Benzene, Toluene, Ethylbenzene and Xylene (BTEX) Concentrations in Urban Areas Impacted by Chemical and Petrochemical Industrial Emissions.

The Metropolitan Region of Rio de Janeiro is the second largest urban and industrial region in Brazil. While the south and south-east areas are affected by vehicular emissions, the districts and cities located in the northern area are subjected to industrial emissions and have the poorest air quality of the region. In this study, BTEX concentrations were determined in the District of Irajá, a residential area located in the north of the city of Rio de Janeiro, approximately 25 km from the industrial zone, as well as in the District of Jardim Primavera, in the city of Duque de Caxias. The mean values for total BTEX concentrations were 38.4 ± 11.7 and 44.6 ± 29.3 µg m-3, in Irajá and Jardim Primavera, respectively, which are higher than those previously reported for other areas. The benzene/toluene rates, (approximately 0.5 for both sampling sites), were also higher than typical values that were determined for diesel and gasoline emissions through dynamometer experiments.

Understanding high tropospheric ozone episodes in Bangu, Rio de Janeiro, Brazil.

This study investigates the potential factors that contribute to frequent high levels of ozone in Bangu, one of the most critical areas in the city of Rio de Janeiro, regarding ozone levels and air quality. Speciated non-oxygenated volatile organic compounds (VOCs) were measured using method TO-15 (US EPA). The measured concentrations and kinetic and mechanistic analysis of VOC reactivity showed that alkanes were the most important compounds. Ozone concentrations were simulated for a base case representing a day with high ozone levels. Simulated results and statistical multivariate analysis showed that the high ozone concentrations did not seem to be closely related to local emissions but rather were related to pollutant transport and low measured NOx levels and were triggered by photochemical activity. The differences between weekdays and weekends were also investigated, showing that ozone concentrations were also higher during weekends, mainly on Sunday, when the diesel heavy vehicle fleet was reduced and lower NO emissions were observed. The VOC/NOx ratios correspond to a VOC-limited process, which leads to higher ozone concentrations under low NOx conditions.

Preliminary Study of Ambiente Levels and Exposure to BTEX in the Rio de Janeiro Olympic Metropolitan Region, Brazil.

This study aims to determine BTEX concentrations in the Metropolitan Region of Rio de Janeiro (MRRJ, Brazil) and evaluate potential health risks of benzene and ethylbenzene exposure based on the collected data, in 2015, the year before the Rio 2016 Olympic Games. Samples were collected and analyzed following method TO-15 (U.S.EPA). Toluene was the most abundant compound in all samples (mean concentration 16.72 ± 15.70 µg m-3). The average benzene concentration in ambient air (3.44 ± 3.14 µg m-3) was slightly lower than the yearly average "upper assessment threshold", 3.5 µg m-3, established by EU Directive 2008/50/EC. The calculated cancer risk values were > 1 × 10-6 for all samples, clearly indicating a potential cancer risk and the importance of fixed measurements by the monitoring stations to assess ambient air quality in the urban areas of the MRRJ. Calculated ratios for the BTEX species indicate that these compounds are predominantly emitted from vehicular sources with a contribution from industrial sources.

The Impact of COVID-19 Partial Lockdown on Primary Pollutant Concentrations in the Atmosphere of Rio de Janeiro and São Paulo Megacities (Brazil).

As COVID-19 spread all over the world, most of the countries adopted some kind of restrictions to avoid the collapse of health systems. In Brazil, São Paulo and Rio the Janeiro, the two most populated cities in the country, were the first to determine social distancing. In this study, the impact of the social distancing measures on the concentrations of the three main primary air pollutants (PM10, NO2 and CO) was analyzed. CO levels showed the most significant reductions (up to 100%) since it is related to light-duty vehicular emissions. NO2 also showed reductions (9.1%-41.8%) while PM10 levels were only reduced in the 1st lockdown week. The decrease of pollutants was not directly proportional to the vehicular flux reduction, because it depends on other factors such as the transport of air masses from industrial and rural areas. The differences observed can be explained considering the fleet characteristics in the two cities and the response of the population to the social distancing recommendations.

Impact of the Petrochemical Complex on the Air Quality of an Urban Area in the City of Rio de Janeiro, Brazil.

