Surface ozone trends reversal for June and December in an Atlantic natural coastal environment.

Surface ozone and temperature trends were investigated using records from 2000 to 2021 in Southwestern Europe, at El Arenosillo observatory, focusing on June and December. The ozone trends for daily percentiles were increasing in June for lower percentiles (2.5 ± 1.2 ppb decade-1 for the 5th percentile) and decreasing for higher (- 2.2 ± 1.4 ppb decade-1 for the 95th percentile); in December, the trends were growing in the entire range of percentiles, with a peak of 2.2 ± 0.8 ppb decade-1. A declining trend was obtained for the geopotential height at the pressure level of 850 hPa (Z850) in June while highlighting the upward trend in December (26.3 ± 6.5 m decade-1). The hourly trends for ozone and temperature were also explored in these months. In June, the nocturnal ozone trends were growing (4.0 ± 1.2 ppb decade-1 or 10% decade-1 at 8:00 UTC) associated with temperature rises while in the daytime, a decrease in temperature was observed along with an ozone decreasing trend (- 2.6 ± 1.6 ppb decade-1 or - 5% decade-1 at 18:00 UTC). Hourly ozone and temperature trends in December were increasing with peaks of 3.0 ± 0.9 ppb decade-1 (~ 8% decade-1) at 12:00 UTC and 1.6 ± 0.3 °C decade-1 at 19:00 UTC. Two representative scenarios of these months were studied. The ozone decreases in June could be associated with several factors, decreasing in temperatures and a possible weakening of the anticyclonic conditions leading to changes in the mesoscale processes' development. The strengthening of the Azores anticyclone in December could be enhancing the upward ozone trend observed. It is unknown whether the reversal ozone pattern trends found in this region are a local phenomenon; although we suggest that it could be happening on a larger scale as well, future studies should be carried out.

Oxidation capacity changes in the atmosphere of large urban areas in Europe: Modelling and experimental campaigns in atmospheric simulation chambers.

Air pollution is a major concern for human health and the environment. Consequently, environmental standards have become stricter to improve air quality. Thanks to this, the ambient levels of O3 precursors such as VOCs and NOX have decreased. However, O3 levels in Europe, especially during winter, have increased, potentially impacting on atmospheric oxidation capacity and the associated chemistry of tropospheric oxidants. In this work, we focus on recent changes in the oxidation capacity of urban atmospheres. The study is conducted with the results of the CMAQ modelling system with a regional resolution with 12 × 12 km2 across the entire European continent for the winter (January) and summer (July) of 2007 and 2015. The 2015 meteorological data is used for both years to emphasise emission changes during the studied period. We scrutinise the changes in ambient concentration levels of the main tropospheric oxidants (O3 and HOX radicals) in five representative cities, Valencia, Madrid, Milan, Berlin, and The Hague. The enhanced O3 formation in winter seems to be due to the low VOC/NOX ratio, while the opposite trend in summer may be related to a relatively high ratio. Additionally, photooxidation experiments are carried out in the EUPHORE chambers to study the effect of changes in NOX concentration and NO/NO2 ratio on the variation of the given oxidants at constant VOCs concentrations. For the baseline experiments, two scenarios are selected based on the model results of 2015: two representative winter and summer days of low and high pollution in Berlin and Madrid, respectively. The role of VOC/NOX and NO/NO2 ratios on atmospheric reactivity is discussed. As a result, it is first suggested that further decreases in ambient NOX levels are required to reduce ambient O3 levels. Moreover, additional factors should be considered when designing local-specific emission abatement strategies.

Saharan air outflow variability in the 1980-2020 period.

