability. Bacterial numbers and resistance influenced susceptibility by regulating compensation and bacteriostasis, while carbon metabolism and microbial community impacted energy, electron transfer, and gene composition. These findings provide valuable insights into the complex interplay between antibiotics and denitrification patterns in groundwater.

Enhancing biocathode denitrification performance with nano-Fe3O4 under polarity period reversal.

The presence of excessive concentrations of nitrate poses a threat to both the environment and human health, and the bioelectrochemical systems (BESs) are attractive green technologies for nitrate removal. However, the denitrification efficiency in the BESs is still limited by slow biofilm formation and nitrate removal. In this work, we demonstrate the efficacy of novel combination of magnetite nanoparticles (nano-Fe3O4) with the anode-cathode polarity period reversal (PPR-Fe3O4) for improving the performance of BESs. After only two-week cultivation, the highest cathodic current density (7.71 ± 1.01 A m-2) and NO3--N removal rate (8.19 ± 0.97 g m-2 d-1) reported to date were obtained in the PPR-Fe3O4 process (i.e., polarity period reversal with nano-Fe3O4 added) at applied working voltage of -0.2 and -0.5 V (vs Ag/AgCl) under bioanodic and biocathodic conditions, respectively. Compared with the polarity reversal once only process, the PPR process (i.e., polarity period reversal in the absence of nano-Fe3O4) enhanced bioelectroactivity through increasing biofilm biomass and altering microbial community structure. Nano-Fe3O4 could enhance extracellular electron transfer as a result of promoting the formation of extracellular polymers containing Fe3O4 and reducing charge transfer resistance of bioelectrodes. This work develops a novel biocathode denitrification strategy to achieve efficient nitrate removal after rapid cultivation.

Pd/Cu bimetallic nano-catalyst supported on anion exchange resin (A520E) for nitrate removal from water: High property and stability.

High nitrate concentration in water can lead to eutrophication and the disruption of healthy aquatic ecosystems. Additionally, in the human digestive system, it has the potential to be reduced to nitrite, which can be damaging to people's physical health. Catalytic hydrogenation of nitrate is one of the strategies for removing nitrate from water. Using A520E resin as support, we prepared Pd/Cu nano-catalyst (Pd/Cu@A520E) according to a liquid phase reduction method. A520E could improve the transfer process of nitrate in the solution to the activity sites of Pd/Cu nanoparticles, thus increase the reaction rate of nitrate reduction. Pd/Cu bimetallic nano-particles were evenly distributed on/in the resin with a size range from 2 nm to 10 nm. The External Circulating System equipped with Venturi tube (ECSV) was designed to improve the utilization efficiency of H2 in both batch tests and long-term continuous-flow tests. Nearly 100% of nitrate removal efficiency and above 90% of N2 selectivity were achieved in both batch tests and continuous-flow tests. Coexisting Cl- and SO42- at 300 mg/L showed little impact on the property of Pd/Cu@A520E. Pd/Cu@A520E also showed high nitrate removal property and stability in continuous-flow tests of more than 800 h. NO3- was adsorbed onto the active sites (functional groups and Pd/Cu particle sites), meanwhile H2 was adsorbed onto the active sites of Pd/Cu@A520E to form Pd [H]. Then the adsorbed NO3- was reduced into N2 (main product) or NH4+ by Pd [H]. In addition, Pd/Cu@A520E showed high nitrate removal property from municipal waste water.

Digestive interaction between dietary nitrite and dairy products generates novel nitrated linolenic acid products.

Nitrated fatty acids are important anti-inflammatory and protective lipids formed in the gastric compartment, with conjugated linoleic acid (rumenic acid, RA, 9Z,11E-18:2) being the primary substrate for lipid nitration. The recently reported identification of nitrated rumelenic acid (NO2-RLA) in human urine has led to hypothesize that rumelenic acid (RLA, 9Z,11E,15Z-18:3) from dairy fat is responsible for the formation of NO2-RLA. To evaluate the source and mechanism of NO2-RLA formation, 15N labeled standards of NO2-RLA were synthesized and characterized. Afterward, milk fat with different RA and RLA levels was administered to mice in the presence of nitrite, and the appearance of nitrated fatty acids in plasma and urine followed. We confirmed the formation of NO2-RLA and defined the main metabolites in plasma, urine, and tissues. In conclusion, RLA obtained from dairy products is the main substrate for forming this novel electrophilic lipid reported to be present in human urine.

Co-application of concentrated biogas slurry and pyroligneous liquor mitigates ammonia emission and sustainably releases ammonium from paddy soil.

