Emission factors for a biofuel impacted fleet in South America's largest metropolitan area.

The Metropolitan Area of São Paulo (MASP) is among the largest urban areas in the Southern Hemisphere. Vehicular emissions are of great concern in metropolitan areas and MASP is unique due to the use of biofuels on a large scale (sugarcane ethanol and biodiesel). In this work, tunnel measurements were employed to assess vehicle emissions and to calculate emission factors (EFs) for heavy-duty and light-duty vehicles (HDVs and LDVs). The EFs were determined for particulate matter (PM) and its chemical compounds. The EFs obtained for 2018 were compared with previous tunnel experiments performed in the same area. An overall trend of reduction of fine and coarse PM, organic carbon (OC), and elemental carbon (EC) EFs for both LDVs and HDVs was observed if compared to those observed in past years, suggesting the effectiveness of vehicular emissions control policies implemented in Brazil. A predominance of Fe, Cu, Al, and Ba emissions was observed for the LDV fleet in the fine fraction. Cu presented higher emissions than two decades ago, which was associated with the increased use of ethanol fuel in the region. For HDVs, Zn and Pb were mostly emitted in the fine mode and were linked with lubricating oil emissions from diesel vehicles. A predominance in the emission of three- and four-ring polycyclic aromatic hydrocarbons (PAHs) for HDVs and five-ring PAHs for LDVs agreed with what was observed in previous studies. The use of biofuels may explain the lower PAH emissions for LDVs (including carcinogenic benzo[a]pyrene) compared to those observed in other countries. The tendency observed was that LDVs emitted higher amounts of carcinogenic species. The use of these real EFs in air quality modeling resulted in more accurate simulations of PM concentrations, showing the importance of updating data with real-world measurements.

Exhaust emissions of gaseous and particle size-segregated water-soluble organic compounds from diesel-biodiesel blends.

This study assessed the emissions of gaseous pollutants and particle size distributed water-soluble organics (WSO) from a diesel vehicle fuelled with ultralow sulphur diesel (B0) and 10 (B10), 20 (B20), and 30% (B30) biodiesel blends in a chassis dynamometer tested under transient mode. Particulate emission sampling was carried out in an ultraviolet (UV) test chamber using a 10-stage impactor. Samples were grouped into three size fractions and analysed by gas chromatography-mass spectrometry. Increasing the biofuel ratio up to 30% in the fuel reduced WSO emissions by 20.9% in comparison with conventional diesel. Organic acids accounted for 82-89% of WSO in all tested fuels. Dicarboxylic acids were the most abundant compound class, followed by hydroxy, aromatic, and linear alkanoic acids. Correlations between compounds demonstrated that adding biodiesel to diesel fuel reduces the emissions of nitrogen oxides (NOx), benzene, toluene, ethylbenzene and xylenes (BTEX), methane (CH4), total and nonmethane hydrocarbons (THC and NMHC), and dicarboxylic and hydroxy acids, but increases emissions of carbon dioxide (CO2) and alkanoic and aromatic acids. Emissions of dicarboxylic and hydroxy acids were strongly correlated with the biodiesel content. WSO emissions of coarse and fine (1.0-10 µm) particles decreased with the increasing biofuel content in fuel blend. The total share of ultrafine (0.18-1.0 µm) and nanoparticles (< 0.18 µm) increased in WSOs emissions from B20 and B30 blends, when compared with petrodiesel. The biodiesel content also affected the chemical profile of WSO size fractions.

PM2.5 chemical composition and health risks by inhalation near a chemical complex.

Particulate matter (PM2.5) samples were collected in the vicinity of an industrial chemical pole and analysed for organic and elemental carbon (OC and EC), 47 trace elements and around 150 organic constituents. On average, OC and EC accounted for 25.2% and 11.4% of the PM2.5 mass, respectively. Organic compounds comprised polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, anhydrosugars, phenolics, aromatic ketones, glycerol derivatives, aliphatic alcohols, sterols, and carboxyl groups, including aromatic, carboxylic and dicarboxylic acids. Enrichment factors > 100 were obtained for Pb, Cd, Zn, Cu, Sn, B, Se, Bi, Sb and Mo, showing the contribution of industrial emissions and nearby major roads. Principal component analysis revealed that vehicle, industrial and biomass burning emissions accounted for 66%, 11% and 9%, respectively, of the total PM2.5-bound PAHs. Some of the detected organic constituents are likely associated with plasticiser ingredients and thermal stabilisers used in the manufacture of PVC and other plastics in the industrial complex. Photooxidation products of both anthropogenic (e.g., toluene) and biogenic (e.g., isoprene and pinenes) precursors were also observed. It was estimated that biomass burning accounted for 13.8% of the PM2.5 concentrations and that secondary OC represented 37.6% of the total OC. The lifetime cancer risk from inhalation exposure to PM2.5-bound PAHs was found to be negligible, but it exceeded the threshold of 10-6 for metal(loi)s, mainly due to Cr and As.

Cooking activities in a domestic kitchen: Chemical and toxicological profiling of emissions.