Airborne dust represents a hazard to the environment and human health. The outflow of air masses carrying dust from northern Africa, the world's largest active dust source, to the North Atlantic and Mediterranean regions is modulated by atmospheric conditions. However, how global warming-driven changes on atmospheric circulation have influenced North African air outflow in the recent past is not well understood. Here, we explore the Saharan air outflow from northwestern Africa over the 1980 to 2020 period. We find a decrease in the transport to the Atlantic Ocean and the Iberian Peninsula of -0.29 ± 0.16% dec-1 and -0.66 ± 0.18% dec-1, respectively, and an increasing trend to the Mediterranean Sea (0.24 ± 0.18% dec-1) and Europe (0.60 ± 0.18% dec-1). The results indicate that the strengthening of the Atlantic high pressure system and the Saharan thermal low, both associated with the narrowing of the Intertropical Convergence Zone and the Hadley Cell expansion under global warming, could be favoring the Saharan outflow to the Mediterranean Sea and Europe in detriment of transport to the Atlantic Ocean. The results also show that present-day Saharan air arrives at these regions at higher altitudes and in shorter timescales than decades ago. This is associated to the increase in surface heating conditions in the Sahara, 0.41 ± 0.02 °C dec-1, that can inject air into windier upper atmospheric levels, thereby allowing higher and faster air transport. Our results suggest a change in the Saharan air outflow likely associated with global warming and with potentially significant implications for the temporal and spatial patterns of North African dust export.

Analysis of emissions-driven changes in the oxidation capacity of the atmosphere in Europe.

Anthropogenic emissions in Europe have been gradually reduced thanks to a combination of factors, including restrictive regulation and policy implementation, fuel switching, technological developments, and improved energy efficiencies. Many measures have been specifically introduced to meet the annual and hourly limit value of NO2 for the protection of human health, mainly targeting traffic emissions. Due to NOX reduction policies in Europe, NO2 levels have generally declined, but O3 concentrations have been found to increase. This phenomenon would cause changes in the oxidant capacity of the atmosphere, altering the concentration of tropospheric oxidants in urban areas. The Community Multiscale Air Quality (CMAQ) modelling system has been used to study concentration changes of NO2, O3 and the main radicals in Europe between 2007 and 2015 for two months representatives of winter and summer conditions (January and July). In addition to describing the general situation in Europe, variations in pollutants along with NOX emission changes over 67 large European cities have been analysed by means of statistical methods. NOX emissions and NO2 concentrations decreased in both seasons during the period in all the selected cities. In most of them O3 concentrations increased in winter but decreased in summer. The concentration of the OH radical, the main oxidant during the daytime, shows an increase in winter. This is also the case for the main cities in summer although we found a general decrease in continent for this season. The NO3 radical, the main night-time oxidant, was found to increase in winter and decrease in summer. HNO3 shows a concentration decline in both seasons. The studied cities are classified in five groups by means of k-mean clustering procedure. We identified five groups with specific patterns, suggesting that the oxidant capacity of the European urban atmospheres has reacted differently to NOX emission abatement policies.

Formaldehyde, acrolein and other carbonyls in dwellings of university students. Levels and source characterization.

Fifteen carbonyl compounds were investigated in the living rooms and bedrooms of 25 university student flats in the urban area of Ciudad Real (Central Southern Spain) in wintertime. Carbonyls were sampled using Radiello ® passive samplers refilled in the laboratory according to the method described in ISO 16000-3 Standard. The most abundant carbonyls in the living rooms and bedrooms were formaldehyde, acetone, acetaldehyde, hexaldehyde and butyraldehyde. The median concentration levels in the living rooms and bedrooms were: 28.6 and 34.2 µg m-3 for formaldehyde, 18.3 and 23.1 µg m-3 for acetone, 14.3 and 15.8 µg m-3 for acetaldehyde, 11.4 and 14.1 µg m-3 for hexaldehyde and 10.8 and 12.4 µg m-3 for butyraldehyde. The median concentration of formaldehyde, benzaldehyde, valeraldehyde and hexaldehyde was significantly higher in the bedrooms than in the living rooms. Indoor concentrations were significantly higher than outdoor concentrations for all carbonyl measured, indicating that sources in the indoor environment are prevailing in all flats. Principal component analysis, multiple linear regressions and Spearman correlation coefficients were used to investigate the origin, the indoor pollutants determinants and to establish common sources between carbonyls. Eight components were extracted from the application of PCA to the indoor and outdoor measurements accounting for 97.7% of the total variance. Formaldehyde, acetone, acetaldehyde and acrolein presented different indoor sources. In the multiple linear regression analysis, higher formaldehyde concentrations were found in those living rooms with wood floor and smoking was positively associated to acetone, propionaldehyde, benzaldehyde and isovaleraldehyde. Formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde and benzaldehyde concentrations were compared with relevant international guidelines, being their concentrations below recommended values except acrolein, where all measured flats exceeded the reference levels; it would be important to focus on the characterization of emission sources of acrolein in indoor air in order to minimise the exposure and health risk.

