A Study of the Reaction of OH Radicals with N-Methyl Pyrrolidinone,N-Methyl Succinimide and N-Formyl Pyrrolidinone

A study of the oxidation mechanism of N-methyl pyrrolidinone (C₅H₉NO, NMP) initiated by hydroxyl radicals was made at EUPHORE at atmospheric pressure (1000 ± 10) mbar of air and ambient temperature (T = 300 ± 5 K). The main products were N-methyl succinimide (NMS) (52 ± 4)% and N-formyl pyrrolidinone (FP) (23 ± 9)%. The relative rate technique was used to determine the rate constants of OH with NMP, NMS and FP, the measured values were (in units of cm³ molecule ^{− 1} s^{− 1}): k_NMP = (2.2 ± 0.4) × 10^{− 11}, k_NMS = (1.4 ± 0.3) × 10^{− 12} and k_FP = (6 ± 1) × 10^{− 12}. The results are presented and discussed in terms of the atmospheric impact.     

The Heterogeneous Reaction of NO<Subscript>2</Subscript> with NH<Subscript>4</Subscript>Cl: A Molecular Diffusion Tube Study

The heterogeneous interaction of nitrogen dioxide with ammonium chloride was investigated in a molecular diffusion tube experiment at 295–335 K and interpreted using Monte Carlo trajectory calculations. The surface residence time (τ_surf) of NO₂ on NH₄Cl is equal to 15 μs at 295 K, increases with temperature up to 323 K (τ_surf = 45 μs) and probably decreases beyond 323 K. The same experiment also yields uptake coefficients, γ, which are derived from the absolute number of surviving molecules effusing out of the diffusion tube. The rate of uptake of NO₂ on NH₄Cl followed a rate law first order in [NO₂] and the uptake coefficient γ is equal to 7 × 10⁻⁵ at 295 K, increases with temperature up to 323 K (γ = 2.1 × 10⁻⁴) and probably decreases beyond 323 K. Nitrous acid, water and nitrogen were detected as products. From these products, it is concluded that the reaction of NO₂ with NH₄Cl is a reverse disproportionation reaction where two moles of NO₂ result in ammonium nitrite, NH₄NO₂, as an intermediate, and nitryl chloride, NO₂Cl. NH₄NO₂ decomposes in two pathways, one to nitrous acid, HONO and NH₃, the other to nitrogen and water. The branching ratio for the production of HONO + NH₃ to that of N₂ + H₂O is approximately 20 at 298 K and increases with increasing temperature.     

Uptake of the NO <Subscript>3</Subscript> Radical on Aqueous Surfaces

Using a single drop experiment, the uptake of NO₃ radicals on aqueous solutions of the dye Alizarin Red S and NaCl was measured at 293 K. Uptake coefficients in the range (1.7–3.1) ⋅ 10^{− 3} were measured on Alizarin Red S solutions. The uptake coefficients measured on NaCl solutions were in the range of (1.1–2.0) ⋅ 10⁻³ depending on the salt concentration. Both experiments lead to a consistent result for the mass accommodation coefficient of α_NO3 = (4.2_{− 1.7}^+2.2)⋅ 10⁻³. The product H(D_l k_Cl−^II)^0.5 for the NO₃ radical was determined to be (1.9 ± 0.2) M atm^{− 1} cm s^−0.5 M^−0.5 s^−0.5 by fitting the uptake data for the NaCl solutions to the so-called resistance model. The yield of the chemical NO₃ radical source was characterized using UV-VIS and FT-IR spectroscopy. The amount of gas-phase NO₃ radicals measured at elevated humidities was less than expected. Instead, a rise of the gas-phase HNO₃ concentration was found indicating a conversion of gas-phase NO₃ radicals to gas-phase HNO₃ on the moist reactor walls.     

