Exhaust particle number and composition for diesel and gasoline passenger cars under transient driving conditions: Real-world emissions down to 1.5 nm.

Recent recommendations given by WHO include systematic measurements of ambient particle number concentration and black carbon (BC) concentrations. In India and several other highly polluted areas, the air quality problems are severe and the need for air quality related information is urgent. This study focuses on particle number emissions and BC emissions of passenger cars that are technologically relevant from an Indian perspective. Particle number and BC were investigated under real-world conditions for driving cycles typical for Indian urban environments. Two mobile laboratories and advanced aerosol and trace gas instrumentation were utilized. Our study shows that passenger cars without exhaust particle filtration can emit in real-world conditions large number of particles, and especially at deceleration a significant fraction of particle number can be even in 1.5-10 nm particle sizes. The mass concentration of exhaust plume particles was dominated by BC that was emitted especially at acceleration conditions. However, exhaust particles contained also organic compounds, indicating the roles of engine oil and fuel in exhaust particle formation. In general, our study was motivated by serious Indian air quality problems, by the recognized lack of emission information related to Indian traffic, and by the recent WHO air quality guidance; our results emphasize the importance of monitoring particle number concentrations and BC also in Indian urban areas and especially in traffic environments where people can be significantly exposed to fresh exhaust emissions.

Sub-23 nm Particles Dominate Non-Volatile Particle Number Emissions of Road Traffic.

Ultrafine particles (<100 nm) in urban air are a serious health hazard not yet fully understood. Therefore, particle number concentration monitoring was recently included in the WHO air quality guidelines. At present, e.g., the EU regulates particle number only regarding the emissions of solid particles larger than 23 nm emitted by vehicles. The aim of this study was to examine the non-volatile fraction of sub-23 nm particles in a traffic-influenced urban environment. We measured the number concentration of particles larger than 1.4, 3, 10, and 23 nm in May 2018. Volatile compounds were thermally removed in the sampling line and the line losses were carefully determined. According to our results, the sub-23 nm particles dominated the non-volatile number concentrations. Additionally, based on the determined particle number emission factors, the traffic emissions of non-volatile sub-10 nm particles can be even 3 times higher than those of particles larger than 10 nm. Yet, only a fraction of urban sub-10 nm particles consisted of non-volatiles. Thus, while the results highlight the role of ultrafine particles in the traffic-influenced urban air, a careful consideration is needed in terms of future particle number standards to cover the varying factors affecting measured concentrations.

Toxicity of exhaust emissions from high aromatic and non-aromatic diesel fuels using in vitro ALI exposure system.

The differences in the traffic fuels have been shown to affect exhaust emissions and their toxicity. Especially, the aromatic content of diesel fuel is an important factor considering the emissions, notably particulate matter (PM) concentrations. The ultra-fine particles (UFP, particles with a diameter of <100 nm) are important components of engine emissions and connected to various health effects, such as pulmonary and systematic inflammation, and cardiovascular disorders. Studying the toxicity of the UFPs and how different fuel options can be used for mitigating the emissions and toxicity is crucial. In the present study, emissions from a heavy-duty diesel engine were used to assess the exhaust emission toxicity with a thermophoresis-based in vitro air-liquid interface (ALI) exposure system. The aim of the study was to evaluate the toxicity of engine exhaust and the potential effect of 20 % aromatic fossil diesel and 0 % aromatic renewable diesel fuel on emission toxicity. The results of the present study show that the aromatic content of the fuel increases emission toxicity, which was seen as an increase in genotoxicity, distinct inflammatory responses, and alterations in the cell cycle. The increase in genotoxicity was most likely due to the PM phase of the exhaust, as the exposures with high-efficiency particulate absorbing (HEPA)-filtered exhaust resulted in a negligible increase in genotoxicity. However, the solely gaseous exposures still elicited immunological responses. Overall, the present study shows that decreasing the aromatic content of the fuels could be a significant measure in mitigating traffic exhaust toxicity.

Black carbon toxicity dependence on particle coating: Measurements with a novel cell exposure method.

Black carbon (BC) is a component of ambient particulate matter which originates from incomplete combustion emissions. BC is regarded as an important short-lived climate forcer, and a significant public health hazard. These two concerns have made BC a focus in aerosol science. Even though, the toxicity of BC particles is well recognized, the mechanism of toxicity for BC as a part of the total gas and particle emission mixture from combustion is still largely unknown and studies concerning it are scarce. In the present study, using a novel thermophoresis-based air-liquid interface (ALI) in vitro exposure system, we studied the toxicity of combustion-generated aerosols containing high levels of BC, diluted to atmospheric levels (1 to 10 µg/m3). Applying multiple different aerosol treatments, we simulated different sources and atmospheric aging processes, and utilizing several toxicological endpoints, we thoroughly examined emission toxicity. Our results revealed that an organic coating on the BC particles increased the toxicity, which was seen as larger genotoxicity and immunosuppression. Furthermore, aging of the aerosol also increased its toxicity. A deeper statistical analysis of the results supported our initial conclusions and additionally revealed that toxicity increased with decreasing particle size. These findings regarding BC toxicity can be applied to support policies and technologies to reduce the most hazardous compositions of BC emissions. Additionally, our study showed that the thermophoretic ALI system is both a suitable and useful tool for toxicological studies of emission aerosols.

