Low Ammonium Concentrations Research Articles

Fallen Leaves as a Substrate for Biogas Production

Fallen leaves in cities are often treated as waste; therefore, they are collected, transported outside urban areas, and composted, which contributes to greenhouse gas (GHG) emissions. Instead of this conventional management approach, fallen leaves could be utilized as a feedstock in biogas production, helping to reduce GHG emissions, increase renewable energy generation, and provide fertilizer. The aim of this study was to compare the mono-digestion of fallen leaves from three tree species commonly found in parks and along streets—northern red oak (Quercus rubra L.), small-leaved lime (Tilia cordata Mill.), and Norway maple (Acer platanoides L.)—in both wet and dry anaerobic digestion (AD) systems. A biochemical methane potential (BMP) test was conducted in batch assays for each of the three substrates in both AD technologies at a temperature of 38 ± 1 °C. The highest specific methane yield (SMY) was obtained from Quercus leaves in wet AD technology, with a methane yield of 115.69 ± 4.11 NL kgVS−1. The lowest SMY (55.23 ± 3.36 NL kgVS−1) was observed during the dry AD of Tilia leaves. The type of technology had no significant impact on the SMY of Acer and Tilia leaves; however, the methane yield from Quercus leaves in wet AD was significantly higher (p < 0.05) than that from dry AD. Studies on the use of fallen leaves from Tilia cordata, Quercus rubra, and Acer platanoides as substrates in mono-digestion technology have shown their limited suitability for biogas production. Nevertheless, this feedstock may be more effectively used as a co-substrate, mainly due to the low concentrations of ammonia (NH3) and hydrogen sulfide (H2S) in the biogas produced from these leaves, both of which are considered inhibitors of the AD process.

Electrochemical Synthesis of Nitrite and Nitrate via Cathodic Oxygen Activation in Liquefied Ammonia.

The electrochemical oxidation of ammonia (NH3) enables decentralized small-scale synthesis of nitrate (NO3-) and nitrite (NO2-) under ambient conditions by directly utilizing renewable energy. Yet, their electrosynthesis has been restricted to aqueous media and low ammonia concentrations. For the first time, we demonstrate here a strategy enabling the direct electrooxidation of liquefied NH3 to NO3- and NO2- by using molecular oxygen, achieving combined Faraday efficiencies above 40%.

Influence of NH3 flow rate on the photoelectric properties of high Al content p-AlGaN.

High Al content (60%) p-AlGaN with different NH3 flow rates was grown using metal-organic chemical vapor deposition (MOCVD), and changes in its photoelectric properties were studied using the Hall effect tester (Hall) and cathodoluminescence (CL) spectrometer. The results show that the film resistivity increases from 3.8 Ω·cm to 46.5 Ω·cm with increasing NH3 flow rate. The impurity peak intensity of p-AlGaN grown under high NH3 flow conditions is particularly high, indicating numerous point defects. The results of high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) show a large number of Ga interstitial atoms (Gai) at the interface. As Gai acts as a donor, this may be the main reason for the increase in resistivity. And under high NH3 flow conditions, a lattice distortion and a high density of dislocation occur between p-AlGaN and p-GaN, which can lead to enhanced carrier scattering and decreased mobility. Additional validation via LED growth experiments indicates that the luminescence intensity of samples with low ammonia concentration increased by more than 13000 times.

Contrasting nitrogen dynamics across the Mid‐Atlantic Bight shelfbreak front: Insights from nitrate dual isotopes and nitrifier gene abundance