Measurements of the HONO photodissociation constant

Measurements of the photodissociation constant for nitrous acid (j _HONO) were made at an urban site in Toronto, Canada, during the months of May–July 2005, using an optically thin actinometer. Operating details of the j _HONO monitor are reported, along with laboratory tests. Measurements of j _HONO were obtained for solar zenith angles ranging from 20–75^∘, under clear and cloudy skies. Maximum error estimates on j _HONO under clear skies range from 11% at sunrise, to 4% at solar noon, with a minimum detection limit of 5.7 × 10⁻⁴/sec for our actinometer. Measured clear-sky values of j _HONO were compared with values calculated by a four-stream discrete ordinate radiative transfer (RT) model (ACD TUV version 4.1), and were found to be within better than 10% agreement for solar zenith angles < 65^∘. For conditions of scattered cloud, enhancement and suppression of the j _HONO values occurred by as much as 16%–70%, and 59%–80%, respectively. The integrated band area of the nπ^∗ transition for gas-phase nitrous acid yields an oscillator strength, f = (1.06 ± 0.044)×10⁻³ (based on clear-sky data), 19.1% higher than the value reported by Bongartz et al. (1991).     

Kinetics of the reactions of soot surface-bound polycyclic aromatic hydrocarbons with NO<Subscript>2</Subscript>

The kinetics of heterogeneous reactions of NO₂ with 17 polycyclic aromatic hydrocarbons (PAHs) adsorbed on laboratory generated kerosene soot surface was studied over the temperature range (255–330) K in a low pressure flow reactor combined with an electron-impact mass spectrometer. The kinetics of soot-bound PAH consumption due to their desorption and reaction with NO₂ were monitored using off-line HPLC measurements of their concentrations in soot samples as a function of reaction time, NO₂ concentrations in the gas phase being analyzed by mass spectrometer. No measurable decay of PAHs due to the reaction with NO₂ was observed under experimental conditions of the study (maximum NO₂ concentration of 5.5 × 10¹⁴ molecule cm⁻³ and reaction time of 45 min), which allowed to determine the upper limits of the first-order rate constants for the heterogeneous reactions of 17 soot-bound PAHs with NO₂: k < 5.0 × 10⁻⁵ s⁻¹ (for most PAHs studied). Comparison of these results to previous studies carried on different carbonaceous substrates, showed that heterogeneous reactivity of PAHs towards NO₂ is, probably, dependent on the substrate nature even for resembling, although different carbonaceous materials. Results show that particulate PAHs degradation by NO₂ alone is of minor importance in the atmosphere     

A comparison of evaporative cooling with infrared heating beneath a cirrus cloud

Data for this study were collected by the instruments mounted on the NCAR King Air and rawinsonde during the First ISCCP (International Satellite Cloud Climatology Project) Regional Experiment (FIRE) on 19 October, 1986. The main purpose of this study is to understand the basic concept of evaporative cooling in a dry layer below a cirrus generating cell. Relative humidity with respect to liquid water RH_W and temperature lapse rate γ_e below the cirrus base at about 6.7 km were about 40% and 3.7°C km⁻¹, respectively. Evaporative cooling rate (ECR) in the 1.5 km thick subcloud layer was estimated to be approximately 0.1 to 2°C h⁻¹ and it was found to be comparable with the infrared heating rate calculated from radiation measurements. Because of ice crystal evaporation, RH_W in the same layer may reach saturation with respect to ice in 1.5 hours.     

Studying air pollution with kitt peak solar flux atlas — analysis method and results of observation

For the measurement of atmospheric NO2 vertical column density (VCD), Kitt Peak Solar Flux Atlas can be substituted as an extraterrestrial solar radiation. Compared with differential analysis method, the Taylor expansion of integrated transfer equation underestimates the VCD. This underestimation is as large as 35% when the amount of NO2 is 1 × 1017 cm－2 and observation is conducted with an air mass factor of 10. Even when the VCD is 2 × 1016 cm－2 and the air mass factor is 4, the relative error of the retrieved VCD is still no less than 3%. If the observation is restricted under the small air mass factor condition (≤4), with Kitt Peak Solar spectrum as an extraterrestrial solar radiation, only an atmospheric layer of 2 km thick from ground can be studied, which will make the absorption too weak to be detected by normal instruments.The VCD in winter Tokyo area was observed and analyzed by differential method, which shows a good precision even when the absorption is as low as 3%. The largest average VCD was about 1.3 × 1017 cm－2, and the lowest was about 1.3 × 1016 cm－2. The trend of its variation was almost the same as the ground level observation by Saltzman reagent method.     