Real-world particle emissions and secondary aerosol formation from a diesel oxidation catalyst and scrubber equipped ship operating with two fuels in a SECA area.

SOx Emissions Control Areas (SECAs) have been established to reduce harmful effects of atmospheric sulfur. Typical technological changes for ships to conform with these regulations have included the combustion of low-sulfur fuels or installment of SOx scrubbers. This paper presents experimental findings from high-end real-time measurements of gaseous and particulate pollutants onboard a Roll-on/Roll-off Passenger ship sailing inside a SECA equipped with a diesel oxidation catalyst (DOC) and a scrubber as the exhaust aftertreatment. The ship operates between two ports and switched off the SOx scrubbing when approaching one of the ports and used low-sulfur fuel instead. Measurement results showed that the scrubber effectively reduced SO2 concentrations with over 99% rate. In terms of fuel, the engine-out PM was higher for heavy fuel oil than for marine gas oil. During open sea cruising (65% load) the major chemical components in PM having emission factor of 1.7 g kgfuel-1 were sulfate (66%) and organics (30%) whereas the contribution of black carbon (BC) in PM was low (∼4%). Decreased engine load on the other hand increased exhaust concentrations of BC by a factor exceeding four. As a novel finding, the secondary aerosol formation potential of the emitted exhaust measured with an oxidation flow reactor and an aerosol mass spectrometer was found negligible. Thus, it seems that either DOC, scrubber, or their combination is efficient in eliminating SOA precursors. Overall, results indicate that in addition to targeting sulfur and NOx emissions from shipping, future work should focus on mitigating harmful particle emissions.

Strategies To Diminish the Emissions of Particles and Secondary Aerosol Formation from Diesel Engines.

Particle emissions and secondary aerosol formation from internal combustion engines deteriorate air quality and significantly affect human wellbeing and health. Both the direct particle emissions and the emissions of compounds contributing to secondary aerosol formation depend on choices made in selecting fuels, engine technologies, and exhaust aftertreatment (EAT). Here we study how catalytic EATs, particle filtration, and fuel choices affect these emissions concerning heavy-duty diesel engine. We observed that the most advanced EAT decreased the emissions of fresh exhaust particle mass as much as 98% (from 44.7 to 0.73 mg/kWh) and the formation of aged exhaust particle mass ∼100% (from 106.2 to ∼0 mg/kWh). The composition of emitted particles depended significantly on the EAT and oxidative aging. While black carbon typically dominated the composition of fresh exhaust particles, aged particles contained more sulfates and organics. The fuel choices had minor effects on the secondary aerosol formation, implicating that, in diesel engines, either the lubricant is a significant source of secondary aerosol precursors or the precursors are formed in the combustion process. Results indicate that the utilization of EAT in diesel engines would produce benefits with respect to exhaust burden on air quality, and thus their utilization should be promoted especially in geographical areas suffering from poor air quality.

Impact of wood combustion for secondary heating and recreational purposes on particulate air pollution in a suburb in Finland.

Little information is available on the concentrations of ambient fine particles (PM2.5) in residential areas where wood combustion is common for recreational purposes and secondary heating. Further, the validity of central site measurements of PM2.5 as a measure of exposure is unclear. Therefore, outdoor PM2.5 samples were repeatedly collected at a central site and home outdoor locations from a panel of 29 residents in a suburb in Kuopio, Finland. Source apportionment results from the central site were used to estimate the contributions from local sources, including wood combustion, to PM2.5 and absorption coefficient (ABS) at home outdoor locations. Correlations between the central and home outdoor concentrations of PM2.5, ABS, and their local components were analyzed for each home. At the central site, the average PM2.5 was 6.0 µg m(-)(3) during the heating season, and the contribution from wood combustion (16%) was higher than the contribution from exhaust emissions (12%). Central site measurements predicted poorly daily variation in PM2.5 from local sources. In conclusion, wood combustion significantly affects air quality also in areas where it is not the primary heating source. In epidemiological panel studies, central site measurements may not sufficiently capture daily variation in exposure to PM2.5 from local wood combustion.

