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Nature ; 565(7741): 587-593, 2019 01.
Artigo em Inglês | MEDLINE | ID: mdl-30700872


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).

Environ Sci Technol ; 52(14): 7720-7728, 2018 07 17.
Artigo em Inglês | MEDLINE | ID: mdl-29894174


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.

Poluentes Atmosféricos , Corrida , Biocombustíveis , Veículos Automotores , Gás Natural , Emissões de Veículos
Environ Sci Technol ; 48(11): 6168-76, 2014 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-24810838


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.

Poluentes Atmosféricos/química , Terpenos/química , Aerossóis/análise , Aerossóis/química , Poluentes Atmosféricos/análise , Gases/química , Oxirredução , Processos Fotoquímicos , Terpenos/análise , Volatilização
Environ Sci Technol ; 47(2): 773-80, 2013 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-23163334


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.

Gasolina/análise , Nanopartículas/análise , Material Particulado/análise , Navios/instrumentação , Emissões de Veículos/análise , Óxido Nítrico/química , Tamanho da Partícula , Enxofre/análise , Dióxido de Enxofre/química , Ureia/química , Volatilização
Environ Sci Technol ; 46(21): 11660-9, 2012 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-22985264


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.

Butanóis/química , Cicloexenos/química , Radical Hidroxila/química , Oxidantes/química , Ozônio/química , Terpenos/química , Aerossóis , Simulação por Computador , Limoneno , Modelos Químicos , Temperatura , Volatilização , Água/química