Rain-aerosol coupling in the tropical atmosphere of Southeast Asia: distribution and scavenging ratios of major ionic species

Both aerosol and rainwater samples were collected and analyzed for ionic species at a coastal site in Southeast Asia over a period of 9 months (January–September 2006) covering different monsoons. In general, the occurrence and distribution of ionic species showed a distinct seasonal variation in response to changes in air mass origins. Real-time physical characterization of aerosol particles during rain events showed changes in particle number distributions which were used to assess particle removal processes associated with precipitation, or scavenging. The mean scavenging coefficients for particles in the range 10–500 nm and 500–10 μm were 7.0 × 10⁻⁵ ± 2.8 × 10⁻⁵ s⁻¹ and 1.9 × 10⁻⁴ ± 1.6 × 10⁻⁵ s⁻¹, respectively. A critical analysis of the scavenging coefficients obtained from this study suggested that the wet removal of aerosol particles was greatly influenced by rain intensity, and was particle size-dependent as well. The scavenging ratios, another parameter used to characterize particle removal processes by precipitation, for NH₄ ⁺, Cl⁻, SO₄ ²⁻, and NO₃ ⁻ were found to be higher than those of Na⁺, K⁺, and Ca²⁺ of oceanic and crustal origins. This enrichment implied that gaseous species NH₃, HCl, and HNO₃ could also be washed out readily. These additional sources of ions in precipitation presumably counter-balanced the dilution effect caused by high total precipitation volume in the marine and tropical area.     

High resolution simulation of recent Arctic and Antarctic stratospheric chemical ozone loss compared to observations

Simulations of polar ozone losses were performed using the three-dimensional high-resolution (1^∘ × 1^∘) chemical transport model MIMOSA-CHIM. Three Arctic winters 1999–2000, 2001–2002, 2002–2003 and three Antarctic winters 2001, 2002, and 2003 were considered for the study. The cumulative ozone loss in the Arctic winter 2002–2003 reached around 35% at 475 K inside the vortex, as compared to more than 60% in 1999–2000. During 1999–2000, denitrification induces a maximum of about 23% extra ozone loss at 475 K as compared to 17% in 2002–2003. Unlike these two colder Arctic winters, the 2001–2002 Arctic was warmer and did not experience much ozone loss. Sensitivity tests showed that the chosen resolution of 1^∘ × 1^∘ provides a better evaluation of ozone loss at the edge of the polar vortex in high solar zenith angle conditions. The simulation results for ozone, ClO, HNO₃, N₂O, and NO _y for winters 1999–2000 and 2002–2003 were compared with measurements on board ER-2 and Geophysica aircraft respectively. Sensitivity tests showed that increasing heating rates calculated by the model by 50% and doubling the PSC (Polar Stratospheric Clouds) particle density (from 5 × 10⁻³ to 10⁻² cm⁻³) refines the agreement with in situ ozone, N₂O and NO _y levels. In this configuration, simulated ClO levels are increased and are in better agreement with observations in January but are overestimated by about 20% in March. The use of the Burkholder et al. (1990) Cl₂O₂ absorption cross-sections slightly increases further ClO levels especially in high solar zenith angle conditions. Comparisons of the modelled ozone values with ozonesonde measurement in the Antarctic winter 2003 and with Polar Ozone and Aerosol Measurement III (POAM III) measurements in the Antarctic winters 2001 and 2002, shows that the simulations underestimate the ozone loss rate at the end of the ozone destruction period. A slightly better agreement is obtained with the use of Burkholder et al. (1990) Cl₂O₂ absorption cross-sections.     

Secondary aerosol formation and identification of regional source locations by PSCF analysis in the Indo-Gangetic region of India

