Advancements in Catalysts for Electrochemical Nitrate Reduction: A Sustainable Approach for Mitigating Nitrate Pollution: A Review

Nitrate pollution is of great importance in both the environmental and health contexts, necessitating the development of efficient mitigation strategies. This review provides a comprehensive analysis of the many catalysts employed in the electrochemical reduction of nitrate to ammonia, and presents a viable environmentally friendly approach to address the issue of nitrate pollution. Hence, the electrochemical transformation of nitrate to ammonia serves the dual purpose of addressing nitrate pollution in water bodies, and is a useful agricultural resource. This review examines a range of catalyst materials such as noble and non-noble metals, metal oxides, carbon-based materials, nitrogen-doped carbon species, metal complexes, and semiconductor photocatalysts. It evaluates catalytic efficiency, selectivity, stability, and overall process optimization. The performance of catalysts is influenced by various factors, including reaction conditions, catalyst structure, loading techniques, and electrode interfaces. Comparative analysis was performed to evaluate the catalytic activity, selectivity, Faradaic efficiency, current density, stability, and durability of the catalysts. This assessment offers significant perspectives on the structural, compositional, and electrochemical characteristics that affect the efficacy of these catalysts, thus informing future investigations and advancements in this domain. In addition to mitigating nitrate pollution, the electrochemical reduction of nitrate to ammonia is in line with sustainable agricultural methods, resource conservation, and the utilization of renewable energy resources. This study explores the factors that affect the catalytic efficiency, provides new opportunities to address nitrate pollution, and promotes the development of sustainable environmental solutions.

Sources and health risks of nitrate pollution in surface water in the Weihe River watershed,China

Owing to the significant reductions in streamflow and an increase in human activities in recent years,the quality of surface water in Weihe River continues to pose environmental health concerns.We utilized hydrochemistry and nitrogen and oxygen isotopes to elucidate the status and identify sources of nitrate pollution in the south and north banks for three seasons(flood,dry,and mean-flow periods)in the Weihe River watershed.A Bayesian isotope mixing model was applied to estimate the contributions of four potential NO_(3)-sources to river pollution(manure and sewage,soil nitrogen,inorganic fertilizer,and nitrate in precipitation).The U.S.Environmental Protection Agency(USEPA)evaluation model was implemented to evaluate the health risks associated with nitrate pollution in the surface water.Nitrate pollution was most severe during the dry period because the river flow was small.Due to the influence of the topography and land use type of the Weihe River,the pollution in the main stream was greater than that of the tributaries,and the pollution of the south bank was greater than that of the north bank.During the flood and mean-flow periods,δ^(15)N and δ^(18)O were mainly distributed in the NH_(4)^(+) of the fertilizer and soil nitrogen.During the dry period,δ^(15)N and δ^(18)O were mainly distributed in domestic sewage and manure regions.According to the Stable Isotope Analysis in R(SIAR)model,manure and sewage were the major nitrate sources during the dry period(73%).However,a decrease in the contribution from domestic sewage and manure was observed during the flood period(45%)compared to the dry period,but with a significantly increased contribution from soil nitrogen(23%)and inorganic fertilizer(21%).The health risk value in the dry period was higher than that in the wet and mean flow periods,and children are more susceptible to nitrate pollution than adults.Therefore,reducing the discharge of domestic sewage and manure and improving the utilization rate of nitrogen fertilizers may be effective measures to improve water quality in the watershed.

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.

Spatial and statistical assessment of nitrate contamination in groundwater:Case of Sais Basin, Morocco

The objective of this study is to evaluate the nitrate contamination in the plioquaternary aquifer of Sais Basin based on a statistical approach. A total of 98 samples were collected in the cultivated area during the spring and autumn period of 2018. The results show that 55% and 57% of the samples in spring and autumn respectively exceed the threshold fixed by WHO(50 mg/L). However, nitrate concentrations do not show seasonal and spatial variation(p>0.05). The results of the correlation matrix, principal component analysis(PCA), and hierarchical cluster analysis(HCA) suggest that nitrate pollution is related to anthropogenic source. Moreover, multiple linear regression results show that NO3 is more positively explained in the spring period by Ca and SO4 and negatively explained by pH and HCO3. Regarding the autumn period, nitrate pollution is positively explained by Ca and negatively by pH. This study proposes a useful statistical platform for assessing nitrate pollution in groundwater.

