Eric Villenave

The hydration mechanism of 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a relevant marker of secondary organic aerosol formation from the atmospheric oxidation of α-pinene, has been investigated using the matrix-isolation infrared spectroscopy technique. The experimental results were supported by theoretical calculations. Monomers of MBTCA and heterocomplexes MBTCA-n(H₂O) were identified. The presence of intramolecularly H-bonded monomers was experimentally identified, in accordance with the calculations. Heterocomplexes, i.e., aggregates with water, were found much more stable than homocomplexes. The results clearly demonstrate the affinity of MBTCA carboxylic functions for water molecules, and thus its ability to form an H-bond network, leading to the solvation of the molecule. This is the first experimental observation, evidencing the primary hydration stages of one relevant marker of secondary organic aerosol formation and aging. Although fundamental, such a molecular study helps in a better understanding of critical steps in cloud condensation nuclei formation.

The massive use of pesticides in agriculture has led to widespread contamination of the environment, particularly the atmospheric compartment. Thirty-six pesticides, most used in viticulture, were monitored in ambient air using polyurethane foams as passive air samplers (PUF-PAS). Spatiotemporal data were collected from the samplers for 10 months (February–December 2013), using two different sampling times (1 and 2 months) at two different sites in a chateau vineyard in Gironde (France). A high-volume active air sampler was also deployed in June. Samples were extracted with dichloromethane using accelerated solvent extraction (ASE) (PUFs from both passive and active) or microwave-assisted extraction (MAE) (filters from active sampling). Extracts were analyzed by both gas and liquid chromatography coupled with tandem mass spectrometry. A total of 23 airborne pesticides were detected at least once. Concentrations in PUF exposed one month ranged from below the limits of quantification (LOQs) to 23,481 ng PUF⁻¹. The highest concentrations were for folpet, boscalid, chlorpyrifos-methyl, and metalaxyl-m—23,481, 17,615, 3931, and 3324 ng PUF⁻¹. Clear seasonal trends were observed for most of the pesticides detected, the highest levels (in the ng m⁻³ range or the µg PUF⁻¹ range) being measured during their application period. Impregnation levels at both sites were heterogeneous, but the same pesticides were involved. Sampling rates (Rs) were also estimated using a high-volume active air sampler and varied significantly from one pesticide to another. These results provide preliminary information on the seasonality of pesticide concentrations in vineyard areas and evidence for the effectiveness of PUF-PAS to monitor pesticides in ambient air.

The present work is an extensive laboratory study of organosulfate (OS) formation from the reaction of α-pinene oxidation products or proxies with acidified ammonium sulfate aerosols in three different acidity conditions ((NH4)2SO4 0.06 M; (NH4)2SO4/H2SO4 0.06 M/0.005 M; (NH4)2SO4/H2SO4 0.03 M/0.05 M). The kinetics of the reactions of α-pinene, α-pinene oxide, isopinocampheol, pinanediol and myrtenal with ammonium sulfate particles were studied using a quasi-static reactor. The reaction of α-pinene oxide with the highly acidic ammonium sulfate particles was determined to be 7, 10, 21 and 24 times faster than for isopinocampheol, α-pinene, pinanedial and myrtenal, respectively for an OS precursor concentration of 1 ppm and after 1h reaction time. The effective rate coefficients for OS formation from α-pinene oxide were determined to be two orders of magnitude higher in highly acidic conditions than for the two other acidity conditions. For α-pinene oxide reactions with highly acidic ammonium sulfate particles, OS formation was observed to increase linearly with (i) the time of reaction up to 400 minutes (r2 > 0.95) and (ii) α-pinene oxide gas-phase concentration. However, OS formation from α-pinene oxide reactions with slightly acidic or pure ammonium sulfate particles was limited, with a plateau ([OS]max = 0.62 ± 0.03 µg) reached after around 15-20 minutes. Organosulfate dimers (m/z 401 and m/z 481) were detected not only with highly acidic particles but also with slightly acidic and pure ammonium sulfate particles, indicating that oligomerization processes do not require strong acidity conditions. Dehydration products of organosulfates (m/z 231 and m/z 383) were observed only under highly acidic conditions, indicating the key role of H2SO4 on the dehydration of organosulfates and the formation of olefins in the atmosphere. Finally, this kinetic study was completed with simulation chamber experiments in which mass concentration of organosulfates was shown to depend on the available sulfate amount present in the particle phase (r2 = 0.96). In conclusion, this relative comparison between 5 organosulfate precursors shows that epoxide was the most efficient reactant to form organosulfates via heterogeneous gas-particle reactions and illustrates how gas-particle reactions may play an important role in OS formation and hence in the atmospheric fate of organic carbon. The kinetic data presented in this work provides strong support to organosulfate formation mechanisms proposed in the companion paper.

Secondary organic aerosol (SOA) is known to account for a major fraction of airborne particulate matter, with significant impacts on air quality and climate at the global scale. Despite the substantial amount of research studies achieved during these last decades, the source apportionment of the SOA fraction remains difficult due to the complexity of the physicochemical processes involved. The selection and use of appropriate approaches are a major challenge for the atmospheric science community. Several methodologies are nowadays available to perform quantitative and/or predictive assessments of the SOA amount and composition. This review summarizes the current knowledge on the most commonly used approaches to evaluate secondary organic carbon (SOC) contents: elemental carbon (EC) tracer method, chemical mass balance (CMB), SOA tracer method, radiocarbon (¹⁴C) measurement and positive matrix factorization (PMF). The principles, limitations, challenges and good practices of each of these methodologies are discussed in the present article. Based on a comprehensive—although not exhaustive—review of research papers published during the last decade (2006–2016), SOC estimates obtained using these methodologies are also summarized for different regions across the world. Conclusions of some studies which are directly comparing the performances of different methodologies are then specifically discussed. An overall picture of SOC contributions and concentrations obtained worldwide for urban sites under similar conditions (i.e., geographical and seasonal ones) is also proposed here. Finally, further needs to improve SOC apportionment methodologies are also identified and discussed.