Summertime Clean-Background Ozone Concentrations Derived from Ozone Precursor Relationships are Lower than Previous Estimates in the Southeast United States.

Background ozone in this study is defined as the amount of ozone that is not affected by the emissions of ozone precursors in the region of study and is transported from the distant troposphere or the stratosphere. It is one of the factors that must be considered in regional ozone control strategies. Different methods have been applied to define the background ozone level. We develop a new method based on the O3-CO-HCHO relationships, which can be applied to both observation and modeling data for regions with high isoprene emission ozone, such as the Southeast United States. We make use of the extensive aircraft and surface observations in the Southeast in the summer of 2013. Compared to the diagnostic results using the relationship of O3-NOz (total reactive nitrogen excluding nitrogen oxides), zero-emission (model-only), and 5th percentile methods, the new method is most consistent using observation or model data and the resulting background ozone concentrations are 4-50% lower than the other methods for field campaigns. Using this method, we find that the summertime background ozone at the surface is in the range of 10-15 ppbv in the inland areas of the Southeast, which is lower than that reported in previous studies. This background ozone tends to increase from urban centers to rural regions and from the surface to higher altitude due to changing ozone lifetime driven by anthropogenic emissions and dry deposition to the surface. The better quantification of background ozone using the new method highlights the importance of the contributions by natural emissions to ozone and the necessity to control anthropogenic emissions in ozone nonattainment areas of the Southeast.

Emission source-based ozone isopleth and isosurface diagrams and their significance in ozone pollution control strategies.

In the past decade, ozone (O3) pollution has been continuously worsening in most developing countries. The accurate identification of the nonlinear relationship between O3 and its precursors is a prerequisite for formulating effective O3 control measures. At present, precursor-based O3 isopleth diagrams are widely used to infer O3 control strategy at a particular location. However, there is frequently a large gap between the O3-precursor nonlinearity delineated by the O3 isopleths and the emission source control measures to reduce O3 levels. Consequently, we developed an emission source-based O3 isopleth diagram that directly illustrates the O3 level changes in response to synergistic control on two types of emission sources using a validated numerical modeling system and the latest regional emission inventory. Isopleths can be further upgraded to isosurfaces when co-control on three types of emission sources is investigated. Using Guangzhou and Foshan as examples, we demonstrate that similar precursor-based O3 isopleths can be associated with significantly different emission source co-control strategies. In Guangzhou, controlling solvent use emissions was the most effective approach to reduce peak O3 levels. In Foshan, co-control of on-road mobile, solvent use, and fixed combustion sources with a ratio of 3:1:2 or 3:1:3 was best to effectively reduce the peak O3 levels below 145 ppbv. This study underscores the importance of using emission source-based O3 isopleths and isosurface diagrams to guide a precursor emission control strategy that can effectively reduce the peak O3 levels in a particular area.

Diurnal emission variation of ozone precursors: Impacts on ozone formation during Sep. 2019.

With the issue of ozone (O3) pollution having increasingly gained visibility and prominence in China, the Chinese government explored various policies to mitigate O3 pollution. In some provinces and cities, diurnal regulations of O3 precursor were implemented, such as shifting O3 precursor emission processes to nighttime and offering preferential refueling at night. However, the effectiveness of these policies remains unverified, and their impact on the O3 generation process requires further elucidation. In this study, we utilized a regional climate and air quality model (WRF-Chem, v4.5) to test three scenarios aimed at exploring the impact of diurnal industry emission variation of O3 precursors on O3 formation. Significant O3 variations were observed mainly in urban areas. Shifting volatile organic compounds (VOCs) to nighttime have slight decreased daytime O3 levels while moving nitrogen oxides (NOx) to nighttime elevates O3 levels. Simultaneously moving both to nighttime showed combined effects. Process analysis indicates that the diurnal variation in O3 was mainly attributed to chemical process and vertical mixing in urban areas, while advection becomes more important in non-urban areas, contributing to the changes in O3 and O3 precursors levels through regional transportation. Further photochemical analysis reveals that the O3 photochemical production in urban areas was affected by reduced daytime O3 precursors emissions. Specifically, decreasing VOCs lowered the daytime O3 production by reducing the ROx radicals (ROx = HO + HO˙2 + RO˙2), whereas decreasing NOx promoted the daytime O3 production by weakening ROx radical loss. Our results demonstrate that diurnal regulation of O3 precursors will disrupt the ROx radical and O3 formation in local areas, resulting in a change in O3 concentration and atmospheric oxidation capacity, which should be considered in formulating new relevant policies.

The impact of urban agglomeration on ozone precursor conditions: A systematic investigation across global agglomerations utilizing multi-source geospatial datasets.

