Atmospheric Chemistry and Physics最新文献

We present the collective evaluation of the regional scale models that took part in the fourth edition of the Air Quality Model Evaluation International Initiative (AQMEII). The activity consists of the evaluation and intercomparison of regional scale air quality models run over North American (NA) and European (EU) domains for 2016 (NA) and 2010 (EU). The focus of the paper is ozone dry deposition. Dry deposition is among the most important processes of removal of chemical compounds from the atmosphere and an important contributor to the overall chemical budget of the latter. Furthermore ozone dry deposition is very important as it can be severely detrimental to vegetation physiology. The collective evaluation begins with an operational evaluation, namely a direct comparison of model-simulated predictions with monitoring data aiming at assessing model performance (Dennis et al., 2010). Following the AQMEII protocol and Dennis et al. (2010), we also perform a probabilistic evaluation in the form of ensemble analyses and an introductory diagnostic evaluation. The latter, analyses the role of dry deposition in comparison with dynamic and radiative processes and land-use/land-cover types (LULC), in determining surface ozone variability. Important differences are found across dry deposition results when the same LULC is considered. Furthermore, we found that models use very different LULC masks, thus introducing an additional level of diversity in the model results. The study stresses that, as for other kinds of prior and problem-defining information (emissions, topography or land-water masks), the choice of a LULC mask should not be at modeller's discretion. Furthermore, LULC should be considered as a variable to be evaluated in any future model intercomparison, unless set as common input information. The differences in LULC selection can have a substantial impact on model results, making the task of evaluating dry deposition modules across different regional-scale models very difficult.

Exceedances of critical loads for deposition of sulfur (S) and nitrogen (N) in different ecosystems were estimated using European and North American ensembles of air quality models, under the Air Quality Model Evaluation International Initiative Phase 4 (AQMEII4), to identify where the risk of ecosystem harm is expected to occur based on model deposition estimates. The ensembles were driven by common emissions and lateral boundary condition inputs. Model output was regridded to common North American and European 0.125° resolution domains, which were then used to calculate critical load exceedances. Targeted deposition diagnostics implemented in AQMEII4 allowed for an unprecedented level of post-simulation analysis to be carried out and facilitated the identification of specific causes of model-to-model variability in critical load exceedance estimates. Datasets for North American critical loads for acidity for forest soil water and aquatic ecosystems were created for this analysis. These were combined with the ensemble deposition predictions to show a substantial decrease in the area and number of locations in exceedance between 2010 and 2016 (forest soils: 13.2% to 6.1 %; aquatic ecosystems: 21.2% to 11.4 %). All models agreed regarding the direction of the ensemble exceedance change between 2010 and 2016. The North American ensemble also predicted a decrease in both the severity and total area in exceedance between the years 2010 and 2016 for eutrophication-impacted ecosystems in the USA (sensitive epiphytic lichen: 81.5% to 75.8 %). The exceedances for herbaceous-community richness also decreased between 2010 and 2016, from 13.9% to 3.9 %. The uncertainty associated with the North American eutrophication results is high; there were sharp differences between the models in predictions of both total N deposition and the change in N deposition and hence in the predicted eutrophication exceedances between the 2 years. The European ensemble was used to predict relatively static exceedances of critical loads with respect to acidification (4.48% to 4.32% from 2009 to 2010), while eutrophication exceedance increased slightly (60.2% to 62.2 %). While most models showed the same changes in critical load exceedances as the ensemble between the 2 years, the spatial extent and magnitude of exceedances varied significantly between the models. The reasons for this variation were examined in detail by first ranking the relative contribution of different sources of sulfur and nitrogen deposition in terms of deposited mass and model-to-model variability in that deposited mass, followed by their analysis using AQMEII4 diagnostics, along with evaluation of the most recent literature. All models in both the North American and European ensembles had net annual negative biases with respect to the observed wet deposition of sulfate, nitrate, and ammonium. Diagnostics and recent literature suggest that this bias may stem from insufficient cloud scavenging of aero

