Absence Of Nitrogen Oxides Research Articles

Dielectric Properties of Materials Used for Microwave-Based NOx Gas Dosimeters.

Nitrogen oxides (NOx), primarily generated from combustion processes, pose significant health and environmental risks. To improve the coordination of measures against excessive NOx emissions, it is necessary to effectively monitor ambient NOx concentrations, which requires the development of precise and cost-efficient detection methods. This study focuses on developing a microwave- or radio frequency (RF)-based gas dosimeter for NOx detection and addresses the optimization of the dosimeter design by examining the dielectric properties of LTCC-based (Low-Temperature Co-fired Ceramics) sensor substrates and barium-based NOx storage materials. The measurements taken utilizing the Microwave Cavity Perturbation (MCP) method revealed that these materials exhibit more pronounced changes in dielectric losses when storing NOx at elevated temperatures. Consequently, operating such a dosimeter at high temperatures (above 300 °C) is recommended to maximize the sensor signal. To evaluate their high-temperature applicability, LTCC substrates were analyzed by measuring their dielectric losses at temperatures up to 600 °C. In terms of NOx storage materials, coating barium on high-surface-area alumina resolved issues related to limited NOx adsorption in pure barium carbonate powders. Additionally, the adsorption of both NO and NO2 was enabled by the application of a platinum catalyst. The change in dielectric losses, which provides the main signal for an RF-based gas dosimeter, only depends on the stored amount of NOx and not on the specific type of nitrogen oxide. Although the change in dielectric losses increases with the temperature, the maximum storage capacity of the material decreases significantly. In addition, at temperatures above 350 °C, NOx is mostly weakly bound, so it will desorb in the absence of NOx. Therefore, in the future development of a reliable RF-based NOx dosimeter, the trade-off between the sensor signal strength and adsorption behavior must be addressed.

Dimers in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity

Abstract. The formation of secondary organic aerosol (SOA) from both ozonolysis and hydroxyl radical (OH)-initiated oxidation of α-pinene under conditions of high nitric oxide (NO) concentrations with varying relative humidity (RH) and aerosol acidity was investigated in the University of North Carolina dual outdoor smog chamber facility. SOA formation from ozonolysis of α-pinene was enhanced relative to that from OH-initiated oxidation in the presence of initially high-NO conditions. However, no effect of RH on SOA mass was evident. Ozone (O3)-initiated oxidation of α-pinene in the presence of ammonium sulfate (AS) seed coated with organic aerosol from OH-initiated oxidation of α-pinene showed reduced nucleation compared to ozonolysis in the presence of pure AS seed aerosol. The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), with a focus on the formation of carboxylic acids and high-molecular weight dimers. A total of eight carboxylic acids and four dimers were identified, constituting between 8 and 12% of the total α-pinene SOA mass. OH-initiated oxidation of α-pinene in the presence of nitrogen oxides (NOx) resulted in the formation of highly oxidized carboxylic acids, such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). The formation of dimers was observed only in SOA produced from the ozonolysis of α-pinene in the absence of NOx, with increased concentrations by a factor of two at higher RH (50–90%) relative to lower RH (30–50%). The increased formation of dimers correlates with an observed increase in new particle formation at higher RH due to nucleation. Increased aerosol acidity was found to have a negligible effect on the formation of the dimers. SOA mass yield did not influence the chemical composition of SOA formed from α-pinene ozonolysis with respect to carboxylic acids and dimers. The results support the formation of the high-molecular weight dimers through gas-phase reactions of the stabilized Criegee Intermediate (sCI) formed from the ozonolysis of α-pinene. The high molecular weight and polar nature of dimers formed in the gas phase may explain increased particle number concentration as a result of homogenous nucleation. Since three of these dimers (i.e. pinyl-diaterpenyl dimer (MW 358), pinyl-diaterebyl dimer (MW 344) and pinonyl-pinyl dimer (MW 368)) have been observed in both laboratory-generated and ambient fine organic aerosol samples, we conclude that the dimers observed in this study can be used as tracers for the O3-initiated oxidation of α-pinene, and are therefore indicative of enhanced anthropogenic activities, and that the high molecular weight and low volatility dimers result in homogenous nucleation under laboratory conditions, increasing the particle number concentration.

