Indoor heterogeneous photochemistry of furfural drives emissions of nitrous acid

People spend approximately 80% of their time indoor, making the understanding of the indoor chemistry an important task for safety. The high surface-area-to-volume ratio characteristic of indoor environments leads the semi-volatile organic compounds (sVOCs) to deposit on the surfaces. Using a long path absorption photometer (LOPAP), this work investigates the formation of nitrous acid (HONO) through the photochemistry of adsorbed nitrate anions and its enhancement by the presence of furfural. Using a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS), this work also investigates the surface emissions of VOCs from irradiated films of furfural and a mix of furfural and nitrate anions. Among the emitted VOCs, 2(5H)-furanone/2-Butenedial was observed at high concentrations, leading to maleic anhydride formation after UV irradiation. Moreover, the addition of potassium nitrate to the film formed NO_x and HONO concentrations up to 10 ppb, which scales to ca. 4 ppb for realistic indoor conditions. This work helps to understand the high levels of HONO and NO_x measured indoors.     

Synthesis of p‐aminophenol from the hydrogenation of nitrobenzene over metal–solid acid bifunctional catalyst

BACKGROUND: A single‐step conversion of nitrobenzene (NB) to p‐aminophenol (PAP) through catalytic hydrogenation is a widely used synthesis route for PAP. The main shortcoming of this route is the use of sulfuric acid for rearrangement of the phenylhydroxylamine (PHA) intermediate. In this paper, S₂O₈^2?/ZrO₂ (PSZ) solid acid and Pt‐S₂O₈^2?/ZrO₂ (Pt‐PSZ) bifunctional catalysts were prepared for the synthesis of PAP in non‐acid medium. RESULTS: Calcination temperature has a substantial effect on the acidity, structure and activity for PHA rearrangement of PSZ. The highest PAP yield was 33.8% over PSZ calcined at 823 K when the reaction was carried out in water at 423 K. A high PAP yield of 23.9% was achieved by a single‐step reaction of nitrobenzene over Pt‐PSZ bifunctional catalysts. CONCLUSION: PSZ solid acid exhibits high activity for PHA rearrangement. Perfect tetragonal ZrO₂ and much stronger acid sites play important roles in catalytic activity. Inhibiting the hydrogenation activity by reducing the amount of Pt loading on Pt‐PSZ can improve the competition of PHA rearrangement on acid sites with hydrogenation of PHA on metal active sites, resulting in better selectivity to PAP. Copyright © 2008 Society of Chemical Industry     

Alkylated ureas: mineralization and evaluation as N sources

An incubation experiment was conducted for 11 weeks to study the mineralization of ten alkylated ureas and urea in soil. Six of the alkylated ureas viz. methylurea(MU), 1,3-dimethylurea(1,3DMU), 1,1-dimethylurea(1,1DMU), ethylurea(EU), 1,3-diethylurea(1,3DEU) and butylurea(BU) and urea mineralized during the experiment. Urea mineralized immediately, while alkylated ureas mineralized after an incubation period ranging from less than a week to four weeks (delay period of mineralization). The delay period increased in the following sequence MU < 1,3DMU < EU < BU < 1,1DMU < 1,3DEU, but after the delay period was over the compounds mineralized almost as rapidly as urea. The delay period varied according to the number of carbon atoms in the alkyl group and their position with respect to each other on the molecule. It appeared to be specific for each compound and was apparently not influenced by the presence of urea or other alkylated ureas. This character can be used to develop mixture of various alkylated ureas to obtain N mineralization at the desired time. Rapid evolution of CO₂ and N₂O was observed during the mineralization of urea as well as alkylated ureas. Increase in soil pH was also observed during this period. The simultaneous ocurrence of these events suggested the formation of urea as an intermediate during the mieralization of alkylated ureas. None of the alkylated ureas showed adverse affect on emergence of wheat seedlings and except DEU and BU at high concentration no other alkylated urea showed any adverse effect on initial growth of wheat seedlings.     

