Contrasting effects of urban trees on air quality: From the aerodynamic effects in streets to impacts of biogenic emissions in cities.

Urban trees are often not considered in air-quality models although they can significantly impact the concentrations of pollutants. Gas and particles can deposit on leaf surfaces, lowering their concentrations, but the tree crown aerodynamic effect is antagonist, limiting the dispersion of pollutants in streets. Furthermore, trees emit Biogenic Volatile Organic Compounds (BVOCs) that react with other compounds to form ozone and secondary organic aerosols. This study aims to quantify the impacts of these three tree effects (dry deposition, aerodynamic effect and BVOC emissions) on air quality from the regional to the street scale over Paris city. Each tree effect is added in the model chain CHIMERE/MUNICH/SSH-aerosol. The tree location and characteristics are determined using the Paris tree inventory, combined with allometric equations. The air-quality simulations are performed over June and July 2022. The results show that the aerodynamic tree effect increases the concentrations of gas and particles emitted in streets, such as NOx (+4.6 % on average in streets with trees and up to +37 % for NO2). This effect increases with the tree Leaf Area Index and it is more important in streets with high traffic, suggesting to limit the planting of trees with large crowns on high-traffic streets. The effect of dry deposition of gas and particles on leaves is very limited, reducing the concentrations of O3 concentrations by -0.6 % on average and at most -2.5 %. Tree biogenic emissions largely increase the isoprene and monoterpene concentrations, bringing the simulated concentrations closer to observations. Over the two-week sensitivity analysis, biogenic emissions induce an increase of O3, organic particles and PM2.5 street concentrations by respectively +1.1, +2.4 and + 0.5 % on average over all streets. This concentration increase may reach locally +3.5, +12.3 and + 2.9 % respectively for O3, organic particles and PM2.5, suggesting to prefer the plantation of low-emitting VOC species in cities.

Ozonolysis of 2-Methyl-2-pentenal: New Insights from Master Equation Modeling.

Experimental and theoretical studies were carried out to investigate the ozonolysis of trans-2-methyl-2-pentenal. The experiments were conducted in atmospheric simulation chambers coupled to a Fourier transform infrared (FTIR) spectrometer and a gas chromatograph-mass spectrometer at room temperature and atmospheric pressure in the presence of an excess of cyclohexane in dry conditions (RH < 1%). The ozonolysis reaction was investigated theoretically from the results of accurate density functional (M06-2X) and ab initio [CCSD(T)] computations, employing the AVTZ basis set. The sequence of reaction steps was established, and the system of kinetics equations was modeled using MESMER. In the first step, a primary ozonide is formed, which then decomposes along two pathways. The principal ozonolysis products are propanal, methylglyoxal, ethylformate, and a secondary ozonide. An interesting competition between sequential reaction steps and well-skipping is found, which leads to an inversion of the expected methylglyoxal/propanal product ratio at temperatures below 210 K. The mechanism of the "hot ester" reaction channel of the Criegee intermediate was revisited. The computed ozonolysis rate constant and product branching ratio are in excellent agreement with the experimental data that are also reported in the present work.

Sunlight Induces the Production of Atmospheric Volatile Organic Compounds (VOCs) from Thermokarst Ponds.

Ground subsidence caused by permafrost thawing causes the formation of thermokarst ponds, where organic compounds from eroding permafrost accumulate. We photolyzed water samples from two such ponds in Northern Quebec and discovered the emission of volatile organic compounds (VOCs) using mass spectrometry. One pond near peat-covered permafrost mounds was organic-rich, while the other near sandy mounds was organic-poor. Compounds up to C10 were detected, comprising the atoms of O, N, and S. The main compounds were methanol, acetaldehyde, and acetone. Hourly VOC fluxes under actinic fluxes similar to local solar fluxes might reach up to 1.7 nmol C m-2 s-1. Unexpectedly, the fluxes of VOCs from the organic-poor pond were greater than those from the organic-rich pond. We suggest that different segregations of organics at the air/water interface may partly explain this observation. This study indicates that sunlit thermokarst ponds are a significant source of atmospheric VOCs, which may affect the environment and climate via ozone and aerosol formation. Further work is required for understanding the relationship between the pond's organic composition and VOC emission fluxes.