AbstractObservations and model studies suggest that front dynamics can enhance phytoplankton productivity. This study tested whether frontal systems also increase the abundance of nitrifying microbes and nitrogen recycling during repeat sampling transects across the Mid‐Atlantic Bight shelfbreak in July 2019. We measured ammonium concentrations, nitrate dual isotopes (δ15N, δ18O), and ammonia monooxygenase subunit A (amoA) genes of ammonia‐oxidizing archaea (AOA) and bacteria (AOB). In subsurface shelf waters, ammonium concentrations exceeded 2 μmol L−1, due to a temporary imbalance in regeneration from sinking particles and subsequent nitrification. The inverse correlation between nitrate δ15N values and ammonium concentrations confirmed nitrate was partially or entirely from local nitrification on the shelf. In contrast, the shelfbreak frontal zone and slope sea subsurface waters had much lower ammonium concentrations (0.1–0.2 μmol L−1) due to tight coupling between ammonium regeneration and nitrification. The deviation of nitrate δ15N and δ18O from algal uptake‐driven 1 : 1 ratio suggests concurrent nitrification in the euphotic zone. The shelfbreak front acted as an ecological boundary where AOA and AOB amoA gene numbers were partitioned, with AOAs abounding in slope waters and AOBs in shelf waters, likely due to ammonium availability. At certain slope stations, deep‐water nutrient inputs via isopycnal lifting induced by Gulf Stream intrusions caused unexpectedly high phytoplankton biomass, which doubled nitrifier abundance and potentially stimulated both ammonium regeneration and nitrification. These findings demonstrate distinct distributions of nitrifying microbes along the salinity gradient from shelf to slope and highlight the significant influence of coastal ocean‐western boundary current interactions on nitrogen biogeochemistry.

Effects of Coprecipitation Conditions on the Electrochemical Properties of Cobalt-Free LiNi0.9Mn0.1-xAlxO2 Cathodes.

Commercializing high-nickel, cobalt-free cathodes, such as LiNi0.9Mn0.1-xAlxO2 (NMA-90), hinges on effectively incorporating Al3+ during the hydroxide coprecipitation reaction. However, Al3+ coprecipitation is nontrivial as Al3+ possesses unique precipitation properties compared to Ni2+ and Mn2+, which impact the final precursor morphology and consequently the cathode properties. In this study, the nuance of Al3+ coprecipitation and its influence on the cycling stability of NMA with increasing Al3+ content is elucidated. While low reaction pH and ammonia concentration are suitable for producing Al-free LiNi0.9Mn0.1O2 (NM-90) effectively, the same coprecipitation environment leads to porous precursor morphology and poor cycle life in Al-containing LiNi0.9Mn0.08Al0.02O2 (NMA-900802) and LiNi0.9Mn0.05Al0.05O2 (NMA-900505). By systematically increasing the reaction pH and ammonia concentration for the Al-containing compositions, the precursor morphology becomes denser and the cathode cycling stability is greatly improved. It is hypothesized that the improvement in cycling stability stems from the reduction in Al(OH)3 nucleation, which promotes hydroxide particle growth with optimal Al3+ incorporation into the cathode lattice.

Assessing the effectiveness of SO2, NOx, and NH3 emission reductions in mitigating winter PM2.5 in Taiwan using CMAQ

