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By quantifying the absorption of black carbon (BC), brown carbon (BrC) and the lensing effect, we found that BrC dominates the total absorption at 450 nm, and the largest absorption contribution proportion of BrC could reach 78.3% during heavy pollution. The average absorption enhancement (Eabs) at 530 nm was only 1.38, indicating that BC is not coated well here. The average value of the absorption Ångstrom exponent (AAE) between 450 nm and 530 nm was 5.3, suggesting a high concentration of BrC in Wangdu. CHN+ was the greatest contributor to the light absorption of molecules detected in MSOC with a proportion of 12.2–22.4%, in which the polycyclic aromatic nitrogen heterocycles (PANHs) were the dominant compounds. The C6H5NO3 and its homologous series accounted for 3.0–11.3%, and the C15H9N and its homologous series, including one C16H11N and three C17H13N compounds, accounted for 5.1–12.3%. The absorption of these PANHs is comparable to that of nitro–aromatics, which should attract more attention to the impact of climate radiative forcing. [ABSTRACT FROM AUTHOR]

Brown carbon is a type of strong light-absorbing carbonaceous aerosol associated with radiative forcing. Nevertheless, the difficulty in correlating the chemical composition of brown carbon with its light absorption properties impairs the proper elucidation of its role in radiative forcing. Here, we have used a time-dependent density functional theory (TD-DFT)-based procedure to revisit the "real-world" absorption spectra of polycyclic aromatic hydrocarbons (PAHs) over the city of Porto, in Portugal, while correcting the spectra for their quantity in PM10 particulate matter. Our aim is to, by comparing these new results with those obtained previously regarding PM2.5 data, evaluate the role of different groupings of particulate matter in the light absorption of brown carbon. The results indicate that irrespective of the absorption spectra corresponding to their PM10 or PM2.5 data, the studied PAHs should contribute to radiative forcing by light absorption at UVA and (sub)visible wavelengths. However, the identity of the individual PAH species that contribute the most for the considered wavelengths can be quite different. Thus, different groupings of particulate matter appear to provide distinct contributions to light absorption and radiative forcing over the same location, even when considering the same class of molecular compounds. [ABSTRACT FROM AUTHOR]

Brown carbon is a type of carbonaceous aerosol with strong light absorption in the ultraviolet and visible wavelengths that leads to radiative forcing. However, it is difficult to correlate the chemical composition of brown carbon with its atmospheric light absorption properties, which translates into significant uncertainty. Thus, a time-dependent density functional theory (TD-DFT) approach was used to model the real-world absorption properties of 14 polycyclic aromatic hydrocarbons (PAHs) over three regions of the Basque Country (Spain): Bilbao, Urretxu, and Azpeitia. The data were corrected for atmospheric concentration. The results show that the absorption spectra over each region are qualitatively identical, with the absorption intensities being significantly higher over Bilbao than over Azpeitia and Urretxu. Furthermore, it was found that the light absorption by PAHs should be more relevant for radiative forcing when it occurs at UVA and (sub)visible wavelengths. Finally, among the 14 studied PAHs, benzo[b]fluoranthene, pyrene, fluoranthene, benzo[a]pyrene, and benzo[k]fluoranthene and benzoperylene were identified as the molecules with larger contributions to radiative forcing. [ABSTRACT FROM AUTHOR]

The current understanding of water-soluble organic aerosol (OA) composition, sources, transformations, and effects is still limited to outdoor scenarios. However, the OA is also an important component of particulate matter indoors, whose complexity impairs a full structural and molecular identification. The current limited knowledge on indoor OA, and particularly on its water-soluble organic matter (WSOM) fraction is the basis of this feature paper. Inspired by studies on outdoor OA, this paper discusses and prioritizes issues related to indoor water-soluble OA and their effects on human health, providing a basis for future research in the field. The following three main topics are addressed: (1) what is known about the origin, mass contribution, and health effects of WSOM in outdoor air particles; (2) the current state-of-the-art on the WSOM in indoor air particles, the main challenges and opportunities for its chemical characterization and cytotoxicity evaluation; and (3) why the aerosol WSOM should be considered in future indoor air quality studies. While challenging, studies on the WSOM fraction in air particles are highly necessary to fully understand its origin, fate, toxicity, and long-term risks indoors. [ABSTRACT FROM AUTHOR]

Water-soluble organic aerosols (OA) are an important component of air particles and one of the key drivers that impact both climate and human health. Understanding the processes involving water-soluble OA depends on how well the chemical composition of this aerosol component is decoded. Yet, obtaining detailed information faces several challenges, including water-soluble OA collection, extraction, and chemical complexity. This review highlights the multidimensional non-targeted analytical strategies that have been developed and employed for providing new insights into the structural and molecular features of water-soluble organic components present in air particles. First, the most prominent high-resolution mass spectrometric methods for near real-time measurements of water-soluble OA and their limitations are discussed. Afterward, a special emphasis is given to the degree of compositional information provided by offline multidimensional analytical techniques, namely excitation–emission (EEM) fluorescence spectroscopy, high-resolution mass spectrometry and two-dimensional nuclear magnetic resonance (NMR) spectroscopy and their hyphenation with chromatographic systems. The major challenges ahead on the application of these multidimensional analytical strategies for OA research are also addressed so that they can be used advantageously in future studies. [ABSTRACT FROM AUTHOR]

