[Identification of Impacts from Meteorology and Local and Transported Photochemical Generation on Ozone Trends in Changsha from 2018 to 2020].

Ozone (O3) pollution in Hunan province has become the most important factor among the six common conventional pollutants (i.e., NO2, SO2, CO, O3, PM10, and PM2.5) in the atmospheric environment. Further investigation has indicated that the relevant studies of O3 are insufficient. Therefore, it is essential to clarify the key driving factors of O3 variations for government regulators. In this study, a combined method consisting of a generalized additive model (GAM), empirical orthogonal function (EOF), and absolute principal component scores (APCs) model was employed to identify and quantify the impacts of meteorology and local photochemical generation (local) and that transported from outside (nonlocal) on O3 variations from 2018-2020. Simultaneously, the driving factors of O3 annual values from 2018 to 2019 and from 2019 to 2020 in Changsha were analyzed. The results showed that O3 episodes were commonly caused by meteorology when the relative contribution from precursors was high, on the short-term time scale. Overall, on the temporal scale, meteorology and local were the driving factors for the increasing annual O3 from 2018 to 2019. Additionally, the contribution from meteorology, local, and nonlocal decreased from 2019 to 2020, leading to a lower level of O3 concentration in 2020. Geographically, the east, north, and south of Changsha were mainly affected by meteorology, local, and nonlocal, respectively. Throughout the three years, nonlocal exhibited a sustained decreasing trend, whereas the tendencies from meteorology and local varied by year and geography. Local contribution in the north of Changsha increased from 2018 to 2019, which was likely attributed to the increasing biogenic volatile organic compound emission (BVOCs), and it became lower in the south owing to the strengthened consumption by NOx. Impacts from meteorology on O3 in all sites were enhanced from 2018 to 2019. By contrast, local contribution decreased in the north and increased in the south with the decline in BVOC and NOx emissions from 2019 to 2020, when the meteorological impacts on O3 in the whole area became weak.

Integrated assessment of volatile organic compounds from industrial biomass boilers in China: emission characteristics, influencing factors, and ozone formation potential.

Industrial biomass boilers (IBBs) are widely promoted in China as a type of clean energy. However, they emit large amount of volatile organic compounds (VOCs) and the emission characteristics and the underlying factors are largely unknown due to the sampling difficulties. In this study, three wood pellet-fueled and two wood residue-fueled IBBs were selected to investigate the characteristics of VOC emissions and to discover their underlying impacting factors. The emission factor of VOCs varied from 21.6 ± 2.8 mg/kg to 286.2 ± 10.8 mg/kg for the IBBs. Oxygenated VOCs (OVOCs) were the largest group, contributing to 30.3 - 73.6% of the VOC emissions. Significant differences were revealed in the VOC source profiles between wood pellet-fueled and wood residue-fueled IBBs. Operating load, excess air, furnace temperature, and fuel type were identified as the primary factors influencing VOC emissions. The excess air coefficient should be limited below 3.5, roughly corresponding to the operating load of 62% and furnace temperature of 630 °C, to effectively reduce VOC emissions. VOC emissions also showed great differences in different combustion phases, with the ignition phase having much greater VOC emissions than the stable combustion and the ember phases. The ozone formation potential (OFP) ranged from 4.3 to 31.2 mg/m3 for the IBBs, and the wood residue-fueled IBBs yielded higher OFP than the wood pellet-fueled ones. This study underscored the importance of OVOCs in IBB emissions, and reducing OVOC emissions should be prioritized in formulating control measures to mitigate their impacts on the atmospheric environment and human health.

Remarkable spring increase overwhelmed hard-earned autumn decrease in ozone pollution from 2005 to 2017 at a suburban site in Hong Kong, South China.

