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Abstract: In this study, we apply several recently proposed models to the evolution of secondary organic aerosols (SOA) and organic gases advected from downtown Mexico City at: an altitude of similar to 3.5 km during three days of aging, in a way that is directly comparable to simulations in regional and global models. We constrain the model with and compare its results to available observations. The model SOA formed from oxidation of volatile organic compounds (V-SOA) when using a non-aging SOA parameterization cannot explain the observed SOA concentrations in aged pollution, despite the increasing importance of the low-NO, channel. However, when using an aging SOA parameterization, V-SOA alone is similar to the regional aircraft observations, highlighting the wide diversity in current V-SOA formulations. When the SOA formed from oxidation of semivolatile and intermediate volatility organic vapors (SI-SOA) is computed following Robinson et al. (2007) the model matches the observed SOA mass, but its 0/C is similar to 2 x too low. With the parameterization of Grieshop et al. (2009), the total SOA mass is similar to 2 x too high, but 0/C and volatility are closer to the observations. Heating or dilution cause the evaporation of a substantial fraction of the model SOA; this fraction is reduced by aging although differently for heating vs dilution. Lifting of the airmass to the free-troposphere during dry convection substantially increases SOA by condensation of semivolatile vapors; this effect is reduced by aging.
Keywords: Mexico-city, volatility, semivolatile, transport, campaign
Published in RUNG: 11.04.2021; Views: 1946; Downloads: 0
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Abstract: Peroxyacetyl nitrate (PAN) formed in the atmospheric oxidation of non-methane volatile organic compounds (NMVOCs) is the principal tropospheric reservoir for nitrogen oxide radicals (NOx = NO + NO2). PAN enables the transport and release of NOx to the remote troposphere with major implications for the global distributions of ozone and OH, the main tropospheric oxidants. Simulation of PAN is a challenge for global models because of the dependence of PAN on vertical transport as well as complex and uncertain NMVOC sources and chemistry. Here we use an improved representation of NMVOCs in a global 3-D chemical transport model (GEOS-Chem) and show that it can simulate PAN observations from aircraft campaigns worldwide. The immediate carbonyl precursors for PAN formation include acetaldehyde (44 % of the global source), methylglyoxal (30 %), acetone (7 %), and a suite of other isoprene and terpene oxidation products (19 %). A diversity of NMVOC emissions is responsible for PAN formation globally including isoprene (37 %) and alkanes (14 %). Anthropogenic sources are dominant in the extratropical Northern Hemisphere outside the growing season. Open fires appear to play little role except at high northern latitudes in spring, although results are very sensitive to plume chemistry and plume rise. Lightning NOx is the dominant contributor to the observed PAN maximum in the free troposphere over the South Atlantic.
Keywords: peroxyacetyl nitrate, non-methane volatile organic compounds, global 3-D chemical transport model, GEOS-chem
Published in RUNG: 11.04.2021; Views: 2327; Downloads: 0
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Abstract: The radiative properties of soot particles depend on their morphology and mixing state, but their evolution during transport is still elusive. Here we report observations from an electron microscopy analysis of individual particles transported in the free troposphere over long distances to the remote Pico Mountain Observatory in the Azores in the North Atlantic. Approximately 70% of the soot particles were highly compact and of those 26% were thinly coated. Discrete dipole approximation simulations indicate that this compaction results in an increase in soot single scattering albedo by a factor of <= 2.17. The top of the atmosphere direct radiative forcing is typically smaller for highly compact than mass-equivalent lacy soot. The forcing estimated using Mie theory is within 12% of the forcing estimated using the discrete dipole approximation for a high surface albedo, implying that Mie calculations may provide a reasonable approximation for compact soot above remote marine clouds.
