Nitrate Research Articles

Adsorptive removal of a nitrate ion from the aqueous solution of sodium nitrate by application of double fixed-bed column

This study focuses on the removal of nitrate ions from aqueous solutions using rice husk activated carbon (RHAC). The RHAC was subjected to characterization via Fourier transform infrared (FTIR), scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), and X-ray florescence (XRF) to ascertain its functional groups, surface morphology, and oxide/elemental composition, respectively. Batch experiments were conducted to assess the impact of nitrate concentration, bed height, and number of packing layers on removal efficiency. FTIR spectra revealed favorable sorption-related functional groups within RHAC, while SEM analysis indicated the presence of effective sorption sites on its surface. EDS analysis of the rice husk adsorbent before adsorption (RHBS) demonstrated a significant composition of Si (42.20%), O (35.30%), and Ca (12.33%). The batch study unveiled a concentration-dependent decrease in nitrate removal efficiency, alongside the enhanced performance with increased bed height and number of packing layers. Kinetic data fitting favored the Yoon–Nelson and Adams–Bohart models. Overall, RHAC exhibited efficient nitrate ion removal, with column performance notably improved by utilizing multiple packing layers. These results will enhance our understanding of the mechanisms involved in removing nitrate ions and highlight the potential effectiveness of RHAC, especially when utilized with multiple packing arrangements in column setups.

General synthesis of high-entropy single-atom nanocages for electrosynthesis of ammonia from nitrate

Given the growing emphasis on energy efficiency, environmental sustainability, and agricultural demand, there’s a pressing need for decentralized and scalable ammonia production. Converting nitrate ions electrochemically, which are commonly found in industrial wastewater and polluted groundwater, into ammonia offers a viable approach for both wastewater treatment and ammonia production yet limited by low producibility and scalability. Here we report a versatile and scalable solution-phase synthesis of high-entropy single-atom nanocages (HESA NCs) in which Fe and other five metals-Co, Cu, Zn, Cd, and In-are isolated via cyano-bridges and coordinated with C and N, respectively. Incorporating and isolating the five metals into the matrix of Fe resulted in Fe-C5 active sites with a minimized symmetry of lattice as well as facilitated water dissociation and thus hydrogenation process. As a result, the Fe-HESA NCs exhibited a high selectivity toward NH3 from the electrocatalytic reduction of nitrate with a Faradaic efficiency of 93.4% while maintaining a high yield rate of 81.4 mg h−1 mg−1.

Reduction with zinc — Impact on the determination of nitrite and nitrate ions using microfluidic paper-based analytical devices

We used a microfluidic paper-based analytical device (μPAD) to investigate the influence that zinc reduction exerts on the determination of nitrite and nitrate ions in natural water samples. The μPAD consists of layered channels for the reduction of nitrate to nitrite with zinc powder and the subsequent detection of nitrite with Griess reagent. The amount of zinc, number of layers, and reaction time for the reduction were optimized to obtain an intense signal for nitrate. Initially, the sensitivity to nitrate corresponded to 55% that of nitrite, which implied an incomplete reduction. We found, however, that zinc decreased the sensitivity to nitrite in both the μPAD and spectrophotometry. The sensitivity to nitrite was decreased by 48% in spectrophotometry and 68% in the μPAD following the reaction with zinc. One of the reasons for the decreased sensitivity is attributed to the production of ammonia, as we elucidated that both nitrite and nitrate produced ammonia via the reaction with zinc. The results suggest that the total concentration of nitrite and nitrate must be corrected by constructing a calibration curve for nitrite with zinc, in addition to developing curves for nitrate with zinc and for nitrite without zinc. Using these calibration curves, the absorbance at different concentration ratios of nitrite and nitrate ions could be reproduced via calculation using the calibration curves with zinc for nitrite and nitrate. Eventually, the developed μPAD was applied to the determination of nitrite and nitrate ions in natural water samples, and the results were compared with those using a conventional spectrophotometric method. The results of the μPAD are in good agreement with those of conventional spectrophotometry, which suggests that the μPAD is reliable for the measurement of nitrite and nitrate ions in natural water samples.