Thermal diffusivity of fluids in a broad region around the critical point

Dynamic light scattering is a suitable method for the investigation of transport properties such as the thermal diffusivity of optically transparent fluids. The main advantages of the method are its quickness, the fact of the thermodynamic state of equilibrium of the sample (gradients are not required), and the relatively simple evaluation of data without the necessity of calibration. However, an insufficient production of intensity of scattered light may be a limiting effect. For that reason the vicinity of the gas-liquid critical point represents the classical range of application. In this paper, it is shown that by means of an appropriate choice of experimental apparatus, measurements are also feasible in an extended range of states. Broad regions around critical points of three pure fluids (sulfur hexafluoride, SF₆; ethane, C₂H₆; nitrous oxide, N₂O) over temperature ranges ¦T-T _c¦ of 0.02 to 50 K and density ranges (/_c) of 0.2 to 2 were investigated. In this region the thermal diffusivity shows great variations with temperature and density and cannot be described by means of ideal-gas behavior or relations for liquids. The measurements were carried out along the coexistence curve for both phases, along the critical isochore and along some isotherms with TT _c. The measured or calculated density, pressure, and thermal diffusivity data as well as some correlations are presented.     

Electrochemical copolymerization of aniline with m-aminophenol and novel electrical properties of the copolymer in the wide pH range

A copolymer, poly(aniline-co-m-aminophenol), has been synthesized using repeated potential cycling. The monomer concentration ratio, acid concentration and applied potential strongly affect the copolymerization rate and the properties of the copolymer. The optimum conditions for the copolymerization are that the scan potential range is controlled between −0.10 and 0.95 V (vs.SCE), and a solution consists of 0.34 M aniline, 0.012 M m-aminophenol and 2 M H₂SO₄. The IR spectra of the copolymers demonstrate that the m-aminophenol units are included in the copolymer chains. The cyclic voltammograms of the copolymers in 0.3 M Na₂SO₄ solution with various pH values were performed at the potential ranges from −0.20 to 0.80 V and at a scan rate of 60 mV s⁻¹. The results indicate that the copolymer still hold 41.7% of the electrochemical activity when the copolymer electrode was transferred from a solution of pH 5.0 to a solution of pH 11.0 in the potential range of −0.20 to 0.80 V. An impedance plot of the copolymer in a solution with pH 12.0 and at 0.40 V is constructed of a semicircle and a Warburg line with a slope of 1. This means that the electrode reaction of the copolymer at pH 12.0 is also under mass transfer control. The conductivity of the copolymer prepared under the optimum conditions is 1.42 S cm⁻¹, and slightly depends on the pH value. Thus, the pH dependence of the electrical properties of the copolymer is improved compared with poly(aniline-co-o-aminophenol), and is much better than that of the parent polyaniline.     

Impact of agriculture on soil consumption of atmospheric CH4 and a comparison of CH4 and N2O flux in subarctic, temperate and tropical grasslands

Increasing concentrations of methane (CH₄) in the atmosphere are projected to account for about 25% of the net radiative forcing. Biospheric emissions of CH₄ to the atmosphere total approximately 400 Tg C y^-1. An estimated 300 Tg of CH₄-C y^-1 is oxidized in the atmosphere by hydroxyl radicals while about 40 Tg y^-1 remains in the atmosphere. Approximately 40 Tg y^-1 of the atmospheric burden is oxidized in aerobic soils. Research efforts during the past several years have focused on quantifying CH₄ sources while relatively less effort has been directed toward quantifying and understanding the soil sink for atmospheric CH₄. Recent research has demonstrated that land use change, including agricultural use of native forest and grassland systems has decreased the soil sink for atmospheric methane. Some agricultural systems consume atmospheric CH₄ at rates less than 10% of those found in comparable undisturbed soils. While it has been necessary to change land use practices over the past centuries to meet the required production of food and fiber, we need to recognize and account for impacts of land use change on the biogeochemical nutrient cycles in the biosphere. Changes that have ensued in these cycles have and will impact the atmospheric concentrations of CH₄ and N₂O. Since CH₄ and N₂O production and consumption are accomplished by a variety of soil microorganisms, the influence of changing agricultural, forest, and, demographic patterns has been large. Existing management and technological practices may already exist to limit the effect of land use change and agriculture on trace gas fluxes. It is therefore important to understand how management and land use affect trace gas fluxes and to observe the effect of new technology on them. This paper describes the role of aerobic soils in the global CH₄ budget and the impact of agriculture on this soil CH₄ sink. Examples from field studies made across subarctic, temperate and tropical climate gradients in grasslands are used to demonstrate the influence of nutrient cycle perturbations on the soil consumption of atmospheric CH₄ and in increased N₂O emissions. This revised version was published online in August 2006 with corrections to the Cover Date.     