Assessment of CO2 and aerosol (PM2.5, PM10, UFP) concentrations during the reopening of schools in the COVID-19 pandemic: The case of a metropolitan area in Central-Southern Spain.

Public health authorities have been paramount in guaranteeing that adequate fresh air ventilation is promoted in classrooms to avoid SARS-CoV-2 transmission in educational environments. In this work it was aimed to assess ventilation conditions (carbon dioxide, CO2) and suspended particulate matter (PM2.5, PM10 and UFP) levels in 19 classrooms - including preschool, primary and secondary education - located in the metropolitan area of Ciudad Real, Central-Southern Spain, during the school's reopening (from September 30th until October 27th, 2020) after about 7 months of lockdown due to COVID-19 pandemic. The classrooms that presented the worst indoor environmental conditions, according to the highest peak of concentration obtained, were particularly explored to identify the possible influencing factors and respective opportunities for improvement. Briefly, findings suggested that although ventilation promoted through opening windows and doors according to official recommendations is guaranteeing adequate ventilation conditions in most of the studied classrooms, thus minimizing the risk of SARS-CoV-2 airborne transmission, a total of 5 (26%) surveyed classrooms were found to exceed the recommended CO2 concentration limit value (700 ppm). In general, preschool rooms were the educational environments that registered better ventilation conditions, while secondary classrooms exhibited the highest peak and average CO2 concentrations. In turn, for PM2.5, PM10 and UFP, the concentrations assessed in preschools were, on average about 2-fold greater than the levels obtained in both primary and secondary classrooms. In fact, the indoor PM2.5 and PM10 concentrations substantially exceeded the recommended limits of 8hr-exposure, established by WHO, in 63% and 32% of the surveyed classrooms, respectively. Overall, it is expected that the findings presented in this study will assist the establishment of evidence-based measures (namely based on ensuring proper ventilation rates and air filtration) to mitigate preventable environmental harm in public school buildings, mainly at local and national levels.

Ambient levels of volatile organic compounds and criteria pollutants in the most industrialized area of central Iberian Peninsula: intercomparison with an urban site.

This work presents observations of volatile organic compounds (VOCs), including carbonyls, particulate matter 2.5 (PM2.5) (included in the most recent ambient air quality standards because of its harmful effect on health), PM10 and other important pollutants, CO, SO2, NOx and ozone, over the most industrialized area in the central Iberian Peninsula. Nearly two years of data obtained through a mobile laboratory are used for this purpose. Different concentration ratios and correlations were calculated to assess the effect of the anthropogenic or biogenic processes on the observed VOC levels. The diurnal profile for SO2 is different in Puertollano and it does not coincide with the maxima of the other primary pollutants such as benzene, toluene and xylenes (BTX), CO and NO. This behaviour could be attributed to the fact that SO2 mainly comes from industrial activities. However, an impact of the industry on air quality was detected not only by the results obtained for SO2, but also by the toluene/benzene, T/B, ratio (7.5). Finally, correlations between meteorological conditions and pollution distribution have been considered; also, the analysis of the back trajectories together with Spearman correlation coefficients have been carried out to understand the origin and pathway in some events with unusual high pollutant values.

