Kinetics of the gas-phase reactions of NO3 radicals with ethyl acrylate,n-butyl acrylate,methyl methacrylate and ethyl methacrylate

The relative rate method has been used to determine the rate constants for the gas-phase reactions of NO₃ radicals with a series of acrylate esters: ethyl acrylate (k₁), n-butyl acrylate (k₂), methyl methacrylate (k₃) and ethyl methacrylate (k₄) at 298 ± 1 K and 760 Torr. The obtained rate constants are k₁ = (1.8 ± 0.25) × 10^?16 cm³ molecule^?1 s^?1, k₂ = (2.1 ± 0.33) × 10^?16 cm³ molecule^?1 s^?1, k₃ = (3.6 ± 1.2) × 10^?15 cm³ molecule^?1 s^?1, k₄ = (4.9 ± 1.7) × 10^?15 cm³ molecule^?1 s^?1. The experimental rate constants are in good agreement with theoretical rate constants calculated by an algorithm of the correlation between the rate constants and the orbital energies for the reactions of unsaturated VOCs with NO₃ radicals. In addition, the atmospheric lifetimes of the compound against NO₃ attack are estimated and the results show that NO₃ reactions contribute little to the atmospheric losses of acrylate esters except in polluted regions.     

Gas-phase chemistry of benzyl alcohol: Reaction rate constants and products with OH radical and ozone

A bimolecular rate constant, k_{OH+Benzyl alcohol}, of (28 ± 7) × 10^?12 cm³ molecule^?1 s^?1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with benzyl alcohol, at (297 ± 3) K and 1 atm total pressure. Additionally, an upper limit of the bimolecular rate constant, k_{O3+Benzyl alcohol}, of approximately 6 × 10^?19 cm³ molecule^?1 s^?1 was determined by monitoring the decrease in benzyl alcohol concentration over time in an excess of ozone (O₃). To more clearly define part of benzyl alcohol's indoor environment degradation mechanism, the products of the benzyl alcohol + OH were also investigated. The derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to positively identify benzaldehyde, glyoxal and 4-oxopentanal as benzyl alcohol/OH reaction products. The elucidation of other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible benzyl alcohol/OH reaction mechanisms based on previously published volatile organic compound/OH gas-phase reaction mechanisms.     

Extent of H-atom abstraction from OH + p-cymene and upper limits to the formation of cresols from OH + m-xylene and OH + p-cymene

Aromatic hydrocarbons are important constituents of vehicle exhaust and of non-methane volatile organic compounds in ambient air in urban areas. It has recently been proposed that dealkylation is a significant pathway for the OH radical-initiated reactions, leading to the formation of phenolic compounds and/or oxepins (Noda, J., Volkamer, R., Molina, M.J., 2009. Dealkylation of alkylbenzenes: a significant pathway in the toluene, o-, m-, and p-xylene + OH reaction. Journal of Physical Chemistry A 113, 9658–9666.). We have investigated the formation of cresols from the reactions of OH radicals with m-xylene and p-cymene, and obtain upper limits of <1% for formation of each cresol isomer from OH + m-xylene and <2% for formation of each cresol isomer from OH + p-cymene. In addition, we have measured the formation yield of 4-methylacetophenone (the major product formed subsequent to H-atom abstraction from the CH(CH₃)₂ group) in the OH + p-cymene reaction to be 14.8 ± 3.2%, and estimate that H-atom abstraction from the CH₃ and CH(CH₃)₂ groups in p-cymene accounts for 20 ± 4% of the overall OH radical reaction. We also used a relative rate technique to measure the rate constant for the reaction of OH radicals with 4-methylacetophenone to be (4.50 ± 0.43) × 10^?12 cm³ molecule^?1 s^?1 at 297 ± 2 K.     

