A review of gas-phase chemical mechanisms commonly used in atmospheric chemistry modelling

The atmospheric chemical mechanism is an essential component of airshed models used for investigating the chemical behaviors and impacts of species. Since the first tropospheric chemical mechanism was proposed in the 1960s, various mechanisms including Master Chemical Mechanism (MCM), Carbon Bond Mechanism (CBM), Statewide Air Pollution Research Center (SAPRC) and Regional Atmospheric Chemistry Mechanism (RACM) have been developed for different research purposes. This work summarizes the development and applications of these mechanisms, introduces their compositions and lumping methods, and compares the ways the mechanisms treat radicals with box model simulations. CBM can reproduce urban pollution events with relatively low cost compared to SAPRC and RACM, whereas the chemical behaviors of radicals and the photochemical production of ozone are described in detail in RACM. The photolysis rates of some oxygenated compounds are low in SAPRC07, which may result in underestimation of radical levels. As an explicit chemical mechanism, MCM describes the chemical processes of primary pollutants and their oxidation products in detail. MCM can be used to investigate certain chemical processes; however, due to its large size, it is rarely used in regional model simulations. A box model case study showed that the chemical behavior of OH and HO₂ radicals and the production of ozone were well described by all mechanisms. CBM and SAPRC underestimated the radical levels for different chemical treatments, leading to low ozone production values in both cases. MCM and RACM are widely used in box model studies, while CBM and SAPRC are often selected in regional simulations.     

Multi-process and multi-pollutant control technology for ultra-low emissions in the iron and steel industry

The iron and steel industry is not only an important foundation of the national economy, but also the largest source of industrial air pollution. Due to the current status of emissions in the iron and steel industry, ultra-low pollutant emission control technology has been researched and developed. Liquid-phase proportion control technology has been developed for magnesian fluxed pellets, and a blast furnace smelting demonstration project has been established to use a high proportion of fluxed pellets (80%) for the first time in China to realize source emission reduction of SO₂ and NO_x. Based on the characteristics of high NO_x concentrations and the coexistence of multiple pollutants in coke oven flue gas, low-NO_x combustion coupled with multi-pollutant cooperative control technology with activated carbon was developed to achieve efficient removal of multiple pollutants and resource utilization of sulfur. Based on the characteristics of co-existing multiple pollutants in pellet flue gas, selective non-catalytic reduction (SNCR) coupled with ozone oxidation and spray drying adsorption (SDA) was developed, which significantly reduces the operating cost of the system. In the light of the high humidity and high alkalinity in flue gas, filter materials with high humidity resistance and corrosion resistance were manufactured, and an integrated pre-charged bag dust collector device was developed, which realized ultra-low emission of fine particles and reduced filtration resistance and energy consumption in the system. Through source emission reduction, process control and end-treatment technologies, five demonstration projects were built, providing a full set of technical solutions for ultra-low emissions of dust, SO₂, NO_x, SO₃, mercury and other pollutants, and offering technical support for the green development of the iron and steel industry.     

NdFeB磁体表面环保型Zn-Al涂层的盐雾腐蚀行为

目的 研究NdFeB磁体表面环保型Zn-Al涂层在盐雾环境中的腐蚀行为。方法 采用SEM、XRD、EDS、拉曼光谱、傅里叶变换红外光谱等对Zn-Al涂层的形貌、物相、成分结构进行分析。通过电化学曲线探究Zn-Al涂层在盐雾环境中的腐蚀机理。结果 在NdFeB磁体表面制备的环保型Zn-Al涂层的耐盐雾腐蚀时间不少于1 000 h。在盐雾腐蚀环境中,Zn-Al涂层表面逐渐被白锈覆盖,失去金属光泽,腐蚀至1 126 h时,Zn-Al涂层表面出现红色锈点,涂层微观组织呈蜂窝状结构,并出现微裂纹。腐蚀产物由Zn_(5)(OH)_(8)Cl_(2)·H_(2)O、Al_(9)SiAl_(12)(OH)_(18)(AlO_(4))(Si_(5)O_(16))Cl、Fe_(2)O_(3)和极少量的Zn、Al组成。腐蚀前期,Zn-Al涂层表面的钝化膜、硅烷膜起保护作用;随腐蚀进行,膜层破坏暴露出片状金属粉,金属粉活化,涂层发挥牺牲阳极保护作用;腐蚀后期,腐蚀介质通过涂层微裂纹穿透涂层至磁体,涂层牺牲阳极的保护作用和物理屏蔽保护作用显著减弱,直至失效。结论 环保型Zn-Al涂层可显著提高NdFeB磁体的耐中性盐雾腐蚀性能。     

