José Albaladejo

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.

Application of cluster analysis to surface ozone, NO2 and SO2 daily patterns in an industrial area in Central-Southern Spain measured with a DOAS system

The daily variations of surface ozone, NO₂ and SO₂ have been investigated in a heavily industrialised area in the centre of the Iberian Peninsula (Puertollano) using hourly values recorded during two years (2008-2009) with an active LP-DOAS system. The meteorological conditions and air masses have been studied using the HYSPLIT model. The maximum hourly levels of these air pollutants exceeded 100 ppb for ozone, 150 ppb for SO₂ and 210 ppb for NO₂. However, mean values for ozone, NO₂ and SO₂ were of 49, 10 and 3 ppb respectively. Daily-monthly evolutions (defined as daily evolutions for different months) have been analysed in order to know the general daily behaviour of these species. Air pollution problems have been identified using the thresholds defined in the European Directive 2008. The limits to protect human health (human health protection limitations) have been exceeded during the study period. In order to find a set of representative daily cycles for each pollutant at different air quality regimes, a K-mean cluster technique has been applied. Five and four optimal cluster numbers have been obtained for the daily patterns of ozone and SO₂ respectively. In addition, we studied the daily variation of the temperature, relative and specific humidity and wind speed associated with each air pollutant daily pattern. Ozone daily patterns showed typical daily variations with one exception of a cluster which presents a peak in the early morning. For SO₂, the first two clusters present a low mixing ratio, however cluster 3 and 4 are less frequent but with higher levels. The more frequent air pollutant daily patterns do not exceed the threshold defined in the Directive. Nevertheless, clusters with lower frequency (representing between 5 and 7% of days) exceed the thresholds and could be considered as air pollution events.

Gas-phase chemistry of atmospheric Cl atoms : a PLP-RF kinetic study with a series of ketones

The pulsed laser photolysis-resonance fluorescence technique (PLP-RF) has been used to determine the absolute rate coefficients for the gas-phase reactions of Cl atoms with a series of ketones at room temperature (298 K). The rate coefficients obtained (in units of cm 3 molecule -1 s -1 ) are: 2-butanone (3.30±0.20) × 10- 11 , 2,3-butadione (4.92±0.44) × 10 -13 , 2-pentanone (4.57±0.28) × 10 -11 , 3-pentanone (4.50±0.32) × 10 -11 , 2-hexanone (6.54±0.58) x 10 -11 , 3-hexanone (6.69±0.62) x 10 -11 and cyclohcxanone (6.75±0.52) x 10 -11 . The measured values were independent of pressure over the range 20-200 Torr. These rate coefficients were compared with previous studies carried out by different techniques, when data were available. Results and atmospheric implications are discussed and compared with the reactivity with OH radicals.

Relative and absolute kinetic studies of 2-butanol and related alcohols with tropospheric Cl atoms

A newly constructed chamber/Fourier transform infrared system was used to determine the relative rate coefficient, k(i), for the gas-phase reaction of Cl atoms with 2-butanol (k(1)), 2-methyl-2-butanol (k(2)), 3-methyl-2-butanol (k(3)), 2,3-dimethyl-2-butanol (k(4)) and 2-pentanol (k(5)). Experiments were performed at (298 +/- 2) K, in 740 Torr total pressure of synthetic air, and the measured rate coefficients were, in cm(3) molecule(-1) s(-1) units (+/-2sigma): k(1)=(1.32 +/- 0.14) x 10(-10), k(2)=(7.0 +/- 2.2) x 10(-11), k(3)=(1.17 +/- 0.14) x 10(-10), k(4)=(1.03 +/- 0.17) x 10(-10) and k(5)=(2.18 +/- 0.36) x 10(-10), respectively. Also, all the above rate coefficients (except for 2-pentanol) were investigated as a function of temperature (267-384 K) by pulsed laser photolysis-resonance fluorescence (PLP-RF). The obtained kinetic data were used to derive the Arrhenius expressions: k(1)(T)=(6.16 +/- 0.58) x 10(-11)exp[(174 +/- 58)/T], k(2)(T)=(2.48 +/- 0.17) x 10(-11)exp[(328 +/- 42)/T], k(3)(T)=(6.29 +/- 0.57) x 10(-11)exp[(192 +/- 56)/T], and k(4)(T)=(4.80 +/- 0.43) x 10(-11)exp[(221 +/- 56)/T](in units of cm(3) molecule(-1) s(-1) and +/-sigma). Results and mechanism are discussed and compared with the reported reactivity with OH radicals. Some atmospheric implications derived from this study are also reported.

