Elsevier

Science of The Total Environment

Volume 658, 25 March 2019, Pages 1423-1439
Science of The Total Environment

Characterization of the water soluble fraction in ultrafine, fine, and coarse atmospheric aerosol

https://doi.org/10.1016/j.scitotenv.2018.12.298Get rights and content

Highlights

  • Determination of 94 water soluble compounds in ultrafine, fine and coarse aerosol

  • Particle size distribution of l- and d-amino acids in urban aerosol

  • Factor analysis identified different sources for free amino acids and sugars.

  • Six different sources were identified with positive matrix factorization.

  • Each identified source had a specific particle size distribution.

Abstract

Water soluble organic carbon significantly contributes to aerosol's carbon mass and its chemical composition is poorly characterized due to the huge number of species. In this study, we determined 94 water-soluble compounds: inorganic ions (Cl, Br, I, NO3, SO42−,K+, Mg+, Na+, NH4+, Ca2+), organic acids (methanesulfonic acid and C2-C7 carboxylic acids), monosaccharides, alcohol-sugars, levoglucosan and its isomers, sucrose, phenolic compounds, free l- and d-amino acids and photo-oxidation products of α-pinene (cis-pinonic acid and pinic acid). The sampling was conducted using a micro-orifice uniform deposit impactor (MOUDI) at the urban area of Mestre-Venice from March to May 2016. The main aim of this work is to identify the source of each detected compound, evaluating its particle size distribution. Clear differences in size distributions were observed for each class of analyzed compounds.

The positive matrix factorization (PMF) model was used to identify six factors related to different sources: a) primary biogenic aerosol particles with particle size > 10 μm; b) secondary sulfate contribution; c) biomass burning; d) primary biogenic aerosol particles distributed between 10 and 1 μm; e) an aged sea salt input and f) SOA pinene. Each factor was also characterized by different composition in waters soluble compounds and different particles size distribution.

Introduction

Particulate matter can influence chemical and radiative properties of the atmosphere. These particles can transport material through the atmosphere, and they can act as cloud condensation nuclei (CCN), affecting the optical proprieties of the atmosphere (Seinfeld and Pandis, 2006).

Natural and anthropogenic sources can contribute to the principal dimensional classes (coarse, fine and ultrafine) of atmospheric particulate matter. Globally, about 10–20% of the aerosol are emitted by anthropogenic sources, but local scenarios and human activities can increase drastically the anthropogenic contribution (Seinfeld and Pandis, 2006). In urban areas, coarse particles are mainly produced by soil/crustal resuspension (rural activities, mining activities, biological sources) or industrial activities (i.e. cement factory, construction or demolitions) while fine particles are principally emitted by road traffic, firewood, domestic and residential emissions (Almeida et al., 2005). Fine particles are also formed from the photo-oxidation of volatile organic compounds (VOCs) in urban atmosphere (Zhang et al., 2003). Primary aerosol is defined as the particles directly emitted by natural or anthropogenic sources, while secondary aerosol results by processes such as gas-to-particles conversion or photochemical transformations.

The characterization of the chemical composition and particle size distribution of urban aerosol particles can help to identify sources and their impact on the climatic system (Sun and Ariya, 2006) and on human health (Harrison and Yin, 2000). The investigations on aerosol chemistry were mainly focused on the inorganic ions (Dordević et al., 2012; Fuzzi et al., 2007; Putaud et al., 2004; Stortini et al., 2009) and on the estimation of the total contribution of water soluble organic carbon (WSOC) (Cavalli et al., 2004; Fuzzi et al., 2007; Graham et al., 2002; Matta et al., 2003; Timonen et al., 2008; Yang et al., 2004, Yang et al., 2005 and others). WSOC fraction has received considerable attention in recent years, because several compounds can act as CCN (Huff Hartz et al., 2006; Rosenørn et al., 2006), with a consequent important role in the atmospheric processes. Nowadays, the molecular composition of WSOC is currently poorly understood due to the large number of compounds involved and the difficulties encountered during their individual identification. WSOC, based on their solubility, condensability and atmospheric occurrence, can be distinguished in mono- and di-carboxylic acids, carbonyls, polyols, polyglycols, keto-carboxylic acids, ethers, organic nitrates and nitro compounds, aliphatic amines and amino acids, and miscellaneous multifunctional compounds (Saxena and Hildemann, 1996). Carboxylic acids are the most often investigated (Kawamura and Sakaguchi, 1999; Miyazaki et al., 2011; Mochida et al., 2007; Wang et al., 2006, Wang et al., 2007), but some studies were also performed on other WSOC, such as sugars (Medeiros et al., 2006; Scaramboni et al., 2015; Yttri et al., 2011, Yttri et al., 2007) or amino acids (Matos et al., 2016 and its references). The characterization of water-soluble compounds in the ultrafine aerosol fraction is still poorly investigated.

