A simple and rapid visual method for the determination of ammonia nitrogen in environmental waters using thymol

Simple visual and spectrophotometric methods for the determination of ammonia nitrogen in water are proposed, based on the color development of indothymol blue formed between ammonia and thymol. The color development was accelerated by nitroprusside to complete in 3 min. This color development is remarkably rapid compared with that of the other conventional methods with indothymol blue and indophenol blue. The concentration range of ammonia nitrogen spectrophotometrically determined was 0.04–1.2 mg/L NH₄-N. The absorbance per 1 μg NH₄-N was 0.0215 (molar absorptivity = 1.51 × 10⁴) at 690 nm. The visual method not using any instrument as an in situ method in field works was developed based on the optimum conditions for the established spectrophotometric method. This visual method was successfully applied to the determination of ammonia nitrogen in environmental waters. Received: 21 December 1998 / Revised: 31 May 1999 / /Accepted: 4 June 1999     

A simple and rapid in situ preconcentration method for trace ammonia nitrogen in environmental water samples using a solid-phase extraction followed by spectrophotometric determination.

A simple and rapid in situ preconcentration method for the spectrophotometric determination of trace ammonia nitrogen in environmental water samples has been developed based on solid-phase extraction using a small column packed with octadecyl group-bonded silica gel (Sep-Pak C18 cartridge). A water sample was taken into a graduated syringe for easy and simple operation and prevention of contamination immediately after sample collection. Ammonia in the sample was reacted with hypochlorite and thymol to be converted into indothymol blue; then the formed indothymol blue was collected as an ion pair between indothymol blue and tetrabutylammonium ion on a Sep-Pak C18 cartridge. The indothymol blue on the cartridge was stable for 4 days. The retained indothymol blue was easily eluted with a mixture of methanol and 0.01 mol/l sodium hydroxide solution. The color intensity due to the indothymol blue was spectrophotometrically measured at 725 nm. The proposed method was successfully applied to environmental water samples such as river water.     

The spectrophotometric determination of ammonia in natural waters with particular reference to sea-water

The conditions for the precise spectrophotometric determination of microgram amounts of ammonia by means of the sodium phenate-hypochlorite method of RUSSELL have been investigated. Several modifications of her procedure have been introduced, particularly in the time and temperature used for development of the blue colour. BEER'S Law is obeyed up to a concentration of 2 mg NH₄-N/1 and ammonia can be determined with a standard deviation of 0.7%. The method can be used for the determination of up to at least 6 mg NH₄-N/l if recourse is made to a calibration curve. The interference of a number of inorganic ions has been studied, none of those which occur in natural fresh waters causes any marked diminution of the colour. The method can, therefore, be employed directly for the determination of ammonia in fresh waters. The most serious interferences are produced by copper and hydroxylamine. Hydrazine, however, does not interfere with the determination of ammonia unless it is present to the extent of at least 500 times the weight of the ammonia.The phenate-hypochlorite method cannot be used for the direct estimation of ammonia in sea-water owing to the interference of magnesium and calcium ions. The ammonia is therefore separated from the sea-water by a preliminary distillation under reduced pressure in a slow current of air as suggested by KROGH. A metaborate buffer has been employed for the liberation of the ammonia, and the optimum conditions of alkalinity for its separation determined. If two distillation apparatus are used concurrently 40–50 samples of sea-water may be examined per day with a standard deviation of less than 1 mg NH₄-N/m³Amino acids and urea do not interfere in either the sodium phenate-hypochlorite procedure or the distillation.     

A simple colorimetric method for the determination of ammonia in seawater

A method is proposed for the determination of trace amounts of ammonia in seawater. After calcium and magnesium have been chelated with CDTA, the blue colour obtained with hypochlorite and thymol-acetone is measured at 630 nm. The sensitivity is 1.3 ng NH₄⁺-N/cm².     

An automated spectromphotometric field monitor for water quality parameters : Determination of ammonia

A portable, automated spectrophotometric field monitor is described for the determination of total ammonia in river water. The linear calibration range (0–5000 μg NH₃-N) and precision (0.7–2.1%; n=6) of the monitor were evaluated in the loaboratory. The monitor was designed to operate unattended for a minimum of one week, after which tme the reagent solutions (bromothymol blue and sodium hydroxide) and the standard solutions were renewed and the teflon gas-diffusion membrane replaced. Results are presented for a three-day field trial on the River Avon near Bristol.     

