Secondary organic aerosol reduced by mixture of atmospheric vapours.

Secondary organic aerosol contributes to the atmospheric particle burden with implications for air quality and climate. Biogenic volatile organic compounds such as terpenoids emitted from plants are important secondary organic aerosol precursors with isoprene dominating the emissions of biogenic volatile organic compounds globally. However, the particle mass from isoprene oxidation is generally modest compared to that of other terpenoids. Here we show that isoprene, carbon monoxide and methane can each suppress the instantaneous mass and the overall mass yield derived from monoterpenes in mixtures of atmospheric vapours. We find that isoprene 'scavenges' hydroxyl radicals, preventing their reaction with monoterpenes, and the resulting isoprene peroxy radicals scavenge highly oxygenated monoterpene products. These effects reduce the yield of low-volatility products that would otherwise form secondary organic aerosol. Global model calculations indicate that oxidant and product scavenging can operate effectively in the real atmosphere. Thus highly reactive compounds (such as isoprene) that produce a modest amount of aerosol are not necessarily net producers of secondary organic particle mass and their oxidation in mixtures of atmospheric vapours can suppress both particle number and mass of secondary organic aerosol. We suggest that formation mechanisms of secondary organic aerosol in the atmosphere need to be considered more realistically, accounting for mechanistic interactions between the products of oxidizing precursor molecules (as is recognized to be necessary when modelling ozone production).

Emissions and Secondary Formation of Air Pollutants from Modern Heavy-Duty Trucks in Real-World Traffic-Chemical Characteristics Using On-Line Mass Spectrometry.

Complying with stricter emissions standards, a new generation of heavy-duty trucks (HDTs) has gradually increased its market share and now accounts for a large percentage of on-road mileage. The potential to improve air quality depends on an actual reduction in both emissions and subsequent formation of secondary pollutants. In this study, the emissions in real-world traffic from Euro VI-compliant HDTs were compared to those from older classes, represented by Euro V, using high-resolution time-of-flight chemical ionization mass spectrometry. Gas-phase primary emissions of several hundred species were observed for 70 HDTs. Furthermore, the particle phase and secondary pollutant formation (gas and particle phase) were evaluated for a number of HDTs. The reduction in primary emission factors (EFs) was evident (∼90%) and in line with a reduction of 28-97% for the typical regulated pollutants. Secondary production of most gas- and particle-phase compounds, for example, nitric acid, organic acids, and carbonyls, after photochemical aging in an oxidation flow reactor exceeded the primary emissions (EFAged/EFFresh ratio ≥2). Byproducts from urea-selective catalytic reduction systems had both primary and secondary sources. A non-negative matrix factorization analysis highlighted the issue of vehicle maintenance as a remaining concern. However, the adoption of Euro VI has a significant positive effect on emissions in real-world traffic and should be considered in, for example, urban air quality assessments.

Fresh and Oxidized Emissions from In-Use Transit Buses Running on Diesel, Biodiesel, and CNG.

The potential effect of changing to a nonfossil fuel vehicle fleet was investigated by measuring primary emissions (by extractive sampling of bus plumes) and secondary mass formation, using a Gothenburg Potential Aerosol Mass (Go:PAM) reactor, from 29 in-use transit buses. Regarding fresh emissions, diesel (DSL) buses without a diesel particulate filter (DPF) emitted the highest median mass of particles, whereas compressed natural gas (CNG) buses emitted the lowest (MdEFPM 514 and 11 mg kgfuel-1, respectively). Rapeseed methyl ester (RME) buses showed smaller MdEFPM and particle sizes than DSL buses. DSL (no DPF) and hybrid-electric RME (RMEHEV) buses exhibited the highest particle numbers (MdEFPN 12 × 1014 # kgfuel-1). RMEHEV buses displayed a significant nucleation mode ( Dp< 20 nm). EFPN of CNG buses spanned the highest to lowest values measured. Low MdEFPN and MdEFPM were observed for a DPF-equipped DSL bus. Secondary particle formation resulting from exhaust aging was generally important for all the buses (79% showed an average EFPM:AGED/EFPM:FRESH ratio >10) and fuel types tested, suggesting an important nonfuel dependent source. The results suggest that the potential for forming secondary mass should be considered in future fuel shifts, since the environmental impact is different when only considering the primary emissions.