Secondary aerosol formation was studied at Allahabad in the Indo-Gangetic region during a field campaign called Land Campaign-II in December 2004 (northern winter). Regional source locations of the ionic species in PM₁₀ were identified by using Potential Source Contribution Function (PSCF analysis). On an average, the concentration of water soluble inorganic ions (sum of anions and cations) was 63.2 μgm⁻³. Amongst the water soluble ions, average NO₃⁻ concentration was the highest (25.0 μgm⁻³) followed by SO₄²⁻ (15.8 μgm⁻³) and NH₄⁺ (13.8 μgm⁻³) concentrations. These species, contributed 87% of the total mass of water soluble species, indicating that most of the water soluble PM₁₀ was composed of NH₄NO₃ and (NH₄)₂SO₄/NH₄HSO₄ or (NH₄)₃H(SO₄)₂ particles. Further, the concentrations of SO₄²⁻, NO₃⁻, and NH4⁺ aerosols increased at high relative humidity levels up to the deliquescence point (∼63% RH) for salts of these species suggesting that high humidity levels favor the conversion and partitioning of gaseous SO₂, NO_x, and NH₃ to their aerosol phase. Additionally, lowering of ambient temperature as the winter progressed also resulted in an increase of NO₃⁻ and NH₄⁺ concentrations, probably due to the semi volatile nature of ammonium nitrate. PSCF analysis identified regions along the Indo-Gangetic Plain (IGP) including Northern and Central Uttar Pradesh, Punjab, Haryana, Northern Pakistan, and parts of Rajasthan as source regions of airborne nitrate. Similar source regions, along with Northeastern Madhya Pradesh were identified for sulfate.     

Water interaction with MgCl<Subscript>2</Subscript>×6H<Subscript>2</Subscript>O and NaCl surfaces: measurements of the uptake coefficient

The uptake of water vapor on MgCl₂×6H₂O and NaCl salt dry solid films was studied over the temperature range 240 to 340 K and at 1 Torr pressure of helium using a flow reactor coupled to a modulated molecular beam mass spectrometer. The H₂O to salt uptake data were obtained from the kinetics of H₂O loss on salt coated Pyrex rods. The following Arrhenius expression was obtained for the initial uptake coefficient of H₂O on MgCl₂×6H₂O films: γ ₀ (MgCl₂) = (6.5 ± 1.0) × 10⁻⁶ exp[(470 ± 40)/T] (calculated with specific BET surface area, quoted uncertainties are 1σ statistical). The rate of H₂O adsorption on NaCl was found to be much lower than on MgCl₂×6H₂O, and only an upper limit was determined for the corresponding uptake coefficient: γ (NaCl) ≤ 5.6 × 10⁻⁶ at T = 300 K. The results show that the rate of H₂O adsorption to salt surfaces is drastically dependent on the salt sample composition.     

Tropical cyclones and polar lows: Velocity,size, and energy scales,and relation to the 26°C cyclone origin criteria

The goal of this paper is to quantitatively formulate some necessary conditions for the development of intense atmospheric vortices. Specifically, these criteria are discussed for tropical cyclones (TC) and polar lows (PL) by using bulk formulas for fluxes of momentum, sensible heating, and latent heating between the ocean and the atmosphere. The velocity scale is used in two forms: (1) as expressed through the buoyancy flux b and the Coriolis parameter l_c for rotating fluids convection, and (2) as expressed with the cube of velocity times the drag coefficient through the formula for total kinetic energy dissipation in the atmospheric boundary layer. In the quasistationary case the dissipation equals the generation of the energy. In both cases the velocity scale can be expressed through temperature and humidity differences between the ocean and the atmosphere in terms of the reduced gravity, and both forms produce quite comparable velocity scales. Using parameters b and l_c, we can form scales of the area and, by adding the mass of a unit air column, a scale of the total kinetic energy as well. These scales nicely explain the much smaller size of a PL, as compared to a TC, and the total kinetic energy of a TC is of the order 10¹⁸-10¹⁹ J. It will be shown that wind of 33 m s^-1 is produced when the total enthalpy fluxes between the ocean and the atmosphere are about 700 W m^-2 for a TC and 1700 W m^-2 for a PL, in association with the much larger role of the latent heat in the first case and the stricter geostrophic constraints and larger static stability in the second case. This replaces the mystical role of 26^oC as a criterion for TC origin. The buoyancy flux, a product of the reduced gravity and the wind speed, together with the atmospheric static stability, determines the rate of the penetrating convection. It is known from the observations that the formation time for a PL reaching an altitude of 5--6 km can be only a few hours, and a day, or even half a day, for a TC reaching 15--18 km. These two facts allow us to construct curves on the plane of T^s and ΔT=T_s-T_a to determine possibilities for forming an intense vortex. Here, T_a is the atmospheric temperature at the height z=10 m. A PL should have ΔT>20^oC in accordance with the observations and numerical simulations. The conditions for a TC are not so straightforward but our diagram shows that the temperature difference of a few degrees, or possibly even a fraction of a degree, might be sufficient for TC development for a range of static stabilities and development times.     

Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.     

Atmospheric inorganic nitrogen in marine aerosol and precipitation and its deposition to the North and South Pacific Oceans

Aerosol and rain samples were collected between 48°N and 55°S during the KH-08-2 and MR08-06 cruises conducted over the North and South Pacific Ocean in 2008 and 2009, to estimate dry and wet deposition fluxes of atmospheric inorganic nitrogen (N). Inorganic N in aerosols was composed of ~68% NH₄⁺ and ~32% NO₃^– (median values for all data), with ~81% and ~45% of each species being present on fine mode aerosol, respectively. Concentrations of NH₄⁺ and NO₃⁻ in rainwater ranged from 1.7–55 μmol L⁻¹ and 0.16–18 μmol L⁻¹, respectively, accounting for ~87% by NH₄⁺ and ~13% by NO₃⁻ of total inorganic N (median values for all data). A significant correlation (r = 0.74, p < 0.05, n = 10) between NH₄⁺ and methanesulfonic acid (MSA) was found in rainwater samples collected over the South Pacific, whereas no significant correlations were found between NH₄⁺ and MSA in rainwater collected over the subarctic (r = 0.42, p > 0.1, n = 6) and subtropical (r = 0.33, p > 0.5, n = 6) western North Pacific, suggesting that emissions of ammonia (NH₃) by marine biological activity from the ocean could become a significant source of NH₄⁺ over the South Pacific. While NO₃⁻ was the dominant inorganic N species in dry deposition, inorganic N supplied to surface waters by wet deposition was predominantly by NH₄⁺ (42–99% of the wet deposition fluxes for total inorganic N). We estimated mean total (dry + wet) deposition fluxes of atmospheric total inorganic N in the Pacific Ocean to be 32–64 μmol m⁻² d⁻¹, with 66–99% of this by wet deposition, indicating that wet deposition plays a more important role in the supply of atmospheric inorganic N than dry deposition.     

Fourier transform infrared kinetic studies of the reaction of HONO with HNO3, NO3 and N2O5 at 295 K

The kinetics of the reaction of nitrous acid (HONO) with nitric acid (HNO₃), nitrate radicals (NO₃) and dinitrogen pentoxide (N₂O₅) have been studied using Fourier transform infrared spectroscopy. Experiments were performed at 700 torr total pressure using synthetic air or argon as diluents. From the observed decay of HONO in the presence of HNO₃ a rate constant of k<7×10^-19 cm³ molecule^-1 s^-1 was derived for the reaction of HONO with HNO₃. From the observed decay of HONO in the presence of mixtures of N₂O₅ and NO₂ we have also derived upper limits for the rate constants of the reactions of HONO with NO₃ and N₂O₅ of 2×10^-15 and 7×10^-19 cm³ molecule^-1 s^-1, respectively. These results are discussed with respect to previous studies and to the atmospheric chemistry of HONO.     

Evaluation of Haney-Type Surface ThermalBoundary Conditions Using a CoupledAtmosphere and Ocean Model

A coupled atmosphere-ocean model developed at the Institute for Space Studies at NASA Goddard Space Flight Center (Russell et al., 1995) was used to verify the validity of Haney-type surface thermal boundary condition, which linearly connects net downward surface heat flux Q to air / sea temperature difference △T by a relaxation coefficient k. The model was initiated from the National Centers for Environmental Prediction (NCEP) atmospheric observations for 1 December 1977, and from the National Ocean Data Center (NODC) global climatological mean December temperature and salinity fields at 1° ×1° resolution. The time step is 7.5 minutes. We integrated the model for 450 days and obtained a complete model-generated global data set of daily mean downward net surface flux Q, surface air temperature TA,and sea surface temperature To. Then, we calculated the cross-correlation coefficients (CCC) between Q and △T. The ensemble mean CCC fields show (a) no correlation between Q and △T in the equatorial regions, and (b) evident correlation (CCC≥ 0.7) between Q and △T in the middle and high latitudes.Additionally, we did the variance analysis and found that when k= 120 W m-2K-1, the two standard deviations, σQ and σk△T, are quite close in the middle and high latitudes. These results agree quite well with a previous research (Chu et al., 1998) on analyzing the NCEP re-analyzed surface data, except that a smaller value of k (80 W m-2K-1) was found in the previous study.     