Influences of nitrification inhibitor 3,4-dimethyl pyrazole phosphate on nitrogen and soil salt-ion leaching

An undisturbed heavy clay soil column experiment was conducted to examine the influence of the new nitrification inhibitor, 3,4- dimethylpyrazole phosphate （DMPP）, on nitrogen and soil salt-ion leaching. Regular urea was selected as the nitrogen source in the soil. The results showed that the cumulative leaching losses of soil nitrate-N under the treatment of urea with DMPP were from 57.5% to 63.3% lower than those of the treatment of urea without DMPP. The use of nitrification inhibitors as nitrate leaching retardants may be a proposal in regulations to prevent groundwater contaminant. However, there were no great difference between urea and urea with DMPP treatments on ammonium-N leaching. Moreover, the soil salt-ion leaching losses of Ca^2＋, Mg^2＋, K^＋, and Na^＋ were reduced from 26.6% to 28.8%, 21.3% to 27.8%, 33.3% to 35.5%, and 21.7% to 32.1%, respectively. So, the leaching losses of soil salt-ion were declined for nitrification inhibitor DMPP addition, being beneficial to shallow groundwater protection and growth of crop. These results indicated the possibility of ammonium or ammonium producing compounds using nitrification inhibitor DMPP to control the nitrate and nutrient cation leaching losses, minimizing the risk of nitrate pollution in shallow groundwater.

Effective and selective electrocatalytic nitrate reduction to ammonia on urchin-like and defect-enriched titanium oxide microparticles

This work reported a facile approach to surface oxygen vacancy(O_(v))-enriched urchin-like TiO_(2) microparticles(U-TiO_(2)),which were highly effective and durable in catalyzing selective nitrate reduction to ammonia(NOgRR),Specifically,the U-TiO_(2)delivered a mass activity of 1.15 min^(-1)mg^(-1)calyst.a low yield of toxic NO_(2)^(-)-N intermediate(≤0.4mg/L)and an exceptional high NH_(3)^(-)-N selectivity of 98.1%in treating 22.5 mg/L of NO_(3)^(-)-N under a potential of-0.60V vs.RHE,outperforming most of the reported oxidebased catalysts.When comparing the performance of U-TiO_(2)with that of the solid amorphous TiO_(2) counterpart(A-TiO_(2))that had close particle size but more O_(v) on surfaces,we identified that the O_(v) was the reactive sites,but rather than its content,the NO_(3)RR kinetics were primarily limited by the electron and mass transfer at U-TiO_(2)/water interfaces.Accordingly,the superior performance of U-TiO_(2)to A-TiO_(2)could be ascribed to the hierarchical urchin-like structure in U-TiO_(2).The in-situ DEMS test revealed that the NO_(3)RR on U-TiO_(2)followed a pathway of ^(*)NO_(3)^(-)→^(*)NO_(2)^(-)→^(*)NO→^(*)N→^(*)NH^(-)→^(*)NH_(2)→^(*)NH_(3).We also demonstrated that the U-TiO_(2) could keep its robust performance under a wide NO_(3)^(-)-N concentration range and in the presence of some co-existing ions(such as Ca^(2+),Cl^(-),Mg^(2+)).However,the presence of humic acid and CO_(3)^(2-) in water slowed down the NO_(3)RR on U-TiO_(2).This work provides a more fundamental insight into the O_(v)-driven NO_(3)RR process on TiO_(2),which should benefit for the development of eficient TiO_(2)-based catalvsts.

Sanitary Surveys and Hydrochemistry of Groundwater in Two Urban Towns (Ado-Ekiti and Ijero-Ekiti), Southwestern Nigeria