Stable partial nitritation of mature landfill leachate in a continuous flow bioreactor: Long-term performance,microbial community evolution,and mechanisms

A continuous flow bioreactor was operated for 300 days to investigate partial nitritation (PN) of mature landfill leachate, establishing the long-term performance of the system in terms of the microbial community composition, evolution, and interactions. The stable operation phase (31–300 d) began after a 30 days of start-up period, reaching an average nitrite accumulation ratio (NAR) of 94.43% and a ratio of nitrite nitrogen to ammonia nitrogen (NO₂⁻-N/NH₄⁺-N) of 1.16. Some fulvic-like and humic-like compounds and proteins were effectively degraded in anaerobic and anoxic tanks, which was consistent with the corresponding abundance of methanogens and syntrophic bacteria in the anaerobic tank, and organic matter degrading bacteria in the anoxic tank. The ammonia-oxidizing bacteria (AOB) Nitrosomonas was found to be the key functional bacteria, exhibiting an increase in abundance from 0.27% to 6.38%, due to its collaborative interactions with organic matter degrading bacteria. In-situ inhibition of nitrite-oxidizing bacteria (NOB) was achieved using a combination of free ammonia (FA) and free nitrous acid (FNA), low dissolved oxygen (DO) with fewer bioavailable organics conditions were employed to maintain stable PN and a specific ratio of NO₂⁻-N/NH₄⁺-N, without an adverse impact on AOB. The synergistic relationships between AOB and both denitrifying bacteria and organic matter degrading bacteria, were found to contribute to the enhanced PN performance and microbial community structure stability. These findings provide a theoretical guidance for the effective application of PN-Anammox for mature landfill leachate treatment.     

A spot test for ammonium ion by the color band formation method

Removing nutrients from wastewaters is important in controlling eutrophication. Processes for removing nutrients require accurate control of operational conditions, and it is necessary to monitor nutrient concentrations during the removal process. For this purpose, a simple and accurate analytical method is especially important for small-scale wastewater treatment facilities. Here, we report a simple colorimetric method for determining NH₄⁺-N in wastewater. The method is to detect NH₄⁺-N by a color band length formed in a minicolumn, and similar methods for heavy metals detection were reported by Morosanova et al. In this study, the length of the color band of indonaphthol dye trapped on an adsorbent in a minicolumn was linearly correlated with NH₄⁺-N concentration in the range 1-10 mg NH₄⁺-N l⁻¹ under optimized conditions. This methods was developed on the basis of our previously reported color band methods for orthophosphate and nitrite determination, but the adsorbent used in this work consisted of an admixture of synthetic hydrotalcite particles and poly(vinyl chloride) particles coated with equal amounts of benzylcetyldimethylammonium chloride and biphenyl. When the method was applied to actual wastewaters, the results corresponded well with the results obtained by the standard method, and suspended solids (SS) and dissolved organic pollutants did not interfere with detection.     

<Emphasis Type="Italic">In situ</Emphasis> IR Spectroscopic and XPS Study of Surface Complexes and Their Transformations during Ammonia Oxidation to Nitrous Oxide over an Mn-Bi-O/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalyst

Surface complexes resulting from the interaction between ammonia and a manganese-bismuth oxide catalyst were studied by IR spectroscopy and XPS. At the first stage, ammonia reacts with the catalyst to form the surface complexes [NH] and [NH₂] via abstraction of hydrogen atoms even at room temperature. Bringing the catalyst into contact with flowing air at room temperature or with helium under heating results in further hydrogen abstraction and simultaneous formation of [N] from [NH₂] and [NH]. The nitrogen atoms are localized on both reduced (Mn²⁺) and oxidized (Mn^δ+, 2 < δ < 3) sites. Atomic nitrogen is highly mobile and reacts readily with the weakly bound oxygen of the oxidized (Mn^δ+-N) active site. The nitrogen atoms localized on oxidized sites play the key role in N₂O formation. Nitrous oxide is readily formed through the interaction between two Mn^δ+-N species. N₂ molecules result from the recombination of nitrogen atoms localized on reduced (Mn²⁺-N) sites.__________Translated from Kinetika i Kataliz, Vol. 46, No. 4, 2005, pp. 590–600.Original Russian Text Copyright © 2005 by Slavinskaya, Chesalov, Boronin, Polukhina, Noskov.     

