Elsevier

Atmospheric Environment

Volume 161, July 2017, Pages 144-154
Atmospheric Environment

Sources and atmospheric chemistry of oxy- and nitro-PAHs in the ambient air of Grenoble (France)

https://doi.org/10.1016/j.atmosenv.2017.04.042Get rights and content

Highlights

  • PACs measured over a year together with an extended aerosol chemical characterization.

  • Cold period was affected by primary emissions especially from residential heating.

  • The highest (2 + 3)-NFlt/1-NP ratio was surprisingly observed during the winter period.

  • Different secondary processes involved during the severe PM pollution events observed.

  • Marker of PAH oxidation identified based on field observations and literature data.

Abstract

Total individual concentrations (in both gaseous and particulate phases) of 80 polycyclic aromatic compounds (PACs) including 32 nitro-PAHs, 27 oxy-PAHs (polycyclic aromatic hydrocarbons) and 21 parent PAHs have been investigated over a year in the ambient air of Grenoble (France) together with an extended aerosol chemical characterization. The results indicated that their concentrations were strongly affected by primary emissions in cold period, especially from residential heating (i.e. biomass burning). Besides, secondary processes occurred in summer but also in cold period under specific conditions such as during long thermal inversion layer periods and severe PM pollution events. Different secondary processes were involved during both PM pollution events observed in March–April and in December 2013. During the first one, long range transport of air masses, nitrate chemistry and secondary nitro-PAH formation seemed linked. During the second one, the accumulation of primary pollutants over several consecutive days enhanced secondary chemical processes notably highlighted by the dramatic increase of oxy-PAH concentrations. The study of the time trends of ratios of individual nitro- or oxy-PAHs to parent PAHs, in combination with key primary or secondary aerosol species and literature data, allowed the identification of potential molecular markers of PAH oxidation. Finally, 6H-dibenzo[b,d]pyran-6-one, biphenyl-2,2’-dicarboxaldehyde and 3-nitrophenanthrene have been selected to be the best candidates as markers of PAH oxidation processes in ambient air.

Introduction

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental substances, mainly emitted by anthropogenic incomplete combustion processes (Keyte et al., 2013, Ravindra et al., 2008, Shen et al., 2013). PAHs are of major health concern, because of their carcinogenic, mutagenic and teratogenic properties (IARC, 2010, Kim et al., 2013).

In the atmosphere, PAH oxidation through homogeneous and heterogeneous reactions lead to the formation of oxy- and nitro-PAHs (Atkinson and Arey, 2007, Keyte et al., 2013). These latter species are also emitted concomitantly with PAHs during incomplete combustion processes (Chen et al., 2015, Karavalakis et al., 2010, Nalin et al., 2016). Oxy- and nitro-PAHs are potentially more mutagenic than PAHs (Durant et al., 1996, Jariyasopit et al., 2014a, Jariyasopit et al., 2014b, Pedersen et al., 2005, Rosenkranz and Mermelstein, 1985) and some of these substances are also suspected to be carcinogenic (IARC, 2012, IARC, 2013). The identification of the origins of oxy- and nitro-PAHs is challenging, due to the coexistence of their primary and/or secondary sources (Keyte et al., 2013). Several compounds have been identified as typical PAH oxidation by-products and may be used as indicators of such chemical processes. For instance, (E)-2-formylcinnamaldehyde and 6H-dibenzo[b,d]pyran-6-one are typical by-products of naphthalene and phenanthrene oxidation processes, respectively (Lee et al., 2012, Sasaki et al., 1997). Usually, molecular ratios between PAH derivatives and parent PAHs, or between well-known secondary and primary compounds are calculated in order to highlight the influence of primary or secondary oxy- and nitro-PAHs sources or to study the potential origin of these compounds. For instance, the concentration ratio of 2-nitrofluoranthene (2-NFlt, a secondary compound, Arey et al., 1986, Atkinson et al., 1990) to 1-nitropyrene (1-NP, a primary compound from diesel exhaust, Keyte et al., 2016) has been extensively used to assess the primary vs secondary sources of nitro-PAHs in ambient air (e.g. Albinet et al., 2007, Albinet et al., 2008a, Bamford and Baker, 2003, Bandowe et al., 2014, Ciccioli et al., 1996, Huang et al., 2014, Marino et al., 2000, Ringuet et al., 2012a, Ringuet et al., 2012b, Wang et al., 2014). Considering the same degradation rates for both compounds (Fan et al., 1996), a ratio of [2-NFlt]/[1-NP] higher than 5 indicates the predominance of secondary formation of nitro-PAHs while, a ratio lower than 5 highlights the strong influence of primary nitro-PAH emission sources. Quinones-to-parent PAH concentration ratios have also been investigated in order to evaluate the photochemical formation of oxy-PAHs during long range transport of air masses (Alam et al., 2013, Alam et al., 2014, Harrison et al., 2016).

The overall objective of this work was to identify specific oxy- and nitro-PAHs, based on ambient air field analysis combined with literature knowledge, that could further be used as molecular markers of PAH oxidation and of secondary organic aerosol (SOA) formation in typical urban environment. The individual annual concentration trends of these compounds, specifically for substances known to be primary emitted or, conversely, by-products of secondary processes, together with characteristic polycyclic aromatic compound (PAC: PAHs, nitro- and oxy-PAHs) diagnostic ratios has also been investigated to evaluate the primary vs secondary sources of oxy- and nitro-PAHs. This work is an additional analysis of the PAC data already reported in a previous paper (Tomaz et al., 2016).

Section snippets

Sampling site

The measurement site was located at the urban background sampling station of “Les Frênes”, (45° 09′ 41″ N, 5° 44′ 07″ E, 220 m above sea level) in Grenoble (France) (Fig. A1), considered as the most densely populated urban area of the French Alps. The city is surrounded by three mountainous areas. Earlier studies showed that residential heating, mainly biomass combustion, accounts for the main source of PM2.5 during winter (Favez et al., 2010, Favez et al., 2012). In addition to traffic and

Overview of PM chemical composition and pollution events

The year 2013 was affected by two severe national PM pollution events (PM10 concentrations > 50 μg m−3 for at least 3 consecutive days) occurring during the cold season (defined as the period from January 1st to April 10th and from the October 1st to December 31st, 2013). They were observed on all the northern part of France from 02/25/2013 to 04/08/2013, and from 12/09/2013 to 12/19/2013 (Fig. 1, A31 and A32).

The first PM pollution event could be divided into two parts (Fig. 1):

  • -

    February–March

Conclusion

Individual concentrations of about 60 oxy- and nitro-PAHs were measured over a year in Grenoble-Les Frênes, jointly with specific primary or secondary aerosol species. In cold period, oxy- and nitro-PAH concentrations were controlled by emissions from residential heating (e.g. biomass burning) together with secondary processes occurring under specific conditions such as pollutant accumulation or long range transport of air masses. The study of the time trends of the ratios of oxy- or nitro-PAHs

Acknowledgments

The authors wish to thank the French Ministry of Environment (MEEM) and the French Ministry of Research for their financial support. This work was done as part of the LCSQA activities (French reference laboratory for air quality monitoring). Authors thank Air Rhône-Alpes for PAC sampling, air quality and meteorological data, Nadine Guillaumet and Noémie Nuttens for PAH analysis, Nathalie Bocquet and Robin Aujay for sample preparation and Patrick Bodu for the graphical abstract design.

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