Pollution characteristics and health risk assessment of polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons during heating season in Beijing

Polycyclic aromatic hydrocarbons(PAHs)and their nitrated derivatives(NPAHs)attract continuous attention due to their outstanding carcinogenicity and mutagenicity.In order to investigate the diurnal variations,sources,formation mechanism,and health risk assessment of them in heating season,particulate matter(PM)were collected in Beijing urban area from December 26,2017 to January 17,2018.PAHs and NPAHs in PM were quantitatively analyzed via gas chromatography-mass spectrometry(GC-MS).Average daily concentrations of PAHs and NPAHs were(78±54)ng/m^(3)and(783±684)pg/m^(3),respectively.The concentrations of them were significantly higher at nighttime than at daytime,and NPAHs concentrations were 1-2 orders of magnitude lower than PAHs concentrations.In the heating season,the dominant species of PAHs include benzo[b]fluoranthene,fluoranthene,pyrene,and chrysene,while 9-nitroanthracene,2+3-nitrofluoranthene,and 2-nitropyrene were dominant species for NPAHs.NPAHs were found to have a single peak during heating and to be primarily distributed in the 0.4-0.7μm particle size.Primary emissions such as biomass burning,coal combustion,and traffic emissions were the major sources of PAHs.NPAHs were produced by the primary source of vehicle emissions and the secondary reaction triggered by OH radicals,as well as biomass burning during daytime.According to the health risk assessment,the total carcinogenic risk was higher in adults than in children.While upon oral ingestion,the carcinogenic risk in children was higher than that of adults,but the risk of adults was higher than children through skin contact and respiratory inhalation.

House dust mite allergens and nitrated products: Identification and risk assessment in indoor dust

Air pollutants can potentially lead to nitration of allergic proteins,thus promoting sensitization of these allergens.However,little is currently known about the nitration status of house dust mite(HDM)allergens.We identified the occurrence of nitrated products of two major HDM allergens Der f 1 and Der p 1 in dust samples collected from college dormitories in eastern China and assessed their associated health risk.The results showed that both non-nitrated and nitrated forms of the two allergens were detected in the dust in the range of non-detected(ND)-10.6,1.44-15.4,ND-22.4,ND-7.28μg/g for non-nitrated Der f 1,nitrated Der f 1,non-nitrated Der p 1 and nitrated Der p 1,respectively.The median rates of nitration were determined as 74.0%for Der f 1 and 20.4% for Der p 1 at consideration of one nitration site.Further analysis reveals that the levels of HDM allergens and their nitrated products were found to be generally higher during winter,in dormitories of lower altitude and with female occupants.Furthermore,the calculated risk indexes were at considerably high levels.Our findings suggest that nitrated HDM allergens have already accumulated in the environment at such significant levels and their associated health risk calls for our immediate attention.

Preliminary discussion on the ignition mechanism of exploding foil initiators igniting boron potassium nitrate

Exploding foil initiator(EFI)is a kind of advanced device for initiating explosives,but its function is unstable when it comes to directly igniting pyrotechnics.To solve the problem,this research aims to reveal the ignition mechanism of EFIs directly igniting pyrotechnics.An oscilloscope,a photon Doppler velocimetry,and a plasma spectrum measurement system were employed to obtain information of electric characteristics,impact pressure,and plasma temperature.The results of the electric characteristics and the impact pressure were inconsistent with ignition results.The only thing that the ignition success tests had in common was that their plasma all had a relatively long period of high-temperature duration(HTD).It eventually concludes that the ignition mechanism in this research is the microconvection heat transfer rather than the shock initiation,which differs from that of exploding foil initiators detonating explosives.Furthermore,the methods for evaluating the ignition success of semiconductor bridge initiators are not entirely applicable to the tests mentioned in this paper.The HTD is the critical parameter for judging the ignition success,and it is influenced by two factors:the late time discharge and the energy of the electric explosion.The longer time of the late time discharge and the more energy of the electric explosion,the easier it is to expand the HTD,which improves the probability of the ignition success.

