Dielectric Barrier Discharge for Ammonia Production

The leading after-treatment technology for NOx removal process in Diesel engines for stationary and mobile applications is the selective catalytic reduction of oxides of nitrogen [NOx] by ammonia [NH₃]. A novel non-thermal plasma electrode with a needle array in a dielectric barrier discharge reactor, powered by a high frequency neon transformer, is used for the thermal decomposition of solid urea [(NH₂)CO(NH₂)] to produce ammonia. The thermolysis of urea produces iso-cyanic acid [HNCO] as a byproduct, besides ammonia, which can react with water in the gas phase, thus giving carbon dioxide and more ammonia. The presence of water fed before and/or after the plasma reactor was studied to assess its effect on the amount of produced ammonia. Results clearly showed that water fed to the entrance of the reactor can efficiently promote the reaction of iso-cyanic acid to produce ammonia and this result can be improved when air is used as carrier gas for 115 V of input voltage to a neon transformer and with a gas flow rate of 4 L/min.     

Environmentally friendly method for determination of ammonia nitrogen in fertilisers and wastewaters based on flow injection-spectrophotometric detection using natural reagent from orchid flower

Crude aqueous extract from the orchid ‘Dendrobium Sonia earsakul’ was utilised as a natural product reagent in flow injection analysis (FIA) incorporating a gas diffusion unit (GD) for the determination of ammonia nitrogen. Sample solution was injected into a NaOH donor stream to generate ammonia gas (NH₃). In the GD unit, NH₃ diffused across a PTFE gas-permeable membrane into the acceptor stream of the orchid extract. As the result, the aqueous orchid reagent became more alkaline and its colour changed from purple to green. The change in the colour of orchid acceptor correlated with the concentration of ammonia nitrogen in the sample and its absorbance monitored by a spectrophotometer at 600 nm. Ammonia nitrogen in chemical fertiliser samples and wastewater samples from agricultural fields were determined and reported as %N (w/w) and mg N L^?1, respectively. For chemical fertilisers which contained high content of ammonia nitrogen, a flow rate of 1.0 mL min^?1 and injection volume of 100 µL were used with a linear range of 5–40 mmol L^?1 and detection limit of 2.12 mmol L^?1. However, a higher sensitivity was required for wastewater samples having low ammonia nitrogen content. The flow rate was reduced to 0.3 mL min^?1 and the injection volume increased to 1000 µL. As a result, detection limit of 0.76 mmol L^?1 was achieved with linear range of 1–5 mmol L^?1. The results of our method agreed well with that using the OPA method employing fluorescence detection.     

Determination of Ammonia in Water Using Flow Injection Analysis with Automatic Pervaporation Enrichment

Abstract

An automated ammonia monitoring system has been developed by putting a pervaporation unit in an enrichment cycle used in flow injection analysis mode. In the proposed system, an enrichment cycle was equipped to enable the adjustment for the measuring range of ammonium by controlling the duration of the enrichment circulation. Therefore, the system was capable to determine ammonia in both the surface water with low ammonia concentration and the ammonia-rich wastewater with the linear dynamic range of 0.05–15 mg l^?1 and 15–50 mg l^?1, respectively. The relative standard deviations were less than 1.9% and the quantification limit is as low as 0.03 mg l^?1. The sampling frequency is 8–10 h^?1.     

Synthesis and characterization of methanesulfonic acid doped poly(2-chloroaniline), study of its physical properties and ammonia gas sensing application

The poly(2-chloroaniline) was prepared by in situ chemical oxidative polymerization method using ammonium thiosulphate as an oxidant and methanesulfonic acid as a dopant. The optical absorption spectra showed bands for π-π* transition of the benzenoid ring at 265 nm and at 350 nm for n-π* transition of the quinonoid ring. The broad band appeared around 550 nm was due to transition of electrons from the valance band to the conduction band, this also confirmed the good electrical conductivity of the polymer. The X-ray diffraction pattern showed characteristic diffraction peak at 2θ = 26° confirming a emeraldine salt form of the poly(2-chloroaniline). The electrical conductivity of the polymer measured by the two probe method at room temperature was 2.21×10^?3 S/cm, which was found to be thermally activated. The linear increase in conductivity with increase in the temperature suggested the electron hopping mechanism. The methanesulfonic acid doped poly(2-chloroaniline) presents a linear dependency of its electrical resistance with an increase in ammonia gas concentration (1 ppm to 300 ppm) and creates a promising sensing material for ammonia gas sensing applications.     