Photolysis study of fluorinated ketones under natural sunlight conditions.

UV-visible absorption cross-sections are reported for CF3C(O)CH3, CF3C(O)CH2CH3, and CH3CH2C(O)CH(CH3)2. The photolysis rate constants of CF3C(O)CH3, CF3C(O)CH2CH3, and CF3CF2C(O)CF(CF3)2 were measured from smog-chamber experiments carried out in a 400 L Teflon-bag reactor under sunlight irradiation. Actinic radiation profiles from the "Tropospheric Ultraviolet and Visible Radiation Model" were used to obtain quantum efficiencies of photolysis: 0.34 ± 0.08, 0.24 ± 0.06, and (4.4 ± 0.6) × 10(-2) for CF3C(O)CH3, CF3C(O)CH2CH3, and CF3CF2C(O)CF(CF3)2, respectively. These values correspond to wavelength ranges of 295-345 nm (for CF3C(O)CH3 and CF3C(O)CH2CH3) and 295-360 nm (for CF3CF2C(O)CF(CF3)2). The photolysis rate constants change significantly with the seasons, with the yearly averages being (2.3 ± 0.7) × 10(-6), (1.8 ± 0.6) × 10(-6), and (2.1 ± 0.8) × 10(-6) s(-1) for CF3C(O)CH3, CF3C(O)CH2CH3, and CF3CF2C(O)CF(CF3)2, respectively. Photolysis processes are fast and responsible for the short gas-phase lifetimes of the studied ketones, which are 5.1 ± 2.2, 6.5 ± 2.5 and 5.5 ± 1.5 days. The radiative forcing efficiencies are provided to assess the contribution of emissions of these gases to climate change. As a result of the short atmospheric lifetimes, their global warming potentials are negligible. Theoretical calculations involving ground and excited states justify the higher photolysis quantum efficiencies of CF3C(O)CH3 and CF3C(O)CH2CH3 compared to CF3CF2C(O)CF(CF3)2, which shows increased photolysis rate constants in the absence of O2.

Levels and sources of volatile organic compounds including carbonyls in indoor air of homes of Puertollano, the most industrialized city in central Iberian Peninsula. Estimation of health risk.

Twenty nine organic air pollutants including carbonyl compounds, alkanes, aromatic hydrocarbons and terpenes were measured in the indoor environment of different houses together with the corresponding outdoor measurements in Puertollano, the most industrialized city in central Iberian Peninsula. VOCs were sampled during 8 weeks using Radiello(®) passive samplers, and a questionnaire on potential VOCs sources was filled out by the occupants. The results show that formaldehyde and hexanal was the most abundant VOCs measured in indoor air, with a median concentration of 55.5 and 46.4µgm(-3), respectively followed by butanal (29.1µgm(-3)), acetone (28.4µgm(-3)) and acetaldehyde (21.4µgm(-3)). After carbonyls, n-dodecane (13.1µgm(-3)) and terpenes (α-pinene, 13.4µgm(-3) and limonene, 13.4µgm(-3)) were the compounds with higher median concentrations. The indoor/outdoor (I/O) ratios demonstrated that sources in the indoor environment are prevailing for most of the investigated VOCs especially for limonene, α-pinene, hexanal, formaldehyde, pentanal, acetaldehyde, o-xylene, n-dodecane and acetone with I/O ratio >6. Multiple linear regressions were applied to investigate the indoor VOC determinants and Spearman correlation coefficients were used to establish common sources between VOCs. Finally, the lifetime cancer risk associated to formaldehyde, acetaldehyde and benzene exposure was estimated and they varied from 7.8×10(-5) to 4.1×10(-4) for formaldehyde, from 8.6×10(-6) to 3.5×10(-5) for acetaldehyde and from 2.0×10(-6) to 1.5×10(-5) for benzene. For formaldehyde, the attributed risk in most sampled homes was two orders of magnitude higher than the one (10(-6)) proposed as acceptable by risk management bodies.