The formation of SOA and chemical tracer compounds from the photooxidation of naphthalene and its methyl analogs in the presence and absence of nitrogen oxides

Abstract. Laboratory smog chamber experiments have been carried out to investigate secondary organic aerosol (SOA) formation from the photooxidation of naphthalene and its methyl analogs, 1- and 2-methylnaphthalene (1-MN and 2-MN, respectively). Laboratory smog chamber irradiations were conducted in a flow mode to ensure adequate collection of the aerosol at reasonably low reactant concentrations and in the presence and absence of nitrogen oxides. Phthalic acid and methyl analogs were identified following BSTFA derivatization of the aerosol extract. These compounds were examined to determine whether they could serve as reasonable molecular tracers to estimate the contributions of these precursors to ambient PM2.5. Measurements were also made to determine aerosol parameters from secondary organic aerosol from naphthalene, 1-MN, and 2-MN. A mass fraction approach was used to establish factors which could be applied to phthalic acid concentrations in ambient aerosols, assuming a negligible contribution from primary sources. Phthalic anhydride uptake (and hydrolysis) was tested and found to represent a moderate filter artifact in filter measurements with and without in-line denuders. This study provided the opportunity to examine differences using authentic standards for phthalic acid compared to surrogate standards. While the mass fraction based on a surrogate compounds was somewhat lower, the differences are largely unimportant. For naphthalene, mass fractions of 0.0199 (recommended for ambient samples) and 0.0206 were determined in the presence and absence of nitrogen oxides, respectively, based on phthalic acid standards. The mass fractions determined from the laboratory data were applied to ambient samples where phthalic acid was found and expressed "as naphthalene" since phthalic acid was found to be produced in the particle phase from other methylnaphthalenes. The mass fraction values were applied to samples taken during the 2005 SOAR Study in Riverside, CA and 2010 CalNex Study in Pasadena. In both studies an undetermined isomer of methylphthalic acid was detected in addition to phthalic acid. Laboratory experiment retention times and mass spectra suggest that the major precursor for this compound is 2-MN. For the CalNex Study, SOC values for the 2-ring precursor PAHs (as naphthalene) were found to range from below the detection limit to 20 ngC m−3 which with the laboratory mass fraction data suggests an upper limit of approximately 1 μg m−3 for SOA due to 2-ring PAHs. Temporal data over the course of the one-month CalNex study suggest that primary sources of phthalic acid were probably negligible during this study period. However, the values must still be considered upper limits given a potential hydrolysis reaction or uptake of phthalic anhydride (subsequently hydrolyzed) onto the collection media.

Ozone Based Atomic Layer Deposition of Hafnium Oxide and Impact of Nitrogen Oxide Species

It has recently been reported that nitrogen oxide species (e.g., N2O5, NO2, NO3, and/or N2O) can have an impact on ozone based atomic layer deposition (ALD) of metal oxides when ozone is generated by dielectric barrier discharge (DBD) in O2/N2 mixtures. In this work, we further investigate the effect of the O2/N2 ratio in the DBD for HfO2 ALD using HfCl4 as metal precursor. Using O3 in the absence of nitrogen oxides, uniform HfO2 layers are obtained between 200 and 250°C in a hot wall cross flow reactor. The self-limiting nature of the O3 and HfCl4 reaction is demonstrated at 225°C and the growth-per-cycle is 0.12 nm. At higher temperature, O3 decomposes at the HfO2 coated reactor walls, resulting in a decreasing HfO2 thickness over Si substrates in the direction of the gas flow. Using O3 in combination with nitrogen oxides by DBD in N2/O2 mixtures, we obtained uniform HfO2 layers in the 200–300°C temperature range. At 300°C, the GPC is 0.14 nm and the HfO2 films show a low impurity content. Both processes produce high quality dielectric layers in Pt gated capacitors.

The formation of secondary organic aerosol from the isoprene + OH reaction in the absence of NO<sub>x</sub>

Abstract. The reaction of isoprene (C5H8) with hydroxyl radicals has been studied in the absence of nitrogen oxides (NOx) to determine physical and chemical characteristics of the secondary organic aerosol formed. Experiments were conducted using a smog chamber operated in a steady-state mode permitting measurements of moderately low aerosol levels. GC-MS analysis was conducted to measure methyl butenediols in the gas phase and polyols in the aerosol phase. Analyses were made to obtain several bulk aerosol parameters from the reaction including values for the organic mass to organic carbon ratio, the effective enthalpy of vaporization (ΔHvapeff), organic peroxide fraction, and the aerosol yield. The gas phase analysis showed the presence of methacrolein, methyl vinyl ketone, and four isomers of the methyl butenediols. These gas-phase compounds may serve as precursors for one or more of several compounds detected in the aerosol phase including 2-methylglyceric acid, three 2-methyl alkenetriols, and two 2-methyl tetrols. In contrast to most previous studies, the 2-methyl tetrols (and the 2-methyl alkenetriols) were found to form in the absence of acidic sulfate aerosol. However, reaction conditions did not favor the production of HO2 radicals, thus allowing RO2+RO2 reactions to proceed more readily than if higher HO2 levels had been generated. SOA/SOC (i.e. OM/OC) was found to average 1.9 in the absence of NOx. The effective enthalpy of vaporization was measured as 38.6 kJ mol−1, consistent with values used previously in modeling studies. The yields in this work (using an independent technique than used previously) are lower than those of Kroll et al. (2006) for similar aerosol masses. SOC yields reported in this work range from 0.5–1.4% for carbon masses between 17 and 49 μgC m−3.

