Primary Organic Aerosols

Seasonal characteristics of organic aerosol chemical composition and volatility in Stuttgart, Germany

Abstract: . The chemical composition and volatility of organic aerosol (OA) particles were investigated during July–August 2017 and February–March 2018 in the city of Stuttgart, one of the most polluted cities in Germany. Total non-refractory particle mass was measured with a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS; hereafter AMS). Aerosol particles were collected on filters and analyzed in the laboratory with a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-HR-ToF-CIMS; hereafter CIMS), yielding the molecular composition of oxygenated OA (OOA) compounds. While the average organic mass loadings are lower in the summer period ( 5.1±3.2 µ g m −3 ) than in the winter period ( 8.4±5.6 µ g m −3 ), we find relatively larger mass contributions of organics measured by AMS in summer ( 68.8±13.4 %) compared to winter ( 34.8±9.5 %). CIMS mass spectra show OOA compounds in summer have O : C of 0.82±0.02 and are more influenced by biogenic emissions, while OOA compounds in winter have O : C of 0.89±0.06 and are more influenced by biomass burning emissions. Volatility parametrization analysis shows that OOA in winter is less volatile with higher contributions of low-volatility organic compounds (LVOCs) and extremely low-volatility organic compounds (ELVOCs). We partially explain this by the higher contributions of compounds with shorter carbon chain lengths and a higher number of oxygen atoms, i.e., higher O : C in winter. Organic compounds desorbing from the particles deposited on the filter samples also exhibit a shift of signal to higher desorption temperatures (i.e., lower apparent volatility) in winter. This is consistent with the relatively higher O : C in winter but may also be related to higher particle viscosity due to the higher contributions of larger-molecular-weight LVOCs and ELVOCs, interactions between different species and/or particles (particle matrix), and/or thermal decomposition of larger molecules. The results suggest that whereas lower temperature in winter may lead to increased partitioning of semi-volatile organic compounds (SVOCs) into the particle phase, this does not result in a higher overall volatility of OOA in winter and that the difference in sources and/or chemistry between the seasons plays a more important role. Our study provides insights into the seasonal variation of the molecular composition and volatility of ambient OA particles and into their potential sources.

Microscopic morphology and elemental composition of atmospheric particles from seven micro-environments in Xi’an:

Abstract: This paper characterizes the morphological and elemental compositions of individual particles in seven micro-environments of Xi’an. Atmospheric particulate matter samples were collected at one subu...

Multi-year analysis of aerosol optical properties at various timescales using AERONET data in tropical West Africa

Abstract: The optical properties of aerosols are investigated using multi-year analysis from the Ilorin AERONET site (8.320° N, 4.340° E) in Nigeria, in tropical West Africa. Characterization at five wavelengths (440, 550, 675, 870 and 1020 nm) were carried out to investigate the absorption and scattering tendencies of aerosol properties at multi-timescale. Results show large aerosol optical thickness (AOT) at 550 nm in a mixed aerosol load with 74% coarse mode dominance and 24% fine mode particles densely distributed in the dry-cold/Harmattan season (DJF) and sparsely distributed in the wet season (June–Oct). The volume size distribution (VSD) pattern shows higher variations and dominance for the coarse mode in the dry season than for the accumulation mode. The Angstrom exponent (AE) α and τ 550 show regular variations, with seasonal averaged maximum α > 1 and τ 550 peak at ~ 1.0. Values of α > 1 were observed in wet seasons; ~1.1 (Aug), 1.04 (Sep). Averaged single scattering albedo (SSA) is confined to values between 0.83 and 0.97, with the highest values in October and lowest values in DJF due to biomass burning (BB) emissions mixed with transported desert dust that are composed of iron oxides (hematite) absorbing mineral. Seasonal ϖ 0 increases with increasing wavelength and absorption was found to be the highest at 440 nm, with a total absorption of 0.16. The asymmetry parameter g shows minor interannual variations. The highest value of >0.70 was found at the shortest wavelength (440 nm), and was found to decrease as wavelengths increased. The real part of the refractive index (RR) ranges between 1.17 and 1.44 depending on seasons, and the imaginary part of the refractive index (RI) shows higher absorption for dry season (0.009).