Relative rate measurements of reactions of unsaturated alcohols with atomic chlorine as a function of temperature

The kinetics of two structurally similar unsaturated alcohols, 3-butene-2-ol and 2-methyl-3-butene-2-ol (MBO232), with Cl atoms have been investigated for the first time, as a function of temperature using a relative method. As far as we know, the present work also provides the first value for 3-buten-2-ol. The coefficient at room temperature was also obtained for 2-propene-1-ol (allyl alcohol). The reactions were investigated using a 400 L Teflon reaction chamber coupled with gas chromatograph-coupled with flame-ionization detection (GC-FID) detection. The experiments were performed at atmospheric pressure and at temperatures between 256 and 298 K in air or nitrogen as the bath gas. The obtained kinetic data were used to derive the Arrhenius expressions, k_MBO232=(2.83±2.50)×10⁻¹⁴ exp (2670±249)/T, k_3-buten-2-ol=(0.65±1.60)×10⁻¹⁵ exp (3656±695)/T (in units of cm³ molecule⁻¹ s⁻¹). Finally, results and atmospheric implications are discussed and compared with the reactivity with OH and NO₃ radicals.     

The rate and mechanism of the gas-phase oxidation of hydroxyacetone

The rate and mechanism for gas-phase destruction of hydroxyacetone, CH₃C(O)CH₂OH, by reaction with OH, Cl-atoms, and by photolysis have been determined. The first quantitative UV absorption spectrum of hydroxyacetone is reported over the wavelength range 235 to 340 nm; the spectrum is blue-shifted by about 15 nm relative to that of acetone and peaks at 266 nm, with a maximum absorption cross section of (6.7±0.6) ×10^-20 cm² molecule^-1. Measurable absorption extends out to about 330 nm. The quantum yield for photolysis of hydroxyacetone in the region relevant to the troposphere (λ>290 nm) was found to be significantly less than unity. Rate coefficients for the reaction of hydroxyacetone with OH radicals and Cl-atoms were determined at 298 K using the relative rate technique. The rate coefficient for reaction with OH was found to be (3.0±0.7)×10^-12 cm³ molecule^-1 s^-1, while the rate coefficient for reaction with Cl-atoms was found to be (5.6±0.7)×10^-11 cm³ molecule^-1 s^-1. Both values agree well with previous studies. The data were used to determine the lifetime of hydroxyacetone in the troposphere. Reaction with OH is the major gas-phase destruction mechanism for this compound, limiting its lifetime to about 4 days, while photolysis is found to be only of minor importance.     

A PLP–LIF kinetic study of the atmospheric reactivity of a series of C4–C7 saturated and unsaturated aliphatic aldehydes with OH

Absolute rate coefficients for the reaction of OH radical with a series of saturated and unsaturated aliphatic aldehydes were measured with the pulsed laser photolysis/laser-induced fluorescence technique at room temperature and as a function of total pressure (p_T=100–400 Torr). No pressure dependence of the rate coefficients was observed. The weighted average values obtained, k_OH±2σ, in units of 10⁻¹¹ cm³ molecule⁻¹ s⁻¹, were 2.88±0.26 for n-butanal, 2.48±0.24 for n-pentanal, 2.60±0.21 for n-hexanal, 2.96±0.23 for n-heptanal, 3.51±0.71 for crotonaldehyde, 2.35±0.32 for trans-2-pentenal, 2.95±0.45 for trans-2-hexenal and 2.45±0.30 for trans-2-heptenal, respectively. The results are compared with previous data when available and with the corresponding coefficients for the reactions with NO₃ and O₃. The dominant tropospheric chemical loss process for these aliphatic aldehydes is the daytime reaction with OH, except in the case of trans-2-heptenal where the estimated lifetime for the reaction with NO₃ radical is smaller than the corresponding value for the OH reaction.     

Night-time tropospheric chemistry of the unsaturated alcohols (Z)-pent-2-en-1-ol and pent-1-en-3-ol: Kinetic studies of reactions of NO3 and N2O5 with stress-induced plant emissions