Indoor heterogeneous photochemistry of molds and their contribution to HONO formation.

To better understand the impact of molds on indoor air quality, we studied the photochemistry of microbial films made by Aspergillus niger species, a common indoor mold. Specifically, we investigated their implication in the conversion of adsorbed nitrate anions into gaseous nitrous acid (HONO) and nitrogen oxides (NOx ), as well as the related VOC emissions under different indoor conditions, using a high-resolution proton transfer reaction-time of flight-mass spectrometer (PTR-TOF-MS) and a long path absorption photometer (LOPAP). The different mold preparations were characterized by the means of direct injection into an Orbitrap high-resolution mass spectrometer with a heated electrospray ionization (ESI-Orbitrap-MS). The formation of a wide range of VOCs, having emission profiles sensitive to the types of films (either doped by potassium nitrate or not), cultivation time, UV-light irradiation, potassium nitrate concentration and relative humidity was observed. The formation of nitrous acid from these films was also determined and found to be dependent on light and relative humidity. Finally, the reaction paths for the NOx and HONO production are proposed. This work helps to better understand the implication of microbial surfaces as a new indoor source for HONO emission.

Indoor heterogeneous photochemistry of furfural drives emissions of nitrous acid.

People spend approximately 80% of their time indoor, making the understanding of the indoor chemistry an important task for safety. The high surface-area-to-volume ratio characteristic of indoor environments leads the semi-volatile organic compounds (sVOCs) to deposit on the surfaces. Using a long path absorption photometer (LOPAP), this work investigates the formation of nitrous acid (HONO) through the photochemistry of adsorbed nitrate anions and its enhancement by the presence of furfural. Using a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS), this work also investigates the surface emissions of VOCs from irradiated films of furfural and a mix of furfural and nitrate anions. Among the emitted VOCs, 2(5H)-furanone/2-Butenedial was observed at high concentrations, leading to maleic anhydride formation after UV irradiation. Moreover, the addition of potassium nitrate to the film formed NOx and HONO concentrations up to 10 ppb, which scales to ca. 4 ppb for realistic indoor conditions. This work helps to understand the high levels of HONO and NOx measured indoors.

Influence of indoor chemistry on the emission of mVOCs from Aspergillus niger molds.

People spend 80% of their time indoors exposed to poor air quality due to mold growth in humid air as well as human activities (painting, cooking, cleaning, smoking…). To better understand the impact of molds on indoor air quality, we studied the emission of microbial Volatile Organic Compounds (mVOCs) from Aspergillus niger, cultivated on malt agar extract, using a high-resolution proton transfer reaction- time of flight- mass spectrometer (PTR-TOF-MS). These emissions were studied for different cultivation time and indoor relative humidities. Our results show that the concentration of the known C4-C9 mVOCs tracers of the microbial activity (like 1-octen-3-ol, 3-methylfuran, 2-pentanone, dimethyl sulfide, dimethyl disulfide, nitromethane, 1,3-octadiene…) was the highest in the early stage of growth. However, these emissions decreased substantially after a cultivation time of 10-14 days and were highly affected by the relative humidity. In addition, the emissions of certain mVOCs were sensitive to indoor light, suggesting an impact of photochemistry on the relative amounts of indoor mVOCs. Based on this study, an estimation of the mVOC concentration for a standard living room was established at different air exchange rates and their indoor lifetimes toward hydroxyl radicals and ozone were also estimated. These findings give insights on possible mVOCs levels in moisture-damaged buildings for an early detection of microbial activity and new evidences about the effect of indoor light on their emission.

Gas-phase UV absorption spectra and OH-oxidation kinetics of 1H-1,2,3-triazole and pyrazole.

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): σ 206 nm, 1H-1H-1,2,3-triazole = 2.04 × 10-18 and σ 203 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.