Nitrated and parent PAHs in the surface water of Lake Taihu,China:Occurrence,distribution,source,and human health risk assessment

Nitrated polycyclic aromatic hydrocarbons(NPAHs)have toxic potentials that are higher than those of their corresponding parent polycyclic aromatic hydrocarbons(PAHs)and thus have received increasing attention in recent years.In this study,the occurrence,distribution,source,and human health risk assessment of 15 NPAHs and 16 PAHs were investigated in the surface water from 20 sampling sites of Lake Taihu during the dry,normal,and flood seasons of 2018.The PAH concentrations ranged from 255 to 7298 ng/L and the NPAH concentrations ranged from not-detected(ND)to 212 ng/L.Among the target analytes,2-nitrofluorene(2-n Flu)was the predominant NPAH,with a detection frequency ranging from 85%to 90%and a maximum concentration of 56.2 ng/L.The three-ringed and four-ringed NPAHs and PAHs comprised the majority of the detected compounds.In terms of seasonal variation,the highest levels of the NPAHs and PAHs were in the dry season and flood season,respectively.Diagnostic ratio analysis indicated that the prime source of NPAHs was direct combustion,whereas in the case of PAHs the contribution was predominantly from a mixed pattern including pollution from unburned petroleum and petroleum combustion.The human health risk of NPAHs and PAHs was evaluated using a lifetime carcinogenic risk assessment model.The carcinogenic risk level of the targets ranged from 2.09×10^(-7)to 5.75×10^(-5)and some surface water samples posed a potential health risk.

Diurnal variation of nitrated polycyclic aromatic hydrocarbons in PM_(10) at a roadside site in Xiamen,China

Intensive daytime and nighttime sampling was carried out from 23 Oct to 31 Dec 2008 to investigate the occurrence of nitrated polycyclic aromatic hydrocarbons （NPAHs） in PM1o at a roadside site in Xiamen, China. At the same time, six PMt0 samples were collected from a nearby roadway tunnel for comparison. Six NPAHs, namely 9-nitroanthracene, 2- and 3-nitrofluoranthene, 1- nitropyrene, 7-nitrobenz[a]anthracene, and 6-nitrobenzo[a]pyrene, were identified and quantified using GC/MS in negative ion chemical ionization mode. The average total concentration of six NPAHs （~NPAHs） in the cold season （26 Nov-31 Dec） was 2.3 （daytime） and 9.9 （nighttime） times higher than those in the warm season. Significant statistical difference （p 〈 0.01, 2-tailed） of ∑NPAHs between daytime and nighttime was found during both the warm and cold seasons. NPAHs were significantly positively correlated with their parent PAHs and nitrogen dioxide but negatively correlated with ambient temperature. The ratio of 2 ＋ 3-nitrofluoranthene to 1- nitropyrene exhibited a similar diurnal pattern as ZNPAHs and was generally greater than 5, indicating the importance of secondary atmospheric formation. The diurnal variations of NPAHs were all influenced by the diurnal variations of PAHs, nitrogen dioxide, sunlight, and temperature. The daily inhalable exposure to the six NPAHs in the tunnel was much higher than the roadside values in the warm season but only slightly higher than those in the cold season.

Strategies of selective electroreduction of aqueous nitrate to N_(2) in chloride-free system:A critical review

Electroreduction of nitrate has been gaining wide attention in recent years owing to it's beneficial for converting nitrate into benign N_(2) from the perspective of electrocatalytic denitrification or into value-added ammonia from the perspective of electrocatalytic NH_(3) synthesis.By reason of the undesired formation of ammonia is dominant during electroreduction of nitrate-containing wastewater,chloride has been widely used to improve N_(2) selectivity.Nevertheless,selective electroreduction of nitrate to N2 gas in chloride-containing system poses several drawbacks.In this review,we focus on the key strategies for efficiently enhancing N_(2) selectivity of electroreduction of nitrate in chloride-free system,including optimal selection of elements,combining an active metal catalyst with another metal,manipulating the crystalline morphology and facet orientation,constructing core–shell structure catalysts,etc.Before summarizing the strategies,four possible reaction pathways of electro-reduction of nitrate to N_(2) are discussed.Overall,this review attempts to provide practical strategies for enhancing N2 selectivity without the aid of electrochlorination and highlight directions for future research for designing appropriate electrocatalyst for final electrocatalytic denitrifi-cation.

