Observationally constrained modeling of atmospheric oxidation capacity and photochemical reactivity in Shanghai, China

16 pags., 8 figs., 2 tabs.An observation-based model coupled to the Master Chemical Mechanism (V3.3.1) and constrained by a full suite of observations was developed to study atmospheric oxidation capacity (AOC), OH reactivity, OH chain length and HOx (=OHCHO) budget for three different ozone (O3) concentration levels in Shanghai, China. Five months of observations from 1 May to 30 September 2018 showed that the air quality level is lightly polluted or worse (Ambient Air Quality Index, AQI, of > 100) for 12 d, of which ozone is the primary pollutant for 10 d, indicating ozone pollution was the main air quality challenge in Shanghai during summer of 2018. The levels of ozone and its precursors, as well as meteorological parameters, revealed the significant differences among different ozone levels, indicating that the high level of precursors is the precondition of ozone pollution, and strong radiation is an essential driving force. By increasing the input JNO value by 40 %, the simulated O3 level increased by 30 %-40 % correspondingly under the same level of precursors. The simulation results show that AOC, dominated by reactions involving OH radicals during the daytime, has a positive correlation with ozone levels. The reactions with non-methane volatile organic compounds (NMVOCs; 30 %-36 %), carbon monoxide (CO; 26 %-31 %) and nitrogen dioxide (NO; 21 %-29 %) dominated the OH reactivity under different ozone levels in Shanghai. Among the NMVOCs, alkenes and oxygenated VOCs (OVOCs) played a key role in OH reactivity, defined as the inverse of the OH lifetime. A longer OH chain length was found in clean conditions primarily due to low NO in the atmosphere. The high level of radical precursors (e.g., O3, HONO and OVOCs) promotes the production and cycling of HOx, and the daytime HOx primary source shifted from HONO photolysis in the morning to O3 photolysis in the afternoon. For the sinks of radicals, the reaction with NO dominated radical termination during the morning rush hour, while the reactions of radical-radical also contributed to the sinks of HOx in the afternoon. Furthermore, the top four species contributing to ozone formation potential (OFP) were HCHO, toluene, ethylene and m/p-xylene. The concentration ratio (∼ 23 %) of these four species to total NMVOCs is not proportional to their contribution (∼ 55 %) to OFP, implying that controlling key VOC species emission is more effective than limiting the total concentration of VOC in preventing and controlling ozone pollution.This research has been supported by the National Key Research and Development Program of China (grant nos. 2017YFC0210002, 2016YFC0200401 and 2018YFC0213801), the National Natural Science Foundation of China (grant nos. 41775113, 21777026 and 21607104), the Shanghai Pujiang Talent Program (grant no. 17PJC015), and the Shanghai Rising-Star Program (grant no. 18QA1403600). This work was also funded by The Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning and Shanghai Thousand Talents Program

Emissions of volatile organic compounds (VOCs) from cooking and their speciation: A case study for Shanghai with implications for China

Cooking emission is one of sources for ambient volatile organic compounds (VOCs), which is deleterious to air quality, climate and human health. These emissions are especially of great interest in large cities of East and Southeast Asia. We conducted a case study in which VOC emissions from kitchen extraction stacks have been sampled in total 57 times in the Megacity Shanghai. To obtain representative data, we sampled VOC emissions from kitchens, including restaurants of seven common cuisine types, canteens, and family kitchens. VOC species profiles and their chemical reactivities have been determined. The results showed that 51.26% ± 23.87% of alkane and 24.33 ± 11.69% of oxygenated VOCs (O-VOCs) dominate the VOC cooking emissions. Yet, the VOCs with the largest ozone formation potential (OFP) and secondary organic aerosol potential (SOAP) were from the alkene and aromatic categories, accounting for 6.8–97.0% and 73.8–98.0%, respectively. Barbequing has the most potential of harming people's heath due to its significant higher emissions of acetaldehyde, hexanal, and acrolein. Methodologies for calculating VOC emission factors (EF) for restaurants that take into account VOCs emitted per person (EFperson), per kitchen stove (EFkitchen stove) and per hour (EFhour) are developed and discussed. Methodologies for deriving VOC emission inventories (S) from restaurants are further defined and discussed based on two categories: cuisine types (Stype) and restaurant scales (Sscale). The range of Stype and Sscale are 4124.33–7818.04 t/year and 1355.11–2402.21 t/year, respectively. We also found that Stype and Sscale for 100,000 people are 17.07–32.36 t/year and 5.61–9.95 t/year, respectively. Based on Environmental Kuznets Curve, the annual total amount of VOCs emissions from catering industry in different provinces in China was estimated, which was 5680.53 t/year, 6122.43 t/year, and 66,244.59 t/year for Shangdong and Guangdong provinces and whole China, respectively. Large and medium-scaled restaurants should be paid more attention with respect to regulation of VOCs

