Elsevier

Atmospheric Environment

Volume 141, September 2016, Pages 263-275
Atmospheric Environment

Multi-year levels and trends of non-methane hydrocarbon concentrations observed in ambient air in France

https://doi.org/10.1016/j.atmosenv.2016.06.059Get rights and content

Highlights

  • Trends analysis for on decade of measurements of NMHCs in ambient air in France.

  • Significant downward trends for the majority of NMHCs species.

  • Significant downward trends for NMHCs emissions in France for the same period.

Abstract

Measurements of 31 non-methane hydrocarbons (NMHCs) were carried out at three urban (Paris, 2003–2014, Strasbourg, 2002–2014 and Lyon, 2007–2014) sites in France over the period of a decade. A trend analysis was applied by means of the Mann-Kendall non-parametric test to annual and seasonal mean concentrations in order to point out changes in specific emission sources and to assess the impact of emission controls and reduction strategies. The trends were compared to those from three rural sites (Peyrusse-Vieille, 2002–2013, Tardière, 2003–2013 and Donon, 1997–2007). The results obtained showed a significant yearly decrease in pollutant concentrations over the study period and for the majority of species in the range of −1 to −7% in accordance with the decrease of NMHC emissions in France (−5 to −9%). Concentrations of long-lived species such as ethane and propane which are recognized as tracers of distant sources and natural gas remained constant. Compounds associated with combustion processes such as acetylene, propene, ethylene and benzene showed a significant decline in the range of −2% to −5% yr−1. These trends are consistent with those recently described at urban and background sites in the northern mid-latitudes and with emission inventories. C7-C9 aromatics such as toluene and xylenes as well as C4-C5 alkanes such as isopentane and isobutane also showed a significant decrease in the range of −3% to −7% yr−1. The decreasing trends in terms of % yr−1 observed at these French urban sites were typically higher for acetylene, ethylene and benzene than those reported for French rural sites of the national observatory of Measurement and Evaluation in Rural areas of trans-boundary Air pollution (MERA). The study also highlighted the difficult choice of a long term sampling site representative of the general trends of pollutant concentrations.

Introduction

As they belong to Volatile Organic Compounds (VOCs), non-methane hydrocarbons (NMHCs) have been subject to controls since the mid-1970s due to their direct effect on human health as some of them contain carcinogenic compounds such as benzene and 1.3-butadiène (WHO, 2006) and their indirect effect on ozone production and secondary organic aerosol formation (Atkinson and Arey, 2003, Hallquist et al., 2009). NMHCs undergo photochemical reactions and could be oxidized forming secondary VOCs which can lead to the formation of many oxidants including ozone and can be partitioned between the gas and particle phase and condense onto preexisting particles forming secondary organic aerosols (Jimenez et al., 2009, Odum et al., 1996).

Urban NMHC sources are mainly anthropogenic in origin (Gaimoz et al., 2011, Borbon et al., 2002, Waked et al., 2012, Olivier et al., 1999). They include traffic emissions, solvent use, gasoline evaporation, gas leakage, residential central heating and many other sources. Therefore, monitoring and reducing NMHC levels have become of great importance.

as a result of their major anthropogenic origin. In both European and the US environmental policies, the reduction of gaseous pollutant emissions by the transport sector has been a main focus and included not only NMHCs but also carbon monoxide (CO) and nitrogen oxides (NOx). Stringent vehicle emission standards have led to the deployment of emission control technologies for tailpipes (e.g., catalytic converters in 1993) and gasoline reformulation (directive 98/70/EC for benzene). In Europe, emission standards were defined in a series of European Union directives staging the progressive introduction of increasingly stringent standards (namely Euro 1 to 6). Since then, additional directives related to the reduction of solvent emissions have been implemented (e.g. directive 99/13/EC). Furthermore, emission protocols were introduced within the UN-ECE under the Gothenberg protocol (ECE, 2013) to abate acidification, eutrophication and ground level ozone to the convention of long-range transboundary air pollution. For example from 2010 up to 2020, the emission ceiling for many pollutants including VOCs, were set for many European countries and also included limit values for specific emission sources. To enable the evaluation of the effects of these emission reduction strategies, directives and policies, rural/urban monitoring networks, including measurements of VOC’s species, have been in operation in Europe and the USA for the past few decades. Some of these monitoring networks are part of European monitoring programs such as EMEP (European Monitoring and Evaluation Program) for rural sites as a part of the program of the Long-Range Transmission of Air Pollutants in Europe while other networks refer to national programs such as the CARB network in California, USA and the Defra hydrocarbons monitoring network for the United Kingdom. For instance, results from a number of these monitoring sites in urban areas in Los Angeles (USA), London, Leeds, Liverpool and Birmingham (United Kingdom) (Warneke et al., 2012, von Schneidemesser et al., 2010, Derwent et al., 2014, Dollard et al., 2007) and in rural areas in Peyrusse-Veille, Tardière and Donon (France), Harwell (United Kingdom) and Pallas and Uto (Finland) (Sauvage et al., 2009, Dollard et al., 2007, Hakola et al., 2006) showed significantly decreasing trends in pollutants concentrations and indicate that emission reductions protocols and policies were effective to some extent.

