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.

Determination of trace elements in the nanometer, ultrafine, fine, and coarse particulate matters in an area affected by light vehicular emissions in the city of Rio de Janeiro.

The objective of this work was to determine the trace element composition in the nanometric, ultrafine, fine, and coarse particulate matters (PM) found in the surrounding area of the UERJ Chemical Technology Applications Institute, using a MSP 120 MOUDI II cascade impactor. After acid extraction, the elements were analyzed via ICP-OES, and the results obtained were treated statistically. The average concentrations of the nanometric, ultrafine, fine, and coarse particles were 11.8, 8.2, 7.7, and 7.1 µg m-3, respectively. The total average concentration of Cd, Ni, Pb, Cr, and Fe complied with the air quality standards recommended by US EPA and WHO. When compared with other locations, the PM fractions found in this study were 1.1 to 346 times greater. Through the calculation of Pearson's correlation coefficient, a high correlation was observed between most of the trace elements studied, especially in the ultrafine, fine, and coarse fractions, which suggests that they are probably caused by the same sources of vehicular emissions. The enrichment factor was calculated to estimate the possible sources. Since Cd, Cu, Pb, and Mo are enriched by anthropic sources, they are probably influenced by vehicular emissions, in particular the wear on tires and brakes, and the burning of fossil fuel.

Prediction of Rate Coefficients for the H2CO + OH → HCO + H2O Reaction at Combustion, Atmospheric and Interstellar Medium Conditions.

Despite the relevance of the H2CO + OH → HCO + H2O reaction for combustion, atmospheric, and interstellar medium conditions, a large discrepancy on energetic and kinetic data for this reaction is still observed in the previous literature. In this work, this hydrogen abstraction reaction has been investigated at the CCSD(T)/CBS level of theory, suggesting that both the prebarrier complex and saddle point are stabilized in relation to the reactants by 3.31 and 1.35 kcal mol-1, respectively. Moreover, from the Gibbs free energy profile of the reaction coordinate, it has been verified that the formation of the prebarrier complex is endergonic, for temperatures above 550 K. Hence, for temperatures lower than 550 K, the reaction is described by a mechanism consisting of three elementary steps, while for higher temperatures it can be assumed to be an elementary reaction. Finally, the prediction of rate coefficients suggests that unified statistical rate theory best applies to the low temperature regime, while canonical variational rate coefficients better fit experimental data at the high temperature regime.

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.

Development and Validation of an Analytical Method for the Detection and Quantification of Bromazepam, Clonazepam and Diazepam by UPLC-MS/MS in Surface Water.

The development of analytical methods capable of determining micropollutants is essential for quality control of drinking water. Benzodiazepines, a class of pharmaceuticals with anxiolytic properties, have received increasing attention as micropollutants. The purpose of this study was to develop an analytical method for determination of three benzodiazepine drugs (bromazepam, clonazepam and diazepam) in surface water. For the extraction of the matrix analytes, SPE cartridges (C18, 500 mg/3 mL) were used. The method was validated according to the quality criteria of the USEPA 8000D Validation Guide. The developed and validated method showed recovery values between 57 and 100%, RSD < 20% and R2 > 0.9949. LD ranged between 2.70 and 5.00 ng L-1 for bromazepam and clonazepam respectively whereas LQ was 0.01 µg L-1 for all analytes. The matrix affected the signal intensity of clonazepam thus evidencing the matrix effect by analysis statistic (F test).

Emissão de gases do efeito estufa de um aterro sanitário no Rio de Janeiro / Greenhouse gases emissions from a landfill in Rio de Janeiro

RESUMO A emissão de metano (CH4) e dióxido de carbono (CO2) em aterros sanitários representa uma das mais importantes fontes de gases de efeito estufa em regiões metropolitanas. O presente trabalho quantificou a taxa de emissão de gases do efeito estufa (GEEs) pela camada de cobertura intermediária do aterro sanitário de Seropédica, Rio de Janeiro, Brasil, assim como a concentração desses gases na atmosfera acima das células do aterro. Um total de 21 amostras na camada de cobertura e 31 na atmosfera acima do aterro foi coletado. Foram utilizadas duas câmaras de fluxo de 0,66 m2 de área e 33,2 L de volume, e amostras foram retiradas com seringas de polipropileno de 60 mL em intervalos de 5 minutos, durante 15 minutos. As amostras foram coletadas em locais com e sem fissura na camada de cobertura intermediária. A análise das amostras foi feita por cromatografia de fase gasosa, por múltiplos detectores. As taxas de emissão dos GEEs observadas variaram entre 0,1 e 575,0 g m-2 dia-1 para CH4 e entre 0,1 e 316,0 g m-2 dia-1 para CO2. As concentrações no ar ambiente variaram entre 3,5 e 150,0 ppm e entre 333 e 655 ppm, para CH4 e CO2, respectivamente. As maiores emissões foram constatadas nos pontos que continham as maiores fissuras no momento da coleta.