Keywords: atmospheric aerosol, soot, long-range transport, free troposphere, single scattering albedo
Published in RUNG: 11.04.2021; Views: 2065; Downloads: 0
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Abstract: Aerosol properties are transformed by atmospheric processes during long-range transport and play a key role in the Earth’s radiative balance. To understand the molecular and physical characteristics of free tropospheric aerosol, we studied samples collected at the Pico Mountain Observatory in the North Atlantic. The observatory is located in the marine free troposphere at 2225m above sea level, on Pico Island in the Azores archipelago. The site is ideal for the study of long-range-transported free tropospheric aerosol with minimal local influence. Three aerosol samples with elevated organic carbon concentrations were selected for detailed analysis. FLEXPART retroplumes indicated that two of the samples were influenced by North American wildfire emissions transported in the free troposphere and one by North American outflow mainly transported within the marine boundary layer. Ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry was used to determine the detailed molecular composition of the samples. Thousands of molecular formulas were assigned to each of the individual samples. On average ~60% of the molecular formulas contained only carbon, hydrogen, and oxygen atoms (CHO), ~ 30% contained nitrogen (CHNO), and ~ 10% contained sulfur (CHOS). The molecular formula compositions of the two wildfire-influenced aerosol samples transported mainly in the free troposphere had relatively low average O=C ratios (0:48 ± 0:13 and 0:45 ± 0:11) despite the 7–10 days of transport time according to FLEXPART. In contrast, the molecular composition of the North American outflow transported mainly in the boundary layer had a higher average O=C ratio (0:57 ± 0:17) with 3 days of transport time. To better understand the difference between free tropospheric transport and boundary layer transport, the meteorological conditions along the FLEXPART simulated transport pathways were extracted from the Global Forecast System analysis for the model grids. We used the extracted meteorological conditions and the observed molecular chemistry to predict the relative-humidity-dependent glass transition temperatures (Tg) of the aerosol components. Comparisons of the Tg to the ambient temperature indicated that a majority of the organic aerosol components transported in the free troposphere were more viscous and therefore less susceptible to oxidation than the organic aerosol components transported in the boundary layer. Although the number of observations is limited, the results suggest that biomass burning organic aerosol injected into the free troposphere is more persistent than organic aerosol in the boundary layer having broader implications for aerosol aging.
Keywords: secondary organic aerosols, brown carbon, particle dispersion model, ultrahigh-resolution FT-ICR MS, Pico Mountain Observatory
Published in RUNG: 10.04.2021; Views: 2317; Downloads: 0
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Abstract: Polycyclic aromatic hydrocarbons (PAHs) are compounds known for their adverse effects on human health. Many of them are proven carcinogens, especially those with 5 and 6 aromatic rings, which under normal tropospheric conditions are found in the particle-phase. Benzo(a)pyrene (BaP) is often measured as their general representative. Sarajevo, the capital of Bosnia and Herzegovina, is among the European cities with the poorest air quality. However, in Sarajevo PAHs are neither routinely measured within the air quality monitoring network nor have been a subject of extended, continuous field studies during the most polluted cold periods of the year. The capital of Croatia, Zagreb, is located approximately 300 km air distance north-west from Sarajevo. PAH mass concentrations in Zagreb have been measured continuously since 1994 within air quality monitoring networks. During winter 2017/2018, the SAFICA project (Sarajevo Canton Winter Field Campaign 2018) was carried out in order to characterize the chemical composition of organic and inorganic aerosol in the Sarajevo Canton. This paper presents the results of PAH measurements in the cities of Sarajevo and Zagreb at one urban location per city. Daily (24 h), continuous samples of PM10 (particulate matter with aerodynamic diameters ≤10 μm) were collected during heating season, from December 27, 2017 to February 27, 2018. Mass concentrations of eleven particle-phase PAHs in Sarajevo and Zagreb from filter samples collected during the same period were compared. The average BaP ambient mass concentrations in Sarajevo and Zagreb were 6.93 ng m−3 and 3.11 ng m−3, respectively. The contribution of BaP to the total PAH mass concentration was similar at both locations (11%). However, much higher contributions of particle-phase fluoranthene and pyrene were found in Sarajevo. Contributions of individual PAH, diagnostic ratios and factor analysis indicate that combustion of gasoline and diesel from vehicle traffic are a potential source of PAHs at both locations, as well as combustion of other liquid fossil fuels (petroleum and fuel oil). Wood burning was occasionally indicated as a PAH emission source in Zagreb, while in Sarajevo the contribution of PAHs from wood and coal combustion was more evident. Calculated value for total carcinogenic potency (TCP) of PAHs, which was estimated using toxic equivalence factors from the literature, in PM10 samples collected in Sarajevo was more than twice higher than in Zagreb (10.6 ng m−3 and 4.7 ng m−3, respectively). BaP had the highest contribution to the TCP at both locations (69 and 67%).
Keywords: carcinogenic potency, diagnostic ratio, factor analysis, PM10, polycyclic aromatic hydrocarbons
Published in RUNG: 09.04.2021; Views: 2141; Downloads: 0
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