Abstract. Taiwan experiences higher air pollution in winter when fine particulate matter (PM2.5) levels frequently surpass national standards. This study employs the Community Multiscale Air Quality model to assess the effectiveness of reducing SO2, NOx, and NH3 emissions on PM2.5 secondary inorganic species (i.e., SO42-, NO3-, and NH4+). For sulfate, ∼ 43.7 % is derived from the chemical reactions of local SO2 emission, emphasizing the substantial contribution of regionally transported sulfate. In contrast, nitrate and ammonium are predominantly influenced by local NOx and NH3 emissions. Reducing SO2 emissions decreases sulfate levels, which in turn leads to more NH3 remaining in the gas phase, resulting in lower ammonium concentrations. Similarly, reducing NOx emissions lowers HNO3 formation, impacting nitrate and ammonium concentrations by decreasing the available HNO3 and leaving more NH3 in the gas phase. A significant finding is that reducing NH3 emissions decreases not only ammonium and nitrate but also sulfate by altering cloud droplet pH and SO2 oxidation processes. While the impact of SO2 reduction on PM2.5 is less than that of NOx and NH3, it emphasizes the complexity of regional sensitivities. Most of western Taiwan is NOx-sensitive, so reducing NOx emissions has a more substantial impact on lowering PM2.5 levels. However, given the higher mass emissions of NOx than NH3 in Taiwan, NH3 has a more significant consequence in mitigating PM2.5 per unit mass emission reduction (i.e., 2.43 × 10−5 and 0.85 × 10−5 µg m−3 (t yr−1)−1​​​​​​​ for NH3 and NOx, respectively, under current emission reduction). The cost-effectiveness analysis suggests that NH3 reduction outperforms SO2 and NOx reduction (i.e., USD 0.06 billion yr−1 µg−1 m3, USD 0.1 billion yr−1 µg−1 m3, and USD 1 billion yr−1 µg−1 m3 for NH3, SO2, and NOx, respectively, under the current emission reduction). Nevertheless, the costs of emission reduction vary due to differences in methodology and regional emission sources. Overall, this study considers both the efficiency and costs, highlighting NH3 emissions reduction as a promising strategy for PM2.5 mitigation in the studied environment in Taiwan.

Affordable droplet-based flow analyzer with peristaltic micro-pumps for fluorescent ammonium sensing

An affordable droplet-based flow analyzer incorporating peristaltic micro-pumps has been developed for fluorescent ammonium sensing. The cost-effective peristaltic micro-pumps, modified using 3D-printing techniques, feature a 3D-printed pump base integrated with a Hall sensor to monitor the rotation of the pump motor. This setup generates a pulse flow instead of a continuous flow, delivering specific volumes (typically between 3 to 4 μL) of solution with each rotation. By using separate pumps to deliver the aqueous and oil phases, these phases merge to form a droplet flowing stream. The relative standard deviation (RSD) values for droplet volumes range from 3.97 % to 5.99 % (n=50) across different pumps. The analyzer utilizes a reaction between ammonium, ortho-phthalaldehyde, and sulfite to produce a fluorescent derivative, allowing for sensitive detection of low ammonium concentrations. A custom light-emitting diode (LED)-based fluorescence detector has been fabricated using 3D printing, ensuring cost-effective production. The analyzer provides a limit of detection of 0.02 μM (3σ) and an RSD of 0.15 % (n=10, 1 μM ammonium). This analyzer offers several practical advantages, including reduced reagent consumption and the potential for further development in distributed on-site analysis. The use of 3D printing facilitates rapid prototyping and customization, making the system adaptable to various analytical applications.

The structure of water-ammonia mixtures from classical and abinitio molecular dynamics.

The structure of aqueous ammonia solutions is investigated through classical molecular dynamics (MD) and abinitio molecular dynamics (AIMD) simulations. We have preliminarily compared three well-known classical force fields for liquid water (SPC, SPC/E, and TIP4P) in order to identify the most accurate one in reproducing AIMD results obtained at the Generalized Gradient Approximation (GGA) and meta-GGA levels of theory. Liquid ammonia has been simulated by implementing an optimized force field recently developed by Chettiyankandy et al. [Fluid Phase Equilib. 511, 112507 (2020)]. Analysis of the radial distribution functions for different ammonia concentrations reveals that the three water force fields provide comparable estimates of the mixture structure, with the SPC/E performing slightly better. Although a fairly good agreement between MD and AIMD is observed for conditions close to the equimolarity, at lower ammonia concentrations, important discrepancies arise, with classical force fields underestimating the number and strength of H-bonds between water molecules and between water and ammonia moieties. Here, we prove that these drawbacks are rooted in a poor sampling of the configurational space spanned by the hydrogen atoms lying in the H-bonds of H2O⋯H2O and, more critically, H2O⋯NH3 neighbors due to the lack of polarization and charge transfer terms. This way, non-polarizable classical force fields underestimate the proton affinity of the nitrogen atom of ammonia in aqueous solutions, which plays a key role under realistic dilute ammonia conditions. Our results witness the need for developing more suited polarizable models that are able to take into account these effects properly.