(Invited) Understanding Potential Losses and pH Distribution in Electrochemical Nitrate Reduction Reaction to Ammonia

Electrochemical nitrate reduction reaction (NO3 -RR) to ammonia is a promising route to eliminate one of the major pollutants in surface and groundwater. When powered by renewable electricity, electrolysis provides a sustainable method to generate ammonia from nitrate ions, facilitating the transition from a linear to a circular economy. Optimizing the physical and chemical properties of electrolysis cells is crucial to make this process economically viable for widespread implementation. Here, we explore how the choice of current density, conductivity, pH, inter-electrode distance, membrane, catalyst, and buffer solution affect nitrate removal performance and efficiency. We develop a modeling framework to investigate the cell characteristics and fluid dynamics during electrochemical NO3-RR using both laminar and bubbly flows. To obtain more precise results, we employed the bubbly flow model (i.e., Multi-phase Fluid) to take into account how gas production near the electrode surface affects liquid velocity, pH distribution, and, ultimately, potential losses. We exploit mass transfer theory to include the current density effect on migration and diffusion. In the absence of a buffer solution, the Nernstian loss became a significant portion of the polarization loss, which increased with current density. We identified the positive effect of the membrane on energy efficiency to be more significant at smaller inter-electrode distances. This study provides insights into the origin of potential losses and pH distribution, enabling electrochemical cell optimization for renewable fuel synthesis. Next, we will discuss our recent work on designing single atom alloys (SAAs) for selective conversion of low concentration nitrate ions in natural wastewater streams from Dairy farm into ammonia. We benchmarked the catalyst's selectivity, activity, and stability following standard protocols established in the field of nitrogen fixation, including control experiments by using an electrolyte that does not contain nitrate ions and performing experiments under the same operating conditions using nitrogen isotopes (i.e., 14NO3 -, 15NO3 -).

Synthesis and characterization of a designed poly(ionic liquid‐modified graphene oxide) nanocomposite: Evaluation of nitrate removal from water and antimicrobial properties

AbstractAddressing the global challenge of water contamination, this study introduces a novel nanocomposite adsorbent—poly(ionic liquid‐modified graphene oxide) (PIL‐MGO)—designed to remove nitrates efficiently from water and combat microbial threats. Leveraging modified graphene oxide and vinyl imidazolium‐based ionic liquid, this research synthesizes an adsorbent via a facile and cost‐effective approach. The performance of PIL‐MGO was rigorously analyzed through a series of characterizations, including Frontier transform infrared spectroscopy, field emitting scanning electron microscopy, energy dispersive X‐ray spectroscopy, and thermogravimetric analysis, revealing its robust structural composition and thermal stability. In our experimental exploration, the adsorbent showcased a remarkable nitrate removal efficiency of up to 97.53%, under optimal conditions of an initial pH of 5, room temperature, initial nitrate concentration of 30 mg/L, a contact time of 30 min, and an adsorbent dosage of 40 mg, with a significant selectivity for nitrate ions over competing anions. Moreover, regeneration of the adsorbent up to 7 cycles indicated only a marginal decline in adsorption efficiency. Furthermore, PIL‐MGO demonstrated considerable antimicrobial properties against bacteria and fungi, indicating its dual utility in water purification and microbial inhibition. These findings suggest that the synthesized nanocomposite holds great promise for addressing environmental and health‐related challenges posed by water pollutants. This study not only underscores the capabilities of PIL‐MGO but also paves the way for further advancements in adsorbent technologies.Highlights A novel nanocomposite was synthesized based on vinyl imidazolium ionic liquid and modified graphene oxide. This newly developed nanocomposite was evaluated as an adsorbent for the removal of nitrate ions from water, demonstrating high removal efficiency. The adsorbent exhibited notable selectivity for nitrate ions, effectively distinguishing them from competing anions such as chloride, bicarbonate, sulfate, and phosphate. The adsorption kinetics of the nanocomposite were best described by the pseudo‐second‐order kinetic model, and the adsorption isotherm aligned well with the Langmuir model. Investigation of the nanocomposite antimicrobial activity displayed considerable inhibitory effects against both bacteria and fungi.