Groundwater contamination in urban cities is imminent in the phase of increased anthropogenic activities apart from the contribution of geogenic contaminants. This study examined the sanitary surveys and hydrochemistry of groundwater in Ado-Ekiti and Ijero-Ekiti to establish the contaminants’ sources, decipher the effects of urbanization on population and explain any relationship between the surveys and the groundwater chemistry. Sanitary surveys of 30 randomly selected wells each from Ado-Ekiti and Ijero-Ekiti were executed by administering and processing appropriately designed questionnaires that addressed salient problems of hygiene and sanitation. The results of the surveys were grouped into very high risk, high risk, intermediate risk, and low risk classes. Subsequently, at each location, in situ parameters (temperature (°C), pH and EC (μS/cm)) were measured using a portable Multi-parameter TestrTM 35 Series S/N: 1382654. At each well, water samples were collected into clean polyethylene bottles in triplicates for cation, anions and e-coli evaluations, respectively. Water samples for cations were acidified by adding two drops of concentrated nitric acid. All samples were kept in a refrigerator at a low temperature of about 4°C before being taken to the Federal University of Technology, Akure, for analyses. Ion chromatography was employed for the anions analysis while the cations were determined using an Atomic Absorption Spectrophotometer Buck 210 model. Membrane filter technique was employed for the e-coli estimation. From the results of the hydrochemistry, the Nitrate Pollution Index (NPI) and Modified Nitrate Pollution Index (MNPI) were estimated and classified into;clean unpolluted, light pollution, moderate pollution, significant pollution, very significant pollution waters. Sanitary surveys in the two cities showed that in the very low risk, intermediate and high-risk categories, Ado-Ekiti had 33.33%, 56.67% and 10% representations, while Ijero-Ekiti had 50%, 23.33% and 26.67% representations, respectively. This observation showed that Ado-Ekiti with higher population and humans’ activities compared to Ijero-Ekiti was less susceptible to pollution. Urbanization has no direct effects on sanitary surveys. The pH of wells’ water in Ado-Ekiti ranged from 4.8 - 8.2, EC (μS/cm) from 101 - 1008, while at Ijero-Ekiti, the pH and EC (μS/cm) varied from 2.1 - 13.8 and 80 - 1008 respectively. Ado-Ekiti wells’ water was more acidic than that of Ijero-Ekiti. Chemical concentrations (mg/L) of Ca2+, Mg2+, Na+, K+, , and Clˉ of the wells’ water in both cities were within WHO-approved standards for drinking water. However, with average concentrations of 142.17 (mg/L) and 252.71 (mg/L) at Ado-Ekiti and Ijero-Ekiti, respectively, exceeded the standard in many locations. Susceptibility to pollution classification employing TDS, NPI and MNPI showed that Ijero-Ekiti was more susceptible to pollution compared to Ado-Ekiti. This assertion was supported by statistical analysis employing correlation, cluster analysis, and principal component analysis. This study showed that urbanization had no direct effects on sanitary surveys and groundwater quality. Pollution of wells’ water in the two cities was, mainly from anthropogenic activities. However, Ijero-Ekiti, with significant anthropogenic activities, had its wells’ water more susceptible to pollution. Sanitary surveys are a complementary method to water quality monitoring.

Groundwater Geochemistry and Saltwater Intrusion in the Dakar Coastal Area, Senegal

Groundwater levels and water samples were collected from 20 drinking water pumping and piezometer wells in the urban area of Dakar coastal region in the year 2019. The pH-value, electrical conductivity, as well as calcium, magnesium, sodium, potassium, chloride, sulfate, bicarbonate, and nitrate concentrations were measured to assess the hydrochemical quality of the infrabasaltic aquifer in the area. The present work carried out a hydrochemical analysis to interpret the groundwater chemistry of the aquifer. The results of this chemical analysis indicate that Na+ > Mg2+ > Ca2+ > K+ was the most dominant cation sequence in the groundwater, while Cl- > HCO3- > SO42- > NO3- was the most dominant one for anions. The chemical analysis of our samples showed, that the Cl-Ca-Mg facies was dominant in the aquifer, while Cl-Na-K and HCO3-Na-K facies represent 20% and 10% of the groundwater sampled, respectively. A comparison of the measured groundwater quality in relation to WHO drinking water quality standards revealed that 80% of the water samples are suitable for drinking purposes. Ca enrichment, Simpson ratio, ratio of sodium chloride, and calculating Base Exchange (BEX) indices for the samples revealed that the groundwater is mainly affected by three factors: seawater intrusion due to aquifer overexploitation on one hand, and freshening processes and nitrate pollution, on the other, mainly caused by the groundwater flow from the unconfined aquifer.