A portion of Alaska's Fairbanks North Star Borough was designated as nonattainment for the 2006 24 h fine particulate matter 2.5 μm or less in diameter (PM_2.5) National Ambient Air Quality Standards (NAAQS) in 2009. PM_2.5 NAAQS exceedances in Fairbanks mainly occur during dark and cold winters, when temperature inversions form and trap high emissions at the surface. Sulfate ( ${\text{SO}}_4^{2-}$ ), often the second-largest contributor to PM_2.5 mass during these wintertime PM episodes, is underpredicted by atmospheric chemical transport models (CTMs). Most CTMs account for primary ${\text{SO}}_4^{2-}$ and secondary ${\text{SO}}_4^{2-}$ formed via gas-phase oxidation of sulfur dioxide ( ${\text{SO}}_2$ ) and in-cloud aqueous oxidation of dissolved S(IV). Dissolution and reaction of ${\text{SO}}_2$ in aqueous aerosols are generally not included in CTMs but can be represented as heterogeneous reactive uptake and may help better represent the high ${\text{SO}}_4^{2-}$ concentrations observed during Fairbanks winters. In addition, hydroxymethanesulfonate (HMS), a particulate sulfur species sometimes misidentified as ${\text{SO}}_4^{2-}$ , is known to form during Fairbanks winters. Heterogeneous formation of ${\text{SO}}_4^{2-}$ and HMS in aerosol liquid water (ALW) was implemented in the Community Multiscale Air Quality (CMAQ) modeling system. CMAQ simulations were performed for wintertime PM episodes in Fairbanks (2008) as well as over the Northern Hemisphere and Contiguous United States (CONUS) for 2015-2016. The added heterogeneous sulfur chemistry reduced model mean sulfate bias by ~0.6 μg m^-3 during a cold winter PM episode in Fairbanks, AK. Improvements in model performance are also seen in Beijing during wintertime haze events (reducing model mean sulfate bias by ~2.9 μgS m^-3). This additional sulfur chemistry also improves modeled summertime ${\text{SO}}_4^{2-}$ bias in the southeastern US, with implications for future modeling of biogenic organosulfates.

This study analyzes ozone (O3) dry deposition fluxes and velocities (Vd) from twelve regional-scale simulations that were performed over North America and Europe in Phase 4 of the Air Quality Model Evaluation International Initiative (AQMEII4). AQMEII4 collected grid-aggregated and land use (LU)-specific O3 Vd and effective conductances and fluxes for the four major dry deposition pathways. Consistent with recent findings in the AQMEII4 point model intercomparison study, analysis of the grid-aggregated fields shows that grid models with similar Vd can exhibit significant differences in the absolute and relative contributions of the different depositional pathways. Analysis of LU-specific Vd and effective conductances reveals a general increase in model spread compared to grid-aggregated values. This indicates that an analysis of only grid-aggregated deposition diagnostics can mask process-specific differences that exist between schemes. An analysis of AQMEII4 LU distributions across models revealed substantial differences in the spatial patterns and abundance of certain LU categories over both domains, especially for non-forest partially vegetated categories such as agricultural areas, shrubland, and grassland. We demonstrate that these differences can significantly contribute to or even drive differences in LU-specific dry deposition fluxes which can increase the variability in model predictions of ozone. Two recommendations for future deposition-focused modeling studies emerging from the AQMEII4 analyses presented here are to 1) routinely generate diagnostic outputs to advance a process-based understanding of modeled deposition and support impact analyses, and 2) recognize the importance of documenting and analyzing the representation of LU across models and work towards harmonizing this aspect when using air-quality grid models and model ensembles for deposition analyses.

Lagrangian tracer simulations are deployed to investigate processes influencing vertical and horizontal dispersion of anthropogenic pollution in Fairbanks, Alaska, during the Alaskan Layered Pollution and Chemical Analysis (ALPACA) 2022 field campaign. Simulated concentrations of carbon monoxide (CO), sulfur dioxide ( $\text{S}{\text{O}}_2$ ), and nitrogen oxides ( $\text{N}{\text{O}}_x$ ), including surface and elevated sources, are the highest at the surface under very cold stable conditions. Pollution enhancements above the surface (50-300 m) are mainly attributed to elevated power plant emissions. Both surface and elevated sources contribute to Fairbanks' regional pollution that is transported downwind, primarily to the south-west, and may contribute to wintertime Arctic haze. Inclusion of a novel power plant plume rise treatment that considers the presence of surface and elevated temperature inversion layers leads to improved agreement with observed CO and $\text{N}{\text{O}}_x$ plumes, with discrepancies attributed to, for example, displacement of plumes by modelled winds. At the surface, model results show that observed CO variability is largely driven by meteorology and, to a lesser extent, by emissions, although simulated tracers are sensitive to modelled vertical dispersion. Modelled underestimation of surface $\text{N}{\text{O}}_x$ during very cold polluted conditions is considerably improved following the inclusion of substantial increases in diesel vehicle $\text{N}{\text{O}}_x$ emissions at cold temperatures (e.g. a factor of 6 at -30°C). In contrast, overestimation of surface $\text{S}{\text{O}}_2$ is attributed mainly to model deficiencies in vertical dispersion of elevated (5-18 m) space heating emissions. This study highlights the need for improvements to local wintertime Arctic anthropogenic surface and elevated emissions and improved simulation of Arctic stable boundary layers.