The night-time tropospheric chemistry of two stress-induced volatile organic compounds (VOCs), (Z)-pent-2-en-1-ol and pent-1-en-3-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO₃) with these pentenols were measured using the discharge-flow technique. Because of the relatively low volatility of these compounds, we employed off-axis continuous-wave cavity-enhanced absorption spectroscopy for detection of NO₃ in order to be able to work in pseudo first-order conditions with the pentenols in large excess over NO₃. The rate coefficients were determined to be (1.53±0.23)×10⁻¹³ and (1.39±0.19)×10⁻¹⁴ cm³ molecule⁻¹ s⁻¹ for reactions of NO₃ with (Z)-pent-2-en-1-ol and pent-1-en-3-ol. An attempt to study the kinetics of these reactions with a relative-rate technique, using N₂O₅ as source of NO₃ resulted in significantly higher apparent rate coefficients. Performing relative-rate experiments in known excesses of NO₂ allowed us to determine the rate coefficients for the N₂O₅ reactions to be (5.0±2.8)×10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ for (Z)-pent-2-en-1-ol, and (9.1±5.8)×10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ for pent-1-en-3-ol. We show that these relatively slow reactions can indeed interfere with rate determinations in conventional relative-rate experiments.     

Heterogeneous reactivity of pyrene and 1-nitropyrene with NO2: Kinetics,product yields and mechanism

The heterogeneous reactivity of nitrogen dioxide with pyrene and 1-nitropyrene (1NP) adsorbed on silica particles has been investigated using a fast-flow-tube in the absence of light. Reactants and products were extracted from particles using pressurised fluid extraction (PFE) and concentration measurements were performed using gas chromatography/mass spectrometry (GC/MS). The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate polycyclic compound concentrations versus reaction time. Experiments were performed at three different NO₂ concentrations and second order rate constants were calculated considering the oxidant concentration. The following rate constant values were obtained at room temperature: k(NO₂ + pyrene) = (9.3 ± 2.3) × 10^?17 cm³ molecule^?1 s^?1 and k(NO₂ + 1NP) = (6.2 ± 1.5) × 10^?18 cm³ molecule^?1 s^?1, showing that the reactivity of 1NP was slower by a factor of 15 than that of pyrene. 1NP was identified as the only NO₂-initiated oxidation product of pyrene and all the three dinitropyrenes were identified in the case of the 1NP reaction. The product quantification allowed showing that the kinetics of oxidation product formation was equal to that measured for parent compounds degradation, within uncertainties, confirming the validity of the reaction kinetics measurements.     

The radiative efficiency of HCF2OCF2OCF2CF2OCF2H (H-Galden 1040x) revisited

The infrared spectrum of HCF₂OCF₂OCF₂CF₂OCF₂H (CAS# 188690-77-9) has been re-measured. The integrated absorption intensity over the range 1000–1500 cm^?1 measured in the present work is (6.65 ± 0.33) × 10^?17 cm² molecule^?1 cm^?1 in 700 Torr of air at 296 K. The radiative efficiency of HCF₂OCF₂OCF₂CF₂OCF₂H is calculated to be 1.02 W m^?2 ppb^?1. The value reported in the 2007 Intergovernmental Panel on Climate Change (IPCC) report is approximately 35% larger reflecting what we believe to be an erroneously high value for the absorption strength of HCF₂OCF₂OCF₂CF₂OCF₂H adopted by the IPCC.     

Atmospheric chemistry of 1-methyl-2-pyrrolidinone

Rate constants for the atmospheric reactions of 1-methyl-2-pyrrolidinone with OH radicals, NO₃ radicals and O₃ have been measured at 296±2 K and atmospheric pressure of air, and the products of the OH radical and NO₃ radical reactions investigated. Using relative rate techniques, rate constants for the gas-phase reactions of OH and NO₃ radicals with 1-methyl-2-pyrrolidinone of (2.15±0.36)×10^-11 cm³ molecule^-1 s^-1 and (1.26±0.40)×10^-13 cm³ molecule^-1 s^-1, respectively, were measured, where the indicated errors include the estimated overall uncertainties in the rate constants for the reference compounds. An upper limit to the rate constant for the O₃ reaction of <1×10^-19 cm³ molecule^-1 s^-1 was also determined. These kinetic data lead to a calculated tropospheric lifetime of 1-methyl-2-pyrrolidinone of a few hours, with both the daytime OH radical reaction and the nighttime NO₃ radical reaction being important loss processes. Products of the OH radical and NO₃ radical reactions were analyzed by gas chromatography with flame ionization detection and combined gas chromatography–mass spectrometry. N-methylsuccinimide and (tentatively) 1-formyl-2-pyrrolidinone were identified as products of both of these reactions. The measured formation yields of N-methylsuccinimide and 1-formyl-2-pyrrolidinone were 44±12% and 41±12%, respectively, from the OH radical reaction and 59±16% and ∼4%, respectively, from the NO₃ radical reaction. Reaction mechanisms consistent with formation of these products are presented.     