Evolution of NO2 levels in Spain from 1996 to 2012.

We report on the evolution of tropospheric nitrogen dioxide (NO2) over Spain, focusing on the densely populated cities of Barcelona, Bilbao, Madrid, Sevilla and Valencia, during 17 years, from 1996 to 2012. This data series combines observations from in-situ air quality monitoring networks and the satellite-based instruments GOME and SCIAMACHY. The results in these five cities show a smooth decrease in the NO2 concentrations of ~2% per year in the period 1996-2008, due to the implementation of emissions control environmental legislation, and a more abrupt descend of ~7% per year from 2008 to 2012 as a consequence of the economic recession. In the whole Spanish territory the NO2 levels have decreased by ~22% from 1996 to 2012. Statistical analysis of several economic indicators is used to investigate the different factors driving the NO2 concentration trends over Spain during the last two decades.

Atmospheric chemistry and environmental assessment of inhalational fluroxene.

Smog chamber/gas chromatography techniques are used to investigate the atmospheric degradation of fluroxene, an anesthetic, through oxidation with OH and Cl radicals at 298 K and under atmospheric pressure of N2 or air. The measured rate constants (k) are: k(fluroxene+OH(.) )=(2.96±0.61)×10(-11) and k(fluroxene+Cl(.) )=(1.62±0.19)×10(-10) cm(3) molecule(-1) s(-1) . The only product detected after the oxidation of fluroxene with OH radicals is 2,2,2-trifluoroethyl formate (79 % and 83 % molar yield in the absence and presence of NOx, respectively). However, after oxidation with Cl radicals, the detected products are 2,2,2-trifluoroethyl formate (78 %), 2,2,2-trifluoroethyl-1-chloroacetate (5 %), and chloroacetaldehyde (4 %), in the absence of NOx, and 2,2,2-trifluoroethyl formate (93 %), 2,2,2-trifluoroethyl-1-chloroacetate (6 %), and chloroacetaldehyde (5 %), in the presence of NOx. The results indicate that, both in the absence and presence of NOx, the main fate of fluroxene is the addition of the oxidant to the double bond and, once the alkoxy radical is formed, the main decomposition pathway is by means of degradation. Moreover, it is expected that 2,2,2-trifluoroethyl formate is the only oxidation product able to actively contribute to climate change. To successfully assess the contribution of fluroxene to global warming, we measure the infrared spectra of fluroxene and 2,2,2-trifluoroethyl formate, and calculate the radiative efficiencies (REs) to be 0.27 and 0.28 W m(-2) ppbv(-1) , respectively. In addition, the cumulative effect owing to the formation of 2,2,2-trifluoroethyl formate is investigated, and the direct, indirect, and net global-warming potentials are calculated by using the REs and lifetimes of fluroxene and 2,2,2-trifluoroethyl formate.

Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO 2) in a coastal rural area in the southwest of Iberian Peninsula.

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX = NO2 + O3), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station "El Arenosillo" was used. The observed daily cycles of NO x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO x -independent 'regional' contribution (i.e. the O3 background), and a linearly NO x -dependent 'local' contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO2 increases with the increase in NO x concentration during the day. The higher proportion of NO2 observed at night must be due to the conversion of NO to NO2 by the NO + O3 reaction. With regards to the source of the local NO x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO + O2 = 2NO2, at high-NO x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO2, J NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.

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.

Behaviour and variability of local and regional oxidant levels (OX = O3 + NO2) measured in a polluted area in central-southern of Iberian Peninsula.