Construction of “ant-like tentacle” structure for ultra-sensitive detection of low-concentration ammonia through colorimetric fluorescent dual-signal gas-sensitive cotton fabric

Detection and monitoring of ammonia (NH3) are crucial in various industries, including plant safety management, food freshness testing, and water pollution control. Nevertheless, creating portable, low-cost, highly sensitive, and easily regenerated ppm-level NH3 sensors poses a significant challenge. In this investigation, an innovative “ant-like tentacle” fabrication strategy was proposed, and a colorimetric fluorescent dual-signal gas-sensitive cotton fabric (PAH-fabric) for NH3 detection was successfully prepared by conventional dyeing using suitable molecular-level photoacid (PAH) sensitive units. The visual recognition lower detection limit of the ultra-low is 1.09 ppm-level. PAH-fabric is not only straightforward, convenient, and cost-effective to prepare, but it can also be efficiently regenerated and recycled multiple times (maintaining excellent gas-sensitive performance even after 100 cycles) by strategically leveraging volatile acid fumigation. Detailed molecular reaction mechanisms involved in the NH3 response and PAH-fabric regeneration are elucidated. PAH-fabric, available either as a portable kit or an alarm system, offers a promising approach for ultra-low NH3 detection. The demonstrated “ant-like tentacle” fabrication strategy introduces numerous possibilities for designing and developing sensors with adjustable response thresholds, particularly those requiring high sensitivity.

The Effective Separation of Gallium, Vanadium, and Aluminum from a Simulated Bayer Solution by Resin Exchange.

The effective recovery of gallium from wastewater discharge in the Bayer process is promising for the long-term development of gallium resources. The adsorption and desorption behavior of gallium (Ga), vanadium (V), and aluminum (Al) ions on a strong acidic styrene cation exchange resin (JK resin) from a simulated Bayer solution was systematically investigated by static experiments. The results showed that the optimum conditions for separating Ga from V and Al were at low temperatures and short contact times, with 78.30%, 15.16%, and 6.63% of the adsorption efficiency at 25 °C and 60 min, respectively, for Ga, V, and Al. The adsorption kinetics of Ga3+ conformed to the pseudo-second order model, and the static saturation adsorption capacity was 18.25 mg/g. The Langmuir model fitted the adsorption isotherm of gallium well, and the maximum adsorption capacity was 1.11 mg/g at 25 °C. FT-IR spectroscopy and XPS showed that the mechanism of the Ga3+ adsorption was only related to the interaction of the oxygen atoms of the amide oxime group (C=NOH). The separation of Ga, V, and Al can be achieved by desorbing 98% of Al with low concentrations of ammonia and 90% of Ga with low concentrations of hydrochloric acid. The results indicate that JK resin is an efficient adsorbent for separating gallium and vanadium in alkaline solutions.

Translocation of probiotics via gut–lung axis enhanced pulmonary immunity of weaned piglets exposed to low concentrations of ammonia