Nitrous oxide emissions from fertilized upland fields in Thailand

Nitrous oxide (N₂O) emission from fertilized maize fields was measured using a closed chamber at four experimental sites in Thailand. The average measured N₂O flux from unfertilized plots through crop season was 4.16 ± 1.52, 5.05 ± 1.65, 5.25 ± 1.68 and 6.74 ± 2.95 g N₂O-N m^-2 h^-1, at Nakhon Sawan, Phra Phutthabat, Khon Kaen and Chiang Mai, respectively. Increased N₂O emissions by the application of nitrogen fertilizer were 0.22–0.44, 0.19–0.38%, 0.12–0.24 and 0.08–0.15% of the applied N, respectively. Compared to other data, N₂O emission rate to applied nitrogen was not significantly different between the data of Thailand and the Temperate Zone.     

Effects of soil solution on the dynamics of N2O emissions: a review

In this review, which consists of two parts, major interactions between nitrous oxide (N₂>O) and soil solution are described. In the first part, as an introduction, concentrations of dissolved N₂>O in different aqueous systems are summarized. An inventory of data on maximal N₂>O concentrations in soil solution (up to 9984 g N₂>O-N l^–1>) and in soil air (up to 8300 ppm) from literature is presented. The peak N₂>O concentrations represent a N₂>O supersaturation in the soil solution up to 30000 times with respect to ambient air and a soil air N₂>O concentration about 25000 times higher than in the atmosphere. The main physico–chemical parameters (solubility, diffusion) controlling N₂>O distribution between soil solution and soil air are outlined. The influences of cultivation practice, nitrogen turnover, water content and temperature on N₂>O a ccumulation in soil solution and soil air are reviewed. In the second part some models of N₂>O dynamics in soils are discussed with emphasis on N₂>O transport processes. A simple qualitative scheme is developed to categorize the effects of the soil solution on N₂>O dynamics in soils. In this scheme the temporary, intensive N₂>O oversaturation of the soil solution is interpreted as a result of gas diffusion inhibition by water (barrier function of soil solution) resulting in an accumulation of N₂>O. In addition, N₂>O supersaturation is an indication that transitory much N₂>O can be stored in the soil solution (storage function of soil solution). Where the soil solution flows up-, down- or sidewards it can act as a relevant transport medium for dissolved N₂>O (transport function of soil solution). This scheme is applied to examples from the literature.     

Measurement of intrinsic rates for homogeneous gas‐phase reactions at high temperatures

A coiled quartz tubular reactor has been designed to measure the intrinsic reaction kinetics for homogeneous reactions at high temperatures up to 1100°C. Actual gas residence times were less than 100 ms. A simple and well‐studied test reaction (i.e., the decomposition of nitrous oxide, N₂O), with published intrinsic kinetics, was used to verify the operation of the experimental reactor. For this system, Peclet numbers (Pe = uL/DL) computed from experimental conversion data were greater than 1000, indicating that the plug flow assumption could be used with this reactor system to determine intrinsic rate expressions with errors of less than 5% for the conditions studied.     

pH对高氨废水限氧半亚硝化过程中N2O释放的影响

为获得半亚硝化系统中强温室气体N2O减量化释放的控制参数,采用SBR处理人工合成高氨废水(进水氨氮质量浓度约为600 mg·L-1),考察不同进水pH(7.5,8.0和8.5)对N2O释放特性的影响.结果表明,不同进水pH下均释放N2O,每个周期内N2O的释放量随进水pH的升高而减小.pH为7.5,8.0及8.5时,N2O释放量分别占进水氨氮的3.81%、2.35%和2.00%.当pH为7.5时,曝气初始50 min内,N2O释放速率先增大后减小,峰值速率为44.5μg·min-1·g-1,之后维持在16.5μg·min-1·g-1;当p H为8.0及8.5时,曝气初期N2O释放峰值速率分别为33.7,22.9μg·min-1·g-1,之后释放速率随pH降低和NO2-积累而逐渐增大.