Product distributions from the OH radical‐induced oxidation of n‐pentane and isopentane (2‐methylbutane) in air

AbstractHydroxyl radicals, generated by photolysis of H2O2, were reacted with n‐pentane and isopentane in air in the absence of nitrogen oxides. The observed product distributions were compared with similar data derived by computer simulations, based on the known reaction mechanisms, to determine relative probabilities for hydrogen abstraction at different sites of the parent compounds and to estimate branching ratios and relative rate coefficients for cross‐combination reactions between different peroxy radicals. For n‐pentane, the distribution of the pentanols indicates probabilities for hydrogen abstraction, in percent, of q1 = 9.1 ± 0.7, q2 = 56.1 ± 1.8, and q3 = 34.8 ± 1.3, which agree with predictions based on the algorithm proposed by Atkinson. Branching ratios needed to harmonize calculated and observed product distributions are somewhat larger than, although still within the error ranges of, the values found by us previously. Comparison between experimental and calculated data confirms the isomerization and decomposition constants recently established for the three pentoxyl radical isomers. The product distribution for isopentane, which is dominated by acetone, acetaldehyde, 2‐methyl‐butan‐2‐ol, and 2‐methyl‐butan‐2‐hydroperoxide, is in harmony with the predicted oxidation mechanism. Probabilities for hydrogen abstraction from isopentane were estimated to occur to 12% at the primary, 28% at the secondary, and 60% at the tertiary sites, again in agreement with predictions based on the algorithm of Atkinson. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 677–688, 2006

Product distributions from the OH radical-induced oxidation of but-1-ene, methyl-substituted but-1-enes and isoprene in NOx-free air

Product distributions resulting from the OH-induced oxidation of but-1-ene, 2-methylbut-1-ene, 3-methylbut-1-ene and isoprene in air were measured in the absence of nitrogen oxides and compared with predictions based on currently accepted oxidation mechanisms. In the case of butenes, the observed distributions of carbonyl compounds, hydroxyketones, hydroxyalkanals and diols were evaluated to obtain probabilities for the initial attack of OH radical on the outer position of the double bond (γ = 0.90 ± 0.03 for 2-Me-but-1-ene and γ = 0.76 ± 0.05 for both but-1-ene and 3-Me-but-1-ene), for the probability of formation of stable products in the self-reaction of secondary β-hydroxyperoxyl radicals (kssb/kss = 0.29 ± 0.07 for but-1-ene and kssb/kss = 0.19 ± 0.06 for 3-Me-but-1-ene), and for the ratio of the reaction with oxygen s. decomposition of β-hydroxyalkoxyl radicals, k3[O2]/(k4 + k3[O2]) = 0.25 ± 0.04 for but-1-ene and = 0.38 ± 0.04 for 3-Me-but-1-ene. The last two values disagree with other published data, which suggest a smaller effect of oxygen. The oxidation of isoprene produced methacrolein and methyl vinyl ketone with a ratio 0.93 ± 0.10, the ratio of methyl vinyl ketone and 3-methylfuran was 7.3 ± 1.0. Other products were 1-hydroxy-3-methylbut-3-en-2-one (identified by mass spectrometry) and 3-methyl-3-oxo-butane (tentatively identified). The overall product distribution was complex and could not be fully elucidated. Computer simulations based on several mechanisms applied the relative probabilities for OH addition found for the but-1-enes. Comparison with the experimental data suggests probabilities for OH addition to the methylated double bond of 0.504 ± 0.027 (outer position) and 0.056 ± 0.003 (inner position), and to the non-methylated double bond of 0.335 ± 0.023 (outer position) and 0.105 ± 0.008 (inner position).

