Measurement and Modeling of Ship-Related Ultrafine Particles and Secondary Organic Aerosols in a Mediterranean Port City.

Maritime transport emerges as a major source of ultrafine particle (UFP) pollution in coastal regions with consequences for the health of people living in port cities. Inhalation of UFPs can cause inflammation and oxidative stress, which are starting points for further diseases. In addition to primary particles, secondary organic aerosol (SOA) may form through the photo-oxidation of volatile organic compounds emitted in ship exhaust. The characterization of size-segregated and chemical properties of particles is essential for assessing the health implications related to shipping. We applied a coupled regional-local chemistry transport modeling system to study the effects of ship emissions on atmospheric concentrations of UFP and SOA in the Mediterranean port city Marseille (France), which is characterized by the combination of high port activity, industrialized emissions, and active photochemistry in summer. Our results show that the average potential impact from local shipping in the port area was 6-9% for SOA and 27-51% for total particle number concentration in July 2020. The estimated oxidative potential of daily mean particulate organic matter related to shipping was lower than the oxidative potential reported for heavy fuel oil (HFO). The lower oxidative potential in this study is very likely due to the low share of ships using HFO during stopover.

Modelling aerosol molecular markers in a 3D air quality model: Focus on anthropogenic organic markers.

We developed and implemented in the 3D air quality model CHIMERE the formation of several key anthropogenic aerosol markers including one primary anthropogenic marker (levoglucosan) and 4 secondary anthropogenic markers (nitrophenols, nitroguaiacols, methylnitrocatechols and phthalic acid). Modelled concentrations have been compared to measurements performed at 12 locations in France for levoglucosan in winter 2014-15, and at a sub-urban station in the Paris region over the whole year 2015 for secondary molecular markers. While a good estimation of levoglucosan concentrations by the model has been obtained for a few sites, a strong underestimation was simulated for most of the stations especially for western locations due to a probable underestimation of residential wood burning emissions. The simulated ratio between wood burning organic matter and particulate phase levoglucosan is constant only at high OM values (>10 µg m-3) indicating that using marker contribution ratio may be valid only under certain conditions. Concentrations of secondary markers were well reproduced by the model for nitrophenols and nitroguaiacols but were underestimated for methylnitrocatechols and phthalic acid highlighting missing formation pathways and/or precursor emissions. By comparing modelled to measured Gas/Particle Partitioning (GPP) of markers, the simulated partitioning of Semi-Volatile Organic Compounds (SVOCs) was evaluated. Except for nitroguaiacols and nitrophenols when ideality was assumed, the GPP for all the markers was underestimated and mainly driven by the hydrophilic partitioning. SVOCs GPP, and more generally of all SVOC contributing to the formation of SOA, could therefore be significantly underestimated by air quality models, especially when only the partitioning on the organic phase is considered. Our results show that marker modelling can give insights on some processes (such as precursor emissions or missing mechanisms) involved in SOA formation and could prove especially useful to evaluate the GPP in 3D air quality models.

Analysis and determination of secondary organic aerosol (SOA) tracers (markers) in particulate matter standard reference material (SRM 1649b, urban dust).

Secondary organic aerosol (SOA) accounts for a significant fraction of particulate matter (PM) in the atmosphere. Source identification, including the SOA fraction, is critical for the effective management of air pollution. Molecular SOA markers (tracers) are key compounds allowing the source apportionment of SOA using different methodologies. Therefore, accurate SOA marker measurements in ambient air PM are important. This study determined the concentrations of 12 key SOA markers (biogenic and anthropogenic) in the urban dust standard reference material available from the National Institute of Standards and Technology (NIST) (SRM 1649b). Two extraction procedures, sonication and QuEChERS-like (quick easy cheap effective rugged and safe), have been compared. Three research laboratories/institutes using two analytical techniques (gas chromatography/mass spectrometry (GC/MS) and ultra-high-pressure liquid chromatography/tandem mass spectrometry (HPLC/MS-MS)) carried out the analyses. The results obtained were all in good agreement, except for 2-methylerythritol. The analysis of this compound still seems to be challenging by both GC/MS (large injection repeatability) and HPLC/MS-MS (separation issues of both 2-methyltetrols: 2-methylthreitol and 2-methylerythritol). Possible inhomogeneity in the SRM for this compound could also explain the large discrepancies observed. Sonication and QuEChERS-like procedures gave comparable results for the extraction of the SOA markers showing that QuEChERS-like extraction is suitable for the analysis of SOA markers in ambient air PM. As this study provides, for the first time, indicative values in a reference material for typical SOA markers, the analysis of SRM 1649b (urban dust) could be used for quality control/assurance purposes. Graphical abstract.