Organic aerosols (OA) are universally regarded as an important component of the atmosphere that have far-ranging impacts on climate forcing and human health. Many of these impacts are related to OA molecular characteristics. Despite the acknowledged importance, current uncertainties related to the source apportionment of molecular properties and environmental impacts make it difficult to confidently predict the net impacts of OA. Here we evaluate the specific molecular compounds as well as bulk structural properties of total suspended particulates in ambient OA collected from key emission sources (marine, biomass burning, and urban) using ultrahigh resolution mass spectrometry (UHR-MS) and proton nuclear magnetic resonance spectroscopy (¹H NMR). UHR-MS and ¹H NMR show that OA within each source is structurally diverse, and the molecular characteristics are described in detail. Principal component analysis (PCA) revealed that (1) aromatic nitrogen species are distinguishing components for these biomass burning aerosols; (2) these urban aerosols are distinguished by having formulas with high O/C ratios and lesser aromatic and condensed aromatic formulas; and (3) these marine aerosols are distinguished by lipid-like compounds of likely marine biological origin. This study provides a unique qualitative approach for enhancing the chemical characterization of OA necessary for molecular source apportionment. [ABSTRACT FROM AUTHOR]

Atmospheric aerosol deposition (wet and dry) is an important source of macro and micronutrients (N, P, C, Si, and Fe) to the oceans. Most of the mass flux of air particles is made of fine mineral particles emitted from arid or semi-arid areas (e.g., deserts) and transported over long distances until deposition to the oceans. However, this atmospheric deposition is affected by anthropogenic activities, which heavily impacts the content and composition of aerosol constituents, contributing to the presence of potentially toxic elements (e.g., Cu). Under this scenario, the deposition of natural and anthropogenic aerosols will impact the biogeochemical cycles of nutrients and toxic elements in the ocean, also affecting (positively or negatively) primary productivity and, ultimately, the marine biota. Given the importance of atmospheric aerosol deposition to the oceans, this paper reviews the existing knowledge on the impacts of aerosol deposition on the biogeochemistry of the upper ocean, and the different responses of marine biota to natural and anthropogenic aerosol input. [ABSTRACT FROM AUTHOR]

The OH-initiated heterogeneous oxidation of semi-solid saccharide particles with varying bulk compositions was investigated in an atmospheric pressure flow tube at 30% relative humidity. Reactive uptake coefficients were determined from the rate loss of the saccharide reactants measured by mass spectrometry at different monosaccharide (methyl-β-d-glucopyranoside, C7H14O6) and disaccharide (lactose, C12H22O11) molar ratios. The reactive uptake for the monosaccharide was found to decrease from 0.53 ± 0.10 to 0.05 ± 0.06 as the mono-to-disaccharide molar ratio changed from 8:1 to 1:1. A reaction–diffusion model was developed in order to determine the effect of chemical composition on the reactive uptake. The observed decays can be reproduced using a Vignes relationship to predict the composition dependence of the reactant diffusion coefficients. The experimental data and model results suggest that the addition of the disaccharide significantly increases the particle viscosity leading to slower mass transport phenomena from the bulk to the particle surface and to a decreased reactivity. These findings illustrate the impact of bulk composition on reactant bulk diffusivity which determines the rate-limiting step during the chemical transformation of semi-solid particles in the atmosphere. [ABSTRACT FROM AUTHOR]

The main emission source in Central and Southern Chilean cities is biomass combustion from residential heating and cooking due to old combustion technologies that are still widely utilized. In order to improve our understanding of biomass burning pollution and how it ages in the atmosphere, emissions from a pellet and wood stoves were studied with the aid of a photochemical chamber. Firewood combustion is an inefficient process that produces higher chamber loading of primary emission (gases and particles) compared to pellets. When these emissions are exposed to UV irradiation secondary particles are formed. However, with both fuels the secondary particle concentration was negligible with regards to the primary initial particle concentration. Observations show that when the initial mass is the same, firewood combustion emissions are more rapidly oxidized compared to emissions from pellet combustion. Particle aging evolution inside the chamber was evaluated using fragment tracer signals, via the mass fractions f44 vs f43 and f44 vs f60 triangles plots. For the same UV irradiation time, it was found that primary particles emitted form from firewood combustion show a slower aging rate compared to those emitted from pellet combustion, but this is due to high primary loading from wood combustion. Particle aging observed inside the chamber was similar to that found it in ambient urban air of Santiago de Chile in spring of 2011, indicating that chamber measurements can be a good indicator for some atmospheric processes. Levoglucosan, a well-known tracer for biomass combustion was also studied. It was found that wood stoves yielded higher levels than pellet stoves. This is due to the higher fuel combustion efficiency in pellet stoves, which yield low levoglucosan levels, making it difficult to use it for evaluation of the impact of pellet emissions on pollution. [ABSTRACT FROM AUTHOR]

Although atmospheric organic N compounds are considered to be important, especially in new particle formation and their contribution to brown carbon, these species are not that well understood. This can be partially attributed to their chemical complexity. Therefore, the aim of this study was to assess the characteristics of organic N compounds utilising comprehensive two-dimensional gas chromatography coupled with a time-of-flight mass spectrometer (GCxGC-TOFMS) in aerosol samples that were collected at a savanna-grassland background region and to determine the possible sources. 135 atmospheric organic N compounds were tentatively characterised and semi-quantified, which included amines, nitriles, amides, urea, pyridine derivatives, amino acids, nitro-and nitroso compounds, imines, cyanates and isocyanates, and azo compounds. Amines contributed to 51% of the semi-quantified concentrations, while nitriles, pyridine derivatives, and amides comprised 20%, 11%, and 8%, respectively, of the semi-quantified concentrations. Amines, nitriles, amides, and pyridine derivatives concentrations were higher during the dry season, which were attributed to meteorology and open biomass burning. Anthropogenic sources impacting air masses measured at Welgegund, as well as regional agricultural activities, were considered as the major sources of amines, while the regional influence of household combustion was most likely the main source of nitriles, amides, and pyridine derivatives. The other organic N species were most likely related to the influence of local and regional agricultural activities. [ABSTRACT FROM AUTHOR]