Atmospheric Lifetimes and Global Warming Potentials of CF3CH2CH2OH and CF3(CH2)2CH2OH

A comprehensive study of several atmospheric degradation routes for two hydrofluoroalcohols, CF(3)(CH(2))(x=1,2)CH(2)OH, is presented. The gas-phase kinetics of their reactions with hydroxyl radicals (OH) and chlorine (Cl) atoms are investigated by absolute and relative techniques, respectively. The room-temperature rate coefficients (±σ, in cm(3) molecule(-1) s(-1)) k(OH) and k(Cl), are respectively (9.7±1.1)×10(-13) and (1.60±0.45)×10(-11) for CF(3)CH(2)CH(2)OH, and (2.62±0.32)×10(-12) and (8.71±0.24)×10(-11) for CF(3)(CH(2))(2)CH(2)OH. Average lifetimes of CF(3)CH(2)CH(2)OH and CF(3)(CH(2))(2)CH(2)OH due to the OH and Cl reactions are estimated to be 12 and 4 days, and greater than 20 and 4 years, respectively. Also, the IR and UV absorption cross sections of CF(3)(CH(2))(x=1,2)CH(2)OH are determined in the spectral ranges of 500-4000 cm(-1) and 200-310 nm. Photolysis of CF(3)(CH(2))(x=1,2)CH(2)OH in the actinic region (λ≥290 nm) is negligible compared to their homogeneous removal. Additionally, computational IR spectra are consistent with the experimental ones, thus giving high confidence in the obtained results. The lifetimes of CF(3)(CH(2))(x=1,2)CH(2)OH and IR spectra reported herein allow the calculation of the direct global warming potential of these hydrofluoroalcohols. The contribution of CF(3)(CH(2))(x)CH(2)OH to radiative forcing of climate change will be negligible.

Atmospheric reactions Cl+CH3–(CH2)n–OH (n=0–4): A kinetic and theoretical study

The reactions of Cl with a series of linear alcohols: methanol (k1), ethanol (k2), 1-propanol (k3), 1-butanol (k4), and 1-pentanol (k5) were investigated as a function of temperature in the range of 264-382 K by laser photolysis-resonance fluorescence. The obtained kinetic data were used to derive the following Arrhenius expressions: k1=(3.55+/-0.22)x10(-10) exp[-(559+/-40)T], k2=(5.25+/-0.52)x10(-11) exp[(190+/-68)T], k3=(2.63+/-0.21)x10(-11) exp[(525+/-51)T], k4=(3.12+/-0.31)x10(-11) exp[(548+/-65)T], and k5=(3.97+/-0.48)x10(-11) exp[(533+/-77)T] (in units of cm(3) molecule(-1) s(-1)). To our knowledge, these are the first absolute kinetic data reported for 1-butanol and 1-pentanol and also the first kinetic study as a function of temperature for these two compounds. Results, mechanism, and tropospheric implications are discussed and compared with the reported reactivity with OH radicals. Moreover, a theoretical insight into the mechanisms of these reactions has also been pursued through ab initio Möller-Plesset second-order perturbation treatment calculations with 6-311G** basis sets. Optimized geometries and vibrational frequencies have been obtained for transition states and molecular complexes appearing along the different reaction pathways. Furthermore, molecular energies have been calculated at quadratic configuration interaction with single, double, and triple excitations level in order to get an estimation of the activation energies.

Laboratory studies of CHF2CF2CH2OH and CF3CF2CH2OH: UV and IR absorption cross sections and OH rate coefficients between 263 and 358 K.

Fluorinated alcohols, such as 2,2,3,3-tetrafluoropropanol (TFPO, CHF(2)CF(2)CH(2)OH) and 2,2,3,3,3-pentafluoropropanol (PFPO, CF(3)CF(2)CH(2)OH), can be potential replacements of hydrofluorocarbons with large global warming potentials, GWPs. IR absorption cross sections for TFPO and PFPO were determined between 4000 and 500 cm(-1) at 298 K. Integrated absorption cross sections (S(int), base e) in the 4000-600 cm(-1) range are (1.92 ± 0.34) × 10(-16) cm(2) molecule(-1) cm(-1) and (2.05 ± 0.50) × 10(-16) cm(2) molecule(-1) cm(-1) for TFPO and PFPO, respectively. Uncertainties are at a 95% confidence level. Ultraviolet absorption spectra were also recorded between 195 and 360 nm at 298 K. In the actinic region (λ > 290 nm), an upper limit of 10(-23) cm(2) molecule(-1) for the absorption cross sections (σ(λ)) was reported. Photolysis in the troposphere is therefore expected to be a negligible loss for these fluoropropanols. In addition, absolute rate coefficients for the reaction of OH radicals with CHF(2)CF(2)CH(2)OH (k(1)) and CF(3)CF(2)CH(2)OH (k(2)) were determined as a function of temperature (T = 263-358 K) by the pulsed laser photolysis/laser induced fluorescence (PLP-LIF) technique. At room temperature, the average values obtained were k(1) = (1.85 ± 0.07) × 10(-13) cm(3) molecule(-1) s(-1) and k(2) = (1.19 ± 0.03) × 10(-13) cm(3) molecule(-1) s(-1). The observed temperature dependence of k(1)(T) and k(2)(T) is described by the following expressions: (1.35 ± 0.23) × 10(-12) exp{-(605 ± 54)/T} and (1.36 ± 0.19) × 10(-12) exp{-(730 ± 43)/T} cm(3) molecule(-1) s(-1), respectively. Since photolysis of TFPO and PFPO in the actinic region is negligible, the tropospheric lifetime (τ) of these species can be approximated by the lifetime due to the homogeneous reaction with OH radicals. Global values of τ(OH) were estimated to be of 3 and 4 months for TFPO and PFPO, respectively. GWPs relative to CO(2) at a time horizon of 500 years were calculated to be 8 and 12 for TFPO and PFPO, respectively. Despite the higher GWP relative to CO(2), these species are not expected to significantly contribute to the greenhouse effect in the next decades since they are short-lived species and will not accumulate in the troposphere even as their emissions grow up.

