Elsevier

Atmospheric Environment

Volume 198, 1 February 2019, Pages 142-157
Atmospheric Environment

Organic markers and OC source apportionment for seasonal variations of PM2.5 at 5 rural sites in France

https://doi.org/10.1016/j.atmosenv.2018.10.027Get rights and content

Highlights

  • Annual chemical composition and seasonal variability of rural PM2.5.

  • Synchronous variability of primary and secondary organic compounds.

  • OC source apportionment using primary molecular markers.

  • 30% of the total OC attributed to the fungal spore during harvesting periods.

  • PSCF analysis highlighted a potential terrestrial additional source of MSA in continental sites.

Abstract

The chemical characterization of PM2.5 was conducted at 5 rural background sites in France for the year 2013. Chemical analysis of daily samples every sixth day included the measurements of organic carbon (OC), elemental carbon (EC), ionic species and several specific primary and secondary organic tracers such as levoglucosan, polyols, methane sulfonic acid (MSA) and oxalate. The sampling sites were spatially distributed in order to be representative of the French atmospheric background. The results showed well identified temporal variations common to all the 5 sampling sites, covering a large fraction of France. During winter, concentrations of the biomass burning marker levoglucosan are significantly increased with high synchronous temporal pattern, indicating the strong impact of this source at a regional scale. During summer, concentrations of primary biogenic markers such as polyols (arabitol, mannitol) increase due to higher biological activities while oxalate contributions to OC also increases, attributed to ageing processes. The sources of primary organic aerosol are investigated using mono-tracer approaches based on these compounds. Results indicate that the relative contributions of wood burning to OC are very high, reaching an average value of 90% during winter for some of the rural sites. Terrestrial primary biogenic organic fraction is significant in summer and fall with a monthly contribution ranging from 4.5 to 9.5% of OC in PM2.5. A synchronous increase is also observed for secondary organic tracers (MSA, oxalic acid) during warm period confirming the influence on the large scale of these compounds that can account for 10–20% and 5–7% of the OC mass, respectively.

Introduction

Chemical composition of European PM continental rural background aerosol has been widely studied these last decades (Alastuey et al., 2016; Putaud et al., 2010, 2004). It contains a large fraction of organic matter (OM) accounting at least for 15–20% for the European rural PM2.5. However, the chemical composition and properties of this OM are still largely unidentified (Hamilton et al., 2005; Putaud et al., 2010), while knowing the sources and the atmospheric processes involved in the formation of this fraction represents a large challenge for the determination of the climatic and health effects on regional and local air quality (Nozière et al., 2015).

Specific chemical markers have been widely used to study the importance of various sources (Bauer et al., 2008b, 2008b; Burshtein et al., 2011; Heo et al., 2013; Medeiros et al., 2006; Womiloju et al., 2003). For instance, levoglucosan is known as a good molecular marker of biomass burning in literature (Fine et al., 2001, 2004; Simoneit et al., 2004; Simoneit, 2002; Nolte et al., 2001) and his concentration served to estimate the biomass burning contribution to OC to atmospheric aerosols in European sites (Bond et al., 2004; Herich et al., 2014; Puxbaum et al., 2007). This leads to the information that biomass burning constitutes an important source of PM2.5 in winter season, amounting up to 18–68% at rural background sites in Europe.