2017年春季常州HONO观测及对大气氧化能力影响的评估

本研究于2017年4月在江苏省常州市环境监测中心使用一套基于湿化学法的仪器对大气中的HONO进行了实时在线观测,HONO浓度范围在0.2～13.9μg·m~(-3)之间,平均值为(2.9±2.3)μg·m~(-3);同时,对O_3、 HCHO、 VOCs、光解频率以及气象参数进行了同步监测.利用MCM箱体模式模拟得到白天·OH浓度最大值范围在1.0×10~6～1.4×10~7个·cm~(-3)之间.同时结合观测结果与模式模拟结果计算了HONO、 O_3、 HCHO和H_2O_2的光解以及烯烃臭氧化反应对·OH的生成速率,定量表征大气氧化性,揭示了这5种来源对大气氧化能力的影响:整体上O_3光解(46.4%)HONO光解(41.1%)烯烃臭氧化反应(10.9%)HCHO光解(1.5%)H_2O_2光解(0.1%);清晨时HONO光解对·OH生成起主要作用,之后随着O_3浓度的增加,O_3光解对·OH的贡献占主导地位;在17:00之后,由于太阳光解频率显著降低,烯烃臭氧化反应对·OH生成有主要贡献;甲醛与过氧化氢的光解对·OH的贡献可忽略.     

SGO改性复合纳滤膜的制备及分盐性能

近年来,水资源短缺,水源污染严重,国家对水处理末端的资源化利用提出了更高的要求,分盐过程也受到越来越多的关注.纳滤膜表面通常带有电荷,可以选择性地透过不同价态的离子.基于纳滤膜表面电荷特性不同,为很好地实现盐的分离,将制备的带有磺酸基团的氧化石墨烯引入到纳滤膜材料中,采用界面聚合法,制备了SGO改性复合纳滤膜. Zeta电位分析表明所制备的复合纳滤膜表面的电荷比不添加SGO的纳滤膜更负;红外光谱分析中酯基基团特征峰的出现表明磺酸基团参与了聚合反应; SEM结构表面,膜表面出现了明显的图灵结构,在0. 2 MPa压力下,纯水通量可达45. 85 L·(m~2·h)-1,对Na2SO4截留率为98. 23%,对Na Cl截留率为24. 93%,10 h运行可以很好地实现对SO_4~(2-)、Cl~-的有效分离,可实现盐的资源化回收.     

中国水禽产业时空演进及影响因素——基于全要素生产率增长视角

水禽产业快速发展离不开技术进步的贡献。准确审视水禽产业全要素生产率的时空演进规律,探讨不同阶段水禽全要素生产率（TFP）的提升策略十分重要。基于中国水禽体系产业经济团队的调研数据和固定观测点数据,结合有关年鉴整理出水禽的投入和产出数据,运用GIS技术分析后得出结论：2010—2018年水禽产业时空演进特征为“东退西进,北向南移”。结合永续盘存法和索洛余值,运用数据包络分析法（DEA-Malmquist）估算全国29个省份水禽TFP指数,比较各地区的TFP增长率和贡献率,进而分析此期间的时空演进规律,结果显示：2014年TFP增长率大幅下跌,2015年又逐渐上升,2016年以后才趋于平稳增长,概括水禽TFP增长率的时空变化规律为先降后升的“U”型走势。运用Tobit模型分析其变动的影响因素,结果表明：受H7N9突发事件影响,水禽产业劳动力投入和资本投入发生了改变,主要影响因素为水电及燃料动力投入、基础设施维护及新增投入、疫苗防疫及医疗投入等,这些因素对水禽TFP增长的时空变动影响显著,进一步说明水禽技术效率有待提升,风险规避机制有待完善。     

北京市典型城区餐饮业VOCs和PM2.5排放量估算

以北京市餐饮企业分布密度最大的西城区为案例区,通过对研究区域内餐饮企业进行实地污染物检测及排放活动水平调查,计算得到基于就餐人数、就餐时间、烹饪油用量和灶头数4种核算基准的餐饮业VOCs和PM_2.5排放因子,并利用排放因子法分别估算该区域在餐饮废气净化设备升级改造前后餐饮企业VOCs和PM_2.5年排放量.结果表明：本研究区域餐饮业废气净化设备升级改造前VOCs排放量范围为319.03~506.38t/a,改造后为92.14~109.89t/a;改造前PM_2.5排放量范围为166.55~211.09t/a,改造后为30.22~36.05t/a,排放量明显减少.餐饮业废气净化设备改造后VOCs和PM_2.5减排率分别为71%~82%和80%~86%,餐饮业废气净化设备升级改造减排效果良好.计算得到以街道为单元的餐饮源VOCs和PM_2.5排放强度范围分别为1.45~4.32t/km²和0.47~1.42t/km².通过PM_2.5实测浓度（小时值）数据分析,餐饮业废气净化设备升级改造前、后PM_2.5浓度平均减少了28.9%,最接近于用油量为核算基准的排放因子降低比例.     