Kinetics of the oxidation of hydrogen sulfite by hydrogen peroxide in aqueous solution:: ionic strength effects and temperature dependence

Conductometry was used to study the kinetics of the oxidation of hydrogen sulfite, HSO⁻₃, by hydrogen peroxide in aqueous non-buffered solution at the low concentration level of 10⁻⁵–10⁻⁶ M, typically found in cloud water. The kinetic data confirm that the rate law reported for the pH range 3–6 at higher concentration levels, rate=k_H·[H⁺]·[HSO⁻₃]·[H₂O₂], is valid at the low concentration level and at low ionic strength I_c. At 298 K and I_c=1.5×10⁻⁴ M, third-order rate constant k_H was found to be k_H=(9.1±0.5)×10⁷ M⁻² s⁻¹. The temperature dependence of k_H led to an activation energy of E_a=29.7±0.9 kJ mol⁻¹. The effect of the ionic strength (adjusted with NaCl) on rate constant k_H was studied in the range I_c=2×10⁻⁴–5.0 M at pH=4.5–5.2 by conductometry and stopped-flow spectrophotometry. The dependence of k_H on I_c can be described with a semi-empirical relationship, which is useful for the purpose of comparison and extrapolation. The kinetic data obtained are critically compared with those reported earlier.     

Laboratory studies on the uptake of aromatic hydrocarbons by ice crystals during vapor depositional crystal growth

Uptake of aromatic hydrocarbons (AH) by ice crystals during vapor deposit growth was investigated in a walk-in cold chamber at temperatures of 242, 251, and 260 K, respectively. Ice crystals were grown from ambient air in the presence of gaseous AH namely: benzene (C₆H₆), toluene (methylbenzene, C₇H₈), the C₈H₁₀ isomers ethylbenzene, o-, m-, p-xylene (dimethylbenzenes), the C₉H₁₂ isomers n-propylbenzene, 4-ethyltoluene, 1,3,5-trimethylbenzene (1,3,5-TMB), 1,2,4-trimethylbenzene (1,2,4-TMB), 1,2,3-trimethylbenzene (1,2,3-TMB), and the C₁₀H₁₄ compound tert.-butylbenzene. Gas-phase concentrations calculated at 295 K were 10.3–20.8 μg m⁻³. Uptake of AH was detected by analyzing vapor deposited ice with a very sensitive method composed of solid-phase micro-extraction (SPME), followed by gas chromatography/mass spectrometry (GC/MS).Ice crystal size was lower than 1 cm. At water vapor extents of 5.8, 6.0 and 8.1 g m⁻³, ice crystal shape changed with decreasing temperatures from a column at a temperature of 260 K, to a plate at 251 K, and to a dendrite at 242 K. Experimentally observed ice growth rates were between 3.3 and 13.3×10⁻³ g s⁻¹ m⁻² and decreased at lower temperatures and lower value of water vapor concentration. Predicted growth rates were mostly slightly higher.Benzene, toluene, ethylbenzene, and xylenes (BTEX) were not detected in ice above their detection limits (DLs) of 25 pg g_ice⁻¹ (toluene, ethylbenzene, xylenes) and 125 pg g_ice⁻¹ (benzene) over the entire temperature range. Median concentrations of n-propylbenzene, 4-ethyltoluene, 1,3,5-TMB, tert.-butylbenzene, 1,2,4-TMB, and 1,2,3-TMB were between 4 and 176 pg g_ice⁻¹ at gas concentrations of 10.3–10.7 μg m⁻³ calculated at 295 K. Uptake coefficients (K) defined as the product of concentration of AH in ice and density of ice related to the product of their concentration in the gas phase and ice mass varied between 0.40 and 10.23. K increased with decreasing temperatures. Values of Gibbs energy (ΔG) were between −4.5 and 2.4 kJ mol⁻¹ and decreased as temperatures were lowered. From the uptake experiments, the uptake enthalpy (ΔH) could be determined between −70.6 and −33.9 kJ mol⁻¹. The uptake entropy (ΔS) was between −281.3 and −126.8 J mol⁻¹ K⁻¹. Values of ΔH and ΔS were rather similar for 4-ethlytoluene, 1,3,5-TMB and tert.-butylbenzene, whereas 1,2,3-TMB showed much higher values.     