In the city of Rio de Janeiro (Brazil), the districts located in the northern area are considered the most critical regarding ozone levels year-round. In this study, the potential factors that contribute to high levels of ozone in the district of Irajá were investigated. The obtained results clearly showed that, in spite of the high correlation of ozone concentrations with wind speed and temperature, ozone episodes depend on the ratios of volatile organic compounds (VOCs) to nitrogen oxides (NOx) rather than on the individual VOC and NOx levels, as expected for the VOC-controlled condition typical of the urban area of Rio de Janeiro. Moreover, high VOCs/NOx ratios are highly dependent on the transport of air masses. When pollutants are transported from urban areas with heavy vehicular flux and high NOx concentrations, ozone levels are reduced. When air masses are transported from the industrial petrochemical area, NOx levels are relatively low, and ozone episodes are frequent.

Levels of Volatile Carbonyl Compounds in the Atlantic Rainforest, in the City of Rio de Janeiro.

When Europeans arrived in America, the Brazilian Atlantic rainforest covered approximately 1,290,000 km2. Now, only 8% of the biome's original vegetation remains. One of the largest areas is Tijuca Forest National Park. In this work, the concentrations of 13 carbonyl compounds in an isolated area inside Tijuca Forest, in an urban park with primary and secondary vegetation (Gericinó Natural Park) and in two typical urban areas (Tijuca District and the city of Nilópolis) were determined. The main compounds were formaldehyde and acetaldehyde. The formaldehyde mean concentrations were 0.98 ± 1.00, 1.27 ± 1.67, 3.09 ± 1.60 and 2.33 ± 2.17 µg m-3 for Tijuca Forest, Gericinó Natural Park, Tijuca District and the city of Nilópolis, respectively. The mean acetaldehyde concentrations were, for the same locations, 0.93 ± 1.05, 2.94 ± 2.54, 2.78 ± 0.91 and 5.48 ± 1.90 µg m-3. The results indicate that the compounds measured within the forest are transported from the city and that the trees play an important role in removing air pollutants. In contrast, the Gericinó protected area is heavily affected by urban emissions, and its capacity to dilute or absorb pollutants is low because of the sparse vegetation.

Isoprene Emissions and Ozone Formation in Urban Conditions: A Case Study in the City of Rio de Janeiro.

The potential role of isoprene oxidative processes, as well as the possible impact of air pollution on isoprene emissions, are more important in tropical cities, surrounded by rainforests. In this study, the contribution of isoprene to ozone formation was determined considering different scenarios, mainly volatile organic compounds/NO x (VOC/NO x ) ratios, and typical atmospheric conditions for the city of Rio de Janeiro, where more than 36% of the urbanized area is covered by vegetation. Ozone isopleths and incremental reactivity coefficients (IR) were evaluated to understand the direct contribution of isoprene to ground-level ozone formation and the negative impact of anthropogenic NO x emissions on the natural atmospheric balance. Although isoprene accounted for only 2.7% of the total VOC mass, excluding the isoprene concentration from the model reduced the maximum ozone value by 14.1%. The calculated IR coefficient (grams of O3 formed per gram of added isoprene) was 2.2 for a VOC/NO x ratio of 8.86.

An Analytical Investigation of Ozone Episodes in Bangu, Rio de Janeiro.

This study investigated the potential factors that contribute to frequent high levels of ozone as well as ozone episodes in Bangu, one of the most critical areas in the city of Rio de Janeiro regarding ozone levels. For 74 days in a two-year period (10.3%), the national air quality standard was exceeded. For the same period, a total of 378 days (51.8%) had ozone concentrations that were between 80 and 160 µg m-3. A statistical analysis of pollutant concentrations and meteorological data as well as a kinetic and mechanistic analysis of VOC reactivity showed that the high ozone concentrations did not seem to be closely related to local emissions but, rather, were related to pollutant transport and triggered by photochemical activity. The mountains in the southern and northern part of the district contribute to the increase of surface temperatures and the accumulation of pollutants. The VOC/NOx ratios corresponded to a VOC-limited process.

Kinetic and mechanistic reactivity. Isoprene impact on ozone levels in an urban area near Tijuca Forest, Rio de Janeiro.