Similar to other studies conducted in urban areas in Europe and the USA, multi-year trends for anthropogenic NMHCs are reported here for the first time for French urban atmospheres. It is based on almost a decade of hourly NMHC measurements in the cities of Paris, Strasbourg and on eight years of weekly measurements for Lyon. This study compares the trends in NMHC levels between urban and rural French atmospheres in order to examine the homogeneity of the trends for France and for other neighboring European countries. In addition, comparison of trends among ambient concentrations, emissions as well as hydrocarbon ratios (μg.m−3/μg.m−3) were used to evaluate the effect of the application of emission reduction strategies and policies on primary pollutants such as alkanes, aromatics and alkenes.

Section snippets

Experimental

A long-term monitoring program for NMHCs was launched in France in 2001 by ADEME (Agence de la Maîtrise de l’Energie et de l’Environnement) and the French Ministry of the Environment. As part of this program which included the implementation of several sites in France, one urban site of Les Halles in Paris (48°51′N, 2°20′E) and one urban/semi-urban site in Strasbourg, Eastern France (48°21′N, 7°25′E), operated by the local Air Quality Monitoring Network (AASQA), were implemented with an on-line

Annual average NMHC levels

Annual average concentrations of some measured NMHC species in the French urban and rural areas from 2003 to 2013 for Paris, 2002–2013 for Strasbourg, 2002–2013 for Peyrusse-Vieille, 2003–2013 for Tardière, 1997–2007 for Donon and 2007–2013 for Lyon are reported in Table 1. These species are recognized as tracers of specific sources/processes.

Similar levels were obtained for Paris, Strasbourg and Lyon (Table 1) for isoprene (a tracer of biogenic emissions), ethane (a tracer of long range

NMHC multi-year trends: french urban and rural atmospheres

Multi-year trend analyses for the measured concentrations in French urban and rural atmospheres are presented and compared to those obtained for the EMEP emissions inventories (EMEP, 2015). The results obtained for the trend analysis of the measured concentrations (Fig. 4) showed a significant decrease for major NMHC in French urban and rural sampling sites with an annual rate change T in the range of −1 to −7% in accordance with daily time series for many pollutants from 2003 to 2013 (Fig. 2)

NMHC multi-year trends: comparison between France, other European and non-European countries

Trends for annual mean concentrations at the urban site of Strasbourg which were comparable to that of Paris except for ethylene and trends for the rural site of Peyrusse-Vieille were compared to the ones recently reported for Los Angeles (USA) (Borbon et al., 2002, Warneke et al., 2012), Marylebone, London and Harwell (United Kingdom), Pallas (Finland) and Hohenpissenberg (Germany) for the last decade (von Schneidemesser et al., 2010, Dollard et al., 2007, Hakola et al., 2006). Strasbourg and

Conclusion

Almost a decade of continuous NMHC measurements at three urban (Paris, Strasbourg, Lyon) sites have been analyzed to evaluate the efficiency of emission control regulations on NMHCs in France. Except for ethane and propane, many NMHC concentrations have been decreasing over the last decade with a −1% to −7% change per year. The results obtained were in line with those reported for total VOC emissions in France from 2002 to 2012 ranging from −5 to −9% using the EMEP emission inventory. The

Acknowledgements:

The Department SAGE Mines Douai contributes to the Central Laboratory of Air Quality Survey (LCSQA), which is funded by the French Ministry in charge of the environment. The authors would like to gratefully thank the French networks AIRPARIF (Paris), ASPA (Strasbourg) and Air-RA (Lyon) for providing NMHC data from monitoring stations, the people from ORAMIP, AIR PAYS de LOIRE and ASPA which are involved in VOC measurements within the MERA/EMEP network and Margaret Dufay for language improvement

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