Insight into the Inhibition of the Poisonous Sulfide Production from Sulfate-Reducing Microbiota in Mariculture Habitat

The production of toxic sulfides is a common environmental problem in mariculture.Therefore,the effective inhibition of sulfidogens is the key to prevent sulfides production.In this study,the possibility and mechanism of nitrate(NO_(3)^(−))inhibiting the activity of the sulfate-reducing microbiota(SRM)from mariculture sediments was investigated.The results showed that 1,3,and 5 mmol L^(−1)NO_(3)^(−)continuously inhibited sulfide production for 1-3 d.As NO_(3)^(−) dosage increased to 7 mmol L^(−1),the duration of inhibition increased to 6 days.Denitrifying product NO_(2)^(−)heavily inhibited the activity of dissimilar sulfate reductase gene(dsrB)by 3 orders,which was the main reason that the sulfate-reducing activity was inhibited.The SRM structure changed significantly with the dosage of NO_(3)^(−),while the abundance of sulfidogens Desulfovibrio species increased due to their capability of detoxifying nitrite through nitrite reductase.Hence,sulfidogens Desulfovibrio species are more adaptable to a high nitrate/nitrite environment,and the traditional control strategies by dosing nitrate/nitrite should be paid more attention to.The findings will serve as helpful guidelines for sulfate-reducing microbiota in the habitat of mariculture to reduce their generation of poisonous sulfide.

Irrigation and nitrogen fertiliser optimisation in protected vegetable fields of northern China:Achieving environmental and agronomic sustainability

Globally,sub-optimal use of nitrogen (N) fertiliser and elevated N irrigation groundwater have led to high leached nitrate (NO_(3)^(–)) losses from protected vegetable field systems.Optimising fertiliser and irrigation management in different soil types is crucial to reduce future N loads from such systems.The present 4-year study examined leached N loads from lysimeter monitoring arrays set up across 18 protected vegetable system sites encompassing the dominant soil types of northern China.The treatments applied at each field site were:1) a high N and high irrigation input treatment (HNHI);2) a low N but high irrigation input treatment (LNHI) and 3) a low N with low irrigation input treatment (LNLI).Results showed that the mean annual leached total nitrogen loads from the HNHI,LNHI and LNLI treatments were 325,294 and 257 kg N ha^(–1) in the fluvo-aquic soil,114,100 and 78 kg N ha^(–1) in the cinnamon soil and 79,68 and 57 kg N ha^(–1) in the black soil,respectively.The N dissolved in irrigation water in the fluvo-aquic soil areas was 8.26-fold higher than in the cinnamon areas.A structural equation model showed that N fertiliser inputs and leaching water amounts explained 14.7 and 81.8%of the variation of leached N loads,respectively.Correspondingly,reducing irrigation water by 21.5%decreased leached N loads by 20.9%,while reducing manure N and chemical N inputs by 22 and 25%decreased leached N loads by only 9.5%. This study highlights that protected vegetable fields dominated by fluvo-aquic soil need management to curtail leached N losses in northern China.

OsNPF3.1,a nitrate,abscisic acid and gibberellin transporter gene,is essential for rice tillering and nitrogen utilization efficiency

