Regulating (ecosystem) services of an urban natural area: a case study in the State of Rio de Janeiro, Brazil.

Peri-urban conserved natural or semi-natural areas provide several ecosystem services and assist in reducing air pollution in cities. The aim of this study is to assess the contribution to the improvement of air quality of a small area (<1 km) adjacent to a city in the Metropolitan Region of Rio de Janeiro (Brazil), which is seriously affected by vehicular and industrial emissions of pollutants. Hydrocarbon (HC) and carbonyl compounds (CC) levels were determined, by employing TO-15 and TO-11A US EPA Methods, respectively, in both the urban and green areas.

An air emission risk assessment of non-criteria pollutants in a tunnel study in Rio de Janeiro, Brazil.

Brazil's significantly large fleet of ethanol-powered vehicles makes it unique with regard to mobile source emissions. An accurate estimation of emission rates is best obtained from studies reflecting real-world vehicular conditions, such as tunnel investigations. Although laboratory-based estimations are standardized, they may not reflect reality.

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).

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.

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 PM, PM, PMC (coarse fraction of PM), NO, SO, NOx, CO, O and the total gaseous oxidant (OX = NO + O) during the pre-lockdown, partial lockdown, full lockdown and two relaxation periods spanning from January to September 2020.

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 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 (PM, NO and CO) was analyzed.

Increased ozone levels during the COVID-19 lockdown: Analysis for the city of Rio de Janeiro, Brazil.

The first COVID-19 case in Brazil was confirmed on February 25, 2020. Partial lockdown measures came into force in the city of Rio de Janeiro, Brazil, on March 23. While CO and NO levels showed significant reductions, PM levels were only reduced in the first partial lockdown week.

The impact of COVID-19 partial lockdown on the air quality of the city of Rio de Janeiro, Brazil.

The first COVID-19 case in Brazil was confirmed on February 25, 2020. On March 16, the state's governor declared public health emergency in the city of Rio de Janeiro and partial lockdown measures came into force a week later. The main goal of this work is to discuss the impact of the measures on the air quality of the city by comparing the particulate matter, carbon monoxide, nitrogen dioxide and ozone concentrations determined during the partial lockdown with values obtained in the same period of 2019 and also with the weeks prior to the virus outbreak.

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.

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 (NO) rather than on the individual VOC and NO levels, as expected for the VOC-controlled condition typical of the urban area of Rio de Janeiro.

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.

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 km. Now, only 8% of the biome's original vegetation remains. One of the largest areas is Tijuca Forest National Park.

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 (VOC/NO ) 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 emissions on the natural atmospheric balance.

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.

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 m 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.

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 NO in various potential reaction paths, including photolysis, to form oxygen atoms, which generate ozone.

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.

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.

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.

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.

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.

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.

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.