Volatile organic compounds (VOCs) play a central role in atmospheric chemistry. In this work, the kinetic and mechanistic reactivities of VOCs are analyzed, and the contribution of the organic compounds emitted by anthropogenic and natural sources is estimated. VOCs react with hydroxyl radicals and other photochemical oxidants, such as ozone and nitrate radicals, which cause the conversion of NO to NO2 in various potential reaction paths, including photolysis, to form oxygen atoms, which generate ozone. The kinetic reactivity was evaluated based on the reaction coefficients for hydroxyl radicals with VOCs. The mechanistic reactivity was estimated using a detailed mechanism and the incremental reactivity scale that Carter proposed. Different scenarios were proposed and discussed, and a minimum set of compounds, which may describe the tropospheric reactivity in the studied area, was determined. The role of isoprene was analyzed in terms of its contribution to ozone formation.

Volatile Organic Compounds in the Atmosphere of the Botanical Garden of the City of Rio de Janeiro: A Preliminary Study.

Volatile organic compounds (VOCs) play a central role in atmospheric chemistry. In this work, VOCs in the Botanical Garden of Rio de Janeiro were determined using the TO-15 Method. The park occupies 1,370,000 m2 in the southern area of the city and is next to the Tijuca Forest, which is considered the largest secondary urban forest in the world. The total VOC concentrations ranged from 43.52 to 168.75 µg m-3, depending on the sampling site and dates. In terms of concentration isoprene represented 4 %-14 % of the total VOC masses. The results suggested that the differences in biomass, distance from the street and activities within the park affected the concentrations of VOCs. The ratios of isoprene/aromatic compounds were higher than those determined in other areas of the city, confirming that the atmosphere of this green area has the contribution of other sources. Kinetic and mechanistic reactivities were also evaluated.

Rate coefficients for the reaction of OH radicals with cis-3-hexene: an experimental and theoretical study.

The kinetics of the cis-3-hexene + OH reaction were investigated by an experimental relative rate method and at the density functional theory level. The experimental set-up consisted of a 200 L Teflon bag, operated at atmospheric pressure and 298 K. OH radicals were produced by the photolysis of H2O2 at 254 nm. Relative rate coefficients were determined by comparing the decays of the cis-3-hexene and reference compounds (cyclohexene, 2-buten-1-ol and allyl ether). The mean second-order rate coefficient value found was (6.27 ± 0.66) × 10(-11) cm(3) molecule(-1) s(-1), the uncertainty being estimated by propagation of errors. Theoretical calculations for the addition reaction of OH to cis-3-hexene have also been performed, at the BHandHLYP/aug-cc-pVDZ level, in order to investigate the reaction mechanism, to clarify the experimental observations and to model the reaction kinetics. Different conformations of the reactants, pre-barrier complexes and saddle points were considered in our calculations. The individual rate coefficients, calculated for each conformer of the reactant, at 298 K, using a microcanonical variational transition state method, are 4.19 × 10(-11) and 1.23 × 10(-10) cm(3) molecule(-1) s(-1). The global rate coefficient was estimated from the Boltzmann distribution of the conformers to be 8.10 × 10(-11) cm(3) molecule(-1) s(-1), which is in agreement with the experimental value. Rate coefficients calculated over the temperature range from 200-500 K are also given. Our results suggest that the complex mechanism, explicitly considering different conformations for the stationary points, must be taken into account for a proper description of the reaction kinetics.

Comparative kinetics of the 3-buten-1-ol and 1-butene reactions with OH radicals: a density functional theory/RRKM investigation.

The compared kinetics of the reactions of unsaturated alcohols and alkenes with OH radicals is a topic of great interest from both the theoretical chemistry and the atmospheric chemistry points of view. The enhanced reactivity of an unsaturated alcohol, with respect to its alkene analogue, toward OH radicals has been previously demonstrated, at 298 K, by experimental and theoretical research. In this work, a new comparative investigation of such reactions is performed for 3-buten-1-ol and 1-butene. The model assumes that the overall kinetics is governed by the first OH addition steps of the mechanism. Calculations have been performed at the DFT level, employing the BHandHLYP functional and the cc-pVDZ and aug-cc-pVDZ basis sets, and the rate coefficients have been determined on the basis of the microcanonical variational transition state theory. The rate coefficients obtained for the OH reactions with 3-buten-1-ol (kOH(31BO)) and 1-butene (kOH(1B)) at 298.15 K are lower than the experimental rate coefficient available in the literature, showing deviations of 18% and 25%, respectively. Negative temperature dependence is verified for these rate coefficients. The kOH(31BO)/kOH(1B) ratios have also been investigated as a function of the temperature, suggesting that at room temperature the unsaturated alcohol reacts with the OH radicals faster than 1-butene, by a factor of 1.2, but at higher temperatures (400-500 K), the alkene should react faster, and that the stabilization of prebarrier complexes and saddle points due to hydrogen bonds is no longer an important factor to govern the reactivity of the unsaturated alcohol toward OH radicals, with respect to the alkene analogue.