光波导二氧化氮气敏传感元件的研究

本文用离子交换法制备K+交换玻璃光波导元件,并在其表面固定纳米级敏感层酞菁铜(CuPc)薄膜,利用光波导气体检测系统对NO2气体进行测试.结果表明,该传感元件常温下对NO2等气体有快速、可逆的响应,并具有重现性好,灵敏度高等特点.     

Measurement of Nitrogen and Nitrogen Isotopic Ratios Using Reduction Pyrolysis Coupled with Mass Spectrometry

Abstract

An analytical system for measuring total nitrogen and its isotopic abundance in a variety of environmental samples has been developed. A reductive pyrolysis system and a directional focusing 6-inch gas mass spectrometer were combined into the analytical system. In the reductive part of the system, nitrogen species are converted to ammonia with an atmosphere of hydrogen in the presence of a heated nickel catalyst. Five percent of the gas stream is split away for measuring total nitrogen by a conductivity detector. The ammonia is removed from the gas stream employing a cold finger reaction vessel.

The hydrogen-free ammonia is decomposed thermally to nitrogen and hydrogen at 1000°C, employing a hot rhenium filament. The N₂ produced from the decomposition is used for measuring the abundance of masses 28 and 29 by mass spectrometry. From this ratio, the ¹⁵N atom fraction is calculated.

Standard samples of N₂, ammonia, orchard leaves and urea have been successfully analyzed to determine isotopic compositions. Samples containing as little as 20 μg of total nitrogen can be analyzed by this system. By the addition of multi-reaction vessels, three samples may be completed per hour.     

Optical Gas Sensor Fabrication Based on Porphyrin-Anchored Electrostatic Self-Assembly onto Tapered Optical Fibers

Tapered optical fibers with nano-assembled coatings of thicknesses of order tens of nanometres were used for the detection of ammonia gas. The film coating was composed of alternate layers of tetrakis-(4-sulfophenyl) porphine (TSPP) and poly(allylamine hydrochloride) (PAH), which were deposited using the electrostatic self-assembly process (ESA). Exposure of a PAH/TSPP nano-assembled non-adiabatic tapered optical fiber with a waist diameter of 10 µm to ammonia induced significant optical changes in the transmission spectrum of the optical fiber. The fiber optic sensor showed a linear sensitivity to the concentration of ammonia in the range of 10–100 ppm, with response and recovery times less than 100 and 240 sec, respectively. The 3σ limit of detection (LOD) was estimated to be ca. 2 ppm.     

Radon measurement in carbonated water with the Lucas cell and charcoal adsorption methods

There have been developed several different methods for measuring radon concentration in water which are now widely used, such as: liquid scintillation counting, Lucas cell counting, gamma and alpha spectroscopy. However, as far as the radon measurements in carbonated water are concerned, there are some issues caused by the gas excess. The aim of our work was to develop a simple method for measuring radon concentration in carbonated water that can be used for in situ measurements. Nevertheless, we propose not one, but two methods for measuring radon concentration in carbonated water. Thus, the first one is based on Lucas scintillation cells, and can be used for on-site measurements, while the second one utilizes activated charcoal adsorption, and needs a setup laboratory for gamma spectrometry measurements. For the evaluation of the methods, we compared the results of the Lucas cell-Luk3C method and of the activated charcoal method, both for non-carbonated and carbonated water. The simplest method for radon concentration determination—Lucas cell method—was successfully applied to fourteen natural carbonated water samples from Borsec to Bilbor area. The radon concentrations obtained ranged from 5.6 ± 0.5 to 39.6 ± 4.0 Bq/L, with a mean of 15.9 ± 2.6 Bq/L, these values are lower than 100 Bq/L, the maximum value recommended by the World Health Organization.     

Optochemical Sensor for Ammonia Based on a Lipophilized pH Indicator in a Hydrophobic Matrix

Abstract

An optical sensor for the determination of ammonia in water based on ion pairing has been investigated. A pH-sensitive dye is immobilized as an ion pair in a silicone matrix. The colour of the dye changes from yellow to blue depending on the concentration of ammonia in the sample solution. This change is reversible. The concentration of ammonia can be determined by measuring the transmittance at a given wavelength.