海盐非均相反应对山东沿海大气O3浓度的影响

通过改进WRF-CMAQ模型中非均相反应模块,定量研究了2017年夏季和冬季海盐与含氮气体非均相反应对我国山东沿海地区大气O₃浓度的影响.模拟结果表明,考虑海盐气溶胶非均相反应后,山东沿海地区夏季O₃小时浓度增加了0.2×10^-9~6.6×10^-9（0.5%~15.5%）,冬季增加了0.8×10^-9~15.3×10^-9（1.7%~27.4%）,ClNO₂在夏季和冬季分别增加了100×10^-12~250×10^-12,300×10^-12~650×10^-12;夏季O₃浓度增加主要集中在山东东部,而冬季O₃的增加则覆盖了山东大部分地区,表明海盐非均相反应对冬季O₃的影响强度及范围均明显高于夏季.海盐非均相反应引起的O₃浓度增加主要发生在日间,特别是8：00~16：00.该反应对渤海及南黄海大气O₃浓度也有影响,且在这些海域生成的O₃可通过4条传输路径影响山东沿海地区,甚至可影响到济南、菏泽等山东中西部地区（距离山东东部海岸线~350km）;海洋大气中O₃的传输可造成山东东部沿海O₃浓度升高0.2×10^-9~15.3×10^-9,山东中西部O₃升高0.3×10^-9~6.2×10^-9.     

Impact of meteorological condition changes on air quality and particulate chemical composition during the COVID-19 lockdown

Stringent quarantine measures during the Coronavirus Disease 2019 (COVID-19) lockdown period (January 23, 2020 to March 15, 2020) have resulted in a distinct decrease in anthropogenic source emissions in North China Plain compared to the paralleled period of 2019. Particularly, 22.7% decrease in NO₂ and 3.0% increase of O₃ was observed in Tianjin, nonlinear relationship between O₃ generation and NO₂ implied that synergetic control of NO_x and VOCs is needed. Deteriorating meteorological condition during the COVID-19 lockdown obscured the actual PM_2.5 reduction. Fireworks transport in 2020 Spring Festival (SF) triggered regional haze pollution. PM_2.5 during the COVID-19 lockdown only reduced by 5.6% in Tianjin. Here we used the dispersion coefficient to normalize the measured PM_2.5 (DN-PM_2.5), aiming to eliminate the adverse meteorological impact and roughly estimate the actual PM_2.5 reduction, which reduced by 17.7% during the COVID-19 lockdown. In terms of PM_2.5 chemical composition, significant NO₃^? increase was observed during the COVID-19 lockdown. However, as a tracer of atmospheric oxidation capacity, odd oxygen (O_x = NO₂ + O₃) was observed to reduce during the COVID-19 lockdown, whereas relative humidity (RH), specific humidity and aerosol liquid water content (ALWC) were observed with noticeable enhancement. Nitrogen oxidation rate (NOR) was observed to increase at higher specific humidity and ALWC, especially in the haze episode occurred during 2020SF, high air humidity and obvious nitrate generation was observed. Anomalously enhanced air humidity may response for the nitrate increase during the COVID-19 lockdown period.     

Electrochemical reduction of Cr(VI) in the presence of sodium alginate and its application in water purification

Chromium (Cr) is used in many manufacturing processes, and its release into natural waters is a major environmental problem today. Low concentrations of Cr(VI) are toxic to human health and living organisms due to the carcinogenic and mutagenic nature of this mineral. This work examined the conversion of Cr(VI) to Cr(III) via electrochemical reduction using gold electrode in an acidic sodium alginate (SA) solution and subsequent removal of the produced Cr(III)-SA by the polymer-enhanced ultrafiltration (PEUF) technique. A solution of SA in nitric acid was used both as an electrolytic medium during the voltammetric measurements and bulk electrolysis and as an extracting agent during the PEUF technique. The electroanalysis of Cr(VI) was performed by linear sweep voltammetry in the presence of acidic SA solution to study its voltammetric behavior as a function of the Cr(VI) concentration, pH, presence of Cr(III), SA concentration and scan rate. In addition, the quantitative reduction of Cr(VI) to Cr(III) was studied through the bulk electrolysis technique.The results showed efficient reduction with well-defined peaks at approximately 0.3 V vs. Ag/AgCl, using a gold working electrode. As the pH increased, the reduction signal strongly decreased until its disappearance. The optimum SA concentration was 10 mmol/L, and it was observed that the presence of Cr(III) did not interfere in the Cr(VI) electroanalysis. Through the quantitative reduction by bulk electrolysis in the presence of acidic SA solution, it was possible to reduce all Cr(VI) to Cr(III) followed by its removal via PEUF.