Low-affinity nitrate transporter genes have been identified in subfamilies 4-8 of the rice nitrate transporter 1(NRT1)/peptide transporter family(NPF),but the OsNPF3 subfamily responsible for nitrate and phytohormone transport and rice growth and development remains unknown.In this study,we described OsNPF3.1 as an essential nitrate and phytohormone transporter gene for rice tillering and nitrogen utilization efficiency(NUtE).OsNPF3.1 possesses four major haplotypes of its promoter sequence in 517 cultivars,and its expression is positively associated with tiller number.Its expression was higher in the basal part,culm,and leaf blade than in other parts of the plant,and was strongly induced by nitrate,abscisic acid(ABA)and gibberellin 3(GA_3)in the root and shoot of rice.Electrophysiological experiments demonstrated that OsNPF3.1 is a pH-dependent low-affinity nitrate transporter,with rice protoplast uptake assays showing it to be an ABA and GA_3 transporter.OsNPF3.1 overexpression significantly promoted ABA accumulation in the roots and GA accumulation in the basal part of the plant which inhibited axillary bud outgrowth and rice tillering,especially at high nitrate concentrations.The NUtE of OsNPF3.1-overexpressing plants was enhanced under low and medium nitrate concentrations,whereas the NUtE of OsNPF3.1 clustered regularly interspaced short palindromic repeats(CRISPR)plants was increased under high nitrate concentrations.The results indicate that OsNPF3.1 transports nitrate and phytohormones in different rice tissues under different nitrate concentrations.The altered OsNPF3.1 expression improves NUtE in the OsNPF3.1-overexpressing and CRISPR lines at low and high nitrate concentrations,respectively.

Nitrate reduction capacity of the oral microbiota is impaired in periodontitis:potential implications for systemic nitric oxide availability

The reduction of nitrate to nitrite by the oral microbiota has been proposed to be important for oral health and results in nitric oxide formation that can improve cardiometabolic conditions. Studies of bacterial composition in subgingival plaque suggest that nitrate-reducing bacteria are associated with periodontal health, but the impact of periodontitis on nitrate-reducing capacity(NRC)and, therefore, nitric oxide availability has not been evaluated. The current study aimed to evaluate how periodontitis affects the NRC of the oral microbiota. First, 16S rRNA sequencing data from five different countries were analyzed, revealing that nitratereducing bacteria were significantly lower in subgingival plaque of periodontitis patients compared with healthy individuals(P < 0.05 in all five datasets with n = 20–82 samples per dataset). Secondly, subgingival plaque, saliva, and plasma samples were obtained from 42 periodontitis patients before and after periodontal treatment. The oral NRC was determined in vitro by incubating saliva with 8 mmol/L nitrate(a concentration found in saliva after nitrate-rich vegetable intake) and compared with the NRC of 15healthy individuals. Salivary NRC was found to be diminished in periodontal patients before treatment(P < 0.05) but recovered to healthy levels 90 days post-treatment. Additionally, the subgingival levels of nitrate-reducing bacteria increased after treatment and correlated negatively with periodontitis-associated bacteria(P < 0.01). No significant effect of periodontal treatment on the baseline saliva and plasma nitrate and nitrite levels was found, indicating that differences in the NRC may only be revealed after nitrate intake. Our results suggest that an impaired NRC in periodontitis could limit dietary nitrate-derived nitric oxide levels, and the effect on systemic health should be explored in future studies.

A review of salivary composition changes induced by fasting and its impact on health

Human saliva is an indispensable fluid that maintains a healthy oral cavity which otherwise can lead to oral diseases(dental caries and periodontitis).In addition,salivary metabolites and microbiome profile provide early detection of systemic diseases such as cancer and obesity.Salivary diagnostic has gained popularity due to its non-invasive sampling technique.Fasting(abstinence from food or drink or both)research for weight loss and improve health is common,but studies using fasting saliva are scarce.Some metabolites in fasting saliva have been reported with interesting results,which can be enhanced by considering different confounding factors.For example,fasting saliva contains higher salivary nitrite,which is related to nitric oxide(NO).NO is a vasodilator supporting the healthy function of endothelial cells and its deficiency is connected to many diseases.The timely supply of NO through exogenous and endogenous means is highlighted and the potential advantage of fasting salivary composition changes in relation to COVID-19 infection is speculated.This review aims to provide a general discussion on the salivary composition,properties,and functions of the whole saliva,including the health benefits of fasting.