ObjectiveLactobacillus salivarius is a probiotic bacteria strain in human and animal diets. The administration of probiotics to weaned piglets may improve their growth by optimizing the gastrointestinal bacterial composition. To further investigate the effect of bacterial communication between the gastrointestinal tract and lungs on bodily immunity, we reared weaned piglets in a low-ammonia gas environment. L. salivarius was supplemented to explore its effects on pulmonary immunity and its potential for bacterial translocation. ResultsOne hundred sixty weaned piglets were allocated to four groups: L. salivarius-supplemented, L. reuteri-supplemented, control, and antibiotic drug (aureomycin)-supplemented. The feeding duration was 28 d. The body weights of piglets administered a strain of Lactobacillus were better than those of the control (P < 0.01). The transcription level of immune factors interleukin 2 (IL-2), IL-4, interferon α (IFN-α), and tumor necrosis factor α (TNF-α) in cells of the ileum and lung was significantly higher (P < 0.01). Lung and ileal mucus tissues were isolated to sequence the bacterial composition, which suggested a higher richness in the lungs at the phylum level, which was not significant in the ileum. Functional bacteria were more abundant in the ileum and lungs. The proportion of the genera of Lactobacillus, Prevotella, Actinobacillus, and Prevotellaceae_ NK3B31_group increased in two tissues, and a lower ratio of Streptococcus, Escherichia-Shigella, and mycoplasma was detected. The correlation between the microbial genus composition and the levels of immune factors suggests that the abundance of Lactobacillus plays the same positive role in the lungs and ileum. Mycoplasmas play a negative role in ileal and pulmonary immunity. More Lactobacillus reuteri and anaerobic probiotic bacteria were detected in the lungs. ConclusionThe colonization of Lactobacillus salivarius and Lactobacillus reuteri in the membrane of the ileum optimized the ileal microbial composition, enrolled other probiotic bacteria translating to the lung, improved the abundance of pulmonary microbiota, and enhanced immunity after exposure to low concentrations of ammonia.

Evaluation of potential adsorbents for simultaneous adsorption of phosphate and ammonium at low concentrations

Evaluation of potential adsorbents to tackle eutrophication caused by low concentrations of phosphate and ammonium are rarely reported in the literature. Besides, the dynamics/mechanisms for removal of these pollutants at low concentration are yet to be explored. In this study we used five different adsorbents, including La-modified zeolite (LMZ), MgFe-modified biochar (MgFe-BC), phoslock, activated alumina (AA), and diatomaceous earth (DE) to evaluate the removal of these pollutants. Among the selected adsorbents in this study, LMZ and AA both exhibited effective and simultaneous adsorption for phosphate and ammonium and the maximum adsorption capacities were 2.47 mg/g and 3.07 mg/g, respectively. The presence of SO42− and CO32− negatively impacted phosphate adsorption, while Fe3+ and K+ ions inhibited ammonium adsorption. LMZ adsorption kinetics was over 3 times faster than other adsorbents within 60 min reaction time. Kinetics studies and isotherms revealed that the removal of phosphate and ammonium was primarily driven by chemical interactions and monolayer adsorption and were better fitted by Langmuir isotherm than the Freundlich isotherm and kinetic study was effectively described by Pseudo-second-order kinetic model. FTIR and XPS analysis revealed that the key mechanisms for phosphate adsorption were electrostatic attraction and inner sphere complexation through ligand exchange, whereas ammonium adsorption was mainly governed by ion exchange. Desorption study revealed that LMZ material was stable after three desorption cycles. This study offers vital knowledge on the nature of adsorption and interactions of potential mesoporous adsorbents with eutrophication-causing pollutants in lakes and rivers and proposes effective remedial mean.

Detecting low-concentration ammonia with a surface acoustic wave sensor using a silver nanoparticles–graphene–polypyrrole hybrid nanocomposite film

In this study, a surface acoustic wave (SAW) resonator coated with graphene/polypyrrole hybrid nanocomposite films decorated with silver nanoparticles (AgNPs-G/PPy) is proposed for detecting ammonia (NH3) in parts-per-billion concentrations. The AgNPs-G/PPy hybrid nanocomposite film was synthesized via in situ chemical oxidative polymerization. Scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction were used to characterize the AgNPs-G/PPy hybrid nanocomposite film, confirming its successful synthesis and identifying a wrinkled multilayered structure. The AgNPs-G/PPy hybrid nanocomposite film was spin-coated onto the surface of a stress-compensated temperature-cut quartz SAW resonator having an operating frequency of 98.5 MHz to create an NH3 gas sensor. NH3 adsorption by the AgNPs-G/PPy hybrid nanocomposite film modulated the acoustic wave velocity, and the corresponding frequency shift served as a sensing signal. The synergistic interaction between the three constituent materials (AgNPs, graphene, and polypyrrole) enhanced the sensitivity, selectivity, and response speed of the sensor for NH3 detection. At room temperature, the proposed sensor exhibited a positive frequency shift of 568 Hz when exposed to 50 ppb of NH3 gas and a rapid response time of less than 60 s. In addition, the SAW sensor exhibited excellent selectivity.

