Diagnosing the Model Bias in Simulating Daily Surface Ozone Variability Using a Machine Learning Method: The Effects of Dry Deposition and Cloud Optical Depth.

Machine learning methods are increasingly used in air quality studies to predict air pollution levels, while few applied them to diagnose and improve the underlying mechanisms controlling air pollution represented in chemical transport models (CTMs). Here, we use the random forest (RF) method to diagnose high biases of surface daily maximum 8 h average (MDA8) ozone concentrations in the GEOS-Chem CTM evaluated against measurements from the nationwide monitoring network in summer 2018 over China. The feature importance results show that cloud optical depth (COD), relative humidity, and precipitation are the top three factors affecting CTM high biases. Such results indicate that the high ozone biases in summer over China mainly occur on wet/cloudy days (∼40% biased high), while biases on dry/clear days are small (within 5%). We link the important features with model parameterizations and variables, identifying model underestimates in the dry deposition velocity and COD on wet/cloudy days. By accounting for the enhanced dry deposition on wet plant cuticles and using satellite observation constrained COD, we find that CTM high ozone biases can be halved with an improved agreement in the temporal variability, highlighting the effects of dry deposition and COD on ozone, as suggested by the RF outcomes.

Spatial and temporal variations of surface background ozone in China analyzed with the grid-stretching capability of GEOS-Chem High Performance.

Surface background ozone, defined as the ozone in the absence of domestic anthropogenic emissions, is important for developing emission reduction strategies. Here we apply the recently developed GEOS-Chem High Performance (GCHP) global atmospheric chemistry model with ∼0.5° stretched resolution over China to understand the sources of Chinese background ozone (CNB) in the metric of daily maximum 8 h average (MDA8) and to identify the drivers of its interannual variability (IAV) from 2015 to 2019. The GCHP ozone simulations over China are evaluated with an ensemble of surface and aircraft measurements. The five-year national-mean CNB ozone is estimated as 37.9 ppbv, with a spatially west-to-southeast downward gradient (55 to 25 ppbv) and a summer peak (42.5 ppbv). High background levels in western China are due to abundant transport from the free troposphere and adjacent foreign regions, while in eastern China, domestic formation from surface natural precursors is also important. We find greater importance of soil nitric oxides (NOx) than biogenic volatile organic compound emissions to CNB ozone in summer (6.4 vs. 3.9 ppbv), as ozone formation becomes increasingly NOx-sensitive when suppressing anthropogenic emissions. The percentage of daily CNB ozone to total surface ozone generally decreases with increasing daily total ozone, indicating an increased contribution of domestic anthropogenic emissions on polluted days. CNB ozone shows the largest IAV in summer, with standard deviations (seasonal means) of ∼5 ppbv over Qinghai-Tibet Plateau (QTP) and >3.5 ppbv in eastern China. CNB values in QTP are strongly correlated with horizontal circulation anomalies in the middle troposphere, while soil NOx emissions largely drive the IAV in the east. El Nino can inhibit CNB ozone formation in Southeast China by increased precipitation and lower temperature locally in spring, but enhance CNB in Southwest China through increased biomass burning emissions in Southeast Asia.

The underappreciated role of agricultural soil nitrogen oxide emissions in ozone pollution regulation in North China.

Intensive agricultural activities in the North China Plain (NCP) lead to substantial emissions of nitrogen oxides (NOx) from soil, while the role of this source on local severe ozone pollution is unknown. Here we use a mechanistic parameterization of soil NOx emissions combined with two atmospheric chemistry models to investigate the issue. We find that the presence of soil NOx emissions in the NCP significantly reduces the sensitivity of ozone to anthropogenic emissions. The maximum ozone air quality improvements in July 2017, as can be achieved by controlling all domestic anthropogenic emissions of air pollutants, decrease by 30% due to the presence of soil NOx. This effect causes an emission control penalty such that large additional emission reductions are required to achieve ozone regulation targets. As NOx emissions from fuel combustion are being controlled, the soil emission penalty would become increasingly prominent and shall be considered in emission control strategies.

Design and synthesis of novel N()-substituted thiosemicarbazones bearing a pyrrole unit as potential anticancer agents.

A series of N(4)-substituted thiosemicarbazones (TSCs) bearing pyrrole unit (1a-1e) were synthesized and fully characterized by elemental analyses, infrared spectra, 1H nuclear magnetic resonance and single crystal X-ray diffraction. The compounds were assessed as potential chemotherapeutic agents. All newly synthesized compounds were screened for their anticancer activity against lung cancer PC-9, esophageal cancer Eca-109 and gastric cancer SGC-7901 cell lines. The results of MTT, Terminal deoxynucleotidyl transferase dUTP nick end labeling and fluorescence-activated cell sorting assays indicated that all the prepared compounds exhibited cytotoxicity against PC-9, Eca-109 and SGC-7901 cells in vitro. All the compounds significantly induced cancer cell apoptosis accompanied by increasing the Bax/Bcl-2 ratio and activation of caspase-3. The structure-activity association was discussed and the potential pre-clinical trials may be conducted. The present findings have a great potential in biomedical applications of novel N(4)-substituted TSCs.