Identifying the Hydrochemical Characteristics,Genetic Mechanisms and Potential Human Health Risks of Fluoride and Nitrate Enriched Groundwater in the Tongzhou District,Beijing,North China

Fluoride and nitrate enriched groundwater are potential threats to the safety of the groundwater supply that may cause significant effects on human health and public safety,especially in aggregated population areas and economic hubs.This study focuses on the high F^(−)and NO_(3)^(−)concentration groundwater in Tongzhou District,Beijing,North China.A total of 36 groundwater samples were collected to analyze the hydrochemical characteristics,elucidate genetic mechanisms and evaluate the potential human health risks.The results of the analysis indicate:Firstly,most of the groundwater samples are characterized by Mg-HCO_(3) and Na-HCO_(3) with the pH ranging from 7.19 to 8.28 and TDS with a large variation across the range 471-2337 mg/L.The NO_(3)^(−)concentration in 38.89%groundwater samples and the F^(−)concentration in 66.67%groundwater samples exceed the permissible limited value.Secondly,F^(−)in groundwater originates predominantly from water-rock interactions and the fluorite dissolution,which is also regulated by cation exchange,competitive adsorption of HCO_(3)−and an alkaline environment.Thirdly,the effect of sewage disposal and agricultural activities have a significant effect on high NO3-concentration,while the high F^(−)concentration is less influenced by anthropogenic activity.The alkaline environment favors nitrification,thus being conducive to the production of NO_(3)^(−).Finally,the health risk assessment is evaluated for different population groups.The results indicate that high NO_(3)^(−)and F^(−)concentration in groundwater would have the largest threat to children’s health.The findings of this study could contribute to the provision of a scientific basis for groundwater supply policy formulation relating to public health in Tongzhou District.

Progress in electrocatalytic nitrate reduction for green energy:Catalyst engineering,mechanisms,and techno-economic feasibility

Ammonia(NH_(3))is an irreplaceable chemical that has been widely demanded to keep the sustainable development of modern society.However,its industrial production consumes a huge amount of energy and releases extraordinary greenhouse gases(GHGs),leading to various environmental issues.Achieving the green production of ammonia is a great challenge,which has been extensively pursued in the last decade.In this review,the most promising strategy,electrochemical nitrate reduction reaction(e-NO_(3)RR),is comprehensively investigated to give a complete understanding of its development and mechanism and provide guidance for future directions.However,owing to the complex reactions and limited selectivity,a comprehensive understanding of the mechanisms is crucial to further development and commercialization.Moreover,NO_(3)^(-)RR is a promising strategy for simultaneous water treatment and NH_(3)production.A detailed overview of the recent progress in NO_(3)^(-)RR for NH_(3)production with nontransition and transition metal based electrocatalysts is summarized.In addition,critical advanced techniques,future challenges,and prospects are discussed to guide future research on transition metal-based catalysts for commercial NH_(3)synthesis by NO_(3)^(-)reduction.

Comprehensive understanding of the thriving electrocatalytic nitrate/nitrite reduction to ammonia under ambient conditions

Ammonia(NH_(3))is a multifunctional compound that is an important feedstock for the agricultural and pharmaceutical industries and attractive energy storage medium.At present,NH_(3)synthesis is highly dependent on the conventional Haber–Bosch process that operates under harsh conditions,which consumes large quantities of fossil fuels and releases a large amount of carbon dioxide.As an alternative,electrosynthesis is a prospective method for producing NH_(3)under normal temperature and pressure conditions.Although electrocatalytic nitrogen reduction to ammonia has attracted considerable attentions,the low solubility of N_(2)and high N≡N cracking energy render the achievements of high NH_(3) yield rate and Faradaic efficiency difficult.Nitrate and nitrite(NO_(x)^(-))are common N-containing pollutants.Due to their high solubilities and low dissociation energy of N=O,NO_(x)^(-)−are ideal raw materials for NH_(3) production.Therefore,electrocatalytic NO_(x)^(-)−reduction to NH_(3)(eNO_(x)RR)is a prospective strategy to simultaneously realise environmental protection and NH_(3) synthesis.This review offers a comprehensive understanding of the thriving eNO_(x)RR under ambient conditions.At first,the popular theory and mechanism of eNO_(x)RR and a summary of the measurement system and evaluation criteria are introduced.Thereafter,various strategies for developing NO_(x)−reduction catalysts are systematically presented and discussed.Finally,the challenges and possible prospects of electrocatalytic NO_(x)^(-1) reduction are outlined to facilitate energy-saving and environmentally friendly large-scale synthesis of NH_(3) in the future.