Liquid-liquid extraction equilibrium study of vanadium(V) from nitrate medium by technical grade D2EHPA dissolved in kerosene

The extraction behaviour of vanadium (V) from nitric acid solutions was studied using technical grade D2EHPA in kerosene as an extractant. The effects of aqueous pH, the concentration of vanadium (V) and nitrate ion in the aqueous phase, and the concentration of D2EHPA in the organic phase were investigated. The extraction equilibration time was 30 min. Metal ion dependencies appeared non-ideal due to the non-constancy of the aqueous phase acidity and the equilibrium extractant concentration. Two types of extraction mechanisms originated from the study of pH dependency. The study conceded that the extraction of vanadium (V) occurred via ion exchange or chelation type of extraction when the pH(eq) <2.50. On the other hand, the solvated ion-pair extraction mechanism occurs when the pH(eq) was above 2.50. The extractant dependencies showed that vanadium (V) species were extracted by one molecule of D2EHPA. The salting-out effect was observed from the effect of nitrate ion concentration. The effect of various types of diluents on vanadium (V) extraction with technical grade D2EHPA was studied; kerosene appeared to be a suitable diluent. The temperature dependence data revealed that the system was exothermic with the ΔH value of -12.34 kJ/mol. The loading capacity was 6.11 g vanadium (V) per 100 g extractant. The H2SO4 (0.5 mol/L) was the right stripping agent for the extracted species.

Nitrate removal from aqueous solution using fuller’s earth and modified fuller’s earth

ABSTRACT Water, a vital resource for ecosystems and human populations, is facing increasing nitrate contamination due to agricultural runoff, industrial discharge and improper waste disposal. The present study focuses on the efficacy of nitrate removal through adsorption using fuller’s earth (FE) and modified fuller’s earth (acid-treated) (MFE) as adsorbents. The impact of initial pH (2.0–7.0), contact time (5–240 min), adsorbent dosage (1–30 g/L), initial nitrate concentration (50–250 mg/L) and temperature (30–50°C) on nitrate removal using fuller’s earth were studied. The maximum nitrate removal was observed at pH 2.0, and equilibrium was reached in 120 min at 30℃. The Freundlich isotherm best fit the equilibrium data. The maximum nitrate uptake of fuller’s earth and modified fuller’s earth were 84.75 mg/g and 85.47 mg/g, respectively. Nitrate removal by FE and MFE followed a second-order kinetic equation. Thermodynamic studies showed spontaneity and the exothermic nature of the nitrate adsorption process. ∆H° values were −44.96 and −42.63 kJmol−1 for FE and MFE and ΔS° was −85.11 and −74.52 Jk−1mol−1 for FE and MFE, respectively. FE, known for its exceptional adsorption capacity owing to its porous structure and high ion-exchange capacity, has demonstrated a remarkable affinity for nitrate ions in batch studies.

Novel ternary nanocomposite (TiO2@Fe3O4-chitosan) system for nitrate removal from water: an adsorption cum photocatalytic approach.

Nitrate pollution of water emerging from various anthropogenic activities has become a major environmental concern because of its deleterious effects on natural water resources. The present work deals with the synthesis of the ternary nanocomposite based on chitosan, iron oxide (Fe3O4), and titanium dioxide (TiO2) and its application for the removal of nitrates from model-contaminated water. Fe3O4 derived through a coprecipitation method was incorporated into the chitosan matrix which was fabricated in the form of beads. The wet gel beads were then successfully coated with sol-gel-derived silver-doped titanium dioxide sol followed by drying under suitable conditions to get the functional nanocomposite beads. The synthesized functional materials were further characterized for their structural, morphological, and textural features using X-ray diffraction analysis, physical property measurement (PPMS), Fourier transform infrared (FTIR) analysis, UV visible spectroscopy analysis (UV-vis), BET surface area analysis (BET), field emission scanning electron microscopic (FESEM), and transmission electron microscopy (TEM) analysis. The ternary nanocomposites were further used for the removal of nitrates via adsorption cum photocatalytic reduction technique from the model contaminated water when subjected to an adsorption study under dark conditions and photocatalytic study under UV/visible/sunlight for a definite time. Fe3O4 in the nanocomposite provides enhanced adsorption features whereas the functional coating of titanium dioxide aids in the removal of nitrates through the photocatalytic reduction technique. The functional beads containing 3% Fe3O4 in the wet gel form (CTA-F3) have excellent nitrate removal efficiency of ~ 97% via adsorption cum solar photocatalysis towards the removal of nitrate ions from 50ppm nitrate solution, whereas the dried nanocomposite beads have got a nitrate removal efficiency of ~ 68% in 1h from 100ppm nitrate solution. Continuous flow adsorption cum photocatalytic study was performed further using the oven-dried functional beads in which flow rate and bed height were varied while maintaining the concentration of feed solution as constant. A nitrate removal efficiency of 65% and an adsorption capacity of 4.1 mgg-1 were obtained for the CTA-F3 beads in the continuous flow adsorption cum photocatalysis experiment for up to 5h when using an inlet concentration of 100ppm, bed height 12cm, and flow rate 5.0mlmin-1. A representative fixed-bed column adsorption experiment conducted using CTA-F3 beads for the treatment of a real groundwater sample shows reasonable results for nitrate removal (71.7% efficiency) along with a significant removal rate for the other anions as well. Thus, the novel adsorbent/photocatalyst developed is suitable for the removal of nitrates from water due to the synergistic effect between Fe3O4, chitosan, and titanium dioxide.