This paper presents a chemical characterization of several water-soluble compounds and their particle size distributions in coarse, fine and ultrafine fractions of aerosol collected at theurban area of Mestre-Venice during spring 2016. The main aim is to improve the characterization of urban aerosol, including some class of compounds (i.e. amino acids, sugars, phenolic compounds, photo-oxidation products of α-pinene) rarely investigated yet. The investigation of sources and its particle size distribution was carried out for each detected compound. Fourteen aerosol samples were collected in spring in order to define the average particle size distribution of each compound restraining particular events. The gravimetric mass was evaluated to estimate the real contribution of water-soluble compounds to the total aerosol mass. Each sample was extracted with ultrapure water to determine 94 water-soluble compounds including ten inorganic ions (Cl, Br, I, NO3, SO42−,K+, Mg+, Na+, NH4+, Ca2+), twelve organic acids (methanesulfonic acid and C2-C7 carboxylic acids), seven monosaccharides (arabinose, fructose, galactose, glucose, mannose, ribose, xylose), eight alcohol-sugars (arabitol, erythritol, mannitol, ribitol, sorbitol, xylitol, galactitol, maltitol), three anhydrosugars (levoglucosan, mannosan and galactosan), sucrose, eleven phenolic compounds, forty free l- and d-amino acids and two photo-oxidation products of α-pinene (cis-pinonic acid and pinic acid). The innovation of this work is the simultaneous determination of several compounds, included species poorly investigated (i.e. amino acids), in ultrafine(<0.1 μm), fine (<1 μm) and coarse aerosol (>1 μm) particles to supply a detailed description of sources and processes in the atmosphere. This is the first study about the particle size distribution of amino acids in the ultrafine, fine and coarse fraction in the urban aerosol.

Positive matrix factorization (PMF) was performed to 1) identify the sources and to define 2) which water-soluble compounds characterized each identified source and 3) which size fraction of atmospheric particles was influenced by each source.

Section snippets

Aerosol sampling

Aerosol sampling was carried out at Scientific Campus of Ca’ Foscari University (45°28′47″N, 12°15′12″E, Mestre-Venice, Italy) from March to May 2016, using the rotating model 120 MOUDI-II™ cascade impactor. The sampler allows to separate particles of different sizes (different aerodynamic diameters) in eleven stages with cut-off at 18 μm (S1), 10 μm (S2), 5.6 μm (S3), 3.2 μm (S4), 1.8 μm (S5), 1.0 μm (S6), 0.56 μm (S7), 0.32 μm (S8), 0.18 μm (S9), 0.10 μm (S10) and 0.056 μm (S11). A final

Comparison between total suspended particles and water soluble compounds

The aerosol mass concentrations of total suspended particles, by considering the sum of different aerosol fractions, ranged between 12 and 47 μg m−3 with a median value of 17 μg m−3. The values are consistent with the concentrations detected in a very close sampling site investigated by Toscano et al. (2011) and in many European cities (Heal et al., 2005; Hueglin et al., 2005; Jourdain and Legrand, 2001; Marcazzan et al., 2001; Pey et al., 2009; Vercauteren et al., 2011; Viana et al., 2015;

Conclusion

Size-segregated aerosol sampling was conducted in an urban area during spring 2016 to improve the knowledge of sources and particle size distributions of WSOC in the atmosphere. This is the first study where 94 water-soluble compounds were simultaneously investigated. The most abundant water-soluble compounds found in these samples were ionic species (91%), while sugars, amino acids, and phenolic compounds represented 2.4%, 0.42% and 0.01%, respectively. Considering the high concentrations of

Acknowledgments

The research was supported by the National Research Council of Italy (Consiglio Nazionale delle Ricerche, CNR). The authors also acknowledge Elga (High Wycombe, UK) for providing ultrapure water.

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