Oxygen‑Coordinated Single Mn Sites for Efficient Electrocatalytic Nitrate Reduction to Ammonia

Electrocatalytic nitrate reduction reaction has attracted increasing attention due to its goal of low carbon emission and environmental protection.Here,we report an efficient NitRR catalyst composed of single Mn sites with atomically dispersed oxygen(O)coordination on bacterial cellulose-converted graphitic carbon(Mn-O-C).Evidence of the atomically dispersed Mn-(O-C_(2))_(4)moieties embedding in the exposed basal plane of carbon surface is confirmed by X-ray absorption spectroscopy.As a result,the as-synthesized Mn-O-C catalyst exhibits superior NitRR activity with an NH_(3)yield rate(RNH_(3))of 1476.9±62.6μg h^(−1)cm^(−2)at−0.7 V(vs.reversible hydrogen electrode,RHE)and a faradaic efficiency(FE)of 89.0±3.8%at−0.5 V(vs.RHE)under ambient conditions.Further,when evaluated with a practical flow cell,Mn-O-C shows a high RNH_(3)of 3706.7±552.0μg h^(−1)cm^(−2)at a current density of 100 mA cm−2,2.5 times of that in the H cell.The in situ FT-IR and Raman spectroscopic studies combined with theoretical calculations indicate that the Mn-(O-C_(2))_(4)sites not only effectively inhibit the competitive hydrogen evolution reaction,but also greatly promote the adsorption and activation of nitrate(NO_(3)^(−)),thus boosting both the FE and selectivity of NH_(3)over Mn-(O-C_(2))_(4)sites.

Electrocatalysts with atomic-level site for nitrate reduction to ammonia

Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such as the traditional Haber-Bosch process,have drawbacks including high energy consumption and significant carbon dioxide emissions.In recent years,the electrocatalytic nitrate reduction reaction(NO_(3)RR)powered by intermittent renewable energy sources has gradually become a multidisciplinary research hotspot,as it allows for the efficient synthesis of NH_(3)under mild conditions.In this review,we focus on the research of electrocatalysts with atomic-level site,which have attracted attention due to their extremely high atomic utilization efficiency and unique structural characteristics in the field of NO_(3)RR.Firstly,we introduce the mechanism of nitrate reduction for ammonia synthesis and discuss the in-situ characterization techniques related to the mechanism study.Secondly,we review the progress of the electrocatalysts with atomic-level site for nitrate reduction and explore the structure-activity relationship to guide the rational design of efficient catalysts.Lastly,the conclusions of this review and the challenges and prospective of this promising field are presented.

Co_(3)O_(4)as an efficient passive NO_(x) adsorber for emission control during cold-start of diesel engines

The Co_(3)O_(4)nanoparticles,dominated by a catalytically active(110)lattice plane,were synthesized as a low-temperature NO_(x) adsorbent to control the cold start emissions from vehicles.These nanoparticles boast a substantial quantity of active chemisorbed oxygen and lattice oxygen,which exhibited a NO_(x) uptake capacity commensurate with Pd/SSZ-13 at 100℃.The primary NO_(x) release temperature falls within a temperature range of 200-350℃,making it perfectly suitable for diesel engines.The characterization results demonstrate that chemisorbed oxygen facilitate nitro/nitrites intermediates formation,contributing to the NO_(x) storage at 100℃,while the nitrites begin to decompose within the 150-200℃range.Fortunately,lattice oxygen likely becomes involved in the activation of nitrites into more stable nitrate within this particular temperature range.The concurrent processes of nitrites decomposition and its conversion to nitrates results in a minimal NO_(x) release between the temperatures of 150-200℃.The nitrate formed via lattice oxygen mainly induces the NO_(x) to be released as NO_(2) within a temperature range of 200-350℃,which is advantageous in enhancing the NO_(x) activity of downstream NH_(3)-SCR catalysts,by boosting the fast SCR reaction pathway.Thanks to its low cost,considerable NO_(x) absorption capacity,and optimal release temperature,Co_(3)O_(4)demonstrates potential as an effective material for passive NO_(x) adsorber applications.