Bifunctional properties of Ag/α-Fe2O3/rGO nanocomposite for supercapacitor and electrochemical nitrate sensing using tetradodecyl ammonium nitrate as ion-selective membrane.

Noble metal nanoparticles incorporated in hybrid nanocomposites are considered as promising candidates for electrochemical applications owing to their physicochemical properties. In this work, we demonstrated the preparation of Fe2O3/rGO nanocomposite by hydrothermal method, followed by in situ Ag binding synthesis for the fabrication of hybrid nanocomposite (Ag/α-Fe2O3/rGO). The crystallographic structure of the hybrid nanocomposite is examined by X-ray diffraction (XRD) analysis which confirms the characteristics of Ag, Fe2O3, and rGO. The microscopic studies and energy-dispersive X-ray analysis (EDS) spectra confirmed the presence and formation of hybrid nanostructures. Raman analysis results further corroborate the formation of composite with significant D and G bands in Fe2O3/rGO and Ag/α-Fe2O3/rGO samples, which follow XRD results. Cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) studies were carried out to analyze the faradaic capacitor behavior. A specific capacitance of 209.09 F/g was observed by GCD studies for Ag/α-Fe2O3/rGO composites at a current density of 1 A/g, which exhibited good capacitance retention of 94% for 5000 cycles at 7 A/g. Furthermore, the Ag/α-Fe2O3/rGO electrode was used for the electrochemical detection of nitrate ions in soil by utilizing an ion-selective membrane over the surface of the Ag/α-Fe2O3/rGO electrode. The fabricated nanocomposite electrode showed a significant change in the peak current values with the concentration of nitrate in a linear range from 10 to 450μM with the sensitivity to be calculated 1.426 μA μM-1cm-2 and limit of detection (LOD) calculated to be 0.18μM. The reproducibility and interference studies showed a promising result to be utilized for detecting nitrate ions in soil and in real-time applications.

Carotenoid accumulation in aerial microalga Coelastrella rubescens KGU-H009 in light- and nitrogen-stress conditions

Some natural carotenoids remain unexplored in terms of their function because they occur only in trace amounts, or their stereochemistry is unclear. It is expected that scientists will discover new physiological activities that have a positive impact on human heath by analysis of such carotenoids. The purpose of this study was to analyze the carotenoids synthesized by the novel aerial microalga Coelastrella rubescens KGU–H009, and the dynamics of their accumulation. Cultivation experiments were conducted for 7 days at 25 °C, combining different light conditions with the presence or absence of nitrate ions. Short-term (2-h) cultivation was also performed, and tests were conducted with the addition of the inhibitor of photosynthesis 3-(3,4-dichlorophenyl)-1, 1-dimethylurea (DCMU). Strain KGU-H009 exhibited its highest carotenoid content (34.5 mg g−1) in the presence of nitrogen sources and strong light. Upon nitrogen source depletion, the content of zeaxanthin and β-carotene decreased, while the content of astaxanthin and adonixanthin increased. Strain KGU-H009 exhibited reversible control of the xanthophyll cycle to adapt to changes in light intensity, but the xanthophyll cycle was inhibited by the addition of DCMU. Strain KGU-H009 demonstrated the ability to synthesize carotenoids involved in both light harvesting and photoprotection, suggesting its adaptability to environmental change.