The purpose of this work is to contribute to the understanding of the photochemical air pollution in central-southern of the Iberian Peninsula, analysing the behaviour and variability of oxidant levels (OX = O(3) + NO(2)), measured in a polluted area with the highest concentration of heavy industry in central Spain. A detailed air pollution database was observed from two monitoring stations. The data period used was 2008 and 2009, around 210,000 data, selected for its pollution and meteorological statistics, which are very representative of the region. Data were collected every 15 min, however hourly values were used to analyse the seasonal and daily ozone, NO, NO(2) and OX cycles. The variation of OX concentrations with NO(x) is investigated, for the first time, in the centre of the Iberian Peninsula. The concentration of OX was calculated using the sum of a NO(x)-independent 'regional' contribution (i.e. the O(3) background), and a linearly NO(x)-dependent 'local' contribution. Monthly dependence of regional and local OX concentration was observed to determine when the maximum values may be expected. The variation of OX concentrations with levels of NO(x) was also measured, in order to pinpoint the atmospheric sources of OX in the polluted areas. The ratios [NO(2)]/[OX] and [NO(2)]/[NO(x)] vs. [NO(x)] were analysed to find the fraction of OX in the form of NO(2), and the possible source of the local NO(x)-dependent contribution, respectively. The progressive increase of the ratio [NO(2)]/[OX] with [NO(x)] observed shows a greater proportion of OX in the form of NO(2) as the level of NO( x ) increases. The higher measured values in the ratio [NO(2)]/[NO(x)] should not be attributed to NO(x) emissions by vehicles; they could be explained by industrial emission, termolecular reactions or formaldehyde and HONO directly emitted by vehicles exhausts. We also estimate the rate of NO(2) photolysis, J (NO(2)) = 0.18-0.64 min(-1), a key atmospheric reaction that influence O(3) production and then the regional air quality. The first surface plot study of annual variation of the daily mean oxidant levels, obtained for this polluted area may be used to improve the atmospheric photochemical dynamic in this region of the Iberian Peninsula where there are undeniable air quality problems.

Surface ozone comparison conducted in two rural areas in central-southern Spain.

PURPOSE: The purpose of this work is to contribute to the understanding of the photochemical air pollution analysing the levels and temporal variations of surface ozone in two rural areas situated in central-southern Spain. METHOD: The study is based on ozone hourly data recorded during the overall period between January 2008 and November 2009. The seasonal and daily ozone cycles as well as the number of exceedances of the threshold established in the European Ozone Directive have been calculated and analysed. RESULTS: This study presents the first ozone data registered at these two rural sites in the Iberian Peninsula plateau. Ozone shows a clear seasonal variation with the lowest values in January and November. High ozone concentrations are interrelated with high radiation intensities, temperature and wind directions. The information threshold defined in the European Ozone Directives was exceeded six times, while the limit for protection of human health was exceeded more than 40 times. The limits to protect the vegetation were also exceeded. CONCLUSIONS: Porzuna (near Cabañeros National Park) presents higher ozone levels than Argamasilla during the night-time and during the daytime of the summer months. Ozone levels are lower in Argamasilla probably due to fresh emissions from the close industrial area of Puertollano. The ozone exceedances of the limits defined in the Ozone Directive point out an ozone problem in this rural region.

Kinetics and mechanism of the atmospheric reactions of atomic chlorine with 1-penten-3-ol and (Z)-2-penten-1-ol: an experimental and theoretical study.