Laboratory measurements of the <Superscript>12</Superscript>C/<Superscript>13</Superscript>C kinetic isotope effects in the gas-phase reactions of unsaturated hydrocarbons with Cl atoms at 298 ± 3 K

The carbon kinetic isotope effects (KIEs) in the reactions of several unsaturated hydrocarbons with chlorine atoms were measured at room temperature and ambient pressure using gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS). All measured KIEs, defined as the ratio of the rate constants for the unlabeled and labeled hydrocarbon reaction k ₁₂/k ₁₃, are greater than unity or normal KIEs. The KIEs, reported in per mil according to ^Cl ɛ = (k ₁₂/k ₁₃−1) × 1000‰ with the number of experimental determinations in parenthesis, are as follows: ethene, 5.65 ± 0.34 (1); propene, 5.56 ± 0.18 (2); 1-butene, 5.93 ± 1.16 (1); 1-pentene, 4.86 ± 0.63 (1); cyclopentene, 3.75 ± 0.14 (1); toluene, 2.89 ± 0.31 (2); ethylbenzene, 2.17 ± 0.17 (2); o-xylene, 1.85 ± 0.54 (2). To our knowledge, these are the first reported KIE measurements for reactions of unsaturated NMHC with Cl atoms. Relative rate constants were determined concurrently to the KIE measurements. For the reactions of cyclopentene and ethylbenzene with Cl atoms, no rate constant has been reported in refereed literature. Our measured rate constants are: cyclopentene (7.32 ± 0.88) relative to propene (2.68 ± 0.32); ethylbenzene (1.15 ± 0.04) relative to o-xylene (1.35 ± 0.21), all × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹. The KIEs in reactions of aromatic hydrocarbons with Cl atoms are similar to previously reported KIEs in Cl-reactions of alkanes with the same numbers of carbon atoms. Unlike the KIEs for previously studied gas-phase hydrocarbon reactions, the KIEs for alkene–Cl reactions do not exhibit a simple inverse dependence on carbon number. This can be explained by competing contributions of normal and inverse isotope effects of individual steps in the reaction mechanism. Implications for the symmetries of the transition state structures in these reactions and the potential relevance of Cl-atom reactions on stable carbon isotope ratios of atmospheric NMHC are discussed.     

Simulation Chamber Studies of the Atmospheric Oxidation of 2-Methyl-3-Buten-2-ol: Reaction with Hydroxyl Radicals and Ozone Under a Variety of Conditions

This article presents a complete study of the diurnal chemical reactivity of the biogenic volatile organic compound (BVOC), 2-methyl-3-buten-2-ol (MBO) in the troposphere. Reactions of MBO with OH and with ozone were studied to analyse the respective parts of both processes in the global budget of MBO atmospheric reactivity. They were investigated under controlled conditions for pressure (atmospheric pressure) and temperature (298 ± 2 K) using three complementary European simulation chambers. Reaction with OH radicals was studied in the presence of and in the absence of NO _x . The kinetic study was carried out by relative rate study using isoprene as a reference. The rate constant found for this reaction was molecule⁻¹ cm³ s⁻¹. FTIR spectroscopy, DNPH- and PFBHA-derivatisation analyses were performed for reactions with both OH radicals and ozone. In both reactions, the hydroxycarbonyl compound, 2-hydroxy-2-methylpropanal (HMPr) was positively identified and quantified, with a yield of in the reaction with OH, and a yield of and 0.84 ± 0.08 in the reaction with ozone under dry (HR < 1%) and humid conditions (HR = 20%–30%). A primary production of two other carbonyl compounds, acetone , and formaldehyde was found in the case of the dry ozonolysis experiments. Under humid conditions, only formaldehyde was co-produced with HMPr as a primary carbonyl compound, with a yield of . For the reaction with OH, three other carbonyl compounds were detected, acetone , formaldehyde and glycolaldehyde . In addition some realistic photo-oxidation experiments were performed to understand in an overall way the transformations of MBO in the atmosphere. The realistic photo-oxidation experiments were conducted in the EUPHORE outdoor simulation chamber. It was found that this compound is a weak secondary aerosol producer (less than 1% of the carbon balance). But it was confirmed that it is a potentially significant source of acetone, Δ[Acetone]/Δ[MBO] = 0.45. With our experimental conditions ([MBO]₀ = 200 ppb, [NO]o = 50 ppb), an ozone yield of Δ[O₃]/Δ[MBO] = 1.05 was found.     