Schiff base-stabilized electron-deficient copper species on MOFs as durable sensor of nitrate in water

The electrochemical sensor has been considered an efficient and portable platform for the rapid quantification of nitrate ions in industrial wastewater and natural water bodies. Albeit of the high sensitivity to NO3−, the electron-deficient copper sites (Cuδ+) were unstable under the negative working potentials for detection (Cuδ+ was readily reduced to Cu0). Herein, the Schiff base was grafted on MIL-125 (Ti) via covalent binding to stabilize the Cuδ+, leading to a composite Cuδ+/Schiff base/MIL-125 (Ti) material (abbreviated as CuSM) for NO3− sensing. Moreover, the unique porous structure of CuSM can speed up the diffusion rate of NO3− from the bulk solution to the surface of the modified electrode, enhancing the sensitivity of NO3− assay. As a result, the CuSM-based sensor not only exhibited a wide linear range from 1.18 µM to 58.8 mM and a low detection limit (S/N = 3) of 0.253 µM but also possesses high specificity, excellent reproducibility (the RSD of the five inter-batch sensors was 1.138%) and the ability to detect real water samples.

A Cytochrome P450 TxtE Model System with Mechanistic and Theoretical Evidence for a Heme Peroxynitrite Active Species.

The cytochrome P450 homolog, TxtE, efficiently catalyzes the direct and regioselective aromatic nitration of the indolyl moiety of L-tryptophan to 4-nitro-L-tryptophan, using nitric oxideand dioxygenas co-substrates. Pathways for such direct and selective nitration of heteroaromatic motifs present platforms for engineering new nitration biocatalysts for pharmacologically beneficial targets, among a medley of other pivotal industrial applications. Precise mechanistic details concerning this pathway are only weakly understood, albeit a heme iron(III)-peroxynitrite active species has been postulated. To shed light on this unique reaction landscape, we investigated the indole nitration pathway of a series of biomimetic ferric heme superoxide mimics, [(Por)FeIII(O2-•)], in the presence of NO. Therein, our model systems gave rise to three distinct nitroindole products, including 4-nitroindole, the product analogous to that obtained with TxtE. Moreover, 15N and 18O isotope labeling studies, along with meticulously designed control experiments lend credence to a heme peroxynitrite active nitrating agent, drawing close similarities to the tryptophan nitration mechanism of TxtE. All organic and inorganic reaction components have been fully characterized using spectroscopic methods. Theoretical investigation into several mechanistic possibilities deem a unique indolyl radical based reaction pathway as the most energetically favorable, products of which, are in excellent agreement with experimental findings.

Mimicking lightning-induced electrochemistry on the early Earth

To test the hypothesis that an abiotic Earth and its inert atmosphere could form chemically reactive carbon- and nitrogen-containing compounds, we designed a plasma electrochemical setup to mimic lightning-induced electrochemistry under steady-state conditions of the early Earth. Air-gap electrochemical reactions at air-water-ground interfaces lead to remarkable yields, with up to 40 moles of carbon dioxide being reduced into carbon monoxide and formic acid, and 3 moles of gaseous nitrogen being fixed into nitrate, nitrite, and ammonium ions, per mole of transmitted electrons. Interfaces enable reactants (e.g., minerals) that may have been on land, in lakes, and in oceans to participate in radical and redox reactions, leading to higher yields compared to gas-phase-only reactions. Cloud-to-ground lightning strikes could have generated high concentrations of reactive molecules locally, establishing diverse feedstocks for early life to emerge and survive globally.

The temperature of maximum in density of aqueous solutions of nitrate and ammonium salts: Testing the Madrid-2019 force field.

The shift in the temperature of maximum in density (TMD) at room pressure of aqueous solutions of a set of five salts containing NO3- and/or NH4+ groups is studied both through experiments and through molecular dynamics simulations using the Madrid-2019 force field for ions and the TIP4P/2005 model for water. The experiments demonstrate the potential transferability and limitations of the Madrid-2019 force field for nitrate and ammonium ions recently developed by our group at different temperatures and add updated information to the reported datasets of TMDs for strong electrolytes. By using the Despretz law, individual ion contributions are extracted for predictive purposes from the experimental values of the shift in the TMD. Interesting findings for the behavior of the shift in the TMD in nitrate salts expose that this property might be particularly challenging for modelization approaches when dealing with polyatomic species.