Gas-phase reaction of (E)-β-farnesene with ozone: Rate coefficient and carbonyl products

The gas-phase ozonolysis of (E)-β-farnesene was investigated in a 3.91 m³ atmospheric simulation chamber at 296 ± 2 K and relative humidity of around 0.1%. The relative rate method was used to determine the reaction rate coefficient of (4.01 ± 0.17) × 10^?16 cm³ molecule^?1 s^?1, where the indicated errors are two least-squares standard deviations and do not include uncertainties in the rate coefficients for the reference compounds (γ-terpinene, cis-cyclooctene and 1,5-cyclooctadiene). Gas phase carbonyl products were collected using a denuder sampling technique and analyzed with GC/MS following derivatization with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA). The reaction products detected were acetone, 4-oxopentanal, methylglyoxal, 4-methylenehex-5-enal, 6-methylhept-5-en-2-one, and (E)-4-methyl-8-methylenedeca-4,9-dienal. A detailed mechanism for the gas-phase ozonolysis of (E)-β-farnesene is proposed, which accounts for all of the products observed in this study. The results of this work indicate that the atmospheric reaction of (E)-β-farnesene with ozone has a lifetime of around 1 h and is another possible source of the ubiquitous carbonyls, acetone, 4-oxopentanal and 6-methylhept-5-en-2-one in the atmosphere.     

Radon exhalation and ultrafine fraction of radon progeny in closed room air

The influence of ²²²Rn exhalation from walls and air exchange (low ventilation rates ν<0.3 h^-1) upon its concentration in room air has been considered. It was found that the radon concentration reachs 84 Bq m^-3 at exhalation and ventilation rates of 66 Bq hm^-2 and 0.28 h^-1, respectively. The radon concentration and the ultrafine fraction f_p of potential α energy concentration as well as the equilibrium factor F of the short-lived radon progeny were also determined in three different completely closed rooms. An electroprecipitation method was applied for determining the ²²²Rn concentration while a single wire-screen technique was used for the determination of ultrafine radon progeny. During the measurements, the radon concentrations were varied between 33 and 134 with a mean value 89 Bq m^-3. A mean ultrafine fraction (f_p) of 0.16 was obtained at a mean aerosol particle concentration (Z) of 1700 cm^-3 and a mean equilibrium factor (F) of 0.33. The obtained mean value of f_p was found to be about five times higher than the value reported in the ICRP publication (f_p=0.03). The attachment rate (X), the deposition rate (q^f) and the deposition velocity (v^f_d) of the ultrafine radionuclide ²¹⁸Po were calculated. A mean value of X was found to be 49 h^-1 at a mean q^f of 46 h^-1 and a mean v^f_d of 4.6 m h^-1. The attachment coefficient β of ²¹⁸Po was found to vary between 0.016 and 0.047 with a mean value 0.028 cm³ h^-1.     