Organic aerosol and global climate modelling: a review

Abstract: The present paper reviews existing knowledge with regard to Organic Aerosol (OA) of importance for global climate modelling and defines critical gaps needed to reduce the involved uncertainties. All pieces required for the representation of OA in a global climate model are sketched out with special attention to Secondary Organic Aerosol (SOA): The emission estimates of primary carbonaceous particles and SOA precursor gases are summarized. The up-to-date understanding of the chemical formation and transformation of condensable organic material is outlined. Knowledge on the hygroscopicity of OA and measurements of optical properties of the organic aerosol constituents are summarized. The mechanisms of interactions of OA with clouds and dry and wet removal processes parameterisations in global models are outlined. This information is synthesized to provide a continuous analysis of the flow from the emitted material to the atmosphere up to the point of the climate impact of the produced organic aerosol. The sources of uncertainties at each step of this process are highlighted as areas that require further studies.

A technology-based global inventory of black and organic carbon emissions from combustion

Abstract: [1] We present a global tabulation of black carbon (BC) and primary organic carbon (OC) particles emitted from combustion. We include emissions from fossil fuels, biofuels, open biomass burning, and burning of urban waste. Previous ‘‘bottom-up’’ inventories of black and organic carbon have assigned emission factors on the basis of fuel type and economic sector alone. Because emission rates are highly dependent on combustion practice, we consider combinations of fuel, combustion type, and emission controls and their prevalence on a regional basis. Central estimates of global annual emissions are 8.0 Tg for black carbon and 33.9 Tg for organic carbon. These estimates are lower than previously published estimates by 25–35%. The present inventory is based on 1996 fuel-use data, updating previous estimates that have relied on consumption data from 1984. An offset between decreased emission factors and increased energy use since the base year of the previous inventory prevents the difference between this work and previous inventories from being greater. The contributions of fossil fuel, biofuel, and open burning are estimated as 38%, 20%, and 42%, respectively, for BC, and 7%, 19%, and 74%, respectively, for OC. We present a bottom-up estimate of uncertainties in source strength by combining uncertainties in particulate matter emission factors, emission characterization, and fuel use. The total uncertainties are about a factor of 2, with uncertainty ranges of 4.3–22 Tg/yr for BC and 17–77 Tg/yr for OC. Low-technology combustion contributes greatly to both the emissions and the uncertainties. Advances in emission characterization for small residential, industrial, and mobile sources and topdown analysis combining field measurements and transport modeling with iterative inventory development will be required to reduce the uncertainties further. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0360 Atmospheric Composition and Structure: Transmission and scattering of radiation; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; KEYWORDS: emission, black carbon, organic carbon, fossil fuel, biofuel, biomass burning

Elemental Carbon-Based Method for Monitoring Occupational Exposures to Particulate Diesel Exhaust

Abstract: Diesel exhaust has been classified a probable human carcinogen, and the National Institute for Occupational Safety and Health (NIOSH) has recommended that employers reduce workers' exposures. Because diesel exhaust is a chemically complex mixture containing thousands of compounds, some measure of exposure must be selected. Previously used methods involving gravimetry or analysis of the soluble organic fraction of diesel soot lack adequate sensitivity and selectivity for low-level determination of particulate diesel exhaust; a new analytical approach was therefore needed. In this paper, results of investigation of a thermal-optical technique for analysis of the carbonaceous fraction of particulate diesel exhaust are reported. With this technique, speciation of organic and elemental carbon is accomplished through temperature and atmosphere control, and by an optical feature that corrects for pyrolytically generated carbon, or “char,” which is formed during the analysis of some materials. The therma...

Atmospheric aerosols: Biogeochemical sources and role in atmospheric chemistry

Abstract: Atmospheric aerosols play important roles in climate and atmospheric chemistry: They scatter sunlight, provide condensation nuclei for cloud droplets, and participate in heterogeneous chemical reactions. Two important aerosol species, sulfate and organic particles, have large natural biogenic sources that depend in a highly complex fashion on environmental and ecological parameters and therefore are prone to influence by global change. Reactions in and on sea-salt aerosol particles may have a strong influence on oxidation processes in the marine boundary layer through the production of halogen radicals, and reactions on mineral aerosols may significantly affect the cycles of nitrogen, sulfur, and atmospheric oxidants.

Rethinking Organic Aerosols: Semivolatile Emissions and Photochemical Aging

Abstract: Most primary organic-particulate emissions are semivolatile; thus, they partially evaporate with atmospheric dilution, creating substantial amounts of low-volatility gas-phase material. Laboratory experiments show that photo-oxidation of diesel emissions rapidly generates organic aerosol, greatly exceeding the contribution from known secondary organic-aerosol precursors. We attribute this unexplained secondary organic-aerosol production to the oxidation of low-volatility gas-phase species. Accounting for partitioning and photochemical processing of primary emissions creates a more regionally distributed aerosol and brings model predictions into better agreement with observations. Controlling organic particulate-matter concentrations will require substantial changes in the approaches that are currently used to measure and regulate emissions.