All measurements were performed with a dual-beam optical meter. The measurement range was from 5.9 × 10^?7 to 1 × 10^?3 M (0.01 to 17 mg/l) in 0.1 M phosphate buffer of pH 8. The detection limit was 10 μg/l. The response times at a flow rate of 2.5 ml/min were 4 min for t₉₀ and 10 min for t₁₀₀ at a change from 41.9 to 82.5 μM ammonia and 12 min for t₉₀ and 48 min for t₁₀₀ at a change from 160 to 0 μM ammonia. The operational lifetime of the ammonia sensor was limited to a period of a few days only. A continuous decrease in baseline signal and relative signal change was observed over the whole measurement. The storage stability was more than 10 months (dry). With respect to possible application of the ammonia sensor to environmental analysis, the influence of pH, typical interferences, such as amines and various detergents on the sensor response was investigated. No interference due to pH was observed in the range from pH 5 to pH 9. With methyl- and ethylamine the response was not completely reversible. The sensor was affected by cationic detergents, but not by anionic or neutral detergents.     

Conductometric sensor for ammonia and ethanol using gold nanoparticle-doped mesoporous TiO2

We describe uniform and high-temperature-stable mesoporous TiO₂ beads functionalized with gold nanoparticles (AuNPs-TiO₂) for use in conductometric sensing of gases and organic vapors. The size of the interconnected main mesopores of the TiO₂ beads ranges from 8 to 15 nm, and the AuNPs have diameters between 8 and 10 nm. The mesoporous TiO₂ beads are formed during calcination while the structure-directing template agent is removed. Monodispersed AuNPs are formed by reduction in-situ and are placed inside the mesoporous TiO₂ framework. This prevents aggregation of the AuNPs even at 500 °C. The materials were characterized by UV–vis spectroscopy, scanning and transmission electron microscopy, nitrogen adsorption-desorption, and X-ray diffraction. Comb-type gold electrodes were then fabricated on an alumina substrate and are shown to display excellent properties in terms of sensing ammonia, ethanol, methanol or acetone. The sensitivity (defined as the ratio of resistivities under vapor and air) of a typical AuNPs(0.5 %)-TiO₂ gas sensor for ethanol reached up to 5.65 at above 600 ppm at 75 °C. Response time and recovery times (t₉₀ ≤ 20 s) are faster than (or comparable to) other metal-doped TiO₂ sensors, and working temperatures are much lower. An interesting observation was made in that the changes in the conductivity of the sensor change with temperature. The sensor prepared with AuNPs(0.5 %)-TiO₂ is of the p-type (in its response to ammonia gas) at 45 °C, but becomes n-type at 20 °C. Obviously, rather slight changes in temperature lead to a complete change in the direction of the conductometric signal change. This may provide a new aspect in terms of selective and highly sensitive detection of ammonia at ambient and slightly elevated temperatures.

We describe uniform and high-temperature-stable mesoporous TiO₂ beads functionalized with gold nanoparticles (AuNPs-TiO₂) for use in conductometric sensing of gases and organic vapors. Interestingly, the changes in the conductivity of typical sensors were opposite with the increasing of temperature.

     

顶空气相色谱法快速测定污水中氨氮含量

研究了一种基于化学反应型顶空气相色谱的快速检测污水氨氮含量新方法。首先在顶空瓶中用过量的甲醛与NH₄⁺反应产生等物质的量的强酸，再用NaHCO₃与新生成的酸反应产生CO₂，最后经过气相色谱定量CO₂，间接得出样品中氨氮的含量。结果表明，氨氮含量与气相色谱信号值之间存在良好的线性相关性，相关系数为0.999，定量限为0.786 mg/L（以N的质量浓度计），相对标准偏差小于2%，加标回收率在95%~105%之间。与国标纳氏试剂法相比，该方法测定结果的相对偏差在±5%以内。该方法检测效率高，适用于快速批量检测污水中氨氮的含量。     

The Wettability Alteration and the Effect of Initial Rock Wettability on Oil Recovery in Surfactant-based Enhanced Oil Recovery Processes