ABSTRACT The emission of methane (CH4) and carbon dioxide (CO2) from landfills is one of the most important sources of greenhouse gases in metropolitan areas. This study quantified the emission rate of greenhouse gases (GHGs) by the intermediate cover layer of Seropédica landfill, in Rio de Janeiro, Brazil, as well as the concentration of these gases in the atmosphere above the landfill cells. A total of 21 samples from the cover layer and 31 samples from the atmosphere above the landfill was collected. Two flow chambers with 0.66 m2 and 33.2 L were used, and the samples were collected with 60 mL polypropylene syringes at five-minute intervals, for 15 minutes. The samples were collected in areas with and without cracks in the intermediate cover layer. Sample analysis was performed by gas chromatography, by multiple detectors. GHGs emission rates varied from 0.1 to 575.0 g m-2 day-1 for CH4 and 0.1 to 316.0 g m-2 day-1 for CO2. The ambient air concentrations ranged from 3.5 to 150.0 ppm and 333 to 655 ppm for CH4 and CO2, respectively. Higher emissions were found in areas containing the larger cracks at the time of collection.

BTEX Emissions from the Largest Landfill in Operation in Rio de Janeiro, Brazil.

The emission rates and the ambient air concentrations of benzene, toluene, ethyl benzene and xylenes (BTEX) were measured over the intermediate cover layer and atmosphere of the Seropédica landfill, Rio de Janeiro, Brazil. BTEX were sampled using coconut shell charcoal cartridges, followed by extraction with dichloromethane and analysis by gas chromatography with mass spectrometry. Thirteen samples were collected in areas with and without cracks in the cover layer, and six samples were collected from the ambient air. The average emission rates were 11.7, 492.2, 153.7, 67.2, and 21.7 µg m- 2 day- 1, respectively, for benzene, toluene, ethyl benzene, m + p-xylenes and o-xylene. No benzene concentrations above the detection limit were observed in ambient air samples. The average concentrations of toluene, ethyl benzene, m + p-xylenes and o-xylene in ambient air samples were 2.14, 1.35, 0.49 and 0.08 µg m- 3, respectively. Higher emissions were found in locations containing larger cracks during the collection.

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.

The relationship between solvent use and BTEX concentrations in occupational environments.

Indoor air quality is an increasing concern; it causes significant damage to health because it is recycled in confined environments for extended periods of time. Among the pollutants found in these environments, benzene, toluene, ethylbenzene, and xylenes (BTEX) are known for their potential toxic, mutagenic, and carcinogenic effects. This study monitored the BTEX concentrations in paint, carpentry, and varnish workplaces and evaluated the potential to cause adverse health effects on workers in these environments. Twenty samples were collected in workplaces, 20 samples were collected outside the area, and eight samples were taken of the products used. Samples were collected using coconut shell cartridges, and chemical analyses were performed by gas chromatography with mass spectrometry. Toluene presented higher indoor concentrations and indoor and outdoor ratios, indicating that the paint and varnish workplaces had significant BTEX sources. The highest benzene and toluene concentrations were obtained from the paint workshop, and higher concentrations of ethylbenzene and xylenes were obtained in the varnish workshop. The highest non-carcinogenic risks were obtained for m + p-xylenes in the varnish work place, and the second highest non-carcinogenic risk was also determined for the same workshop.

Role of carbonyls and aromatics in the formation of tropospheric ozone in Rio de Janeiro, Brazil.

The ozone in Rio de Janeiro has been in violation of national air quality standards. Among all of the monitoring stations, the Bangu neighbourhood has the most violations of the national standard of 160 µg m(-3) for the years 2012 and 2013. This study evaluated the reactivity of the carbonyls and aromatics in the tropospheric ozone formation processes. The samples were collected between July and October of 2013. Carbonyls were sampled using SiO2 cartridges coated with C18 and impregnated with 2,4-dinitrophenylhydrazine and were analysed by HPLC. Activated carbon cartridges and GC/MS were used to measure the concentration of monoaromatic hydrocarbons. An air quality monitoring station provided the concentrations of the criteria pollutants and the meteorological parameters. Cluster analysis and a Pearson correlation matrix were used to determine the formation of groups and the correlation of the variables. The evaluation of the volatile organic compounds (VOC) reaction with OH radicals and the MIR scale was used to extrapolate the reactivity of VOCs to the ozone formation. The average concentrations obtained were 19.7 and 51.9 µg m(-3) for formaldehyde and acetaldehyde, respectively. The mean concentrations obtained for aromatics were 1.5, 6.7, 1.5, 2.6 and 1.6 µg m(-3) for benzene, toluene, ethyl benzene, m+p-xylene and o-xylene, respectively. The cluster analysis indicated the presence of three similar groups, with one formed by gaseous criteria pollutants, another formed by the meteorological parameters, ozone and fine particles, and the last group formed by the aromatics. For the two reactivity scales evaluated, acetaldehyde and toluene were the main ozone precursors.