Theoretical study of Δ-3-(+)-carene oxidation.

In this work, the rate-limiting steps of Δ(3)-carene oxidation by ozone and OH radicals were studied. The thermochemical and kinetic parameters were evaluated using the B3LYP, PBE1PBE and BHandHLYP functionals, coupled cluster methods and the 6-311G(d,p) and 6-311++G(d,p) basis sets. The attack on the double bond may occur in different orientations, leading to different oxidation products. The rate coefficients of each step of the reactions were evaluated using conventional canonical transition-state theory and variational canonical transition-state theory whenever necessary. The theoretical rate coefficient for the ozonolysis mechanism, evaluated at the CCSD(T)/6-31G(d,p)//PBE1PBE/6-311++G(d,p) level, was 2.08 × 10(-17) cm(3) molecule(-1) s(-1). The coefficient for the oxidation initialised by the OH radical, calculated at the BHandHLYP/6-311++G(d,p) level, was 5.06 × 10(-12) cm(3) molecule(-1) s(-1). These values are in reasonable agreement with the experimental results. The importance of these reactions in atmospheric chemistry is discussed.

PM2.5-bound polycyclic aromatic hydrocarbons in an area of Rio de Janeiro, Brazil impacted by emissions of light-duty vehicles fueled by ethanol-blended gasoline.

The aim of this study was to characterize the PM2.5-bound polycyclic aromatic hydrocarbon (PAH) concentrations and their diagnostic ratios in an area impacted by light-duty vehicles fueled by neat ethanol and ethanol-blended gasoline. Samples were collected using a high-volume sampler, extracted, and analyzed for all 16 EPA-priority PAHs using gas chromatography/mass spectrometry (GC/MS) following the EPA 3550B Method. The most abundant PAHs were benzo[g,h,i]perylene, benzo[b]fluoranthene, benzo[a]pyrene and indeno[1,2,3-c,d]pyrene. The total mean concentration was 3.80 ± 2.88 ng m(-3), and the contribution of carcinogenic species was 58 ± 16 % of the total PAHs. The cumulative health hazard from the PAH mixture was determined, and the carcinogenic equivalents and mutagenic equivalents were 0.80 ± 0.82 and 1.17 ± 1.04 ng m(-3), respectively. Diagnostic ratios and normalized ratios were calculated for the individual samples.

Trace metals in PM10 and PM 2.5 samples collected in a highly industrialized chemical/petrochemical area and its urbanized surroundings.

The aim of this study was to determine the potential impact of a highly industrialized area on its urbanized surroundings. The area studied is home to a refinery, a thermoelectric plant and several petrochemical facilities industries. The concentrations of twelve elements were determined in PM10 and PM2.5 samples collected along a busy highway and near the petrochemical complex. Significantly higher concentrations of Ca, Mg, Mn, Fe, Cu and Al were observed in the petrochemical zone, but principal component analysis revealed similar patterns for both the highway site and a site approximately 1.5 km from the petrochemical complex, suggesting that the main pollution source in the area is vehicular flux. Higher concentrations in the industrial area may be attributed to intense diesel-powered truck and bus traffic movement, mainly due to the transport of supplies, fuel and gas. The observed concentrations of the elements Cr, Co, Ni, Cd and Pb were always lower than the detection limits of the technique used.

Tijuca forest contribution to the improvement of air quality and wellbeing of citizens in the city of Rio de Janeiro, Brazil.

