[Characteristics and Driving Factors of O3 Pollution During 13th Five-Year Period in Tianjin].

The spatial distribution, accumulation features, and driving factors of O3 pollution were analyzed using spatial autocorrelation and hotspot analysis and the STIRPAT model based on the high spatiotemporal resolution online monitoring data from 2016 to 2020 in Tianjin. The results showed that the variation characteristics of O3 concentration in Tianjin from 2016 to 2020 had the trend of pollution occurring in advance and the scope of the pollution expanding. The distribution of O3 pollution showed significant aggregation from June to October. High-high value clustering areas included six urban districts, Beichen District, Jinnan District, and Jinghai District. O3 concentration formed high value hot spots in the southwest and low value cold spots in the northeast. Meteorological factors such as temperature, breeze percentage, and sunshine duration, as well as social factors such as NOx emission, VOCs emission, and motor vehicle ownership had significant effects on O3 concentration. The regression fitting effect of the integrated drive STIRPAT model was better than that of the single meteorological factor or social factor models. In order to promote scientific and efficient prevention and control of ozone pollution during the 14th Five-Year Plan period, meteorological conditions require attention; under the goal of "peaking carbon dioxide emissions and achieving carbon neutrality," it is necessary for Tianjin to further improve the emission performance of steel, petrochemicals, thermal power, building materials, and other industries, Additionally, clean upgrading, transformation, and green development should be guided for enterprises to reduce VOCs and NOx emissions. At same time, the increase in fuel vehicle numbers should be controlled, and new energy vehicles should be vigorously promoted to reduce vehicle emissions.

[Spatial-temporal Variation and Driving Factors of Ozone in China from 2019 to 2021 Based on EOF Technique and KZ Filter].

Based on the hourly O3 concentration data of 337 prefectural-level divisions and simultaneous surface meteorological data in China, we applied empirical orthogonal function (EOF) analysis to analyze the main spatial patterns, variation trends, and main meteorological driving factors of O3 concentration in China from March to August in 2019-2021. In this study, a KZ (Kolmogorov-Zurbenko) filter was used to decompose the time series of O3 concentration and simultaneous meteorological factors into corresponding short-term, seasonal, and long-term components in 31 provincial capitals.Then, the stepwise regression was used to establish the relationship between O3 and meteorological factors. Ultimately, the long-term component of O3 concentration after "meteorological adjustment" was reconstructed. The results indicated that the first spatial patterns of O3 concentration showed a convergent change, that is, the volatility of O3 concentration was weakened in the high-value region of variability and enhanced in the low-value region.Before and after the meteorological adjustment, the variation trend of O3 concentration in different cities was different to some extent. The adjusted curve was "flatter" in most cities. Among them, Fuzhou, Haikou, Changsha, Taiyuan, Harbin, and Urumqi were greatly affected by emissions. Shijiazhuang, Jinan, and Guangzhou were greatly affected by meteorological conditions. Beijing, Tianjin, Changchun, and Kunming were greatly affected by emissions and meteorological conditions.

[Main Problems and Refined Solutions of Urban Fugitive Dust Pollution in China].

Fugitive dust poses an important contribution to urban air particulate matter in China. To further improve the level of dust pollution prevention and control, the emission and contribution characteristics of urban fugitive dust were summarized; the main causes of dust pollution were analyzed; and the key links, key indicators, and main measures for prevention and control were clarified, so as to further improve the concept of "accurate dust control." Among all types of fugitive dust sources, road dust and construction dust were the main emission and contribution sources, among which road dust was more prominent. Production activities, vehicle disturbances, and wind erosion were the main dust-generating links of various dust sources. Silt loading was taken as the key control index for road dust prevention and control, whereas silt loading and bare soil (or material) areas were taken as the key control index for construction and other dust sources. Around the key indicators, three main ways to control the road dust and six main measures to control the construction and other dust sources were defined. In addition, some suggestions on the necessary supporting measures for dust control were put forward, so as to provide a comprehensive and beneficial reference for the practical application of dust control in Chinese cities.

[Emission Performance Quantitative Evaluation and Application of Industrial Air Pollution Sources].