Spectrophotometric determination of aromatic primary amines and nitrite by flow injection analysis

Aromatic primary amines are determined by injection into dilute hydrochloric acid carrier which merges sequentially with 4-N-methylaminophenol and dichromate. The purple-red color formed by oxidative coupling of amines with 4-N-methylaminophenol is measured at 530 nm. In contrast to the manual procedure, the flow-injection procedure avoided errors arising from the instability of the coupling intermediate, oxidation of the amine, and too great an excess of the oxidant. The method improves the selectivity for certain amines in the presence of those which are sterically hindered or have an electron-deficient aromatic nucleus. Nitrite is determined by diazotization of sulfanilamide and quantifying the residual sulfanilamide by oxidative coupling. The sample thourghout for the assay of amines (0.05–20 μg ml^?1 NH₂-N) and nitrite (1–10 μg ml^?1 NO₂^--N) was 120 h^?1. A system for the consecutive determination of aromatic primary amines and nitrite is decribed.     

Enhanced ammonia oxidation on BDD induced by inhibition of oxygen evolution reaction

Electrochemical oxidation of ammonia (NH₃ and NH₄ ⁺ ) on boron-doped diamond (BDD) electrode was studied using differential electrochemical mass-spectrometry (DEMS) and chronoamperometry. Electro-oxidation of ammonia induces inhibition of the oxygen evolution reaction (OER) due to adsorption of the ammonia oxidation products on the BDD surface. The inhibition of the OER enhances ammonia electro-oxidation, which becomes the main reaction. The amino radicals, formed during ammonia oxidation, trigger a reaction chain in which molecular oxygen dissolved in solution is involved in the ammonia electro-oxidation. Nitrogen, nitrous oxide, and nitrogen dioxide were detected as the ammonia oxidation products, with nitrogen being the main gaseous product of the oxidation.     

A simplified version of the total kjeldahl nitrogen method using an ammonia extraction ultrasound-assisted purge-and-trap system and ion chromatography for analyses of geological samples

The total Kjeldahl nitrogen (TKN) method was simplified by using a manifold connected to a purge-and-trap system immersed into an ultrasonic (US) bath for simultaneous ammonia (NH₃) extraction from many previously digested samples. Then, ammonia was collected in an acidic solution, converted to ammonium (NH₄⁺), and finally determined by ion chromatography method. Some variables were optimized, such as ultrasonic irradiation power and frequency, ultrasound-assisted NH₃ extraction time, NH₄⁺ mass and sulfuric acid concentration added to the NH₃ collector flask. Recovery tests revealed no changes in the pH values and no conversion of NH₄⁺ into other nitrogen species during the irradiation of NH₄Cl solutions with 25 or 40 kHz ultrasonic waves for up to 20 min. Sediment and oil free sandstone samples and soil certified reference materials (NCS DC 73319, NCS DC 73321 and NCS DC 73326) with different total nitrogen concentrations were analysed. The proposed method is faster, simpler and more sensitive than the classical Kjeldahl steam distillation method. The time for NH₃ extraction by the US-assisted purge-and-trap system (20 min) was half of that by the Kjeldahl steam distillation (40 min) for 10 previously digested samples. The detection limit was 9 μg g⁻¹ N, while for the Kjeldahl classical/indophenol method was 58 μg g⁻¹ N. Precision was always better than 13%. In the proposed method, carcinogenic reagents are not used, contrarily to the indophenol method. Furthermore, the proposed method can be adapted for fixed-NH₄⁺ determination.     

Rapid Detection of Different Types of Soil Nitrogen Using Near-Infrared Hyperspectral Imaging

Rapid and accurate determination of soil nitrogen supply capacity by detecting nitrogen content plays an important role in guiding agricultural production activities. In this study, near-infrared hyperspectral imaging (NIR-HSI) combined with two spectral preprocessing algorithms, two characteristic wavelength selection algorithms and two machine learning algorithms were applied to determine the content of soil nitrogen. Two types of soils (laterite and loess, collected in 2020) and three types of nitrogen fertilizers, namely, ammonium bicarbonate (ammonium nitrogen, NH₄-N), sodium nitrate (nitrate nitrogen, NO₃-N) and urea (urea nitrogen, urea-N), were studied. The NIR characteristic peaks of three types of nitrogen were assigned and regression models were established. By comparing the model average performance indexes after 100 runs, the best model suitable for the detection of nitrogen in different types was obtained. For NH₄-N, R²_p = 0.92, RMSE_P = 0.77% and RPD = 3.63; for NO₃-N, R²_p = 0.92, RMSE_P = 0.74% and RPD = 4.17; for urea-N, R²_p = 0.96, RMSE_P = 0.57% and RPD = 5.24. It can therefore be concluded that HSI spectroscopy combined with multivariate models is suitable for the high-precision detection of various soil N in soils. This study provided a research basis for the development of precision agriculture in the future.     