Smog chamber/GC techniques were used to investigate the atmospheric degradation of two unsaturated alcohols, 1-penten-3-ol and (Z)-2-penten-1-ol, by oxidation with chlorine atoms at atmospheric pressure of N(2) or air, as a function of temperature. The rate coefficients at 298 K were (units in cm(3) molecule(-1) s(-1)): (2.35 ± 0.31) × 10(-10) and (3.00 ± 0.49) × 10(-10) for 1-penten-3-ol and (Z)-2-penten-1-ol, respectively. The identified and quantified gas-phase products (with molar yields in brackets) were carbonyl compounds such as chloroacetaldehyde (33 ± 1%), propionaldehyde (39 ± 1%), acetaldehyde (8 ± 3%) and 1-penten-3-one (2%) from 1-penten-3-ol; and chlorobutyraldehyde (19 ± 1%), propionaldehyde (27 ± 1%), acetaldehyde (18 ± 2%) and (Z)-2-pentenal (36 ± 1%) from (Z)-2-penten-1-ol. A parallel theoretical study at the QCISD(T)6-311G**//MP2/6-311G** level was carried out to facilitate understanding of the reaction mechanism. Both the theoretical and experimental studies indicated that addition of Cl to the double bond of the unsaturated alcohol is the dominant reaction pathway, although the H-abstraction channel cannot be excluded. The atmospheric lifetimes of those unsaturated alcohols were calculated and the results are discussed.

Atmospheric reactions of (H)- and (D)-fluoroalcohols with chlorine atoms.

The reactions of Cl with a series of fluoroalcohols and deuterated fluoroalcohols, CF(3)CH(2)OH (k(4)), CF(3)CH(OH)CH(3) (k(5)), CF(3)CH(OH)CF(3) (k(6)), CF(3)CH(OD)CF(3) (k(7)) and CF(3)CD(OD)CF(3) (k(8)), are investigated as a function of temperature in the range of 268-378 K by laser photolysis-resonance fluorescence. To our knowledge, only the CF(3)CH(2)OH + Cl reaction has been previously studied from a kinetic point of view. The derived Arrhenius expressions obtained using our kinetic data are: k(4) = (1.79+/-0.17) x 10(-13) exp[(410+/-26)/T], k(5) = (1.20+/-0.11) x 10(-12) exp[(394+/-14)/T], k(6) = (2.32+/-0.18) x 10(-13) exp[-(740+/-12)/T], k(7) = (6.45+/-1.87) x 10(-13) exp[-(1136+/-94)/T] and k(8) = (4.19+/-1.09) x 10(-13) exp[-(1378+/-81)/T] (in units of cm(3) molecule(-1) s(-1) and where errors are +/-sigma). Moreover, a theoretical insight into the mechanisms of these reactions is pursued through ab initio Möller-Plesset second-order perturbation treatment calculations with the 6-311G** basis set. Optimized geometries are obtained for reagents, transition states and molecular complexes appearing along the different reaction pathways. Furthermore, molecular energies are calculated at the quadratic configuration interaction with single, double and triple excitations [QCISD(T)] level to obtain an estimation of the activation energies. Finally, the rate constants are calculated through transition-state theory using Wigner's transmission coefficient in order to include the tunnelling-effect corrections.

Kinetic and theoretical study of the reaction of Cl atoms with a series of linear thiols.

The reactions of Cl with a series of linear thiols: 1-propanethiol (k(1)), 1-butanethiol (k(2)), and 1-pentanethiol (k(3)) were investigated as a function of temperature (in the range of 268-379 K) and pressure (in the range of 50-200 Torr) by laser photolysis-resonance fluorescence. Only 1-propanethiol has previously been studied, but at 1 Torr of total pressure. The derived Arrhenius expressions obtained using our kinetic data were as follows: k(1)=(3.97+/-0.44)x10(-11) exp[(410+/-36)T], k(2)=(1.01+/-0.16)x10(-10) exp[(146+/-23)T], and k(3)=(1.28+/-0.10)x10(-10) exp[(129+/-25)T] (in units of cm(3) molecule(-1) s(-1)). Moreover, a theoretical insight into mechanisms of these reactions has also been pursued through ab initio Moller-Plesset second-order perturbation treatment calculations with 6-311G(**) basis set. Optimized geometries have been obtained for transition states and molecular complexes appearing along the different reaction pathways. Furthermore, molecular energies have been calculated at QCISD(T) level in order to get an estimation of the activation energies. Finally, the nature of the molecular complexes and transitions states is analyzed by using kinetic-potential and natural bond orbital total energy decomposition schemes.

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 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.