Diurnal Variations of Atmospheric Hydrogen Peroxide Concentrations in Saxony (Germany)

During a 3-year study, gaseous hydrogenperoxide (H₂O₂) concentrations were measuredas part of the SANA project at the Melpitz FieldResearch Station and in the city of Leipzig. Typicaldaily mean H₂O₂ mixing ratios on sunny dayswere 0.15 to 0.25 ppbv with maximum values of 0.3 to0.5 ppbv at Melpitz, and 0.3 to 0.6 ppbv with maximumvalues of 0.4 to 1.0 ppbv in Leipzig. Over the entireperiod of the project the maximum hourly mean valueswere 2.1 ppbv and 5.3 ppbv in Melpitz and Leipzig,respectively. The data were not complete enough to show a trend.Linear regression analysis shows, that ozone(O₃), temperature and solar radiation arepositively correlated with H₂O₂, whereasnitrogen oxides (NO_x), carbon monoxide (CO) andrelative humidity are negatively correlated. Negativecorrelation between H₂O₂ and CO is caused byjoint occurrence of CO with NO_x in exhaust gases.Negative correlation between H₂O₂ andrelative humidity is not necessarily in contradictionto the accelerating effect of water vapour onH₂O₂ formation. The strong positivecorrelation of H₂O₂ with the dew pointdifference however seems to better reflect theinfluence of water vapour. Multiple linear regression analysis (MLRA) of thecomponents measured, indicates the great influence of CO on the formation of H₂O₂ in the gasphase.     

FTIR studies of reactions between the nitrate radical and haloethenes

Products and mechanisms for the gas-phase reactions of NO₃ radicals with CH₂=CHCl, CH₂=CCl₂, CHCl=CCl₂,cis-CHCl=CHCl andtrans-CHCl=CHCl in air have been studied. The experiments were carried out at 295±2 K and 740±5 Torr in a 480-L Teflon-coated reaction chamber and at 295±2 K and 760±5 Torr in a 250-L stainless steel reactor. NO₃ was generated by the thermal dissociation of N₂O₅. Experiments with¹⁵NO₃ and CD₂CDCl have also been performed. The initially formed nitrate peroxynitrates decay into carbonyl compounds, nitrates, HCl and ClNO₂. In adidtion, there are indications of nitrooxy acid chlorides being produced. The reactions with CH₂=CCl₂ and CHCl=CCl₂ are more complex due to release of chlorine atoms which eventually lead to formation of chloroacid chlorides.A general reaction mechanism is proposed and the observed concentration-time profiles of reactants and products are simulated for each compound. The rate constants for the initial step of NO₃ addition to the chloroethenes are determined as: (2.6±0.5, 9.4±0.9, 2.0±0.4 and 1.4±0.4) × 10^–16 cm³ molecule^–1 s^–1 for CH₂=CHCl, CH₂=CCl₂, CHCl=CCl₂ andcis-CHCl=CHCl, respectively.     

Comparison of the EMEP, RADM2 and RACM Mechanisms

A comparison of the atmospheric chemistry mechanisms EMEP (Co-operative Programme for Monitoring and Evaluation of the Long-Range Transmission of Air Pollutants in Europe), RADM2 (Regional Acid Deposition Model, version 2) and RACM (Regional Atmospheric Chemistry Mechanism) has been conducted. Each mechanism was used to simulate the PLUME case of Kuhn et al. (1998) and to simulate an additional 150 and 81 scenarios with and without emissions, respectively. These simulations covered scenarios that ranged from relatively clean, through rural and polluted urban conditions. Ozone isopleths and scatter plots were generated from the simulations. The mechanisms were compared primarily on the basis of calculated ozone and ozone precursor concentrations. For the gas-phase ozone precursors the differences between the mechanisms were rather small under clean conditions and more significant under polluted conditions. The differences were especially significant for the concentrations of NO₂ and organic peroxy radicals. In general the EMEP mechanism yielded the most ozone and the RADM2 mechanism yielded the least. Furthermore the results suggest that a broad range simulation conditions should be used to compare mechanisms and not just a few selected scenarios.     

膜生物流化床的气液传质特性研究

研究了膜生物流化床的传质特性,结果表明,反应器氧传质系数随着固含率的增加先增加后减小,随着气速和液速的增大而增大;气相含率受气速影响显著并随气速及固含率的增大而升高.载体挂膜后,系统的氧传质系数和气含率降低.     

A Pulsed Laser Photolysis-Resonance Fluorescence Kinetic Study of the Atmospheric Cl Atom-Initiated Oxidation of Propene and a Series of 3-Halopropenes at Room Temperature

Absolute rate coefficient measurements have been carried out for the reactions of Cl atoms with propene and a series of 3-halopropenes, at room temperature (298 ± 2) K using a newly constructed laser photolysis-resonance fluorescence (PLP-RF) system. The rate coefficients obtained (in units of cm³ molecule^–1 s^–1) are: propene (1.40± 0.24) ×10^–10, 3-fluoropropene (4.92 ± 0.42) ×10^–11, 3-chloropropene (7.47 ± 1.50) × 10^–11, 3-bromopropene (1.23± 0.14) ×10^–10 and 3-iodopropene (1.29± 0.15) ×10^–10. In order to test this new system, the reactions of Cl atoms with acetone and isoprene have also been studied and compared with data previously reported. The rate coefficients determined at room temperature for these last two reactions are (2.93 ± 0.20) ×10^–12 cm³ molecule^–1 s^{– 1} and (3.64± 0.20)×10^–10 cm³ molecule^–1 s^–1, respectively. The measured values were independent of pressure over the range 20–200 Torr. The influence of the different halogen atoms substituents on the reactivity of these alkenes with Cl atoms as well as the atmospheric implications of these measurements are studied and discussed for the first time in this work and compared with the reactivity with NO₃ and OH radicals.     

