Impacts of Soil NOx Emission on O3 Air Quality in Rural California.

Nitrogen oxides (NOx) are a key precursor in O3 formation. Although stringent anthropogenic NOx emission controls have been implemented since the early 2000s in the United States, several rural regions of California still suffer from O3 pollution. Previous findings suggest that soils are a dominant source of NOx emissions in California; however, a statewide assessment of the impacts of soil NOx emission (SNOx) on air quality is still lacking. Here we quantified the contribution of SNOx to the NOx budget and the effects of SNOx on surface O3 in California during summer by using WRF-Chem with an updated SNOx scheme, the Berkeley Dalhousie Iowa Soil NO Parameterization (BDISNP). The model with BDISNP shows a better agreement with TROPOMI NO2 columns, giving confidence in the SNOx estimates. We estimate that 40.1% of the state's total NOx emissions in July 2018 are from soils, and SNOx could exceed anthropogenic sources over croplands, which accounts for 50.7% of NOx emissions. Such considerable amounts of SNOx enhance the monthly mean NO2 columns by 34.7% (53.3%) and surface NO2 concentrations by 176.5% (114.0%), leading to an additional 23.0% (23.2%) of surface O3 concentration in California (cropland). Our results highlight the cobenefits of limiting SNOx to help improve air quality and human health in rural California.

Silicon is a frequent component of atmospheric nanoparticles.

Nanoparticles are the largest fraction of aerosol loading by number. Knowledge of the chemical components present in nanoparticulate matter is needed to understand nanoparticle health and climatic impacts. In this work, we present field measurements using the Nano Aerosol Mass Spectrometer (NAMS), which provides quantitative elemental composition of nanoparticles around 20 nm diameter. NAMS measurements indicate that the element silicon (Si) is a frequent component of nanoparticles. Nanoparticulate Si is most abundant in locations heavily impacted by anthropogenic activities. Wind direction correlations suggest the sources of Si are diffuse, and diurnal trends suggest nanoparticulate Si may result from photochemical processing of gas phase Si-containing compounds, such as cyclic siloxanes. Atmospheric modeling of oxidized cyclic siloxanes is consistent with a diffuse photochemical source of aerosol Si. More broadly, these observations indicate a previously overlooked anthropogenic source of nanoaerosol mass. Further investigation is needed to fully resolve its atmospheric role.

Improvement of Surface PM2.5 Diurnal Variation Simulations in East Africa for the MAIA Satellite Mission.

The Multi-Angle Imager for Aerosols (MAIA), supported by NASA and the Italian Space Agency, is planned for launch into space in 2025. As part of its mission goal, outputs from a chemical transport model, the Unified Inputs for Weather Research and Forecasting Model coupled with Chemistry (UI-WRF-Chem), will be used together with satellite data and surface observations for estimating surface PM2.5. Here, we develop a method to improve UI-WRF-Chem with surface observations at the U.S. embassy in Ethiopia, one of MAIA's primary target areas in east Africa. The method inversely models the diurnal profile and amount of anthropogenic aerosol and trace gas emissions. Low-cost PurpleAir sensor data are used for validation after applying calibration functions obtained from the collocated data at the embassy. With the emission updates in UI-WRF-Chem, independent validation for February 2022 at several different PurpleAir sites shows an increase in the linear correlation coefficients from 0.1-0.7 to 0.6-0.9 between observations and simulations of the diurnal variation of surface PM2.5. Furthermore, even by using the emissions optimized for February 2021, the UI-WRF-Chem forecast for March 2022 is also improved. Annual update of monthly emissions via inverse modeling has the potential and is needed to improve MAIA's estimate of surface PM2.5.

Lung cell exposure to secondary photochemical aerosols generated from OH oxidation of cyclic siloxanes.

To study the fate of cyclic volatile methyl siloxanes (cVMS) undergoing photooxidation in the environment and to assess the acute toxicity of inhaled secondary aerosols from cVMS, we used an oxidative flow reactor (OFR) to produce aerosols from oxidation of decamethylcyclopentasiloxane (D5). The aerosols produced from this process were characterized for size, shape, and chemical composition. We found that the OFR produced aerosols composed of silicon and oxygen, arranged in chain agglomerates, with primary particles of approximately 31 nm in diameter. Lung cells were exposed to the secondary organosilicon aerosols at estimated doses of 54-116 ng/cm2 using a Vitrocell air-liquid interface system, and organic gases and ozone exposure was minimized through a series of denuders. Siloxane aerosols were not found to be highly toxic.

Physical properties of secondary photochemical aerosol from OH oxidation of a cyclic siloxane.

Cyclic volatile methyl siloxanes (cVMS) are high-production chemicals present in many personal care products. They are volatile, hydrophobic, and relatively long-lived due to slow oxidation kinetics. Evidence from chamber and ambient studies indicates that oxidation products may be found in the condensed aerosol phase. In this work, we use an oxidation flow reactor to produce ~ 100 µgm-3 of organosilicon aerosol from OH oxidation of decamethyl-cyclopentasiloxane (D5) with aerosol mass fractions (i.e., yields) of 0.2-0.5. The aerosols were assessed for concentration, size distribution, morphology, sensitivity to seed aerosol, hygroscopicity, volatility and chemical composition through a combination of aerosol size distribution measurement, tandem differential mobility analysis, and electron microscopy. Similar aerosols were produced when vapor from solid antiperspirant was used as the reaction precursor. Aerosol yield was sensitive to chamber OH and to seed aerosol, suggesting sensitivity of lower-volatility species and recovered yields to oxidation conditions and chamber operation. The D5 oxidation aerosol products were relatively non-hygroscopic, with an average hygroscopicity kappa of ~ 0.01, and nearly non-volatile up to 190 °C temperature. Parameters for exploratory treatment as a semi-volatile organic aerosol in atmospheric models are provided.

Comprehensive atmospheric modeling of reactive cyclic siloxanes and their oxidation products.

Cyclic volatile methyl siloxanes (cVMSs) are important components in personal care products that transport and react in the atmosphere. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and their gas-phase oxidation products have been incorporated into the Community Multiscale Air Quality (CMAQ) model. Gas-phase oxidation products, as the precursor to secondary organic aerosol from this compound class, were included to quantify the maximum potential for aerosol formation from gas-phase reactions with OH. Four 1-month periods were modeled to quantify typical concentrations, seasonal variability, spatial patterns, and vertical profiles. Typical model concentrations showed parent compounds were highly dependent on population density as cities had monthly averaged peak D5 concentrations up to 432ngm-3. Peak oxidized D5 concentrations were significantly less, up to 9ngm-3, and were located downwind of major urban areas. Model results were compared to available measurements and previous simulation results. Seasonal variation was analyzed and differences in seasonal influences were observed between urban and rural locations. Parent compound concentrations in urban and peri-urban locations were sensitive to transport factors, while parent compounds in rural areas and oxidized product concentrations were influenced by large-scale seasonal variability in OH.