While considerable effort has been undertaken to apportion OM associated with anthropogenic sources, primary and secondary biogenic sources which account for a significant fraction of organic aerosols on a global budget are not well known (Glasius et al., 2018; Liang et al., 2017; Tsigaridis and Kanakidou, 2003). The chemical composition at the molecular level stays in discussion with a wide range of characterization methods (Després et al., 2012; Fröhlich-Nowoisky et al., 2016), particularly when it comes to the emission processes of the fraction from biogenic origin (Wéry et al., 2017). Recently, several major classes of organic compounds such as sugars (e.g. glucose, threalose, sucrose), sugars alcohols (e.g. arabitol, mannitol, methylthreitols), organic acids (e.g. n-alkanoic acids) persistently emitted from either primary or secondary biogenic emissions (e.g. soils and associated microbiota, bioaerosols, green algae, or plants) have been widely proposed and used as specific molecular markers for biogenic sources (Caseiro et al., 2007; Fu et al., 2013; Jia et al., 2010b; Pietrogrande et al., 2014; Steinbrecher et al., 2009; Verma et al., 2018; Yttri et al., 2007b, 2007a). For instance, among sugar alcohols (also called as polyols), arabitol and mannitol are particularly widespread in nature and serve as the main energy storage materials in fungi, or as intracellular osmo-regulatory solutes in different microorganisms (Caseiro et al., 2007; Elbert et al., 2007; Liang et al., 2013; Medeiros et al., 2006; Simoneit et al., 2004; Zhang et al., 2010). Their occurrence in PM from different environmental backgrounds (rural, urban, marine, polar) around the world have therefore been used to apportion sources and fungal contribution to OM mass (Fu et al., 2013; Graham et al., 2003; Jia et al., 2010b, 2010a; Liang et al., 2016; Verma et al., 2018; Yttri et al., 2007b; Zhu et al., 2015). However, although the atmospheric concentrations of polyols and co-emitted chemicals have been measured in many parts of the world, quantitative data characterizing simultaneously their abundance and spatial and annual variations in various rural background sites are limited. Yet, such spatial and annual time-series data are necessary to understand the main drivers of the emission processes, still unknown.

In this paper, we present the detailed chemical composition of atmospheric PM2.5 collected at 5 French rural background sites during the year 2013. This study mainly focuses both on the primary organic tracers of anthropogenic and biogenic sources such as levoglucosan and polyols respectively, and on secondary organic tracers such as oxalate and methane sulfonic acid (MSA). The aims are to determine the concentration levels and the annual cycles of these specific organic tracers in order to better assess the contributions of these emission sources. Due to the various rural background typologies of our 5 sites, this study could provide good indications of the OC sources for a large part of the Western European rural background.

Section snippets

Site description and sampling period

PM2.5 aerosol samples were collected simultaneously at 5 rural sites in France during the whole year 2013. The sampling sites were selected in a way to cover an important part of the French national territory. Since they are far enough from any local anthropogenic sources, they are regional representative of the French rural atmospheric background and are also most probably comparable to many other sites of western European rural regions. The sites are located in the North-Eastern (Revin and

PM2.5 mass concentrations

Since TEOM data sets were not complete nor available for all sites over the full year 2013, PM2.5 mass concentrations were calculated based on the reconstructed chemical composition. It is performed with the following equation:[PM2.5]calc=[OM]+[EC]+[nssSO42]+[NO3]+[NH4+]+[seasalt]+[dust]

Sea salt sulfate [ss-SO42-] is calculated by multiplying the mass concentration of sodium by a factor of 0.251 (Seinfeld and Pandis, 2006). The non-sea salt sulfate [nss-SO42-] could then be calculated by

Conclusion

During this study conducted over one year from January to December 2013 at 5 rural background sites in France, we measured a large set of specific organic markers such as sugars, sugar-alcohols and organic acids. These measurements indicate:

  • The concentrations measured for chemical components during this study are within the range of reported values for studies conducted in the European region, highlighting similarities at the continental scale.

  • Similar time series and annual cycles were observed

Acknowledgements

All of the authors would like to thank the staff from the 5 stations for their dedication to maintain the samplings with a very high degree of completion during this one year 2013, and IT Lille Douai as coordinator of the MERA program. Authors thank S. Sauvage (IT Lille Douai) for his helpful comments on the manuscript.

This work was supported by the French Ministry of Environment and the national reference laboratory for air quality monitoring (LCSQA). The work at ANDRA-OPE is funded by ANDRA

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    Now at IMT Lille Douai, Univ. Lille, SAGE - Département Sciences de l'Atmosphère et Génie de l'Environnement, 59 000 Lille, France.

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