Ozone (O3) pollution has been a persistent problem in Hong Kong, particularly in autumn when severe O3 pollution events are often observed. In this study, linear regression analyses of long-term O3 data in suburban Hong Kong revealed that the variation of autumn O3 obviously leveled off during 2005-2017, mainly due to the significant decrease of autumn O3 in 2013-2017 (period II), despite the increase in 2005-2012 (period I). In addition, the rise of O3 in summer and winter also ceased since 2013. In contrary, O3 continuously increased throughout the spring of 2005-2017, especially in period II. Consequently, an incessant increase of overall O3 was observed during 2005-2017. A statistical model combining Kolmogorov-Zurbenko filter with multiple linear regressions, and a photochemical box model incorporating CB05 mechanism were applied to probe the causes of the above trends. In general, O3 production was controlled by VOC-limited regime throughout 13 years. The meteorological variability and regional transport facilitated the O3 growth in period Ι. In contrast, the unchanged O3 level in period II was attributable to the negative impact of meteorological variability and reduction of regional transport effect on O3 formation and accumulation, as well as the negligible change in locally-produced O3. In autumn of period II, the inhibitory meteorological variability, reduced regional transport, and alleviated local production were the driving force for the hard-earned decrease of O3. However, the remarkable rise of spring O3 was caused by the reduction of NOx, especially in the spring of period II. The findings of the long-term and seasonal variations of O3 pollution in Hong Kong are helpful for future O3 mitigation.

[Analysis of Ozone Pollution Spatio-temporal Evolution Characteristics and Identification of Its Long-term Variation Driving Factor over Hunan Province].

Despite the alleviation of particulate matter (PM), the ambient ozone (O3) concentration is continuously increasing in Hunan province where the investigation of O3 pollution has been rarely reported. Accordingly, the spatio-temporal evolution of O3 pollution was first analyzed based on hourly air quality data observed by national monitoring stations from 2015 to 2020 over 14 cities in Hunan province. Afterwards, the combination of meteorological data from the European Center for Medium-range Weather Forecast (ECMWF) and the generalized additive model (GAM) was applied to investigate the driving factors of the O3 long-term trend during this period. The results presented obvious diurnal, monthly, and seasonal characteristics of O3 variations. High O3 concentrations occurred in May and September monthly, and the peak O3 season was autumn. Furthermore, the 90th percentile O3 increased at a rate of 4.7 µg·(m3·a)-1 temporally, and high O3 values mainly occurred in the north-eastern region spatially, in contrast to the low O3 values in the western region. The modeling results indicated that the increase in O3 was mainly ascribed to precursor emissions. Furthermore, meteorology promoted a rise in O3 with the impact magnitude of 1 µg·(m3·a)-1. Remarkably, meteorology accelerated the O3 increases in spring, summer, and the eastern region, whereas it restrained increases in autumn, winter, and the northwest. The effect of meteorology on PM10 was different from O3 during this period. Overall, this study highlighted the importance of meteorological impacts when regulating emission reduction measures for O3 abatement. It required greater effort regarding O3 mitigation to offset the side-effect from meteorology in meteorology-sensitive seasons and regions. Additionally, the regional corporation is indispensable to reduce O3 transportation from upwind.

Evaluation the effect of nanoparticles on the structure of aptamers by analyzing the recognition dynamics of aptamer functionalized nanoparticles.

Aptamer-functionalized nanoparticles have been widely studied as targeted probes in biomedical applications for targeted therapy and imaging. The rigidity of the nanoparticle could stabilized the spatial structure of the aptamer, ensuring the selectivity and affinity for target recognition in the complex environment. The main aim of this article study was to explore the effect of the spatial structure of aptamer in the interaction between aptamer nanoprobes and receptors. We designed and synthesized aptamer functionalized nanoparticle systems with different derivation lengths, and developed a unique kinetic analysis to quantify affinity interactions. The system used silver decahedral nanoparticles (Ag10NPs), which was then chemically functionalized with thrombin (or IgE) aptamers of different tail lengths to produced different nanoprobes, and employed thrombin (or IgE) as target on a surface plasmon resonance (SPR) biosensor to evaluate the binding of these nanoprobes. Kinetic analysis of the SPR binding curve was performed to evaluated the affinity between nanoprobes and targets. Under the premise of eliminating multivalent interactions, we found that the distance between aptamer and nanoparticle could affect the affinity between nanoprobe and target. Furthermore, we found that keeping a certain distance between aptamer and nanoparticle could effectively improved the recognition efficiency of the aptamer nanoprobe and target. It shows that the rigidity of nanomaterials could maintain the spatial structure of the aptamer.

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.

Identification of long-term evolution of ozone sensitivity to precursors based on two-dimensional mutual verification.