Sustainable Hydroponics Using Zero-discharge Nutrient Management and Automated pH Control

Here we review the 400-year history of hydroponic culture and describe a unique management approach that does not require leaching or discarding solution between harvests. Nutrients are maintained at a low and steady concentration by daily additions of a dilute solution that replaces the transpired water along with the nutrients that were removed in growth each day. A stable pH and a low steady-state concentration of ammonium are maintained through automated additions of a solution of nitric acid and ammonium nitrate. Ample solution volume (at least 20 cm deep) stabilizes nutrient concentrations, reduces root density, and improves uniformity. Gentle aeration at ≈100 mL·min−1·L−1 maintains dissolved oxygen near saturation and increases uniformity throughout the rhizosphere. These practices facilitate a uniform, closed, root zone with rigorous pH control that provides the micromolar nutrient concentrations of N and P that are representative of field soils.

Polysaccharides, the active component of Dendrobiumofficinale flower, ameliorates chronic pharyngitis in rats via TLR4/NF-κb pathway regulation

Ethnopharmacological relevanceChronic pharyngitis persistently afflicts a large population and accounts for approximately one-third of otolaryngology patients. Currently, the treatment of CP remains controversial because of the poor outcomes. Dendrobium officinale is a well-used “Yin-nourishing” traditional Chinese medicinal and edible herb used for thousands of years in China. The flowers of D. officinale are often used in folk of China to make tea for voice protection on and throat clearing. Aim of the studyThis study was to evaluate beneficial effects of polysaccharides from D. officinale flower (DOFP) on CP and its potential mechanisms. MethodsChemical characterization of DOFP, including polysaccharide content and monosaccharide composition, structural characterization using Fourier transform infrared spectroscopy were performed. A CP model was established in rats by administering a mixture of Chinese Baijiu and chili pepper liquid, combined with low-concentration ammonia spraying. The general states, amount of oral secretion, and apparent state of the pharynx of CP rats were observed during the period of DOFP administration. Furthermore, hemorheological parameters were measured using an automatic hematology analyzer. The levels of tumor necrosis factor-α (TNF-α), interleukin 1β (1L-1β), lipopolysaccharide (LPS), and D-lactate (D-LA) in the serum were measured by enzyme-linked immunosorbent assay. Morphological changes in the pharynx and colon were observed by hematoxylin-eosin staining. The expression of nuclear factor-κB p65 (NF-κB p65), p-NF-κB p65, cyclooxygenase-2 (COX-2), interleukin 1β（IL-1β）and mucin 5AC (MUC5AC) in the pharynx,Claudin-1, Occludin, and interleukin 6 (IL-6) in the colon was detected by immunohistochemistry and Western Blot. The mRNA expression of TLR4, COX-2, and IL-1β in the pharynx were determined using reverse transcription quantitative real-time PCR. ResultsIn this study, DOFP with a total polysaccharide content of 71.44% and a composition of D-mannose, galacturonic acid, glucose, galactose, and arabinose in a molar ratio of 3.95:2.19:1.00:0.74:1.30, was isolated from the flowers of D. officinale. DOFP improved the general state and exhibited significant effects on reducing oral secretion, alleviating pharyngeal injury, suppressing inflammatory cell infiltration in the pharynx, decreasing the serum levels of TNF-α and IL-1β, and reducing the number of white blood cells and lymphocytes in the model rats. Moreover, the expressions of TLR4, p-NF-κB p65, COX-2, IL-1β and MUC5AC in the pharynx of model rats were obviously inhibited. In addition, the levels of LPS, D-LA in the serum and the protein expression of IL-6 in the colon were downregulated when the protein expression of Occludin and Claudin-1 in the colon were upregulated. ConclusionsDOFP exerts significant ameliorating effects on CP and it likely acts by inhibiting LPS/TLR4-associated inflammatory mediator activation and reducing excessive secretion of mucus by repairing the intestinal barrier in CP rats.