A kinetic study of the reaction of Cl with a series of linear and ramified ketones as a function of temperature

The reactions of Cl atoms with 2,3-butadione (k1), 2-butanone (k2), 2-pentanone (k3), 2-hexanone (k4), 3-methyl-2-butanone (k5), 4-methyl-2-pentanone (k6) and 5-methyl-2-hexanone (k7), were investigated for the first time as a function of temperature (266–380 K), over the pressure range 20–200 Torr, using pulsed laser photolysis-resonance fluorescence (PLP-RF). The Arrhenius expressions for the seven reactions are proposed. The temperature dependence of the studied reactions is discussed; the reaction of Cl atoms with 2,3-butadione exhibits a positive temperature dependence whereas the corresponding reactions with 2-pentanone, 2-hexanone, 4-methyl-2-pentanone and 5-methyl-2-hexanone exhibit a negative temperature dependence and those with 2-butanone and 3-methyl-2-butanone shows only a slightly positive and a negative temperature dependence, respectively. Finally, the results and atmospheric implications are discussed and compared with the reactivity towards the OH radical.

Reactivity of OH and CH3OH Between 22 and 64 K: Modelling the Gas Phase Production of CH3O in Barnard 1B

In the last years, ultra-low temperature chemical kinetic experiments have demonstrated that some gas-phase reactions are much faster than previously thought. One example is the reaction between OH and CH3OH, which has been recently found to be accelerated at low temperatures yielding CH3O as main product. This finding opened the question of whether the CH3O observed in the dense core Barnard 1b could be formed by the gas-phase reaction of CH3OH and OH. Several chemical models including this reaction and grain-surface processes have been developed to explain the observed abundance of CH3O with little success. Here we report for the first time rate coefficients for the gas-phase reaction of OH and CH3OH down to a temperature of 22 K, very close to those in cold interstellar clouds. Two independent experimental set-ups based on the supersonic gas expansion technique coupled to the pulsed laser photolysis-laser induced fluorescence technique were used to determine rate coefficients in the temperature range 22-64 K. The temperature dependence obtained in this work can be expressed as k(22-64 K) = (3.6 ± 0.1) × 10-12(T/300 K)-(1.0±0.2) cm3 molecule-1 s-1. Implementing this expression in a chemical model of a cold dense cloud results in CH3O/CH3OH abundance ratios similar or slightly lower than the value of ∼ 3 × 10-3 observed in Barnard 1b. This finding confirms that the gas-phase reaction between OH and CH3OH is an important contributor to the formation of interstellar CH3O. The role of grain-surface processes in the formation of CH3O, although it cannot be fully neglected, remains controversial.

A preliminary study on ambient levels of carbonyls, benzene, toluene and xylene in the south-west of the Iberian Peninsula (Huelva coast), Spain

We report the first observations of volatile organic compound (VOC) concentrations, including aldehydes, in the coastal, industrial area of Huelva near the Doñana National Park (south-west of the Iberian Peninsula). The periods studied were July–September 2008 and February–November 2009. Formaldehyde, acetaldehyde, acetone, propanal, benzene, toluene and m/p-xylenes were identified and quantified. Acetone and formaldehyde were the most abundant carbonyls, followed by acetaldehyde and propanal. Maximum and minimum values for all these compounds in the period of measurement, and their relationship with meteorological parameters or influence of anthropogenic or biogenic emissions, are analysed. Finally, different concentration ratios and correlations were calculated to assess the effect of the anthropogenic or biogenic processes on the observed VOC levels.