Speciation of organic fraction does matter for source apportionment. Part 1: A one-year campaign in Grenoble (France).

PM10 source apportionment was performed by positive matrix factorization (PMF) using specific primary and secondary organic molecular markers on samples collected over a one year period (2013) at an urban station in Grenoble (France). The results provided a 9-factor optimum solution, including sources rarely apportioned in the literature, such as two types of primary biogenic organic aerosols (fungal spores and plant debris), as well as specific biogenic and anthropogenic secondary organic aerosols (SOA). These sources were identified thanks to the use of key organic markers, namely, polyols, odd number higher alkanes, and several SOA markers related to the oxidation of isoprene, α-pinene, toluene and polycyclic aromatic hydrocarbons (PAHs). Primary and secondary biogenic contributions together accounted for at least 68% of the total organic carbon (OC) in the summer, while anthropogenic primary and secondary sources represented at least 71% of OC during wintertime. A very significant contribution of anthropogenic SOA was estimated in the winter during an intense PM pollution event (PM10>50µgm-3 for several days; 18% of PM10 and 42% of OC). Specific meteorological conditions with a stagnation of pollutants over 10days and possibly Fenton-like chemistry and self-amplification cycle of SOA formation could explain such high anthropogenic SOA concentrations during this period. Finally, PMF outputs were also used to investigate the origins of humic-like substances (HuLiS), which represented 16% of OC on an annual average basis. The results indicated that HuLiS were mainly associated with biomass burning (22%), secondary inorganic (22%), mineral dust (15%) and biogenic SOA (14%) factors. This study is probably the first to state that HuLiS are significantly associated with mineral dust.

Degradation of Methyl 2-Aminobenzoate (Methyl Anthranilate) by H2O2/UV: Effect of Inorganic Anions and Derived Radicals.

This study shows that methyl 2-aminobenzoate (also known as methyl anthranilate, hereafter MA) undergoes direct photolysis under UVC and UVB irradiation and that its photodegradation is further accelerated in the presence of H2O2. Hydrogen peroxide acts as a source of hydroxyl radicals (·OH) under photochemical conditions and yields MA hydroxyderivatives. The trend of MA photodegradation rate vs. H2O2 concentration reaches a plateau because of the combined effects of H2O2 absorption saturation and ·OH scavenging by H2O2. The addition of chloride ions causes scavenging of ·OH, yielding Cl2·- as the most likely reactive species, and it increases the MA photodegradation rate at high H2O2 concentration values. The reaction between Cl2·- and MA, which has second-order rate constant k C l 2 • - + M A = (4.0 ± 0.3) × 108 M-1·s-1 (determined by laser flash photolysis), appears to be more selective than the ·OH process in the presence of H2O2, because Cl2·- undergoes more limited scavenging by H2O2 compared to ·OH. While the addition of carbonate causes ·OH scavenging to produce CO3·- ( k C O 3 • - + M A = (3.1 ± 0.2) × 108 M-1·s-1), carbonate considerably inhibits the photodegradation of MA. A possible explanation is that the elevated pH values of the carbonate solutions make H2O2 to partially occur as HO2-, which reacts very quickly with either ·OH or CO3·- to produce O2·-. The superoxide anion could reduce partially oxidised MA back to the initial substrate, with consequent inhibition of MA photodegradation. Fast MA photodegradation is also observed in the presence of persulphate/UV, which yields SO4·- that reacts effectively with MA ( k S O 4 • - + M A = (5.6 ± 0.4) × 108 M-1·s-1). Irradiated H2O2 is effective in photodegrading MA, but the resulting MA hydroxyderivatives are predicted to be about as toxic as the parent compound for aquatic organisms (most notably, fish and crustaceans).