Synthesis, characterization and sensing applications of TiO2 doped MOF composites for selective detection of ammonia at room temperature

Herein, we have developed a highly sensitive chemiresistive TiO2 doped metal–organic framework(MOF) composite-based sensor for ammonia detection at room temperature. Two novel Ti-MOFs@TiO2 composites are developed employing terephthalic acid and 2-amino terephthalic acid as organic linkers with Titanium tetra isopropoxide (TTIP) as a metal source by solvothermal technique. The morphology and crystallinity of synthesized compounds were characterized by using Field-emission scanning electron microscopy (FE-SEM) with EDX analysis, X-ray diffraction (PXRD), XPS and Brunauer–Emmett–Teller (BET) analysis techniques. MIL-125@TiO2 sensors exhibited a more specific surface area (374.74 m2 g−1) than the other three compounds. For gas-sensing applications, all composite materials were exposed to different gas vapours like ammonia, formaldehyde, acetic acid, ethyl alcohol, acetone, xylene, toluene and benzene at room temperature. The sensing results indicate that the sensors exhibit excellent response at low concentrations of ammonia, formaldehyde and acetic acid gases (1 ppm level). The enhanced sensor response was attributed to MIL-125@TiO2 (85 response at 50 ppm) and NH2-MIL-125@TiO2 (71 response at 50 ppm) towards ammonia gas and shows a better selectivity, sensitivity and repeatability to ammonia gas. All the materials exhibited less response times (between 8 and 45 sec) and more recovery times (between 13 and 125 sec).

Synthesis of Silica Particles with Controlled Microstructure via the Choline Hydroxide Cocatalyzed Stöber Method.

This study investigates the utilization of choline hydroxide as a cocatalyst in the Stöber method to synthesize silica particles with controlled microstructure. Under low ammonia concentration, we add a robust organic base choline hydroxide and systematically explore the influence of choline hydroxide concentration on the hydrolysis and condensation equilibrium of tetraethyl orthosilicate (TEOS). Through the rational control of the water content, we significantly enhance both the size range and polydispersity of the resulting silica particles. Taking advantage of the regulated microstructure induced by controlled hydrolysis and condensation catalyzed by choline hydroxide, we achieved silica particles with hollow structures through hot water etching, exhibiting significantly enhanced surface area. These findings demonstrate the versatility of choline hydroxide as a cocatalyst in tailoring the microstructure of silica particles. In addition, due to its reducing ability and biocompatibility, which are not shared by other reported catalysts, the use of choline hydroxide opens up opportunities for applications in catalysis, sensing, and drug delivery.

Chemiresistive NH3 and H2S sensors based on thin films of vitamin B12 derivatives

Despite the large number of materials, e.g. semiconducting oxides, carbon nanomaterials, conducting polymers and others, that are used as active layers of chemiresistive sensors to ammonia and hydrogen sulfide, the search for new materials remains an urgent task. Special attention is paid to the search for environmentally friendly materials. Corrinoids are naturally occurring coordination complexes consisting of a central cobalt ion and a tetrapyrrole ligand called a corrin ring. Cobalamins and their derivatives are widely used as active layers of optical and electrochemical sensors. At the same time, vitamin B12 derivatives have not been studied as active layers of chemiresistive gas sensors. In this work, films of two vitamin B12 derivatives, viz. dicyanocobyrinic acid heptabutyl ester (DC) and its aquacyano form, aquacyanocobyrinic acid heptabutyl ester (AC), deposited by spin coating and drop casting techniques onto interdigitated electrodes, were tested for the first time as active layers of chemiresistive sensors for the detection of low concentrations of ammonia and hydrogen sulfide (1–50 ppm) in air. It was shown that films of both vitamin B12 derivatives demonstrated reversible sensor response to NH3 and H2S at room temperature. The limit of detection (LOD) of H2S was 0.1 ppm for both vitamin B12 derivatives, while LOD of ammonia was noticeably lower (0.06 ppm) in the case of AC films than in the case of DC films (0.4 ppm). Both sensors demonstrated a fairly low regeneration time, which did not exceed 180 s for 5 ppm of NH3 and 185 s for 5 ppm of H2S.