Treatment of industrial atmospheric emission sources is an important way to improve air quality, but accurate pollution control remains still an urgent challenge. Taking Xiqing District of Tianjin as an example, based on the second national pollution source census, this study carried out a quantitative evaluation of the pollutant emission performance of industrial enterprises and explored the significance, feasibility, and challenges facing emission performance evaluation. The results show that the emission performance of various industries in Xiqing District vary greatly. The pollutant emission performance level is closely related to an industry's own attributes, development scale, and management level. On the whole, the emission performance level of industries with high production process emission coefficients and a high proportion of small and medium-sized enterprises (such as furniture manufacturing, the metal products industry, ferrous metal smelting, and the rolling processing industry) is worse, while the emission performance of high-end industries represented by computer communication and other electronic equipment manufacturing and automobile manufacturing is generally better. The emission performance of different enterprises in the same industry also varies greatly. For example, the 11 enterprises with the worst performance in the metal machinery manufacturing industry only contributed 0.06% of industrial output yet their PM emission contribution reached 8.50%. The 19 worst-performing enterprises in the rubber and plastic industry contributed 4.76% of industrial output yet their VOCs emissions accounted for 43.59% of the total. At the same time, this study presents an emissions reduction plan according to the relevant technical guidelines of the Ministry of Ecology and Environment. Based on this, the cost of emissions reduction could be cut by as much as 90% when the pollutant emissions reductions of the same scale are reduced. The gap in the pollutant emissions performance of various industries and enterprises, the incongruity between economic benefits and environmental costs, and the important guiding role of emission performance evaluation for emissions reductions demonstrate the necessity of performance evaluation. Overall, this research shows that pollutant emission performance evaluation can effectively support macro-industrial structure adjustment and the environmental governance of meso-micro industrial enterprises, providing an important reference for pollution control interventions.

[Characteristics of Ozone and Source Apportionment of the Precursor VOCs in Tianjin Suburbs in Summer].

From June to August 2018, a 1-hr resolution concentration dataset of ozone and its gaseous precursors (volatile organic compounds(VOCs) and NOx), and meteorological parameters were synchronously monitored by online instruments of the Nankai University Air Quality Research Supersite. The relationships and variation characteristics between ozone and its precursors were analyzed. According to the photochemical age, the initial concentrations of VOCs were calculated, and the photochemical loss of the concentration of VOCs during the daytime (06:00-24:00) was corrected. The initial and directly monitored concentrations of VOCs were incorporated into the PMF model for source apportionment. The results indicated that the mean concentration of O3 in Tianjin in summer was (41.3±25.7)×10-9, while that of VOCs was (13.9±12.3)×10-9. The average concentration of alkane (7.0±6.8)×10-9 was clearly higher than that of other VOC species. The species with high concentrations of alkanes were propane and ethane, accounting for 47% of the total alkane concentration. The average ozone formation potential (OFP) in summer was 52.1×10-9, and the OFP value of alkene was the highest and its contribution reached 57%. During the daytime, alkene loss accounted for 75% of the total VOC loss. The major sources of VOCs that were calculated based on the initial concentration data were the chemical industry and solvent usage (25%), automobile exhaust (22%), combustion source (19%), LPG/NG (19%), and gasoline volatilization (15%), respectively. Compared with the apportionment results based on directly monitored concentrations, the contribution of the chemical industry and solvent usage decreased by 4%, while automobile exhaust decreased by 5%. By combining the results of PMF apportionment and the OFP model to analyze the relative contributions of emission sources to ozone formation, and we found that the highest contribution source of ozone was the chemical industry and solvent usage (26%) in summer. Compared with the analysis results based on the directly monitored concentrations, the OFP values of the chemical industry and solvent usage decreased by 7%, while that of NG/LPG apparently decreased by 13%.

[Effects of VOCs on Ozone Formation in the Tianjin Suburbs in Summer].

Volatile organic compounds (VOCs) play an important role in the formation of ozone. The concentrations of VOCs in the Jinnan District of Tianjin were monitored by the Syntech Spectras GC955 online monitoring system, and the ozone generation potential of VOCs was calculated by the maximum incremental activity factor. The results showed that the total concentration of VOCs in the Jinnan District was (32.33±23.77) µg·m-3, in which the mass concentration of alkane was the highest, and propylene, ethylene and toluene had the highest mass concentration. During the observation period, the ozone formation potential (OFP) of TVOC was 107.81 µg·m-3, and the contribution of alkenes to OFP was the largest, which was 55.80%. Ethylene, isoprene, and toluene accounted for the first three places of OFP contribution rate. The backward trajectory analysis showed that TVOC and its OFPs were different under different trajectories. The estimation of VOCs/NOx volume fraction ratio showed that O3 formation was sensitive to VOCs, which showed that atmospheric photochemical pollution has a considerable degree of regional characteristics. The concentration ratio of ethylbenzene/m,p-xylene, and ethane/acetylene can be used to measure the progress of atmospheric chemical reaction and photochemical age in the air mass, which was proved by the aging process of VOC.

[Localization of Soil Wind Erosion Dust Emission Factor in Beijing].