Tropospheric ozone pollution has been continuously worsening in China during the past decade. Identification of long-term evolution of ozone sensitivity to precursors is essential to evaluating the impact of emission reduction measures on ozone pollution. Traditional observation-based model and 3-d numerical model are not suitable for analyzing long-term variation of ozone sensitivity to precursors. In this study, by transforming the conventional ozone isopleth plot into a VOCR isopleth plot in the functional space of NOx and ozone concentrations, we developed a novel approach to identify ozone sensitivity to precursors by simply using long-term monitoring data of ozone, NOx and temperature. This approach estimated ozone formation regimes (OFR) by ozone sensitivity to NOx and temperature separately, and the convergence of OFR serves as a way of mutual verification. We found that ozone formation was generally in the VOCR-limited or transitional regime in Shanghai, the largest metropolitan area in China. However, OFR was shifted to NOx-limited at Pudong station during 2017-19 due much to the stringent NOx emission control. OFR was also shifted to NOx-limited along with the increasing temperature. When temperature was over 30 °C, Shanghai was mostly in a NOx-limited OFR. This highlights that the NOx emission control measures need to be strengthened to reduce peak ozone levels more efficiently. Jinshan station exhibited a different trend with OFR shifted to VOCR-limited in 2017-19, which proved the effectiveness of VOCs emission control on petrochemical sector. However, OFR was shifted to NOx-limited when temperature was over 30 °C, suggesting more stringent VOCs emissions control should be targeted on days with higher temperature.

Synoptic condition-driven summertime ozone formation regime in Shanghai and the implication for dynamic ozone control strategies.

Regarding the continuous worsening of tropospheric ozone pollution, the scenario in Shanghai is a microcosm of the entire China. Understanding the ozone formation regimes (OFRs), their variations, and driving factors is a prerequisite for formulating effective ozone control strategies. Traditional OFR estimation by numerical model, which often involves sensitivity analysis on at least tens of scenarios, is labor-intensive and time-consuming; therefore, it is not appropriate to make OFR forecasts to guide ozone contingency control. In this study, by using a localized modeling system consisting of the Weather Research and Forecasting, Sparse Matrix Operator Kernel Emissions, and Community Multiscale Air Quality models and considering the latest emission inventory over the Yangtze River Delta of China, we discovered a strong connection between the variations of large-scale circulation (LSC) and OFRs over Shanghai in July 2017, thereby providing an alternative way to infer OFR. During the northward movement of Western Pacific Subtropical High from South China Sea, the wind field over Shanghai changed from weak westerly to moderate southwesterly and to one without a distinct direction. The local OFR shifted from anthropogenic volatile organic compounds (AVOCs)-limited to NOx-limited and ultimately to the transitional regime. Such a variation in OFR is essentially driven by the spatial heterogeneity of NOx and AVOC emissions in different directions of Shanghai, brought on by the wind under different LSC patterns. With the existing weather forecasting technology, the LSC patterns can be well-predicted 48-72 h in advance. Hence, we propose the adoption of a dynamic ozone control strategy for Shanghai with the priority control target on AVOC or NOx emission sources adjusted according to the LSC pattern and OFR forecasts in a forthcoming O3 pollution episode. This would serve to maximize the peak ozone reduction under varying pollution conditions.

[Remediation of Decabromodiphenyl Ether Contaminated Sediment Through Plant Roots Enhanced by Exogenous Microbes].

Decabromodiphenyl ether (BDE-209), a main ingredient of brominated flame retardants, has drawn more and more attention because of the pollution it caused in sediment. A pot experiment was conducted in a greenhouse to investigate the impact of Brevibacillus brevis and Enterococcus casselifavus on the enhancement of phytoremediation by Thalia dealbata, which is common in the river bank and was found to be an effective plant for BDE-209 removal. The concentration of organic acids, the amount of microorganisms and the ability of carbon utilization of soil microorganisms in different experimental groups were analyzed. The results showed that the removal rate of BDE-209 in the exogenous microbes containing groups were higher than that of the control. And B. brevis presented the highest enhancement of phytoremediation with the removal rate rising highest to 66% compared with the control (non-rhizosphere group 37.93% and no plant group 39.27%) after 60 days. The removal of BDE-209 in sediment, quantity of microorganism, concentration of organic acids and the ability of carbon utilization of soil microorganisms in rhizosphere sediment were higher than those in non-rhizosphere sediment.