External electron donor and transporter of iron triggers the paths to enhancing collaboration of anammox and denitrification in granular sludge: Bacterial resilience and synergetic promotion mechanism

Autotrophic nitrogen removal via anaerobic ammonium oxidation (anammox) technology currently faces significant challenges in treating low-strength wastewater due to inefficient retention of bacteria and unstable activity under fluctuating conditions. This study demonstrates enhanced resilience and stability of anammox coupled with partial denitrification (PD) in granular sludge, assisted by ferric iron (Fe(III)) and nano zero-valent iron (nZVI). The systems treated wastewater with low concentrations of ammonia (NH4+-N of 50 ∼ 80 mg/L) and nitrate (NO3−-N of 60 ∼ 100 mg/L). Fe(III) and nZVI were intermittently added to two PD coupled with anammox (PD/A) systems, which were subjected to increasing nitrogen loading rates (NLRs) and decreasing temperature. Remarkably, both Fe(III)- and nZVI-assisted systems achieved satisfactory total nitrogen (TN) removal efficiencies of 98.1 % and 96.6 %, respectively, even as the temperature dropped from 28.5℃ to 13.4℃ and the NLR increased from 0.22 to 0.72 kgN/m3/d. Significantly, these two systems exhibited pronounced resilience under the shocking effect of excessive organic load, extremely low pH, and high salinity. The presence of iron, acting as an accelerated electron transporter, enhanced anammox activity and microbial NH4+-N oxidation. Additionally, iron reduced the requirement for an organic carbon source, further stimulating the competitiveness of anammox for nitrite (NO2−-N) against denitrification. Interestingly, metagenomic analysis revealed that the functional bacteria Thauera, responsible for PD, employed versatile metabolic pathways for NO3−-N reduction to NO2−-N using Fe(II) as an electron donor. Overall, this study provides new insights into microbial interactions and versatile metabolism in iron-assisted anammox systems, contributing to more energy-efficient wastewater treatment.

Benefits and limits of biological nitrification inhibitors for plant nitrogen uptake and the environment

Plant growth and high yields are secured by intensive use of nitrogen (N) fertilizer, which, however, pollutes the environment, especially when N is in the form of nitrate. Ammonium is oxidized to nitrate by nitrifiers, but roots can release biological nitrification inhibitors (BNIs). Under what conditions does root-exudation of BNIs facilitate nitrogen N uptake and reduce pollution by N loss to the environment? We modeled the spatial–temporal dynamics of nitrifiers, ammonium, nitrate, and BNIs around a root and simulated root N uptake and net rhizosphere N loss over the plant’s life cycle. We determined the sensitivity of N uptake and loss to variations in the parameter values, testing a broad range of soil–plant-microbial conditions, including concentrations, diffusion, sorption, nitrification, population growth, and uptake kinetics. An increase in BNI exudation reduces net N loss and, under most conditions, increases plant N uptake. BNIs decrease uptake in the case of (1) low ammonium concentrations, (2) high ammonium adsorption to the soil, (3) rapid nitrate- or slow ammonium uptake by the plant, and (4) a slowly growing or (5) fast-declining nitrifier population. Bactericidal inhibitors facilitate uptake more than bacteriostatic ones. Some nitrification, however, is necessary to maximize uptake by both ammonium and nitrate transporter systems. An increase in BNI exudation should be co-selected with improved ammonium uptake. BNIs can reduce N uptake, which may explain why not all species exude BNIs but have a generally positive effect on the environment by increasing rhizosphere N retention.