Utilização de Sistema de Informação Geográfica como ferramenta para gestão do monitoramento da qualidade do ar na Região Metropolitana do Rio de Janeiro / Use of Geographic Information System as a tool for the management of air quality monitoring in the metropolitan area of Rio de Janeiro state

A preocupação com a gestão da qualidade do ar na cidade do Rio de Janeiro tem aumentado nos últimos anos devido aos grandes eventos que a cidade irá receber em um futuro próximo. A utilização de Sistema de Informação Geográfica como uma ferramenta para a gestão da qualidade do ar foi avaliada neste trabalho. Foi feita uma nova delimitação das bacias aéreas com a utilização de dados digitais que proporcionou o surgimento de três novas bacias aéreas e a alteração da configuração espacial das bacias aéreas existentes.

The concern with the air quality management in the city of Rio de Janeiro has increased in recent last years due to the great events that this city will receive in the near future. The use of a Geographic Information System as a tool for the air quality management was evaluated in this work. A new delimitation of air basins was proposed using the digital data suggesting the appearance of three new air basins and the change of the spatial configuration of the existing air basins.

BTEX no interior de salas de aula de spinning / BTEX inside a spinning classroom

Atividades Físicas realizadas em ambientes fechados estão se tornando mais frequente. Estudos têm mostrado que as concentrações de poluentes em ambientes interiores são sempre maiores do que em ambiente abertos. Em locais fechados, onde são realizados exercícios de forma regular, não existe a preocupação com a qualidade do ar, principalmente quando estão sendo realizadas atividades aeróbicas. Neste estudo, foram medidas concentrações de BTEX em uma sala de spinning e as concentrações obtidas foram maiores do que as encontradas em ambientes ao ar livre. No entanto, uma atividade de pintura realizada na sala de spinning gerou concentrações elevadas de todos os BTEX , e, em particular, o tolueno teve concentrações muito maiores. No dia seguinte a realização da pintura, as concentrações de todos os BTEX tinham aumentado significativamente e a concentração de tolueno foi de 274.9 µg/m³. Após a pintura na sala de spinning, o aumento foi de 91% para o benzeno, 907% para o tolueno, 182% para o etilbenzeno, 121% para o m+p-xileno e de 128% para o o-xileno.

Indoors Physical Activities are becoming more frequent. Studies have shown that pollutants concentrations in indoor environments are always greater than in open environments. In indoor locations where regular exercise are performed, there is no concern about air quality, principally when aerobic physical activity are performed. BTEX concentrations in a spinning classroom were measured in this study and were higher than those obtained in an outdoor environment. However, a painting activity of the room revealed that all BTEX concentrations, and in particular Toluene, become much greater. In the day after, the paint concentration of all BTEX increased significantly and the concentration of toluene was 274.9 µg/m³. The BTEX concentration increased after all room was painted, and this increase was from 91% to benzene, 907% for toluene, 182% to ethylbenzene, 121% for m+p-xylene and 128% for o-xylene.

Volatile organic compounds in a residential and commercial urban area with a diesel, compressed natural gas and oxygenated gasoline vehicular fleet.

Air samples were collected in a typical residential and commercial area in Rio de Janeiro, Brazil, where buses and trucks use diesel and light duty vehicles use compressed natural gas, ethanol, and gasohol (gasoline blended with ethanol) as fuel. A total of 66 C3-C12 volatile organic compounds (VOCs) were identified. The most abundant compounds, on a mass concentration basis, included propane, isobutane, i-pentane, m,p-xylene, 1,3,5-trimethylbenzene, toluene, styrene, ethylbenzene, isopropylbenzene, o-xylene and 1,2,4-trimethylbenzene. Two VOCs photochemical reactivity rankings are presented: one involves reaction with OH and the other involves production of ozone.

Atmospheric levels of aldehydes and BTEX and their relationship with vehicular fleet changes in Rio de Janeiro urban area.

A comprehensive monitoring campaign to assess aldehydes and BTEX concentrations was performed during 12 months, in the Tijuca district (Rio de Janeiro), an area with commercial activities and a high flux of vehicles. The mean concentrations of formaldehyde and acetaldehyde were 151 and 30 ppb, respectively. The high formaldehyde/acetaldehyde ratio was attributed to extensive use of compressed natural gas (CNG). The number of CNG vehicles in the metropolitan Region of Rio de Janeiro increased from 23000 in January 2001 to 161000 in January 2005. Monitoring data show that, for the same period, methane and formaldehyde concentrations increased while NO(x) and CO levels diminished. Mean concentrations for benzene, toluene, ethylbenzene, m,p-xylene and o-xylene, were 1.1, 4.8, 3.6, 10.4 and 3.0 micro gm(-3), respectively. Benzene and toluene concentrations were lower than the values determined in 1996, for the same location. The levels of ethylbenzene and xylenes determined in this work are similar to values obtained in 1996. This fact may be explained as a consequence of changes in the gasoline composition.