Urbanization significantly influences ozone via two conditions of its formation: 1) precursor concentration; and 2) chemical regime. Recently, there has been raised concern about the influence of urban agglomerations on these two conditions. Although valuable efforts have been made, some contrary viewpoints exist. Meanwhile, urban agglomerations in developed and developing regions are experiencing different urbanization processes, so a systematic comparison between these two regions is warranted. In this context, by leveraging multi-source geospatial datasets, this paper systematically gauges the influence of urban agglomerations on ozone precursor conditions and further investigates the spatiotemporal variations. Based on the analysis of 71 global agglomerations during 2005-2016, it is found that: 1) not all urban agglomerations have a positive effect on ozone precursor conditions; 2) the negative effects of urban agglomerations can be attributed to the low latitudes and the ecological areas (p < 0.05); 3) the agglomeration influence intensifies with the increase of built-up area, population, and latitude (p < 0.05); 4) the anthropogenic nitrogen oxide (NOx) emission from all sectors can aggravate the magnitude of the urban agglomeration influence (p < 0.05), while for volatile organic compounds (VOCs), only the contribution of industrial emissions is significant (p < 0.05); and 5) in view of the temporal dynamics, the influence of urban agglomeration on ozone precursor condition is opposite in developed and developing regions. This study will provide important insights for future urban agglomeration studies and ozone pollution monitoring with geospatial datasets.

Co-dosing Ozone and Deionized Water as Oxidant Precursors of ZnO Thin Film Growth by Atomic Layer Deposition.

Characteristics of atomic layer deposition (ALD)-grown ZnO thin films on sapphire substrates with and without three-pulsed ozone (O3) as oxidant precursor and post-deposition thermal annealing (TA) are investigated. Deposition temperature and thickness of ZnO epilayers are 180 °C and 85 nm, respectively. Post-deposition thermal annealing is conducted at 300 °C in the ambience of oxygen (O2) for 1 h. With strong oxidizing agent O3 and post-deposition TA in growing ZnO, intrinsic strain and stress are reduced to 0.49% and 2.22 GPa, respectively, with extremely low background electron concentration (9.4 × 1015 cm-3). This is originated from a lower density of thermally activated defects in the analyses of thermal quenching of the integrated intensity of photoluminescence (PL) spectra. TA further facilitates recrystallization forming more defect-free grains and then reduces strain and stress state causing a remarkable decrease of electron concentration and melioration of surface roughness.

[Variation of O3 Concentration in Different Regions of Beijing from 2006-2015].

O3 continuous monitoring data for the Dingling, Guanyuan, Liulihe, and Qianmen sites from 2006-2015 were analyzed to investigate concentration levels, variation trends, temporal variations, and relationships with precursors and meteorological factors. The results showed that the ten year average concentrations of O3 at the Dingling site were the highest at 65.2 µg·m-3, followed by concentrations at Liulihe (53.4 µg·m-3), Guanyuan (49.6 µg·m-3) and Qianmen (40.4 µg·m-3). The O3 concentrations at Dingling showed a decreasing trend[0.5 µg·(m3·a)-1], while O3 concentrations at Guanyuan[0.9 µg·(m3·a)-1], Liulihe[0.3 µg·(m3·a)-1], and Qianmen[0.3 µg·(m3·a)-1] showed an increasing trend. The highest monthly average concentrations appeared during June and August, and the highest frequency occurred in July (17 times) with average concentrations of 99.8 µg·m-3. The lowest monthly average concentrations appeared during November and February, and the highest frequency occurred in January (14 times) with an average concentration of 16.6 µg·m-3. Notably, the time for the peak concentrations of O3 appeared earlier in the day in recent years. The peak concentrations of O3 appeared at 15:00-16:00 during 2013-2015, which was 1-2 hours earlier than previous years. The heavy air pollution of O3 occurred on 11 days at the Dingling site in 2015, which was ten days more than in 2013, indicating O3 pollution in the downwind suburban regions of Beijing in summer became more and more serious. The concentrations of O3 and NO2 at Dingling showed a positive correlation, while the concentrations of O3 and NO2 at the other sites showed a negative correlation, indicating O3 formation in Dingling was sensitive to NO2 chemistry, while O3 formation at the other sites was sensitive to VOC chemistry. The concentrations of O3 showed a positive correlation with temperature and negative correlations with humidity and surface pressure. Temperature had the greatest influence on O3 concentration, followed by surface pressure and humidity. For cases when daily maximum temperature exceeded 30℃ and relative humidity was between 30% and 70%, the probability of the O3 daily maximum 8 h concentration exceeding 200 µg·m-3 was high, indicating the air quality level reached levels for light pollution and moderate pollution.