Biogas production causes vast amounts of biogas slurry (BS). Application of BS to croplands can substitute chemical fertilizers while result in higher ammonia emissions. Tremendous variation of ammonium concentration in different BSs induces imprecise substitution, while concentrated BS holds higher and more stable ammonium. Pyroligneous liquor, an acidic aqueous liquid from biochar production, can be used with concentrated BS to reduce ammonia emission. However, the effects of combining concentrated BS with pyroligneous liquor on ammonia emission and soil (nitrogen) N transformation have been poorly reported. In this study, a field experiment applying concentrated BS only, or combining with 5 %, 10 %, and 20 % pyroligneous liquor (v/v) for substituting 60 % N of single rice cultivation was conducted by contrast with chemical fertilization. The results showed that substituting chemical N fertilizers with concentrated BS increased 24.6 % ammonia emission. In comparison, applying 5 %, 10 %, and 20 % pyroligneous liquor with concentrated BS reduced 4.9 %, 20.3 %, and 24.4 % ammonia emissions, respectively. Applying concentrated BS with more pyroligneous liquor preserved higher ammonium and dissolved organic carbon in floodwater, and induced higher nitrate concentration after fertilization. Whereas soil ammonium and nitrate contents were decreased along with more pyroligneous liquor application before and after the topdressing and exhibited sustainable release until rice harvest. In comparison, the soil N mineralization and nitrification rates were occasionally elevated, while the activities of soil urease, protease, nitrate reductase, and nitrite reductase had multiple responses. Applying concentrated BS only, or combining with 5 %, 10, and 20 % pyroligneous liquor, have little effect on soil basic properties but inorganic N. In summary, applying concentrated BS with >10 % pyroligneous liquor could preserve more N with sustainable release and potentially lower N loss to the atmosphere, and we proposed that applying 13.5 % pyroligneous liquor in concentrated BS could achieve maximum soil fertility and minimum ammonia emission.

Simultaneous removal of nitrate nitrogen and orthophosphate by electroreduction and electrochemical precipitation.

Electrochemical methods can effectively remove nitrate nitrogen (NO3-N) and orthophosphate phosphorus (PO4-P) from wastewater. This work proposed a process for the simultaneous removal of NO3-N and PO4-P by combining electroreduction with electrochemically-induced calcium phosphate precipitation, and its performance and mechanisms were studied. For the treatment of 100 mg L-1 NO3-N and 5 mg L-1 PO4-P, NO3-N removal of 60-90% (per cathode area: 0.25-0.38 mg h-1 cm-2) and 80-90% (per cathode area: 0.33-0.38 mg h-1 cm-2) could be acquired within 3 h in single-chamber cell (SCC) and dual-chamber cell (DCC), while P removal was 80-98% (per cathode area: 0.10-0.12 mg h-1 cm-2) in SCC after 30 min and 98% (per cathode area: 0.37 mg h-1 cm-2) in DCC within 10 min. The faster P removal in DCC was due to the higher pH and more abundant Ca2+ in the cathode chamber of DCC, which was caused by the cation exchange membrane (CEM). Interestingly, NO3-N reduction enhanced P removal because more OH- can be produced by nitrate reduction than hydrogen evolution for an equal-charge reaction. For 10 mg L-1 PO4-P in SCC, when the initial NO3-N was 0, 20, 100, and 500 mg L-1, the P removal efficiencies after 1 h treatment were < 10%, 45-55%, 86-99%, and above 98% respectively. An increase in Ca2+ concentration also promoted P removal. However, Ca and P inhibited nitrate reduction in SCC at the relatively low initial Ca/P, as CaP on the cathode limited the charge or mass transfer process. The removal efficiency of NO3-N in SCC after 3 h reaction can reduce by about 17%, 40%, and 34% for Co3O4/Ti, Co/Ti, and TiO2/Ti. The degree of inhibition of P on NO3-N removal was related to the content and composition of CaP deposited on the cathode. On the cathode, the lower the deposited Ca and P, and the higher the deposited Ca/P molar ratio, the weaker the inhibition of P on NO3-N removal. Especially, P had little or even no inhibition on nitrate reduction when treated in DCC instead of SCC or under high initial Ca/P. It is speculated that under these conditions, a high local pH and local high concentration Ca2+ layer near the cathode led to a decrease in CaP deposition and an increase in Ca/P molar ratio on the cathode. High initial concentrations of NO3-N might also be beneficial in reducing the inhibition of P on nitrate reduction, as few CaP with high Ca/P molar ratios were deposited on the cathode. The evaluation of the real wastewater treatment was also conducted.