Oxidation of Dimethyl Ether and its Interaction with Nitrogen Oxides

AbstractThe oxidation of dimethyl ether (DME) under flow reactor conditions has been studied experimentally and in terms of a detailed chemical kinetic model. The experiments were performed at atmospheric pressure in the temperature range 600–1500 K and at different air/fuel ratios. Of particular interest was the interaction of DME with nitrogen oxides. The results show that the oxidation of DME occurs readily at temperatures above 1000 K, largely independent of the stoichiometry. Addition of NO under stoichiometric and fuel‐rich conditions does not affect the oxidation chemistry for DME, but above 1100 K a minor amount of the NO is reduced to HCN and N2 in reburn‐type reactions. Addition of NO or NO2 under oxidizing conditions significantly enhances the oxidation rate of DME and shifts the temperature for onset of oxidation to lower values, a phenomenon similar to that of NOx‐sensitized oxidation of hydrocarbons.The proposed chemical kinetic model provides a good description of DME oxidation in the absence of nitrogen oxides. Under the conditions of the present study, the conversion of DME proceeds mainly through the high‐temperature mechanism, with little importance of the intermediate peroxy species. In the presence of NO or NO2, the reaction CH3 + NO2 ⇌ CH3O + NO, followed by dissociation of CH3O, readily provides H atoms and thereby promotes the oxidation. At lower temperatures the mechanism involves CH3OCH2O2 and CH3O2 radicals. While the effect of NOx generally is described satisfactorily by the model, deviations at lower temperatures may indicate inadequacies in the reaction subset for these peroxy species.

Heterogeneous processes involving sodium halide particles and ozone: Molecular bromine release in the marine boundary layer in the absence of nitrogen oxides

Heterogeneous reactions involving sodium halide particles and gaseous ozone were investigated by reaction‐chamber experiments in order to explore the possible role of sea‐salt particles as a source of reactive halogen species in the troposphere. In the studies of sodium bromide and ozone, it was found that gaseous bromine molecules were produced in the presence of water vapor with which the salts were almost deliquesced. This preliminary result suggests that reactive bromine species can be released from sea‐salt to the atmosphere of the marine boundary layer in the absence of nitrogen oxides.

Oxidation of toluene in NO? free air: Product distribution and mechanism

Product distributions resulting from the oxidation of toluene in air initiated by chlorine atoms, by toluene photolysis, and by hydroxyl radicals were studied at atmospheric pressure in the absence of nitrogen oxides. In the first case only benzaldehyde and benzylalcohol with a ratio of 7.8 ± 1.7 were observed, from which a branching ratio α = 0.76 ± 0.05 was derived for the radical propagating pathway of the self-reaction of benzylperoxy radicals. In the second and third case the apparent branching ratio decreased to α = 0.56 ± 0.07 and 0.37 ± 0.08, respectively, indicating the occurrence of additional reactions between benzylperoxy and other peroxy radicals. The major ring retaining products resulting from the reaction of OH with toluene were o-cresol, p-cresol. and methyl-p-benzo-quinone (57.9 ± 12.5% reacted carbon, corrected for secondary losses), in addition to 7.7 ± 1.6% benzaldehyde and benzylalcohol arising from methyl hydrogen abstraction. Formaldehyde, acetaldehyde, glyoxal, methylglyoxal, carbon monoxide, and carbon dioxide were observed as ring cleavage products (25.0 ± 7.2%). Except for CO2, which appears to be an important ring cleavage product only under NOχ-free conditions, the distribution of ring cleavage products was similar to that found by Gery et al (1985) in the presence of NOχ. Comparison of experimental data and results from computer simulations show that self-reactions of the hydroxy-methyl-cyclo-hexadienylperoxy radicals are negligible compared to internal rearrangement reactions leading to ring stabilization or ring cleavage. The mechanism of CO2 production appears to require the formation of a Criegee intermediate. © 1996 John Wiley & Sons, Inc.

Atmospheric oxidation of hydrocarbons: Formation of hydroperoxides and peroxyacids

Hydrocarbons at ppm levels in air have been oxidized in the absence of nitrogen oxides. Chlorine atoms served as initiators of the oxidations. Infrared analysis showed alkyl hydroperoxides to be formed early in the oxidation sequences. Aldehydes and ketones were also formed, followed by the appearance of peroxyacids. Peroxyacetic acid was found to be an especially stable reaction product. Laboratory rate data and recent atmospheric measurements of NO, NO 2 and HO 2 indicate that hydroperoxides and peroxyacids are also formed in the real atmosphere.