The Tijuca Forest, one of the largest urban forests in the world, is a protected area of the Brazilian Atlantic Forest, one of the world's biodiversity hotspots. The forest and the Metropolitan Region of Rio de Janeiro coexist and interact, but their mutual influence regarding air quality is still not well known and a more detailed study is needed. Here, air samples were collected inside the forest, in Tijuca National Park (TNP) and Grajaú State Park (GSP) and in two representative urban areas (Tijuca and Del Castilho Districts). Sampling was performed using stainless steel canisters, and ozone precursor hydrocarbons (HCs) were analyzed with the aid of heart-cutting multidimensional gas chromatography. The sampling points within the forest are currently visited by hundreds of people. Total HC concentrations within the green area were clearly lower than in the urbanized districts, in spite of the anthropogenic impact of visitors and the proximity of the urban area. Median values were 21.5, 35.5, 57.9 and 148.6 µg m-3 at TNP, GSP, Tijuca and Del Castilho, respectively. Total HC concentrations were Del Castilho > Tijuca > GSP > TNP. The kinetic reactivity and ozone-forming potential of individual HCs were evaluated, as well as the intrinsic reactivity of air masses. The air masses in the urbanized area showed a higher average reactivity in all scales. In fact, in spite of the forest's contribution to isoprene emissions, its net contribution to ozone formation was lower than that of urbanized air masses, owing to a reduction in HC concentration, particularly for alkenes and monoaromatic compounds. It is not clear if the forest plays a role in the adsorption of pollutants or if it acts as a physical natural barrier to air masses carrying pollutants. Nonetheless, improving air quality within Tijuca Forest is essential to the welfare of citizens.

Determination of carbonyls and size-segregated polycyclic aromatic hydrocarbons, and their nitro and alkyl analogs in emissions from diesel-biodiesel-ethanol blends.

This study characterizes carbonyls (RCHO), polycyclic aromatic hydrocarbons (PAHs), their nitrated (nitro-PAHs) and alkylated (alkyl-PAHs) in particulate matter in the exhaust emissions of a diesel engine. The measurements were made with a standard engine, often found in vans used in Brazil, fueled with pure commercial diesel and mixtures of 10, 20, and 30% biodiesel with 2, 4, and 6% of ethanol. Particulate matter sampling was carried out with a 10-stage cascade impactor. Chemical analyses for PAHs and their derivatives were conducted using gas phase chromatography-mass spectrometry (GC/MS). RCHO were sampled using impingers with 2,4-DNPH and analyzed using HPLC with UV detection. The results showed that emissions of all the PAHs and their derivatives were reduced with the use of biodiesel and ethanol, with the exception of the blend of 30% biodiesel with 4% ethanol. However, all the RCHO emissions increased with biodiesel and ethanol. High correlations were observed between the emissions of PAHs, alkyl-PAHs and nitro-PAHs, which suggests a similarity in the formation mechanisms of these compounds. All PAHs' emissions have a strong negative correlation with biodiesel content and with RCHO emissions and a medium correlation with ethanol content. In contrast, biodiesel and ethanol with the RCHO emissions lead to a positive correlation coefficient of these compounds which is more pronounced for biodiesel than ethanol.

Carbonyl oxides reactions from geraniol-trans-(3,7-dimethylocta-2,6-dien-1-ol), 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal ozonolysis: kinetics and mechanisms.

A density functional theory (DFT) study of the mechanisms of carbonyl oxide reactions from geraniol-trans, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal ozonolysis is presented. The geometries, energies, and harmonic vibrational frequencies of each stationary point were determined by B3LYP/6-31(d,p) and BH&HLYP/cc-pVDZ methods. According to the calculations, the ozonolysis reactions are initiated by the formation of van der Waals (VDW) complexes to yield primary ozonides, which rapidly open to carbonyl oxide compounds. These carbonyl oxide compounds react to form dioxanes and hydroperoxides. The hydroperoxides react by isomerization to form stable products. Glyoxal and methyl-glyoxal have been identified as the final product from geraniol-trans, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal ozonolysis. Our results are in good agreement with the experimental studies.

Kinetics and thermodynamics of limonene ozonolysis.