Dramatically Enhanced Mechanical Properties of Nano-TiN-Dispersed n-Type Bismuth Telluride by Multi-Effect Modulation

Bismuth telluride (Bi2Te3)-based alloys have been extensively employed in energy harvesting and refrigeration applications for decades. However, commercially produced Bi2Te3-based alloys using the zone-melting (ZM) technique often encounter challenges such as insufficient mechanical properties and susceptibility to cracking, particularly in n-type Bi2Te3-based alloys, which severely limit the application scenarios for bismuth telluride devices. In this work, we seek to enhance the mechanical properties of n-type Bi2Te2.7Se0.3 alloys while preserving their thermoelectrical performance by a mixed mechanism of grain refinement and the TiN composite phase-introduced pinning effect. These nanoscale processes, coupled with the addition of TiN, result in a reduction in grain size. The pinning effects of nano-TiN contribute to increased resistance to crack propagation. Finally, the TiN-dispersed Bi2Te2.7Se0.3 samples demonstrate increased hardness, bending strength and compressive strength, reaching 0.98 GPa, 36.3 MPa and 74 MPa. When compared to the ZM ingots, those represent increments of 181%, 60% and 67%, respectively. Moreover, the thermoelectric performance of the TiN-dispersed Bi2Te2.7Se0.3 samples is identical to the ZM ingots. The samples exhibit a peak dimensionless figure of merit (ZT) value of 0.957 at 375 K, with an average ZT value of 0.89 within the 325–450 K temperature range. This work has significantly enhanced mechanical properties, increasing the adaptability and reliability of bismuth telluride devices for various applications, and the multi-effect modulation of mechanical properties demonstrated in this study can be applied to other thermoelectric material systems

Unexpected fast radical production emerges in cool seasons: implications for ozone pollution control

Ozone is a crucial air pollutant that damages human health and vegetation. As it is related to the photo-oxidation of the nitrogen oxides and volatile organic compounds, the summertime reduction of these precursors is the primary focus of current ozone mitigation strategies. During ozone pollution episodes in eastern China, an observed accumulation of daily total oxidants (Ox=NO2+O3) in cool seasons (spring and autumn: 60 ppb and winter 40 ppb) is comparable to that in summer (60 ppb), indicating fast photochemical production of secondary pollutants including ozone over the year. Unrecognized fast radical primary productions are found to counteract the increased termination of hydroxyl radical and unfavorable meteorological conditions to maintain the rapid total oxidant formations in cool seasons. Elucidating and regulating the primary radical sources may be critical for the secondary air pollution control in cool seasons

Assessing the effect of reactive oxygen species and volatile organic compound profiles coming from certain types of Chinese cooking on the toxicity of human bronchial epithelial cells

The International Agency of Research on Cancer identifies high-temperature frying, which features prominently in Chinese cooking, as producing group 2A carcinogens. This study simultaneously characterized particulate and gaseous-phase cooking emissions, monitored their reactive oxygen species (ROS) concentrations, and evaluated their impact on genetic damage and expression in exposed human bronchial epithelial cells. Five types of edible oil, three kinds of seasonings, and two dishes were assessed. Among tested edible oils, heating of soybean oil released the largest particle number concentration (2.09 × 1013 particles/(g cooking material and oil)·h) and volatile organic compounds (VOCs) emissions (12103.42 μg/(g cooking material and oil)·h). Heating of lard produced the greatest particle mass concentration (0.75 mg/(g cooking material and oil)·h). The main finding was that sunflower and rapeseed oils produced the highest ROS concentrations (80.48 and 71.75 nmol/(g cooking material and oil)·h, respectively). ROS formation most likely occurred during the autoxidation of both polyunsaturated and monounsaturated fatty acids. Among all the tested parameters, only ROS concentrations exhibited consistency with cell viability and showed significant correlations with the expression levels of CYP1A1, HIF-1a, and especially with IL-8 (the marker for oxidative stress within the cell). These findings indicate that ROS concentration is potentially a suitable metric for direct assessment of exposure levels and potential toxicity.</p