Capillary electrophoretic determination of ammonia using headspace single-drop microextraction

A new method involving headspace single-drop microextraction (SDME) and capillary electrophoresis (CE) is developed for the preconcentration and determination of ammonia (as dissolved NH₃ and ammonium ion). An aqueous microdrop (5 μL) containing 1 mmol/L H₃PO₄ and 0.5 mmol/L KH₂PO₄ (as internal standard) was used as the acceptor phase. Common experimental parameters (sample and acceptor phase pH, extraction temperature, extraction time) affecting the extraction efficiency were investigated. Proposed SDME-CE method provided about 14-fold enrichment in about 20 min. The calibration curve was linear for concentrations of NH₄⁺ in the range from 5 to 100 μmol/L (R² = 0.996). The LOD (S / N = 3) was estimated to be 1.5 μmol/L of NH₄⁺. Such detection sensitivity is high enough for ammonia determination in common environmental and biological samples. Finally, headspace SDME was applied to determine ammonia in human blood, seawater and milk samples with spiked recoveries in the range of 96-107%.     

Landfill leachate treatment using the sequencing batch biofilm reactor method integrated with the electro-Fenton process

A study was conducted on the treatment of landfill leachate by combining the sequencing batch biofilm reactor (SBBR) method with the electro-Fenton method. The reduction of chemical oxygen demand (COD), biological oxygen demand (BOD₅), and ammonia nitrogen (NH ₄ ⁺ -N) from the leachate by the SBBR method was investigated. For the electro-Fenton experiment, the changes in COD and total organic carbon (TOC) with the increase in H₂O₂ dosage and electrolysis time under optimal conditions were also analysed. The results showed that the average efficiencies of reduction of COD, BOD₅, and NH ₄ ⁺ -N achieved using the SBBR method were 21.6 %, 54.7 %, and 56.1 %, respectively. The bio-effluent was degraded by the subsequent electro-Fenton process, which was rapid over the first 30 min then subsequently slowed. After 60 min of the electro-Fenton treatment, the efficiencies of reduction of TOC, COD, and BOD₅ were 40.5 %, 71.6 %, and 61.0 %, respectively. There is a good correlation between the absorbance of leachate at 254 nm (UV₂₅₄) and COD or TOC during the electro-Fenton treatment.     

Copper(II)-cetyltrimethylammonium chloride-chromal blue G ternary complex and its application to the spectrophotometric determination of copper(II)

A sensitive spectrophotometric method for the determination of copper(II) based on a ternary complex with chromal blue G, a triphenylmethane reagent in the presence of cetyltrimethylammonium chloride, is described. The sensitivity of color reaction between copper and chromal blue G has been greatly increased by the sensitizing action of cetyltrimethylammonium chloride, a cationic surfactant. The color development of the ternary complex can be utilized in the highly sensitive spectrophotometric determination of copper. The molar absorptivity of the binary complex between copper and chromal blue G ε_630nm = 9.56 × 10³liters · mol⁻¹ · cm⁻¹ is enchanced on ternary complex formation to ε_{542 nm} = 4.78 × 10⁴liters · mol⁻¹ · cm⁻¹. The ternary complex gave a maximal absorbance at 542 nm in the pH range 9.8–11. Beer's law is obeyed up to at least 1.2 ppm of copper. The maximal absorbance of the ternary complex was found to develop within 5 min and then it remains constant for several hours. The formation constant of the ternary complex is calculated to be 8.6 × 10¹⁰ under these conditions.     