Humidity Effect and Its Influence on the Seasonal Distribution of Precipitation δ18O in Monsoon Regions

The humidity effect, namely the markedly positive correlation between the stable isotopic ratio in precipitation and the dew-point deficit △Td in the atmosphere, is put forward firstly and the relationships between the δ18O in precipitation and △Td are analyzed for the Urumqi and Kunming stations, which have completely different climatic characteristics. Although the seasonal variations in δ18O and △Td exhibit differences between the two stations, their humidity effect is notable. The correlation coefficient and its confidence level of the humidity effect are higher than those of the amount effect at Kunming, showing the marked influence of the humidity conditions in the atmosphere on stable isotopes in precipitation.Using a kinetic model for stable isotopic fractionation, and according to the seasonal distribution of meanmonthly temperature at 500 hPa at Kunming, the variations of the δ18O in condensate in cloud aresimulated. A very good agreement between the seasonal variations of the simulated mean δ18O and themean monthly temperature at 500 hPa is obtained, showing that the oxygen stable isotope in condensateof cloud experiences a temperature effect. Such a result is markedly different from the amount effect atthe ground. Based on the simulations of seasonal variations of δ18O in falling raindrops, it can be foundthat, in the dry season from November to April, the increasing trend with falling distance of δ18O in fallingraindrops corresponds remarkably to the great ATd, showing a strong evaporation enrichment function infalling raindrops; however, in the wet season from May to October, the δ18O in falling raindrops displaysan unapparent increase corresponding to the small ATd, except in May. By comparing the simulated meanδ18O at the ground with the actual monthly δ18O in precipitation, we see distinctly that the two monthlyδ18O variations agree very well. On average, the δ18O values are relatively lower because of the highlymoist air, heavy rainfall, small △Td and weak evaporation enrichment function of stable isotopes in thefalling raindrops, under the influence of vapor from the oceans; but they are relatively higher because of the dry air, light rainfall, great △Td and strong evaporation enrichment function in falling raindrops, under the control of the continental air mass. Therefore, the δ18O in precipitation at Kunming can be used to indicate the humidity situation in the atmosphere to a certain degree, and thus indicate the intensity of the precipitation and the strength of the monsoon indirectly. The humidity effect changes not only the magnitude of the stable isotopic ratio in precipitation but also its seasonal distribution due to its influence on the strength of the evaporation enrichment of stable isotopes in falling raindrops and the direction of the net mass transfer of stable isotopes between the atmosphere and the raindrops. Consequently, it is inferred that the humidity effect is probably one of the foremost causes generating the amount effect.     

Analysis of Carbon Dioxide Variations in the Atmosphere of Srednja Bijambarska Cave,Bosnia and Herzegovina

The results of one year’s monitoring in Srednja Bijambarska Cave (Bosnia and Herzegovina) are presented and discussed. Temporal variations of the carbon dioxide (CO₂) concentration are controlled by the switching between two ventilation regimes driven by outside temperature changes. A regression model with a simple perfectly mixed volume applied to a cave sector (“Music hall”) resulted in an estimate of ventilation rates between 0.02 h⁻¹ and 0.54 h⁻¹. Carbon dioxide input per plan surface unit is estimated by the model at around 50 × 10⁻⁶ mh⁻¹ during the winter season and up to more than 1000 × 10⁻⁶ mh⁻¹ during the first temperature falls at the end of summer (0.62 μmoles m⁻² s⁻¹ and 12.40 μmoles m⁻² s⁻¹ for normal conditions respectively). These values have been found to be related to the cave ventilation rate and dependent on the availability of CO₂ in the surrounding environment. For airflow close to zero the values of CO₂ input per plan surface have a range in the order of magnitude of a few units × 10⁻⁶ mh⁻¹. Based on two experiments, the anthropogenic contribution from cave visitors has been calculated, at between 0.35 l_CO2 min⁻¹ person⁻¹ and 0.45 l_CO2min⁻¹person⁻¹.