Wettablity alteration of rock surface is an important mechanism for surfactant-based enhanced oil recovery (EOR) processes. Two salt and temperature-tolerant surfactant formulations were developed based on the conditions of high temperature (97–120°C) and high salinity (20 × 10⁴ mg/L) reservoirs where a surfactant-based EOR process is attempted. Both the two sufactant formulations can achieve ultralow interfacial tension level (≤10^?3 mN/m) with crude oil after aging for 125 days at reservoir conditions. Wettability alteration of core slices induced by the two surfactant formulations was evalutated by measuring contact angles. Core flooding experiments were carried out to study the influence of initial rock wettabilities on oil recovery in the crude oil/surfactant/formation water/rock system. The results indicated that the two formulations could turn oil-wet core slices into water-wet at 90–120°C and 20 × 10⁴ mg/L salinity, while the water-wet core slices retained their hydrophilic nature. The core flooding experiments showed that the water-wet cores could yield higher oil recovery compared with the oil-wet cores in water flooding, surfactant, and subsequent water flooding process. The two surfactant formulations could successfully yield additional oil recovery in both oil-wet and water-wet cores.     

Cyclodextrin Polymer Films Optical Waveguide Sensor for Volatile Organic Gas Detection

A sensitive optical waveguide(OWG) sensor which can be used to detect volatile organic compounds(VOCs) was presented. The sensing device(element) was fabricated by means of the immobilization of polyvinyl pyrrolidone(PVP)-cyclodextrin(CD) composite film over a single-mode potassium ion exchanged glass OWG via spin-coating method. The sensor shows higher response to styrene gas than to other VOCs and displays a linear response to styrene gas in a range of 1-1000 μL/L.     

Rhamnolipids Production by Multi-metal-Resistant and Plant-Growth-Promoting Rhizobacteria

The biosurfactant-producing Pseudomonas aeruginosa A11, with plant-growth-promoting (PGP) and multi-metal-resistant (MMR) features was isolated from the rhizosphere of a wild plant Parthenium hysterophorus. The strain A11 was able to utilize glycerol as a carbon source and produce 4,436.9 mg/L of biosurfactant after 120 h of incubation. The biosurfactants was characterized as rhamnolipids (RLs) by thin layer chromatography, Fourier transform infrared spectroscopy, nuclear magnetic resonance, and liquid chromatography–mass spectrometry analysis. Eight different RLs congeners were detected with RhaRhaC₁₀C₁₀ being most abundant. The purified rhamnolipid, dirhamnolipid, and monorhamnolipid reduced the surface tension of water to 29, 36, and 42 mN/m with critical micelle concentration of 83, 125, and 150 mg/L, respectively. The strain A11 demonstrated resistance against all the metals detected in rhizosphere except Hg and Ni. The strain A11 also possessed plant-growth-promoting features like siderophores, hydrogen cyanide, catalase, ammonia production, and phosphate solubilization. The dirhamnolipids formed crystals upon incubation at 4 °C, thus making separation of dirhamnolipids easy. Biosurfactant-producing ability along with MMR and PGP traits of the strain A11 makes it a potential candidate for application in the bacterial assisted enhancement of phytoremediation of heavy-metal-contaminated sites.     

Application of HS-SPME with Poly(1-Vinyl-3-Hexylimidazolium Chloride) Polymeric Ionic Liquid Coating Using GC–MS to Determine Volatile Fatty Acids in Dairy Wastewater

Volatile fatty acids were determined in this study using headspace solid-phase microextraction (HS-SPME) with a poly(1-vinyl-3-hexylimidazolium chloride) polymeric ionic liquid coated fiber followed by gas chromatography–mass spectrometry. Experimental parameters such as extraction time and temperature, sample volume as well as desorption time and temperature were optimized. Detection limits of the method were in the range of 0.13–0.26 mg/L. The coefficient of variation ranged from 0.12 to 6.9 %. The method was applied to determine volatile fatty acids in dairy wastewater from different operations and in bulk wastewater.     

Determination of Chlorophenols in Wastewater with Methyl Chloroformate Derivatization,Solid Phase Extraction,and Gas Chromatography–Mass Spectrometry

The determination of chlorophenols in wastewater with methyl chloroformate derivatization, solid phase extraction, and gas chromatography–mass spectrometry is reported. In order to employ this combined solid phase derivative extraction method, quantitative extraction was performed by the introduction of 100 mL of sample in 1.0 mol L^?1 sodium hydroxide into a column containing 500 mg of packed resin at a flow rate of 1.0 mL/min. The chlorophenols were retained and derivatized quantitatively in the column by the introduction of 0.25 mL of methyl chloroformate. The derivatized analytes were eluted with 5.0 mL of hexane before the effluent was dried under a stream of nitrogen. The dried solution was diluted to a volume of 50 µL with hexane followed by analysis by gas chromatography–mass spectrometry. The preconcentration parameters were optimized and under these conditions: limits of detection from 0.010 to 0.423 µg L^?1, a preconcentration factor of 2500, and precision values from 4.8 to 7.7% as the relative standard deviation were obtained. The method was employed for the analysis of water samples and the recoveries of the analytes were between 76 and 103%.     