Soil wind erosion dust is one of the primary sources of fine particulate matter (PM2.5). Compared with the fugitive dust emission inventory of typical domestic provinces and cities, we found that the maximum among the contribution rates of soil wind erosion dust to the local total fugitive dust PM2.5 emission inventory was about 4 orders of magnitude higher than the minimum. This study provided a wind erosion equation and a determination method of parameter values. The remote sensing interpretation, China soil dataset, and meteorological data of each district in Beijing were used to achieve the spatial distribution of the vegetation coverage factor (V), soil erodibility index (I), and climatic factors (C) in the plain area of Beijing. This study also estimated the emission factor of soil wind erosion dust and its spatial distribution. The main conclusions are as follows: ① Taking 2017 and Beijing city as an example, it was found that the climatic factor (C) was underestimated to different extents by domestic scholars, and PM2.5 emission factors were overestimated or underestimated. ② V, I, and C showed apparent spatial differences and the average values of them were 0.63±0.09, 188±73, and 0.029±0.009, respectively. The maximum values of V, I, and C were 1.5, 2.1, and 4.5 times the minimum among all districts, respectively. ③ The PM2.5 emission factor of soil wind erosion dust in Beijing showed a high spatial distribution in the northwest and southeast. The average emission factor of the city was (0.0018±0.0008) t·(hm2·a)-1, which is 0.54 times the highest emission factor (Xicheng District) and 3.12 times the lowest (Pinggu District). The area proportions of standardized emission factors with higher intensity (0.6 to 0.8] and high intensity (0.8 to 1.0] was 0.72% and 0.04%, respectively.

Effects of PHA-665752 and Cetuximab Combination Treatment on In Vitro and Murine Xenograft Growth of Human Colorectal Cancer Cells with KRAS or BRAF Mutations.

BACKGROUND: It remains unknown whether blockade of c-Met signaling and epidermal growth factor receptor signaling is effective in suppressing the growth of human colorectal cancer (CRC) cells. In this study, we investigated the effects of the c-Met inhibitor PHA-665752 alone and in combination with cetuximab on the growth of human CRC cells in vitro and in mouse xenografts. METHODS: Human CRC cell lines (Caco2, HCT-116, and HT-29) and mice bearing HCT-116 xenografts were treated with cetuximab in the absence or presence of PHA-665752. Cell viability and apoptosis were examined using the MTT and TUNEL assays, respectively. Vimentin was measured by immunohistochemistry as a marker for epithelial-to-mesenchymal transition. Western blotting was used to determine signaling protein expression levels. RESULTS: The MTT assay showed that the growth of Caco2, HCT-116, and HT-29 cells was inhibited by PHA-665752 in a dose-dependent manner, but only Caco2 cell growth was suppressed by cetuximab. Combination treatment with PHA-665752 and cetuximab inhibited the proliferation of Caco2 cells and RAS mutant CRC cell lines. However, relative to the PHA-665752-alone treatment group, HT-29 cells with a BRAF mutation showed no noticeable effect. The mean tumor volume in mice treated with cetuximab in combination with PHA-665752 was significantly smaller than that in the mice treated with only cetuximab (P = 0.033) or PHA-665752 (P < 0.01). Similarly, the expression of vimentin in the mice treated with PHA-665752 in combination with cetuximab was significantly lower than that in the mice treated with cetuximab or PHA-665752 alone (P < 0.05 in each case). TUNEL assays revealed that treatment with PHA-665752 in combination with cetuximab markedly increased CRC cell apoptosis. Western blotting analysis of signaling protein expression showed that PHA- 665752 inhibited Met phosphorylation (P < 0.05). In addition, treatment with cetuximab alone or in combination with PHA-665752 effectively inhibited EGFR phosphorylation (P < 0.05). CONCLUSION: Combination treatment with PHA-665752 and cetuximab suppressed in vitro and in vivo CRC cell growth more than treatment with either agent alone did.

Vertical characteristics of PM2.5 during the heating season in Tianjin, China.

In this study, PM2.5 samples were collected at four heights (10m, 40m, 120m and 220m) at a meteorological tower in the daytime and nighttime during the heating season in Tianjin, China. The vertical variation and diurnal variability of the concentrations of PM2.5 and main chemical compositions were analyzed in clear days and heavy pollution days. Generally, mass concentrations of PM2.5 and the chemical compositions showed a decreasing trend with increasing height, while mass percentages of SO4(2-), NO3(-) and OC showed an increasing trend with increasing height. Concentrations of ion species and carbon compound in PM2.5 samples in the daytime were higher than those collected at night, which was due to intense human activities and suitable meteorological condition in the daytime. The ratios of NO3(-)/SO4(2-) and OC/EC were also considered, and we have observed that their levels on heavy pollution days were higher than those on clear days. In addition, source apportionments were identified quantitatively using the CMB-iteration model. The results indicated that contributions of secondary ion species increased with increasing height, while contributions of other pollutant sources decreased, and contributions of vehicle exhaust were relatively high on clear days.

Particulate matter mass and chemical component concentrations over four Chinese cities along the western Pacific coast.