Potential-dependent insights into the origin of high ammonia yield rate on copper surface via nitrate reduction:A computational and experimental study

Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum solvation model to predict the reaction energetics of NO3RR on pure copper surface in alkaline media.The potential-dependent mechanism on the most prevailing Cu(111)and the minor(100)and(110)facets were established,in consideration of NO_(2)_(−),NO,NH_(3),NH_(2)OH,N_(2),and N_(2)O as the main products.The computational results show that the major Cu(111)is the ideal surface to produce ammonia with the highest onset potential at 0.06 V(until−0.37 V)and the highest optimal potential at−0.31 V for ammonia production without kinetic obstacles in activation energies at critical steps.For other minor facets,the secondary Cu(100)shows activity to ammonia from−0.03 to−0.54 V with the ideal potential at−0.50 V,which requires larger overpotential to overcome kinetic activation energy barriers.The least Cu(110)possesses the longest potential range for ammonia yield from−0.27 to−1.12 V due to the higher adsorption coverage of nitrate,but also with higher tendency to generate di-nitrogen species.Experimental evaluations on commercial Cu/C electrocatalyst validated the accuracy of our proposed mechanism.The most influential(111)surface with highest percentage in electrocatalyst determined the trend of ammonia production.In specific,the onset potential of ammonia production at 0.1 V and emergence of yield rate peak at−0.3 V in experiments precisely located in the predicted potentials on Cu(111).Four critical factors for the high ammonia yield and selectivity on Cu surface via NO3RR are summarized,including high NO3RR activity towards ammonia on the dominant Cu(111)facet,more possibilities to produce ammonia along different pathways on each facet,excellent ability for HER inhibition and suitable surface size to suppress di-nitrogen species formation at high nitrate coverage.Overall,our work provides comprehensive potential-dependent insights into the reaction details of NO3RR to ammonia,which can serve as references for the future development of NO3RR electrocatalysts,achieving higher activity and selectivity by maximizing these characteristics of copper-based materials.

Enabling an Inorganic-Rich Interface via Cationic Surfactant for High-Performance Lithium Metal Batteries

An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.

Hydrogeochemical and isotopic assessment of the origin of NO_(3)^(−)and N-NH_(3)contents in the aquifer located in a closed lacustrine volcano-sedimentary basin in the metropolitan area of Mexico City

To explain the presence and spatial distribution of NO_(3)^(−)and N-NH_(3)in the Aquifer of the Metropolitan Area of Mexico City(AMAMC),a hydrogeochemical and isotopic analysis using^(13)C DIC(as well as the stable isotopes^(18)O and^(2)H)in groundwater was conducted.This aquifer is located in an old closed lacustrine volcano-sedimentary basin;some wells hosted in the semi-confined zone contain high N-NH_(3)concentrations,while others present NO_(3)^(−)contents in the recharge zones(hosted in an oxidizing environment).In this study,a change in the isotopic signature(primarily in^(18)O and^(2)H)was observed from the recharge zones to the basin center in some of the wells with high NO_(3)^(−)concentrations,this behavior can be attributed to evaporation during the incorporation of recently infiltrated water.In addition,the results for^(13)C(along with ^(2) H)in wells with the highest N-NH_(3)concentrations exhibited an atypically broad range of values.Results indicated the occurrence of hydrogeochemical and/or biochemical processes in the aquifer(in an oxidizing or reducing environment),such as organic degradation,bacterial decomposition(primarily in the ancient Lake Texcoco and which acts as a natural sink for carbon,nitrogen,sulfur,and phosphorus),besides rock weathering and dissolution,which may be responsible for a very marked isotopic modification of the^(13)C(and,to a lesser extent,2 H).Methanotrophic bacterial activity and methanogenic activity may be related to N-NH_(3)removal processes by oxidation and residual water incorporation respectively,whereas the increase in the NO_(3)^(−)content in some wells is due to the recent contribution of poor-quality water due to contamination.