Catalytic activity of nZVIx@AC/NF on electroreduction of nitrate to ammonia:Effect of nano-valent iron loading

Nano zero-valent iron (nZVI) has high catalytic activity for nitrate electroreduction, however, it is easy to aggregate due to the nature magnetic properties. Herein we choose coconut activated carbon(AC) as the supporter to disperse the nanoparticles. Coconut AC primarily consists of a large number of micropores and mesopores. The micropores mainly provide large surface area to adsorption the nitrate ions first, and mesopores are responsible for the supporting nZVI particles. The adsorbed nitrate can migrate easily to the nZVI sites for reduction reaction. The aim of this paper is to determine the maximum nZVI loading capacity on AC without agglomeration, and also their corresponding activity for the electroreduction of nitrate to ammonia. The morphology and structural characteristics of the electrodes showed that nZVI can be evenly distributed on AC when the loading lower than 40 wt%, and the highest. NH3 Faradic efficiency of 97.2 % was obtained with nZVI40@AC at −7.5 mA/cm2. In addition, to clarify the sensitivity of the operating parameters the nitrated reduction. Response surface area was applied to evaluate the interactive effect between the operating parameters.

On the selective transport of mixtures of organic and inorganic anions through anion-exchange membranes: A case study about the separation of nitrates and citric acid by electrodialysis

Electrodialysis is finding an increasing number of applications, recently also in the separation and purification of organic acids. This technology involves reducing the use of chemicals and the generation of wastes, as compared to conventionally used processes. Gaining insights about the competitive transport between organic and inorganic ions in ED systems is key to achieving efficient separation processes in the bioresource industry. In the present study, the competitive transport of organic (citrates) and inorganic anions (nitrates) through anion-exchange membranes is investigated, under varying pH conditions, ion concentrations, and applied currents, by means of chronopotentiometry and ED experiments. In the absence of nitrate ions and under acidic conditions (pH 2), the resistance of the membrane system is very high because citric acid is mainly present in its undissociated and uncharged form. In the case of sodium citrate (pH 8), the membrane resistance decreases, especially at high current densities, which promote dissociation reactions and the subsequent concentration increase in ionic species near the membrane. Such phenomenon is identified both in chronopotentiometric curves and in long-term ED experiments by a gradual drop in membrane voltage with time. Although being less concentrated than citrates, the selective removal of nitrates is the most effective choice for the separation of both types of species. The selectivity factor of nitrates over citrates reaches the highest values at low applied current densities (below the limiting current density), with stable permselectivity values higher than 20. Such conditions also lead to the least specific energy consumption per nitrates removed (<0.5 kW·hr·kgNO3--1). Therefore, ED can be used under such favorable operating conditions after a clarification step in order to remove inorganic ions from fermentation broths and increase the purity of organic acids. At higher current densities, the enhanced transport of citrate anions produces a significant drop in selectivity towards nitrates and increases the specific energy consumption.

Ion-Selective Electrode for Nitrates Based on a Black PCV Membrane.

Carbon nanomaterials were introduced into this research as modifiers for polymeric membranes for single-piece electrodes, and their properties were studied for the case of nitrate-selective sensors. The use of graphene, carbon black and carbon nanotubes is shown to significantly improve the potentiometric response, while no redox response was observed. The use of carbon nanomaterials results in a near-Nernstian response (54 mV/pNO3-) towards nitrate ions over a wide linear range (from 10-1 to 10-6 M NO3-). The results obtained by chronopotentiometry and electrochemical impedance spectroscopy reveal little resistance, and the capacitance parameter is as high as 0.9 mF (for graphene-based sensor). The high electrical capacity of electrodes results in the good stability of the potentiometric response and a low potential drift (0.065 mV/h). Introducing carbon nanomaterials into the polymetric membrane, instead of using them as separate layers, allows for the simplification of the sensors' preparation procedure. With single-piece electrodes, one step of the procedure could be omitted, in comparison to the procedure for the preparation of solid-contact electrodes.