OH and HO2 measurements in a forested region of north-western Greece

Boundary layer concentrations of hydroxyl (OH) and hydroperoxyl (HO₂) radicals were measured at 1180 m elevation in a mountainous, forested region of north-western Greece during the AEROsols formation from BIogenic organic Carbon (AEROBIC) field campaign held in July–August 1997. In situ measurements of OH radicals were made by laser-induced fluorescence (LIF) at low pressure, exciting in the (0, 0) band of the A–X system at 308 nm. HO₂ radicals were monitored by chemical titration to OH upon the addition of NO, with subsequent detection by LIF. The instrument was calibrated regularly during the field campaign, and demonstrated a sensitivity towards OH and HO₂ of 5.2×10⁵ and 2.4×10⁶ molecule cm⁻³, respectively, for a signal integration period of 2.5 min and a signal-to-noise ratio of 1. Diurnal cycles of OH and HO₂ were measured on 10 days within a small clearing of a forest of Greek Fir (Abies Borisi-Regis). In total 4165 OH data points and 1501 HO₂ data points were collected at 30 s intervals. Noon-time OH and HO₂ concentrations were between 4–12×10⁶ and 0.4–9×10⁸ molecule cm⁻³, respectively. The performance of the instrument is evaluated, and the data are interpreted in terms of correlations with controlling variables. A significant correlation (r²=0.66) is observed between the OH concentration and the rate of photolysis of ozone, J(O¹D). However, OH persisted into the early evening when J(O¹D) had fallen to very low values, consistent with the modelling study presented in the following paper (Carslaw et al., 2001, OH and HO₂ radical chemistry in a forest region of north-western Greece. Atmospheric Environment 35, 4725–4737) that predicts a significant radical source from the ozonolysis of biogenic alkenes. Normalisation of the OH concentrations for variations in J(O¹D) revealed a bell-shaped dependence of OH upon NO_x (NO+NO₂), which peaked at [NO_x] ∼1.75 ppbv. The diurnal variation of HO₂ was found to be less correlated with J(O¹D) compared to OH.     

Quantitative analysis of volatile organic compounds (VOCs) in atmospheric particles

There are a number of difficulties associated with the quantitative analysis of volatile organic compounds (VOCs) in atmospheric particles. Therefore, majority of the previous studies on VOCs associated with particles have been qualitative. Air samples were collected in Izmir, Turkey to determine ambient particle and gas phase concentrations of several aromatic, oxygenated and halogenated VOCs. Samples were quantitatively analyzed using thermal desorption–gas chromatography/mass spectrometry. Gas-phase concentrations ranged between 0.02 (bromoform) and 4.65 μg m⁻³ (toluene) and were similar to those previously measured at the same site. Particle-phase concentrations ranged from 1 (1,3-dichlorobenzene) to 933 pg m⁻³ (butanol). VOCs were mostly found in gas-phase (99.9±0.25%). However, the particulate VOCs had comparable concentrations to those reported previously for semivolatile organic compounds. The distribution of particle-phase VOCs between fine (d_p<2.5 μm) and coarse (2.5 μm<d_p<10 μm) fractions was also investigated. It was found that VOCs were mostly associated with fine particles.     

Comparison of measured and model-calculated real-world traffic emissions

The quality of an emission calculation model based on emission factors measured on roller test stands and statistical traffic data was evaluated using source strengths and emission factors calculated from real-world exhaust gas concentration differences measured upwind and downwind of a motorway in southwest Germany. Gaseous and particulate emissions were taken into account. Detailed traffic census data were taken during the measurements. The results were compared with findings of similar studies.The main conclusion is the underestimation of CO and NO_x source strengths by the model. On the average, it amounts to 23% in case of CO and 17% for NO_x. The latter underestimation results from an undervaluation by 22% of NO_x emission factors of heavy-duty vehicles (HDVs). There are significant differences between source strengths on working days and weekends because of the different traffic split between light-duty vehicles (LDVs) and HDVs. The mean emission factors of all vehicles from measurements are 1.08 g km⁻¹ veh⁻¹ for NO_x and 2.62 g km⁻¹ veh⁻¹ for CO. The model calculations give 0.92 g km⁻¹ veh⁻¹ for NO_x and 2.14 g km⁻¹ veh⁻¹ for CO.The source strengths of 21 non-methane hydrocarbon (NMHC) compounds quantified are underestimated by the model. The ratio between the measured and model-calculated emissions ranges from 1.3 to 2.1 for BTX and up to 21 for 16 other NMHCs. The reason for the differences is the insufficient knowledge of NMHC emissions of road traffic.Particulate matter emissions are dominated by ultra-fine particles in the 10–40 nm range. As far as aerosols larger than 29 nm are concerned, 1.80×10¹⁴ particles km⁻¹ veh⁻¹ are determined for all vehicles, 1.22×10¹⁴ particles km⁻¹ veh⁻¹ and an aerosol volume of 0.03 cm³ km⁻¹ veh⁻¹ are measured for LDVs, and for HDVs 7.79×10¹⁴ particles km⁻¹ veh⁻¹ and 0.41 cm³ km⁻¹ veh⁻¹ are calculated. Traffic-induced turbulence has been identified to have a decisive influence on exhaust gas dispersion near the source.     