A new evanescent wave ammonia sensor based on polyaniline composite

A single-mode TE(0)-TM(0) optical planar waveguide ammonia sensor based on polyaniline/polymethyl methacrylate (PANI/PMMA) composite is designed and developed. The sensing properties of the photonic sensor to ammonia at room temperature are studied. A significant change is observed in the guided light output power of the sensor after it is exposed to ammonia gas. The metrological parameters (sensitivity, response time and recovery time) of the sensor are strongly influenced by the interaction length (length of sensing region). Compared with the conventional optical ammonia sensor based on absorption spectroscopy, the integrated optical sensor is more sensitive to ammonia.     

Detection of Amines in Lamb Spoilage by Optical Waveguide Sensor Based on Bromophenol Blue-Silicon Composite Film

We herein report the development of a bromophenol blue(BPB)-silicone composite film/K^+-exchange glass optical waveguide(OWG)sensor for the detection of amines produced during the spoilage of lamb.the optical and structural properties of the sensitive thin film were studied by ultra violet-visible(UV-Vis)spectroscopy,and the light source of the OWG detecting system was selected.Gas sensing measurements showed that the sensor exhibited a good selectivity,higli sensitivity,and short response-recovery time towards volatile amine gases in the 0.00117一11.72 mg/g range.The as-prepared optical waveguide device was subsequently applied in the determination of gases(namely trimethylamine,dimethylamine,and ammonia)emitted from the lamb samples(5g)stored at room temperature(25℃)and in a refrigerator(5℃)for 0—4 d,and the total volatile basic nitrogen(TVB-N)contents were detected by UV-Vis spectroscopy,and the results were compared witli those obtained using our detector.It was found that the sensing element was capable of detecting mixed gases produced by the decomposition of lamb samples in a refrigerator for 0.5 h,where the TVB-N content was lower than 35μg/g.     

Synthesis of polypyrrole films for the development of ammonia sensor

In the present investigation, we have synthesized a polypyrrole films by chemical polymerization technique for the development of ammonia sensor. The polypyrrole films were synthesized in an aqueous acidic medium on glass substrate with mild oxidation of ferric chloride at temperature 29°C. The concentrations (molar) of monomer (pyrrole), oxidant (ferric chloride), and dopant (polyvinyl sulfonate) have been optimized for the uniform and porous surface morphology of the synthesized polypyrrole film. The synthesized films were characterized by scanning electron microscopy, ultraviolet‐visible, and Fourier transforms infrared spectroscopy. Ammonia gas sensing behavior of polypyrrole films was studied by using indigenously developed gas sensing chamber. The synthesized polypyrrole film with optimized process parameters shows excellent and reproducible response to low concentration (100 ppm) of ammonia gas. Copyright © 2007 John Wiley & Sons, Ltd.     

An Array of Micro-hollow Surface Dielectric Barrier Discharges for Large-Area Atmospheric-Pressure Surface Treatments

A robust, commercial micro-hollow plasma source was used to generate atmospheric-pressure plasma, of surface area 18 × 18 mm, in ambient air, nitrogen and argon. An electrode system consisting of 105 micro-hollow surface dielectric barrier discharges was powered by sinusoidal high-voltage at a frequency of 26.7 kHz. The influence of the plasmas on the polycarbonate surface was investigated by means of surface energy measurements and X-ray photoelectron spectroscopy. It emerged that short plasma exposures led to significant increases in surface energy. It is suggested that this may arise out of incorporation of polar groups on the polycarbonate surface. A thermal camera was used to monitor the plasma source surface temperatures for the gases at flow rates ranging from 0 to 5 L/min. It was found that the temperature of the micro-hollow ceramic when operated upon in ambient air decreased significantly from 147 °C at 0 L/min to 49 °C at 5 L/min. In order to investigate further the thermal properties of the plasma, optical emission spectroscopy was employed to monitor the vibrational and rotational temperatures of the plasma generated in ambient air. CCD camera spectroscopic measurements estimated plasma thickness and temperature distribution at high spatial resolution.