Parameterization of thermal properties of aging secondary organic aerosol produced by photo-oxidation of selected terpene mixtures.

Formation and evolution of secondary organic aerosols (SOA) from biogenic VOCs influences the Earth's radiative balance. We have examined the photo-oxidation and aging of boreal terpene mixtures in the SAPHIR simulation chamber. Changes in thermal properties and chemical composition, deduced from mass spectrometric measurements, were providing information on the aging of biogenic SOA produced under ambient solar conditions. Effects of precursor mixture, concentration, and photochemical oxidation levels (OH exposure) were evaluated. OH exposure was found to be the major driver in the long term photochemical transformations, i.e., reaction times of several hours up to days, of SOA and its thermal properties, whereas the initial concentrations and terpenoid mixtures had only minor influence. The volatility distributions were parametrized using a sigmoidal function to determine TVFR0.5 (the temperature yielding a 50% particle volume fraction remaining) and the steepness of the volatility distribution. TVFR0.5 increased by 0.3±0.1% (ca. 1 K), while the steepness increased by 0.9±0.3% per hour of 1×10(6) cm(-3) OH exposure. Thus, aging reduces volatility and increases homogeneity of the vapor pressure distribution, presumably because highly volatile fractions become increasingly susceptible to gas phase oxidation, while less volatile fractions are less reactive with gas phase OH.

Onboard measurements of nanoparticles from a SCR-equipped marine diesel engine.

In this study nanoparticle emissions have been characterized onboard a ship with focus on number, size, and volatility. Measurements were conducted on one of the ship's four main 12,600 kW medium-speed diesel engines which use low sulfur marine residual fuel and have a Selective Catalytic Reduction (SCR) system for NO(X) abatement. The particles were measured after the SCR with an engine exhaust particle sizer spectrometer (EEPS), giving particle number and mass distributions in the size range of 5.6-560 nm. The thermal characteristics of the particles were analyzed using a volatility tandem DMA system (VTDMA). A dilution ratio of 450-520 was used which is similar to the initial real-world dilution. At a stable engine load of 75% of the maximum rated power, and after dilution and cooling of the exhaust gas, there was a bimodal number size distribution, with a major peak at ∼10 nm and a smaller peak at around 30-40 nm. The mass distribution peaked around 20 nm and at 50-60 nm. The emission factor for particle number, EF(PN), for an engine load of 75% in the open-sea was found to be 10.4 ± 1.6 × 10(16) (kg fuel)(-1) and about 50% of the particles by number were found to have a nonvolatile core at 250 °C. Additionally, 20 nm particles consist of ∼40% of nonvolatile material by volume (evaporative temperature 250 °C), while the particles with a particle diameter <10 nm evaporate completely at a temperature of 130-150 °C. Emission factors for NO(X), CO, and CO(2) for an engine load of 75% in the open-sea were determined to 4.06 ± 0.3 g (kg fuel)(-1), 2.15 ± 0.06 g (kg fuel)(-1), and 3.23 ± 0.08 kg (kg fuel)(-1), respectively. This work contributes to an improved understanding of particle emissions from shipping using modern pollution reduction measures such as SCR and fuel with low sulfur content.

Concurrent measurements of nitrate at urban and suburban sites identify local nitrate formation as a driver for urban episodic PM2.5 pollution.