Estimating distributions of long-term particulate matter and manganese exposures for residents of Toronto,Canada

Methylcyclopentadienyl manganese tricarbonyl (MMT), a manganese-based gasoline additive, has been used in Canadian gasoline for about 20 yr. Because MMT potentially increases manganese levels in particulate matter resulting from automotive exhausts, a population-based study conducted in Toronto, Canada assessed the levels of personal manganese exposures. Integrated 3-day particulate matter (PM_2.5) exposure measurements, obtained for 922 participant periods over the course of a year (September 1995–August 1996), were analyzed for several constituent elements, including Mn. The 922 measurements included 542 participants who provided a single 3-day observation plus 190 participants who provided two observations (in two different months). In addition to characterizing the distributions of 3-day average exposures, which can be estimated directly from the data, including the second observation for some participants enabled us to use a model-based approach to estimate the long-term (i.e. annual) exposure distributions for PM_2.5 mass and Mn. The model assumes that individuals’ 3-day average exposure measurements within a given month are lognormally distributed and that the correlation between 3-day log-scale measurements k months apart (after seasonal adjustment) depends only on the lag time, k, and not on the time of year. The approach produces a set of simulated annual exposures from which an annual distribution can be inferred using estimated correlations and monthly means and variances (log scale) as model inputs. The model appeared to perform reasonably well for the overall population distribution of PM_2.5 exposures (mean=28 μg m^-3). For example, the model predicted the 95th percentile of the annual distribution to be 62.9 μg m^-3 while the corresponding percentile estimated for the 3-day data was 86.6 μg m^-3. The assumptions of the model did not appear to hold for the overall population of Mn exposures (mean=13.1 ng m^-3). Since the population included persons who were potentially occupationally exposed to Mn (in non-vehicle-related jobs), we used responses to questionnaire items to form a subgroup consisting of non-occupationally exposed participants (671 participant periods), for which the model assumptions did appear to hold. For that subpopulation (mean=9.2 ng m^-3), the model-predicted 95th percentile of the annual Mn distribution was 16.3-ng m^-3, compared with 21.1 ng m^-3 estimated for the 3-day data.     

Nitrous oxide emissions from mineral and organic soils of a Norway spruce stand in South–West Germany

Due to the high temporal and spatial variability of N₂O fluxes, estimates of N₂O emission from temperate forest ecosystems are still highly uncertain, particularly at larger scales. Although highest N₂O emissions with up to 7.0 kg N ha⁻¹ yr⁻¹ were mainly reported for soils affected by stagnant water, most of the reported gas flux measurements were performed at forest sites with well-aerated soils yielding mostly to low mean annual emission rates less than 1.0 kg N ha⁻¹ yr⁻¹. This study compares N₂O fluxes from upland (Cambisols) and temporally water-logged (Gleysols, Histosols) soils of the Central Black Forest (South-West Germany) over a period of 2 yr. Mean annual N₂O fluxes from investigated soils ranged between 0.2 and 3.9 kg N ha⁻¹ yr⁻¹. The fluxes showed a large variability between the different soil types. Emissions could be clearly ranked in the following order: Cambisols (0.26–0.75 kg N ha⁻¹ yr⁻¹)<Gleysols (1.37–2.68 kg N ha⁻¹ yr⁻¹)<Histosol (3.66–3.95 kg N ha⁻¹ yr⁻¹). Although the Cambisols cover two-thirds of the investigated area, only about half of the overall N₂O is emitted from this soil type. Therefore, regional or national N₂O fluxes from temperate forest soils are underestimated if soils characterised by intermediate aeration conditions are disregarded.