Seawater Intrusion and Nitrate Contamination in the Fum Al Wad Coastal Plain,South Morocco

The coastal plain aquifer down gradient of Wad Essaquia Elhamra(WEE),is the main source of groundwater in the arid region of Laayoune Essaquia El Hamra located in south of Morocco.The over-exploitation of this aquifer over the last decade for water supply,agriculture and industry led to deterioration of groundwater quality,including seawater intrusion.The objective of this study is to investigate the spatial variation of groundwater quality,and to assess the influence of sea water intrusion on the groundwater quality using hydro-chemical tools.Several measurement campaigns of physico-chemical parameters of the groundwater were performed,which shows a very high mineralization ratios versus chloride,confirming the double influence of mixing mechanisms of fresh and saline waters and the water-rock interactions.Computed seawater fraction for sampled water shows that the average mixing rate of seawater intrusion reached 10.5%,confirming the marine intrusion in the aquifer.The highest values were registered in coastal wells.In the upstream around Laayoune and the spreading area,nitrate concentrations exceed 50 mg/L which is the threshold set by the World Health Organization,revealing a high level of contamination by domestic sewage.The combination of ionic ratios and seawater fraction is a useful tool to assess marine intrusion.This study reveals that the phenomenon of marine intrusion is not the only process that dominates hydrochemistry of ground water.The high groundwater mineralization is also due to rockwater interaction associated with reverse ion exchange with clay material and anthropogenic pollutants.

Peroxyacetyl nitrate measurements by thermal dissociation-chemical ionization mass spectrometry in an urban environment： performance and characterizations

Peroxyacetyl nitrate （PAN） is an important indicator of photochemical smog and has adverse effects on human health and vegetation growth. A rapid and h!ghly selective technique of thermal dissociation chemical ionization mass spectrometry （TD-CIMS） was recently developed to measure the abundance of PAN in real time; however, it may be subject to artifact in the presence of nitric oxide （NO）. In this study, we tested the interference of the PAN signal induced by NO, evaluated the performance of TD- CIMS in an urban environment, and investigated the concentration and formation of PAN in urban Hong Kong. NO caused a significant underestimation of the PAN signal in TD-CIMS, with the underestimation increasing sharply with NO concentration and decreasing slightly with PAN abundance. A formula was derived to link the loss of PAN signal with the concentrations of NO and PAN, which can be used for data correction in PAN measurements. The corrected PAN data from TD- CIMS were consistent with those from the commonly used gas chromatography with electron capture detection, which confirms the utility of TD-CIMS in an urban environment in which NO is abundant. In autumn of 2010, the hourly average PAN mixing ratio varied from 0.06 ppbv to 5.17 ppbv, indicating the occurrence of photochemical pollution in urban Hong Kong. The tbrmation efficiency of PAN during pollution episodes was as high as 3.9 to 5.9 ppbv per 100 ppbv ozone. The efficiency showed a near-linear increase with NO, concentration, suggesting a control policy of NO,. reduction for PAN pollution.

Wintertime N2O5 uptake coefficients over the North China Plain

The heterogeneous hydrolysis of dinitrogen pentoxide(N2O5)plays an important role in regulating NOx.The N2O5 uptake coefficient,γ(N2O5),was determined using an iterative box model that was constrained to observational data obtained in suburban Beijing from February to March 2016.The box model determined 2289 individualγ(N2O5)values that varied from<0.001 to 0.02 with an average value of 0.0046±0.0039(and a median value of 0.0032).We found the derived winterγ(N2O5)values in Beijing were relatively low as compared to values reported in previous field studies conducted during winter in Hong Kong(average value of 0.014)and the eastern U.S.coast(median value of 0.0143).In our study,field evidence of the suppression ofγ(N2O5)values due to pNO3-content,organics and the enhancement by aerosol liquid water content(ALWC)is in line with previous laboratory study results.Low ALWC,high pNO3-content,and particle morphology(inorganic core with an organic shell)accounted for the lowγ(N2O5)values in the North China Plain(NCP)during wintertime.The field-derivedγ(N2O5)values are well reproduced by a revised parameterization method,which includes the aerosol size distribution,ALWC,nitrate and organic coating,suggesting the feasibility of comprehensive parameterization in the NCP during wintertime.