Volatile organic compounds (VOCs) have direct influences on air quality and climate. They indeed play a key role in atmospheric chemistry as precursors of secondary pollutants, such as ozone (O3) and secondary organic aerosols (SOA). In this respect, long-term datasets of in situ atmospheric measurements are crucial for characterizing the variability of atmospheric chemical composition, its sources, and trends. The ongoing establishment of the Aerosols, Cloud, and Trace gases Research InfraStructure (ACTRIS) allows implementation of the collection and provision of such high-quality datasets. In this context, online and continuous measurements of O3, nitrogen oxides (NOx), and aerosols have been carried out since 2012 at the SIRTA (Site Instrumental de Recherche par Télédétection Atmosphérique) observatory, located in the Paris region, France. Within the last decade, VOC measurements were conducted offline at SIRTA, until the implementation of real-time monitoring which started in January 2020 using a proton-transfer-reaction quadrupole mass spectrometer (PTR-Q-MS). The dataset acquired during the first 2 years of online VOC measurements provides insights into their seasonal and diurnal variabilities. The additional long-term datasets obtained from co-located measurements (NOx, aerosol physical and chemical properties, meteorological parameters) are used to better characterize the atmospheric conditions and to further interpret the obtained results. Results also include insights into VOC main sources and the influence of meteorological conditions and air mass origin on their levels in the Paris region. Due to the COVID-19 pandemic, the year 2020 notably saw a quasi-total lockdown in France in spring and a lighter one in autumn. Therefore, the focus is placed on the impact of these lockdowns on the VOC variability and sources. A change in the behaviour of VOC markers for anthropogenic sources was observed during the first lockdown, reflecting a change in human activities. A comparison with gas chromatography data from the Paris city centre consolidates the regional representativity of the SIRTA station for benzene, while differences are observed for shorter-lived compounds with a notable impact of their local sources. This dataset could be further used as input for atmospheric models and can be found at https://doi.org/10.14768/f8c46735-e6c3-45e2-8f6f-26c6d67c4723 (Simon et al., 2022a).
24 August 2021 in Atmospheric Chemistry and Physics
We analysed the biogenic volatile organic compound (BVOC) emissions from rapeseed leaf litter and their potential to create secondary organic aerosols (SOAs) under three different conditions, i.e., (i) in the presence of UV light irradiation, (ii) in the presence of ozone, and (iii) with both ozone and UV light. These experiments were performed in a controlled atmospheric simulation chamber containing leaf litter samples, where BVOC and aerosol number concentrations were measured for 6 d. Our results show that BVOC emission profiles were affected by UV light irradiation which increased the summed BVOC emissions compared to the experiment with solely O3. Furthermore, the diversity of emitted VOCs from the rapeseed litter also increased in the presence of UV light irradiation. SOA formation was observed when leaf litter was exposed to both UV light and O3, indicating a potential contribution to particle formation or growth at local scales. To our knowledge, this study investigates, for the first time, the effect of UV irradiation and O3 exposure on both VOC emissions and SOA formation for leaf litter samples. A detailed discussion about the processes behind the biological production of the most important VOC is proposed.
In this work, we report the gas phase UV absorption spectra and the kinetics of the OH-oxidation of 1H-1,2,3-triazole and pyrazole. UV spectra were determined between 200 and 250 nm, at 350 ± 2 K and at pressures between 0.09 and 0.3 Torr. The reported maximal UV absorption cross sections are (cm2 per molecule): σ206 nm, 1H–1H-1,2,3-triazole = 2.04 × 10−18 and σ203 nm, pyrazole = 5.44 × 10−18. The very low absorption capacity of these compounds beyond 240 nm indicates that their atmospheric photodissociation is negligible. The OH-oxidation of these species was performed in an atmospheric simulation chamber coupled to an FTIR spectrometer and to a GC/MS over the temperature range 298–357 K and at atmospheric pressure. Experiments were conducted in relative mode using benzaldehyde, trans-2-hexenal and heptane as references. The obtained rate constants at 298 K were (×10−11 cm3 per molecule per s): k(OH + 1H-1,2,3-triazole) = 2.16 ± 0.41; k(OH + pyrazole) = 2.94 ± 0.42. These results were compared to those available in the literature and discussed in terms of structure-reactivity and temperature dependency. Their tropospheric lifetimes with respect to reaction with OH radicals were then estimated.
27 November 2017 in International Journal of Chemical Kinetics