This study investigated the effect of relative humidity (RH) on the chemical composition of gas and particle phases formed from the photooxidation of 1,3-butadiene (13BD) in the presence of NO _x under acidified and non-acidified seed aerosol. The experiments were conducted in a 14.5 m³ smog chamber operated in a steady-state mode. Products were identified by high-performance liquid chromatography, gas chromatography-mass spectrometry, and ultrahigh-performance liquid chromatography coupled with high-resolution mass spectrometry. More than 50 oxygenated products were identified, including 33 oxygenated organics, 10 organosulfates (OSs), PAN, APAN, glyoxal, formaldehyde, and acrolein. Secondary organic aerosol (SOA) mass and reaction products formed depended on RH and on the acidity of the seed aerosol. Based on the Extended Aerosol Inorganics Model (E-AIM), the seed aerosol originated from the acidified and non-acidified solutions was found to exist under aqueous and solid phases, respectively. Although the terms "acidified" and "non-acidified" are true for the solutions from which the seeds were atomized, there are far more fundamental differences between the phase states in which species partition to or from (aqueous/solid), which considerably affects their partitioning and formation mechanisms. SOA mass and most SOA products (i) were higher under acidified seed conditions, where the aerosol particles were deliquescent, than under non-acidified seed conditions, where the aerosol particles did not contain any aqueous phase; (ii) increased with the acidity of the aerosol aqueous phase in the experiments under acidified seed conditions; and (iii) decreased with increasing RH. Glyceric acid, threitols, threonic acids, four dimers, three unknowns, and four organosulfates were among the main species measured under either acidified or non-acidified conditions across all RH levels. Total secondary organic carbon and carbon yield decreased with increasing RH under both acidified and non-acidified seed conditions. The photochemical reactivity of 13BD in our systems decreased with increasing RH and was faster under non-acidified than acidified seed conditions. To determine the contribution of 13BD products to ambient aerosol, we analyzed PM_2.5 samples collected at three European monitoring stations located in Poland. The occurrence of several 13BD SOA products (e.g., glyceric acid, tartronic acid, threonic acid, tartaric acid, and OSs) in the field samples suggests that 13BD could contribute to ambient aerosol formation.

Formaldehyde (HCHO) is an important air pollutant with direct cancer risk and ozone-forming potential. HCHO sources are complex because HCHO is both directly emitted and produced from oxidation of most gas-phase reactive organic carbon. We update the secondary production of HCHO in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM) in the Community Multiscale Air Quality (CMAQ) model. Production of HCHO from isoprene and monoterpenes is increased, correcting an underestimate in the current version. Simulated June-August surface HCHO during peak photochemical production (11:00-15:00 LT, local time) increased by 0.6 ppb (32 %) over the southeastern USA and by 0.2 ppb (13 %) over the contiguous USA. The increased HCHO compares more favorably with satellite-based observations from the TROPOspheric Monitoring Instrument (TROPOMI) and from aircraft-based observations. Evaluation against hourly surface observations indicates a missing nighttime sink that can be improved by increased nighttime deposition, which reduces June-August nocturnal (20:00-04:00 LT) surface HCHO by 1.1 ppb (36 %) over the southeastern USA and 0.5 ppb (29 %) over the contiguous USA. The ability of CRACMM to capture peak levels of HCHO at midday is improved, particularly at sites in the northeastern USA, while peak levels at sites in the southeastern USA are improved, although still lower than observed. Using established risk assessment methods, lifetime exposure of the population in the contiguous USA (~320 million) to ambient HCHO levels predicted here may result in 6200 lifetime cancer cases, with 40 % from controllable anthropogenic emissions of nitrogen oxides and reactive organic compounds. Chemistry updates will be available in CRACMM version 2 (CRACMM2) in CMAQv5.5.