Atmospheric Environment 44 (2010) 1831e1846 Contents lists available at ScienceDirect Atmospheric Environment journal homepage: www.elsevier.com/locate/atmosenv Review Oxygenated polycyclic aromatic hydrocarbons in atmospheric particulate matter: Molecular characterization and occurrence Christophe Walgraeve a, Kristof Demeestere a, Jo Dewulf a, Ralf Zimmermann b,c, Herman Van Langenhove a,* a Research Group EnVOC, Department of Organic Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium b Lehrstuhl für Analytische Chemie, Abteilung für Analytische, Technische und Umweltchemie am Institut für Chemie, Universität Rostock, Dr.-Lorenz-Weg 1, D-18051 Rostock, Germany c Helmholtz-Zentrum München e Deutsches Forschungszentrum für Gesundheit und Umwelt, Institut für Ökologische Chemie, Ingolstädter Landstraße 1, D-85764 Oberschleißheim, Germany article info abstract Article history: Particulate matter (PM) has become a major research issue receiving increasing attention because of its Received 30 March 2009 significant negative impact on human health. There are main indicators that next to the morphological Received in revised form characteristics of the particle, also the chemical composition plays an important role in the adverse 28 November 2009 health effects of PM. In this context, the rather polar organic fraction of PM is expected to play a major Accepted 2 December 2009 role, and advanced analytical techniques are developed to improve the knowledge on the molecular composition of this fraction. One component class that deserves major attention consists of the Keywords: oxygenated polycyclic aromatic hydrocarbons (PAHs). Those compounds are considered to be among the Particulate matter Polycyclic aromatic hydrocarbons key compounds in PM toxicity. This paper presents a comprehensive review focusing on the analysis, fate fi fl Oxygenated and behavior of oxygenated PAHs in the atmosphere. The rst part of the paper brie y introduces (i) the Oxidized main sources and atmospheric pathways of oxygenated PAHs, (ii) available physicalechemical properties Oxygenated PAH and (iii) their health effects. The second and main part of this paper gives a thorough discussion on the Analysis entire analytical sequence necessary to identify and quantify oxygenated PAHs on atmospheric PM. Concentrations Special attention is given to critical parameters and innovations related to (i) sampling, (ii) sample preparation including both extraction and clean-up, and (iii) separation and detection. Third, the state- of-the-art knowledge about the atmospheric occurrence of oxygenated PAHs is discussed, including an extended overview of reported concentrations presented as a function of sampling season and geographical location. A clear seasonal effect is observed with the median of the oxygenated PAHs concentrations during winter being a factor of 3e4 higher than during summer. However, the oxygen- ated PAH/parent PAH ratio is about 20 times higher during summer, indicating the importance of photochemical activity in the atmosphere. Ó 2009 Elsevier Ltd. All rights reserved. 1. Introduction fine particles are responsible for visibility impairment (Cheung et al., 2005; Liu et al., 2008; Yang et al., 2007). Third, PM has In the last years, particulate matter (PM) has become worldwide a significant negative impact on human health (Billet et al., 2007; a major research issue receiving increasing attention because of Harri et al., 2005; Li et al., 2003a; Ma and Ma, 2002; Oliveira et al., several reasons. First, atmospheric PM affects climate processes, 2007; Schober et al., 2006; Vinitketkumnuen et al., 2002), as both directly by absorbing and scattering solar irradiation and highlighted by numerous recent epidemiologic studies (Nawrot indirectly by formation of cloud condensation nuclei (CCN) that et al., 2006; Nawrot and Nemery, 2007; Valavanidis et al., 2006a). may counterbalance global warming (Andreae et al., 2005; Bellouin Negative health effects include asthma, as well as increased respi- et al., 2005; Pio et al., 2007). Secondly, high mass concentrations of ratory and cardiovascular mortality and morbidity (Li et al., 2003b, 2004; Nemmar and Inuwa, 2008; Walker and Mouton, 2008). In Flanders, it has been estimated that out of the five healthy living months that each inhabitant losses because of environmental * Corresponding author. Tel.: þ32 9 264 59 53; fax: þ32 9 264 62 43. fi E-mail address: [email protected] (H. Van Langenhove). pollution 71% is attributed to the inhalation of PM10, i.e. ne URL: http://www.EnVOC.UGent.be particulate matter with an aerodynamic diameter of less than 1352-2310/$ e see front matter Ó 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.atmosenv.2009.12.004 1832 C. Walgraeve