Nitrate (NO3-) is often among the leading components of urban particulate matter (PM) during PM pollution episodes. However, the factors controlling its prevalence remain inadequately understood. In this work, we analyzed concurrent hourly monitoring data of NO3- in PM2.5 at a pair of urban and suburban locations (28 km apart) in Hong Kong for a period of two months. The concentration gradient in PM2.5 NO3- was 3.0 ± 2.9 (urban) vs. 1.3 ± 0.9 µg m-3 (suburban) while that for its precursors nitrogen oxides (NOx) was 38.1 vs 4.1 ppb. NO3- accounted for 45 % of the difference in PM2.5 between the sites. Both sites were characterized to have more available NH3 than HNO3. Urban nitrate episodes, defined as periods of urban-suburban NO3- difference exceeding 2 µg m-3, constituted 21 % of the total measurement hours, with an hourly NO3- average gradient of 4.2 and a peak value of 23.6 µg m-3. Our comparative analysis, together with 3-D air quality model simulations, indicates that the high NOx levels largely explain the excessive NO3- concentrations in our urban site, with the gas phase HNO3 formation reaction contributing significantly during the daytime and the N2O5 hydrolysis pathway playing a prominent role during nighttime. This study presents a first quantitative analysis that unambiguously shows local formation of NO3- in urban environments as a driver for urban episodic PM2.5 pollution, suggesting effective benefits of lowering urban NOx.

Influence of ozone and radical chemistry on limonene organic aerosol production and thermal characteristics.

Limonene has a strong tendency to form secondary organic aerosol (SOA) in the atmosphere and in indoor environments. Initial oxidation occurs mainly via ozone or OH radical chemistry. We studied the effect of O(3) concentrations with or without a OH radical scavenger (2-butanol) on the SOA mass and thermal characteristics using the Gothenburg Flow Reactor for Oxidation Studies at Low Temperatures and a volatility tandem differential mobility analyzer. The SOA mass using 15 ppb limonene was strongly dependent on O(3) concentrations and the presence of a scavenger. The SOA volatility in the presence of a scavenger decreased with increasing levels of O(3), whereas without a scavenger, there was no significant change. A chemical kinetic model was developed to simulate the observations using vapor pressure estimates for compounds that potentially contributed to SOA. The model showed that the product distribution was affected by changes in both OH and ozone concentrations, which partly explained the observed changes in volatility, but was strongly dependent on accurate vapor pressure estimation methods. The model-experiment comparison indicated a need to consider organic peroxides as important SOA constituents. The experimental findings could be explained by secondary condensed-phase ozone chemistry, which competes with OH radicals for the oxidation of primary unsaturated products.

Molecular characterization and optical properties of primary emissions from a residential wood burning boiler.

Modern small-scale biomass burners have been recognized as an important renewable energy source because of the economic and environmental advantages of biomass over fossil fuels. However, the characteristics of their gas and particulate emissions remain incompletely understood, and there is substantial uncertainty concerning their health and climate impacts. Here, we present online measurements conducted during the operation of a residential wood-burning boiler. The measured parameters include gas and particle concentrations, optical absorption and chemical characteristics of gases and particles. Positive matrix factorization was performed to analyze data from a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) equipped with a filter inlet for gases and aerosols (FIGAERO). Six factors were identified and interpreted. Three factors were related to the chemical composition of the fuel representing lignin pyrolysis products, cellulose/hemicellulose pyrolysis products, and nitrogen-containing organics, while three factor were related to the physical characteristics of the emitted compounds: volatile compounds, semi-volatile compounds, and filter-derived compounds. An ordinal analysis was performed based on the factor fractions to identify the most influential masses in each factor, and by deconvoluting high-resolution mass spectra fingerprint molecules for each factor were identified. Results from the factor analysis were linked to the optical properties of the emissions, and lignin and cellulose/hemicellulose pyrolysis products appeared to be the most important sources of brown carbon under the tested burning conditions. It is concluded that the emissions from the complex combustion process can be described by a limited set of physically meaningful factors, which will help to rationalize subsequent transformation and tracing of emissions in the atmosphere and associated impacts on health and climate.