Using density functional methods, the initial reaction steps of limonene ozonolysis have been investigated with a focus on primary ozonide formation and its decomposition to Criegee intermediates and carbonyl compounds. The ozonide formation is highly exothermic, and the decomposition channels have similar free energies of activation, ΔG(‡), indicating that there is no primary pathway for ozonide decomposition. Assuming that ozonide formation is the rate limiting step, the theoretical rate coefficient, k = 1.6 × 10(-16) molecule(-1) cm(3) s(-1), evaluated at the CCSD(T)/6-31G(d,p)//BHandHLYP/cc-pvdz level and 298.15 K for d-limonene is in good agreement with the experimental value, k(exp) = 3.3 × 10(-16) molecule(-1) cm(3) s(-1). The theoretical Arrhenius expression is also in good agreement with experimental results.

A global observational analysis to understand changes in air quality during exceptionally low anthropogenic emission conditions.

This global study, which has been coordinated by the World Meteorological Organization Global Atmospheric Watch (WMO/GAW) programme, aims to understand the behaviour of key air pollutant species during the COVID-19 pandemic period of exceptionally low emissions across the globe. We investigated the effects of the differences in both emissions and regional and local meteorology in 2020 compared with the period 2015-2019. By adopting a globally consistent approach, this comprehensive observational analysis focuses on changes in air quality in and around cities across the globe for the following air pollutants PM2.5, PM10, PMC (coarse fraction of PM), NO2, SO2, NOx, CO, O3 and the total gaseous oxidant (OX = NO2 + O3) during the pre-lockdown, partial lockdown, full lockdown and two relaxation periods spanning from January to September 2020. The analysis is based on in situ ground-based air quality observations at over 540 traffic, background and rural stations, from 63 cities and covering 25 countries over seven geographical regions of the world. Anomalies in the air pollutant concentrations (increases or decreases during 2020 periods compared to equivalent 2015-2019 periods) were calculated and the possible effects of meteorological conditions were analysed by computing anomalies from ERA5 reanalyses and local observations for these periods. We observed a positive correlation between the reductions in NO2 and NOx concentrations and peoples' mobility for most cities. A correlation between PMC and mobility changes was also seen for some Asian and South American cities. A clear signal was not observed for other pollutants, suggesting that sources besides vehicular emissions also substantially contributed to the change in air quality. As a global and regional overview of the changes in ambient concentrations of key air quality species, we observed decreases of up to about 70% in mean NO2 and between 30% and 40% in mean PM2.5 concentrations over 2020 full lockdown compared to the same period in 2015-2019. However, PM2.5 exhibited complex signals, even within the same region, with increases in some Spanish cities, attributed mainly to the long-range transport of African dust and/or biomass burning (corroborated with the analysis of NO2/CO ratio). Some Chinese cities showed similar increases in PM2.5 during the lockdown periods, but in this case, it was likely due to secondary PM formation. Changes in O3 concentrations were highly heterogeneous, with no overall change or small increases (as in the case of Europe), and positive anomalies of 25% and 30% in East Asia and South America, respectively, with Colombia showing the largest positive anomaly of ~70%. The SO2 anomalies were negative for 2020 compared to 2015-2019 (between ~25 to 60%) for all regions. For CO, negative anomalies were observed for all regions with the largest decrease for South America of up to ~40%. The NO2/CO ratio indicated that specific sites (such as those in Spanish cities) were affected by biomass burning plumes, which outweighed the NO2 decrease due to the general reduction in mobility (ratio of ~60%). Analysis of the total oxidant (OX = NO2 + O3) showed that primary NO2 emissions at urban locations were greater than the O3 production, whereas at background sites, OX was mostly driven by the regional contributions rather than local NO2 and O3 concentrations. The present study clearly highlights the importance of meteorology and episodic contributions (e.g., from dust, domestic, agricultural biomass burning and crop fertilizing) when analysing air quality in and around cities even during large emissions reductions. There is still the need to better understand how the chemical responses of secondary pollutants to emission change under complex meteorological conditions, along with climate change and socio-economic drivers may affect future air quality. The implications for regional and global policies are also significant, as our study clearly indicates that PM2.5 concentrations would not likely meet the World Health Organization guidelines in many parts of the world, despite the drastic reductions in mobility. Consequently, revisions of air quality regulation (e.g., the Gothenburg Protocol) with more ambitious targets that are specific to the different regions of the world may well be required.