et al. / Atmospheric Environment 44 (2010) 1831e1846 10 mm(MIRA-T, 2004). The mechanisms through which PM toxicity 2008; Borras and Tortajada-Genaro, 2007; Ciganek et al., 2004; and genotoxicity proceed are still a matter of discussion. Goriaux et al., 2006; Ho and Yu, 2004; Lima et al., 2005; Marr et al., There are major indications that next to the morphological 2006; Naumova et al., 2002; Ravindra et al., 2006a,b; Ryno et al., characteristics of the particle, also the chemical composition plays 2006; Schauer et al., 2003; Turrio-Baldassarri et al., 2003; Valava- an important role in the adverse health effects of PM (Karthikeyan nidis et al., 2006a; Wauters et al., 2008; Wingfors et al., 2001; Yusa and Balasubramanian, 2006; Kennedy, 2007; Kubatova et al., 2004; et al., 2006). This is mainly because of the well-known carcinogenic Li et al., 2003a,b, 2004; Lintelmann et al., 2005; Ma and Ma, 2002). and mutagenic properties of this group of compounds. In addition PM is an extremely complex matrix containing a wide range of to chronic health effects, PAHs are also reported to be responsible chemical species, including inorganic acids and salts, metals, water, for acute health effects e.g. through oxidative stress caused by and a complex mixture of low volatility organic compounds, all in oxidized PAH metabolites (Marie et al., 2009). Both the occurrence highly variable concentrations (Caseiro et al., 2007; Cincinelli et al., and the analytical techniques used for PAHs determination have 2007; Dabek-Zlotorzynska and McGrath, 2000; Di Filippo et al., been reported recently (Chang et al., 2006; Crimmins and Baker, 2005; Huang et al., 2006; Liu et al., 2007; Ochsenkuhn and Och- 2006; Lima et al., 2005; Poster et al., 2006; Pozzoli et al., 2004; senkuhn-Petropoulou, 2008; Simoneit et al., 2007; Tang et al., Ravindra et al., 2008) and will therefore be no subject of this review 2006). Airborne chemical and biological substances can interact paper. with and adsorb on the particles during transport, deposition and In contrast, focus will be put on PAHs derivatives formed collection. Because of the expected high importance of the chem- through atmospheric reactions with oxidative species such as ical composition of PM on its environmental and human health ozone, hydroxyl and nitrate radicals as well as UV induced photo- effects, intensive research is going on to elucidate the molecular reactions (Vione et al., 2006). These PAHs oxidation products are composition of the PM species. However, because of the high typically found in the intermediate polarity PM fractions and complexity of the matrix and the often trace concentrations of include a wide range of compounds that can be classified in nitro- adsorbed micropollutants, this is a challenging task requiring PAHs and oxygenated PAHs. Since both the formation, occurrence, highly advanced sensitive and selective multi-step analytical and chemical analysis of nitro-PAHs is recently reported (Brichac methods and instruments (Chow et al., 2007; Hays and Lavrich, et al., 2004; Delhomme et al., 2007; Dimashki et al., 2000; Hattori 2007). et al., 2007; Ishii et al., 2000a; Kuo et al., 2003; Nicol et al., 2001b; The chemical characterization of transition metals and inorganic Perrini et al., 2005; Prycek et al., 2007; Sienra and Rosazza, 2006b; species present on PM has been intensively investigated already for Vincenti et al., 2001; Xu and Lee, 2001; Zielinska and Samy, 2006), years (Baez et al., 2007; Canepari et al., 2006; Chang et al., 2008; this subgroup is not further considered in this work. Fujimori et al., 2007; Garcia et al., 2008; Karageorgos and Rapso- This paper particularly deals with oxygenated PAHs. In agree- manikis, 2007; Karthikeyan and Balasubramanian, 2006; Kumar ment with Lundstedt et al. (2007), oxygenated PAHs are PAHs et al., 2006; Ochsenkuhn and Ochsenkuhn-Petropoulou, 2008; oxidation products that can be divided into two sub-groups: oxy- Ocskay et al., 2006; Pachon and Vela, 2008; Park et al., 2008; Per- PAHs and hydroxylated PAHs. Oxy-PAHs contain one or more rino et al., 2008; Shah and Shaheen, 2008; Valavanidis et al., 2006a; carbonylic oxygen(s) attached to the aromatic ring structure and Vasconcellos et al., 2007; Wojas and Almquist, 2007; Zhang et al., consist of ketones and quinones. Hydroxylated PAHs are defined as 2007). Excellent recent reviews are presented by Fang et al. (2005), PAHs on which one or more hydroxyl groups are attached. Nieuwenhuijsen et al. (2007) and Smichowski et al. (2008). Strong indications of the toxicological importance of oxygenated However, mainly because of the analytical complexity, the molec- PAHs (Dellinger et al., 2001; Ishii et al., 2000b; Li et al., 2003b; ular characterization of the