A multidisciplinary approach using hydrogeochemistry, δ15NNO3 isotopes, land use, and statistical tools in evaluating nitrate pollution sources and biochemical processes in Costa Rican volcanic aquifers

Nitrate pollution threatens the Barva and Colima multi-aquifer system, the primary drinking water source in the Greater Metropolitan Area of Costa Rica. In addressing nitrate contamination dynamics, this study proposes an integrated approach by combining multivariate statistical analyses, hydrochemical parameters, sewage discharge, and regional land-use and land-cover patterns to assess the extent and degree of contamination, dominant biogeochemical processes, and refine the interpretation of nitrate sources previously derived solely from δ15NNO3 information. Over seven years (2015–2022), 714 groundwater samples from 43 sites were analyzed for nitrate and major ions, including two sampling campaigns for dissolved organic and inorganic carbon, nitrite, ammonium, FeTotal, MnTotal, and δ15NNO3 analyses. The findings presented elevated nitrate concentrations in urban and agricultural/urban areas, surpassing the Maximum Concentration Levels on several occasions, and oxidizing conditions favoring mineralization and nitrification processes in unconfined Barva and locally confined Upper Colima/Lower Colima aquifers. Similar nitrate contents and spatial patterns in agricultural and urban zones in the shallow Barva aquifer suggest comparable contributions from nitrogen fertilizers and urban wastewaters despite the gradual increase in urban land cover and the reduction of agricultural areas. Isotopic analyses and dissolved organic carbon (DOC) indicate a shift in nitrate sources from agricultural to urban areas in both Barva and Colima aquifers. Principal Component and Hierarchical Cluster Analyses link land use, nitrate sources, and water quality. Three distinct sample clusters aligned with forest/grassland, agricultural/urban, and urban land use, emphasizing the impact of anthropogenic activities on groundwater quality, even in the deeper Colima aquifers. The study challenges nitrate isotope mixing models, enhancing accuracy in identifying pollution sources and assessing the spatial extent of contamination by incorporating DOC and other hydrochemical parameters. Similar outcomes, with and without the use of nitrate isotopes, reinforce the usefulness of the integrated approach, providing a practical and cost-effective alternative.

Enhanced electrochemical detection of nitrite and nitrate in water using Chitosan-Copper phthalocyanine nanocomposite

In this investigation, we study the behavior of a hybrid nanomaterial system combining chitosan-based tetrasulfonated copper phthalocyanine catalyst (Chit/Ts-CuPc) modified carbon screen-printed electrodes (CSPE) for the determination of nitrite and nitrate. Under optimal experimental conditions defined by cyclic voltammetry (CV) and square wave voltammetry (SWV) surveys, the functionalized CSPE exhibited significant catalytic activity towards nitrite and nitrate with a considerable enhancement of the cathodic-anodic peak currents. The Chit/Ts-CuPc nanocomposite enabled the sensors to have a broad linear detection range, which allows quantifying analytes at various concentrations, from 40 to 100 µM for nitrite and 1 to 10 µM for nitrate. Low detection limits (3Sb/m) have been achieved, which are 0.06 µM and 0.05 µM for nitrite and nitrate ions, respectively. Moreover, the proposed modified electrode showed its applicability by measuring the concentration of nitrite and nitrate ions with interfering species and in real water samples.

From waste to value: Electrocatalytic reduction of nitrate into ammonia at mono and bimetallic-CNT modified electrodes

The electrochemical transformation of nitrate ions into ammonia (NH3), which ranks among the most widely employed chemicals globally, using mono (Pd, Pt) and bimetallic catalysts (Pd-Cu, Pt-Cu, Ru-Cu) supported on carbon nanotubes (CNT) was studied in acidic medium. The higher conversion and best selectivity towards NH3 corresponding, respectively, to 88 and 80 % were found for Pt_CNT modified electrode, with an initial nitrate concentration of 12.9 mM. The addition of copper as a second metal provides lower percentage of ammonia in comparison with the monometallic Pt_CNT and Pd_CNT electrocatalysts. The prepared electrocatalysts show good mechanical and chemical stability, under the experimental conditions. Principal Component Analysis (PCA) was carried out in order to highlight the effect of experimental parameters on selectivity.