Optical and chemical characterization of aerosols emitted from coal, heavy and light fuel oil, and small-scale wood combustion.

Particle emissions affect radiative forcing in the atmosphere. Therefore, it is essential to know the physical and chemical characteristics of them. This work studied the chemical, physical, and optical characteristics of particle emissions from small-scale wood combustion, coal combustion of a heating and power plant, as well as heavy and light fuel oil combustion at a district heating station. Fine particle (PM1) emissions were the highest in wood combustion with a high fraction of absorbing material. The emissions were lowest from coal combustion mostly because of efficient cleaning techniques used at the power plant. The chemical composition of aerosols from coal and oil combustion included mostly ions and trace elements with a rather low fraction of absorbing material. The single scattering albedo and aerosol forcing efficiency showed that primary particles emitted from wood combustion and some cases of oil combustion would have a clear climate warming effect even over dark earth surfaces. Instead, coal combustion particle emissions had a cooling effect. Secondary processes in the atmosphere will further change the radiative properties of these emissions but are not considered in this study.

A novel particle sampling system for physico-chemical and toxicological characterization of emissions.

Several studies have shown that combustion-derived fine particles cause adverse health effects. Previous toxicological studies on combustion-derived fine particles have rarely involved multiple endpoints and a detailed characterization of chemical composition. In this study, we developed a novel particle sampling system for toxicological and chemical characterization (PSTC), consisting of the Dekati Gravimetric Impactor (DGI) and a porous tube diluter. Physico-chemical and toxicological properties of the particles emitted from various combustion sources were evaluated in two measurement campaigns. First, the DGI was compared with the High-Volume Cascade Impactor (HVCI) and to the Dekati Low-Pressure Impactor (DLPI), using the same dilution system and the same sampling conditions. Only small differences were observed in the mass size distributions, total particulate matter (PM), and particulate matter with diameter smaller than 1 um (PM(1)) concentrations and geometric mass mean diameters (GMMD) between these three impactors. Second, the PSTC was compared with the HVCI sampling system, which has been optimal for collection of particulate samples for toxicological and chemical analyses. Differences were observed in the mass size distributions, total PM and PM(1) emissions, and GMMDs, probably due to the different sampling and dilution methods as well as different sampling substrates which affected the behavior of semi-volatile and volatile organic compounds. However, no significant differences were detected in the in vitro measurements of cytotoxicity between the samples collected with the PSTC and the HVCI systems. In measurements of genotoxicity, significant differences between the two sampling systems were seen only with the particles emitted from the sauna stove. In conclusion, due to compact size, PSTC is an applicable method for use in particle sampling as part of the toxicological and chemical characterization of particulate emissions from different combustion sources. It offers some advantages compared to the previously used high-volume sampling methods including compactness for field measurements, simple preparation of sample substrates and high extraction efficiency.

Toxicological effects of emission particles from fossil- and biodiesel-fueled diesel engine with and without DOC/POC catalytic converter.

There is increasing demand for renewable energy and the use of biodiesel in traffic is a major option when implying this increment. We investigated the toxicological activities of particulate emissions from a nonroad diesel engine, operated with conventional diesel fuel (EN590), and two biodiesels: rapeseed methyl ester (RME) and hydrotreated fresh vegetable oil (HVO). The engine was operated with all fuels either with or without catalyst (DOC/POC). The particulate matter (PM(1)) samples were collected from the dilution tunnel with a high-volume cascade impactor (HVCI). These samples were characterized for ions, elements, and polycyclic aromatic hydrocarbon (PAH) compounds. Mouse RAW264.7 macrophages were exposed to the PM samples for 24 h. Inflammatory mediators, (TNF-α and MIP-2), cytotoxicity, genotoxicity, and oxidative stress (reactive oxygen species [ROS]) were measured. All the samples displayed mostly dose-dependent toxicological activity. EN590 and HVO emission particles had larger inflammatory responses than RME-derived particles. The catalyst somewhat increased the responses per the same mass unit. There were no substantial differences in the cytotoxic responses between the fuels or catalyst use. Genotoxic responses by all the particulate samples were at same level, except weaker for the RME sample with catalyst. Unlike other samples, EN590-derived particles did not significantly increase ROS production. Catalyst increased the oxidative potential of the EN590 and HVO-derived particles, but decreased that with RME. Overall, the use of biodiesel fuels and catalyst decreased the particulate mass emissions compared with the EN590 fuel. Similar studies with different types of diesel engines are needed to assess the potential benefits from biofuel use in engines with modern technologies.

Determination of anthropogenic and biogenic compounds on atmospheric aerosol collected in urban, biomass burning and forest areas in São Paulo, Brazil.