China has witnessed rapid economic growth in the past three decades, especially in coastal areas. Particulate matter (PM) pollution is becoming increasingly serious in China's cities along the western Pacific coast with the rapid development of China's society and economy. This study analyzed PM (PM10 and PM2.5) in terms of their mass and chemical composition in four coastal Chinese cities. The goal was to study the spatial variation and characteristics of PM pollution in sites under different levels of economic development and in diverse natural environments. A distinct trend for concentrations of PM and related chemical species was observed and increased from south to north in Haikou, Ningbo, Qingdao, and Tianjin. Secondary inorganic aerosols, crustal materials, and organic matter dominated the composition of both PM10 and PM2.5. Crustal materials were the most abundant species in the northern coastal areas because these areas have less vegetation cover and lower humidity than southern coastal areas. The presence of high SO4 (2-)/nitrate (NO3 (-)) concentrations indicated that the burning of coals gives significant contributions to PM10 and PM2.5. The differences observed in the characteristics of PM pollution in these coastal cities are probably caused by different levels of industrial and urban development.

Heavy metals in urban ambient PM10 and soil background in eight cities around China.

The ambient PM(10) and background soil samples were collected and analyzed with ICP-AES in eight cities around China to investigate the levels of ten heavy metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pb). The mean concentrations of ten heavy metals in PM(10) of the eight cities of China followed the order of Zn > Pb > Mn > Cu > Ni > Cr > Co > V. The metals in the ambient PM(10) and soil were compared in each city to evaluate the heavy metal mass fraction from anthropogenic sources in ambient air. The CD values in these cities were all above 0.2, indicating that the ingredients spectrums of PM(10) and soil vary markedly. Most heavy metals were enriched in PM(10), except Fe and Ti. The results showed that almost all the cities suffer important heavy metal pollution from anthropogenic sources. The eight cities were also grouped according to their similarity in heavy metals of ambient PM(10) by cluster analysis to investigate the relationship between the heavy metals and the pollution sources of each city. The conclusion was that the eight cities were divided into three clusters which had similar industrial type and economy scale: the first cluster consisted of Shenzhen, Wuxi, and Guiyang; followed by Jinan and Zhengzhou as the second grouping; and the third group had Taiyuan, Urumqi, and Luoyang.

Chemical composition of precipitation and its sources in Hangzhou, China.

To understand the origin and chemical characteristics of precipitation in Hangzhou, rainwater samples were collected from June 2006 to May 2008. All samples were analyzed for pH, electrical conductivity, and major ions (NH4⁺, Ca²âº, Mg²âº, Na⁺, K⁺, SO4²â», NO3⁻, F⁻, and Cl⁻). Acidification of precipitation in Hangzhou was serious with volume-weighted mean pH value of 4.5, while frequency of acid rain was 95%. The calculated SO4²â»/NO3⁻ ratio in Hangzhou precipitation was 2.87, which indicated that the precipitation of Hangzhou belonged to sulfate-based acid rain. The results of acid neutralization analysis showed that not all the acidity in the precipitation of Hangzhou was neutralized by alkaline constituents. The results of sea salt contribution analysis showed that nearly all SO4²â», Ca²âº, and Mg²âº and 33.7% of K⁺ were of non-sea origins, while all Na⁺ and Cl⁻ and 66.3% of K⁺ originated from sea sources. The principal component analysis which was used to analyze the sources of various ions indicated that chemical compositions of precipitation in Hangzhou mainly came from terrestrial sources, factory emissions, fuel wood burning, and marine sources.

Determination of buffering capacity of total suspended particle and its source apportionment using the chemical mass balance approach.

The samples of total suspended particle (TSP) from sources and TSP in the ambient atmosphere were collected in 2006 at Tianjin, People's Republic of China and analyzed for 16 chemical elements, two water-soluble ions, total carbon, and organic carbon. On the basis of the chemical mass balance (CMB) model, the contributions of different TSP sources to the ambient TSP were identified. The results showed that resuspended dust has the biggest contributions to the concentration of ambient TSP. The buffering capacity of each TSP source was also determined by an analytical chemistry method, and the result showed that the constructive dust (the dust emitted from construction work) had the strongest buffering capacity among the measured sources, whereas the coal combustion dust had the weakest buffering capacity. A calculation formula of the source of buffering capacity of ambient TSP was developed based on the result of TSP source apportionment and the identification of the buffering capacity of each TSP source in this study. The results of the source apportionment of the buffering capacity of ambient TSP indicated that open sources (including soil dust, resuspended dust, and constructive dust) were the dominant sources of the buffering capacity of the ambient TSP. Acid rain pollution in cities in Northern China might become serious with a decrease of open source pollution without reducing acidic sources. More efforts must be made to evaluate this potential risk, and countermeasures should be proposed as early as possible.