The heterogeneous oxidation of SO2 on aerosol surface

A heterogeneous chemical model is developed by coupling aerosol, gas-phase and liquid-phase chemical model. SO₂ oxidation rates on the aerosol surface are calculated and the influence of some factors is discussed. Model simulations indicate that SO₂ heterogeneous oxidation rates are sensitive to the mass concentration and chemical composition of aerosols, relative humidity, initial values of SO₂ and H₂O₂. The heterogeneous chemical model is coupled with a Eulerian deposition model. Model results show that oxidation of SO₂ on the aerosol surface is found to reduce SO₂ levels by 5%–33%, to increase SO ₄ ^2- - concentrations by 8%–50% in the surface layer. Project supported by the National “85-912” Key Science and Technology Project.     

Reactions of Cl Atoms with Selected VOCs: Kinetics, Products and Mechanisms

The reactions of isoprene, MBO (2-methyl-3-buten-2-ol) and toluene with chlorine atoms have been studied at 298 ± 5 K and 740 ± 5 Torr with the use of FTIR spectroscopy. Major products of the isoprene-Cl reaction and of the MBO-Cl reaction have been identified and quantified, and reaction mechanisms have been tentatively proposed in order to explain the products formed. The reaction between isoprene and Cl atoms yields mainly HCl, formyl chloride, formic acid, methylglyoxal (pyruvic aldehyde), CO and CO2, while the MBO-Cl reaction forms acetone, HCl, formyl chloride, formic acid, CO, CO2. As products from the reaction between toluene and Cl we identified and quantified HCl and benzaldehyde. The rate constants for the reactions of isoprene and toluene with Cl atoms have also been determined using a relative rate method. The measured values are: kisoprene = (5.5 ± 1.0) × 10–10 cm3 molecule–1 s–1 and ktoluene = (5.6 ± 1.3) × 10–11 cm3 molecule–1 s–1. Atmospheric lifetimes have been estimated from these values.     

Simultaneous collection of particles and gases followed by multielement analysis using nuclear techniques

A simple system was constructed for the separation and collection of atmospheric particles and gases. The five-stage sampling train consists of a particle filter followed by four ⁷LiOH-impregnated filters to collect acidic gases. The treated filters quantitatively collect acidic gas-phase species of B, S, Cl, Br, I, As, Se, Sb and Hg. Simultaneous sampling with activated charcoal-impregnated and ⁷LiOH-treated filters revealed that B, S, and As species were found only as acidic gases, while the others had both acidic and nonacidic contributions. Concentrations of up to 48 elements on the particle filters and nine elements on the treated filters were determined using instrumental neutron activation analysis and neutron capture prompt -ray activation analysis. Minimum sampling volume estimates, average filter blank concentrations, and average atmospheric concentrations at College Park, MD and Wallops Island, VA are presented.     

Mechanistic and Kinetic Study of the Gas-Phase Reaction of Atomic Chlorine with Cyclohexanone using an Absolute and a Relative Technique; Influence of Temperature

The reaction of Cl with cyclohexanone (1) was investigated, for the first time, as a function of temperature (273–333 K) and at a low total pressure (1 Torr) with helium as a carrier gas using a discharge flow-mass spectrometry technique (DF-MS). The resulting Arrhenius expression is proposed, k ₁= (7.7 ± 4.1) × 10^–10 exp[–(540 ± 169)/T]. We also report a mechanistic study with the quantitative determination of the products of the reaction of Cl with cyclohexanone. The absolute rate constant derived from this study at 1 Torr of total pressure and room temperature is (1.3 ± 0.2) × 10^–10 cm³ molecule^–1 s^–1. A yield of 0.94 ± 0.10 was found for the H-abstraction channel giving HCl. In relative studies, using a newly constructed relative rate system, the decay of cyclohexanone was followed by gas chromatography coupled with flame-ionisation detection. These relative measurements were performed at atmospheric pressure with synthetic air and room temperature. Rate constant measured using the relative method for reaction (1) is: (1.7 ± 0.3) × 10^–10 cm³ molecule^–1 s^–1. Finally, results and atmospheric implications are discussed and compared with the reactivity with OH radicals.     

Mechanisms and products of the reactions of NO3 with cycloalkenes

The NO₃ radical initiated oxidation of cyclopentene, cyclohexene and 1-methyl-cyclohexene has been studied. The products formed in an N₂O₅-NO₂-N₂-O₂-cycloalkene-static reactor system, at 0.1 MPa and 296 K, were investigated using long path FTIR. The principal products were aldehydes formed via a ring opening process. The reactions also resulted in significant yields of three types of ring retaining nitrooxy-substituted compounds. The average yields of alkyl nitrates from, e.g., reactions with cycloalkene were 25.1% 2-oxo-cyclohexyl nitrate, 22.8% 2-hydroxy-cyclohexyl nitrate and 4.0% 1,2-cyclohexyl dinitrate. The mechanisms involved resembles those proposed for acyclic alkenes. In absence of NO, -oxo and -hydroxy-cycloalkyl nitrates are formed via self reactions of -nitrooxy substituted cycloalkyl peroxy radicals. Estimated branching ratios for the reactants leading to ring retaining products in the presence and in the absence of NO are given and the possible relevance of these reactions for cycloalkenes under tropospheric conditions is discussed.