This study was conducted at three sites of different characteristics in São Paulo State: São Paulo (SPA), Piracicaba (PRB) and Mata Atlântica Forest (MAT). PM(10), n-alkanes, pristane and phytane, PAHs, water-soluble ions and biomass burning tracers like levoglucosan and retene, were determined in quartz fiber filters. Samplings occurred on May 8th to August 8th, 2007 at the MAT site; on August 15th to 29th in 2007 and November 10th to 29th in 2008 at the PRB site and, March 13th to April 4th in 2007 and August 7th to 29th in 2008 at the SPA site. Aliphatic compounds emitted biogenically were less abundant at the urban sites than at the forest site, and its distribution showed the influence of tropical vascular plants. Air mass transport from biomass burning regions is likely to impact the sites with specific molecular markers. The concentrations of all species were variable and dependent of seasonal changes. In the most dry and polluted seasons, n-alkane and cation total concentrations were similar between the megacity and the biomass burning site. PAHs and inorganic ion abundances were higher at São Paulo than Piracicaba, yet, the site influenced by biomass burning seems to be the most impacted by the organic anion abundance in the atmosphere. Pristane and phytane confirm the contamination by petroleum residues at urban sites; at the MAT site, biological activity and long range transport of pollutants might influence the levels of pristane.

High-performance anion-exchange chromatography-mass spectrometry method for determination of levoglucosan, mannosan, and galactosan in atmospheric fine particulate matter.

Biomass burning has a strong influence on the atmospheric aerosol composition through particulate organic, inorganic, and soot emissions. When biomass burns, cellulose and hemicelluloses degrade, producing monosaccharide anhydrides (MAs) such as levoglucosan, mannosan, and galactosan. Therefore, these compounds have been commonly used as tracers for biomass burning. In this study, a fast water-based method was developed for the routine analysis of MAs, based on high-performance anion-exchange chromatography with electrospray ionization mass spectrometry detection. This method combines simple sample preparation, fast separation, and the advantages of the selective detection with MS. Analysis run was optimized to the maximum separation of levoglucosan, mannosan, and galactosan with 15-min analysis. The validation results indicated that the method showed good applicability for determination of MA isomer concentrations in ambient samples. The limit of detection was 100 pg for levoglucosan and 50 pg for mannosan and galactosan. Wide determination ranges enabled the analysis of samples of different concentration levels. The method showed good precision, both for standard solutions (3.9-5.9% RSD) and for fine particle samples (4.3-8.5% RSD). Co-elution of internal standard (carbon-13-labeled levoglucosan) and sugar alcohols with levoglucosan decreased the sensitivity of levoglucosan determination. The method was used to determine the MA concentrations in ambient fine particle samples from urban background (Helsinki) and rural background (Hyytiälä) in Finland. The average levoglucosan, mannosan, and galactosan concentrations were 77, 8.8, and 4.2 ng m(-3) in Helsinki (winter 2008-2009) and 17, 2.3, and 1.4 ng m(-3) in Hyytiälä (spring 2007), respectively. The interrelation of the three MA isomers was fairly constant in the ambient fine particle samples.

Chemical composition of fine particles in fresh smoke plumes from boreal wild-land fires in Europe.

A series of smoke plumes was detected in Helsinki, Finland, during a one-month-lasting period in August 2006. The smoke plumes originated from wildfires close to Finland, and they were short-term and had a high particulate matter (PM) concentration. Physical and chemical properties of fine particles in those smokes were characterised by a wide range of real-time measurements that enabled the examination of individual plume events. Concurrently PM(1) filter samples were collected and analysed off-line. Satellite observations employing MODIS sensor on board of NASA EOS Terra satellite with the dispersion model SILAM and the Fire Assimilation System were used for evaluation of the emission fluxes from wildfires. The model predicted well the timing of the plumes but the predicted PM concentrations differed from the observed. The measurements showed that the major growth in PM concentration was caused by submicrometer particles consisting mainly of particulate organic matter (POM). POM had not totally oxidised during the transport based on the low WSOC-to-OC ratio. The fresh plumes were compared to another major smoke episode that was observed in Helsinki during April-May 2006. The duration and the source areas of the two episode periods differed. The episode in April-May was a period of nearly constantly upraised level of long-range transported PM and it was composed of aged particles when arriving in Helsinki. The two episodes had differences also in the chemical composition of PM. The mass concentrations of biomass burning tracers (levoglucosan, potassium, and oxalate) increased during both the episodes but different concentration levels of elemental carbon and potassium indicated that the episodes differed in the form of burning as well as in the burning material. In spring dry crop residue and hay from the previous season were burnt whereas in August smokes from smouldering and incomplete burning of fresh vegetation were detected.