Molecular Cloning and Characteristic Features of a Novel Extracellular Tyrosinase from <Emphasis Type="Italic">Aspergillus niger</Emphasis> PA2

Biofertilizers have been widely used in many countries for their benefit to soil biological and physicochemical properties. A new microbial biofertilizer containing Phanerochaete chrysosporium and Bacillus thuringiensis was prepared to decrease nicotine content in tobacco leaves by regulating soil nitrogen supply. Soil NO₃ ^?-N, NH₄ ⁺-N, nitrogen supply-related enzyme activities, and nitrogen accumulation in plant leaves throughout the growing period were investigated to explore the mechanism of nicotine reduction. The experimental results indicated that biofertilizer can reduce the nicotine content in tobacco leaves, with a maximum decrement of 16–18 % in mature upper leaves. In the meantime, the total nitrogen in mature lower and middle leaves increased with the application of biofertilizer, while an opposite result was observed in upper leaves. Protein concentration in leaves had similar fluctuation to that of total nitrogen in response to biofertilizer. NO₃ ^?-N content and nitrate reductase activity in biofertilizer-amended soil increased by 92.3 and 42.2 %, respectively, compared to those in the control, whereas the NH₄ ⁺-N and urease activity decreased by 37.8 and 29.3 %, respectively. Nitrogen uptake was improved in the early growing stage, but this phenomenon was not observed during the late growth period. Nicotine decrease is attributing to the adjustment of biofertilizer in soil nitrogen supply and its uptake in tobacco, which result in changes of nitrogen content as well as its distribution in tobacco leaves. The application of biofertilizer containing P. chrysosporium and B. thuringiensis can reduce the nicotine content and improve tobacco quality, which may provide some useful information for tobacco cultivation.     

Ammonium-Nitrogen Recovery from Wastewater by Struvite Crystallization Technology

Struvite crystallization is one of the sustainable approaches for recovering ammonium nitrogen (NH₄-N) from wastewater in the form of a valuable material, in parallel with improving wastewater treatment efficiency. Focusing on NH₄-N recovery, this review discusses the factors influencing struvite crystallization including the effect of foreign elements. It is shown that more than 95% of NH₄-N could be recovered in the form of struvite, a magnesium-ammonium phosphate (MAP) salt, from some kinds of wastewater. This review emphasizes the role of utilizing alternative sources of Mg and P in improving the process sustainability. Additionally, it also explains how the MAP precipitation process could result with significant reduction of other pollutants contributing to total organic carbon, of color and turbidity, which support MAP integration with other treatment methods. The main options of lowering MAP recovery cost are presented; it was shown that applying low-cost materials of both Mg and P could save more than 65% of the process’s cost. Finally, the future research directions to improve NH₄-N recovery are pointed out.     

Quantitative Analysis of Nicorandil in Commercial Tablets by Spectrophotometry

The main aim of this work is to develop and validate a spectrophotometric method for the determination of nicorandil in commercial tablets. The method is based on the reduction of the nitroxy ethyl group of nicorandil into carbonyl compound and nitrite ion by NH₄Cl and Zn dust. The nitrite ion thus formed reacts with potassium iodide and starch in dilute HCl medium to form a blue product, which absorbs maximally at 550 nm. Beer's law is obeyed in the concentration range 0.4‐4.0 μg mL^?1 with molar absorptivity of 7.92 × 10⁴L mol^?1 cm^?1. The detection limit is 0.017 μg mL^?1. The reaction conditions are optimized and validated as per the International Conference on Harmonisation guidelines (USA). The proposed method has been applied successfully for the determination of nicorandil in commercial tablets. The results of analyses are compared statistically with those of the author's spectrophotometric method, which confirmed that there is no significant difference between the methods compared.     

An FTIR study of the rotation of ammonia in solid nitrogen

The infrared spectra of NH₃, NH₂D, NHD₂ and ND₃ in solid nitrogen have been studied with 0.05 cm^?1 resolution. All isotopic species of ammonia rotate around their c axis. The matrix actively participates in this motion. The resulting potential barrier is six-fold, showing that the trapping site has high symmetry. The ammonia inversion, which is strongly perturbed by the nitrogen matrix, is completely inhibited by large concentrations of polar molecules.     

Nitrogen Removal by Chelatococcus daeguensis TAD1 and Its Denitrification Gene Identification

Chelatococcus daeguensis TAD1 was demonstrated to be an aerobic denitrifier. It can utilize not only nitrate and nitrite but also ammonium at high temperature (about 50 °C). The strain had the capability to remove 122.7 and 71.7 mg L^?1 NH₄ ⁺-N by 18 h at 50 and 30 °C, respectively. Triplicate heterotrophic nitrification experiments showed that 32.3 % of removed NH₄ ⁺-N was completely converted to nitrogen gas by 18 h at 50 °C. The denitrification genes involved in C. daeguensis TAD1 were identified and sequenced. It was found that the genes responsible for denitrification in TAD1 were napA, nirK, cnorB, and nosZ. Taken together, TAD1 can be an effective candidate for simultaneous nitrification and denitrificaton at high temperature.