To obtain emission factors and cooking-related chemical signatures, a monitoring campaign was carried out in a modern kitchen where different dishes of the Latin cuisine were prepared. Particulate matter (PM10, PM2.5 and PM1) and total volatile organic compounds (TVOCs) were continuously measured. Passive tubes for carbonyls and a high volume PM10 sampler were simultaneously used. PM10 filters were analysed for organic and elemental carbon and for multiple organic compounds, including polyaromatic hydrocarbons (PAHs). The toxic potential of PM10 was evaluated using a bioluminescence inhibition bioassay. Acrolein was never detected, while formaldehyde and acetaldehyde levels were comparable to those in the background air. The protection limit for TVOCs was always exceeded. Fine particles comprised more than 86% of the PM10 mass concentrations. PM10 emission rates ranged from 124 to 369 µg min-1. Relatively low PAH concentrations were obtained. PM10 encompassed alcohols, acids, plasticisers, alkyl esters, sterols, sugars, polyols, glyceridic compounds, phenolics, among others. Total concentrations were 1.9-5.3 times higher during cooking than in the background air but, for some compounds, differences of tens or hundreds of times were registered. PM10 from grilled pork was found to contribute to non-negligible cancer risks and to be very toxic, while samples from other dishes were categorised as toxic.

Fine Particulate Matter and Gaseous Compounds in Kitchens and Outdoor Air of Different Dwellings.

Passive diffusion tubes for volatile organic compounds (VOCs) and carbonyls and low volume particulate matter (PM2.5) samplers were used simultaneously in kitchens and outdoor air of four dwellings. PM2.5 filters were analysed for their carbonaceous content (organic and elemental carbon, OC and EC) by a thermo-optical technique and for polycyclic aromatic hydrocarbon (PAHs) and plasticisers by GC-MS. The morphology and chemical composition of selected PM2.5 samples were characterised by SEM-EDS. The mean indoor PM2.5 concentrations ranged from 14 µg m-3 to 30 µg m-3, while the outdoor levels varied from 18 µg m-3 to 30 µg m-3. Total carbon represented up to 40% of the PM2.5 mass. In general, the indoor OC/EC ratios were higher than the outdoor values. Indoor-to-outdoor ratios higher than 1 were observed for VOCs, carbonyls and plasticisers. PAH levels were much higher in the outdoor air. The particulate material was mainly composed of soot aggregates, fly ashes and mineral particles. The hazard quotients associated with VOC inhalation suggested a low probability of non-cancer effects, while the cancer risk was found to be low, but not negligible. Residential exposure to PAHs was dominated by benzo[a]pyrene and has shown to pose an insignificant cancer risk.

Emission of trace gases and organic components in smoke particles from a wildfire in a mixed-evergreen forest in Portugal.

On May 2009, both the gas and particulate fractions of smoke from a wildfire in Sever do Vouga, central Portugal, were sampled. Total hydrocarbons and carbon oxides (CO(2) and CO) were measured using automatic analysers with flame ionisation and non-dispersive infrared detectors, respectively. Fine (PM(2.5)) and coarse (PM(2.5-10)) particles from the smoke plume were analysed by a thermal-optical transmission technique to determine the elemental and organic carbon (EC and OC) content. Subsequently, the particle samples were solvent extracted and fractionated by vacuum flash chromatography into different classes of organic compounds. The detailed organic speciation was performed by gas chromatography-mass spectrometry. The CO, CO(2) and total hydrocarbon emission factors (g kg(-1) dry fuel) were 170 ± 83, 1485 ± 147, and 9.8 ± 0.90, respectively. It was observed that the particulate matter and OC emissions are significantly enhanced under smouldering fire conditions. The aerosol emissions were dominated by fine particles whose mass was mainly composed of organic constituents, such as degradation products from biopolymers (e.g. levoglucosan from cellulose, methoxyphenols from lignin). The compound classes also included homologous series (n-alkanes, n-alkenes, n-alkanoic acids and n-alkanols), monosaccharide derivatives from cellulose, steroid and terpenoid biomarkers, and polycyclic aromatic hydrocarbons (PAHs). The most abundant PAH was retene. Even carbon number homologs of monoglycerides were identified for the first time as biomarkers in biomass burning aerosols.

Organic speciation of atmospheric particles in Alvão Natural Park (Portugal).

PM(10) continental rural background aerosols were collected during a summer field campaign (August-September 2006) at Lamas de Olo in the upper zone of the Alvão Natural Park, a mountain region of northern Portugal. In addition to the determination of the carbonaceous content by a thermal-optical method, the organic speciation of aerosols was performed by gas chromatography-mass spectrometry in an effort to evaluate photo-oxidation products of biogenic volatile organic compounds and other markers for source characterization. The detailed analysis revealed relatively high concentrations of polyols and short-chain dicarboxylic, tricarboxylic, hydroxycarboxylic, and oxocarboxylic acids, many of which are thought to be indicators of secondary aerosol formation, accounting for about 70% of global chromatographically resolved mass. Major photo-oxidation products of alpha- and beta-pinene have been detected. The tracers for the photo-oxidation of isoprene comprise two diastereoisomeric 2-methyltetrols, C(5)-alkene triols, and 2-methylglyceric acid, which have only recently been elucidated. In addition, the occurrence of levoglucosan and other biomass combustion tracers indicates that the site was affected by wildfires. This source contributed to more than 80% of the organic carbon mass during a period of strong forest fire influence.