Characterization of submicron particles during autumn in Beijing, China

In this study, we performed a highly time-resolved chemical characterization of nonrefractory submicron particles(NR-PM_1) in Beijing by using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer(HR-ToF-AMS). The results showed the average NR-PM_1 mass concentration to be 56.4 ± 58.0 μg/m~3, with a peak at 307.4 μg/m~3. Due to the high frequency of biomass burning in autumn, submicron particles significantly increased in organic content, which accounted for 51% of NR-PM_1 on average. Secondary inorganic aerosols(sulfate + nitrate + ammonium) accounted for 46% of NR-PM_1, of which sulfate,nitrate, and ammonium contributed 15%, 20%, and 11%, respectively. To determine the intrinsic relationships between the organic and inorganic species, we used the positive matrix factorization(PMF) model to merge the high-resolution mass spectra of the organic species and NO+and NO_2~+ions. The PMF analysis separated the mixed organic and nitrate(NO+and NO_2~+) spectra into four organic factors, including hydrocarbon-like organic aerosol(HOA), oxygenated organic aerosol(OOA), cooking organic aerosol(COA), and biomass burning organic aerosol(BBOA), as well as one nitrate inorganic aerosol(NIA) factor. COA(33%) and OOA(30%) contributed the most to the total organic aerosol(OA) mass, followed by BBOA(20%) and HOA(17%). We successfully quantified the mass concentrations of the organic and inorganic nitrates by the NO+and NO2+ions signal in the organic and NIA factors. The organic nitrate mass varied from 0.01-6.8 μg/m~3, with an average of 1.0 ±1.1 μg/m~3, and organic nitrate components accounted for 10% of the total nitrate mass in this observation.     

Effects of TiO2 nanoparticles on the aquatic plant Spirodela polyrrhiza: Evaluation of growth parameters, pigment contents and antioxidant enzyme activities

Plants are essential components of all ecosystems and play a critical role in environmental fate of nanoparticles. However, the toxicological impacts of nanoparticles on plants are not well documented. Titanium dioxide nanoparticles (TiO₂-NPs) are produced worldwide in large quantities for a wide range of purposes. In the present study, the uptake of TiO₂-NPs by the aquatic plant Spirodela polyrrhiza and the consequent effects on the plant were evaluated. Initially, structural and morphological characteristics of the used TiO₂-NPs were determined using XRD, SEM, TEM and BET techniques. As a result, an anatase structure with the average crystalline size of 8nm was confirmed for the synthesized TiO₂-NPs. Subsequently, entrance of TiO₂-NP_S to plant roots was verified by fluorescence microscopic images. Activity of a number of antioxidant enzymes, as well as, changes in growth parameters and photosynthetic pigment contents as physiological indices were assessed to investigate the effects of TiO₂-NPs on S. polyrrhiza. The increasing concentration of TiO₂-NPs led to the significant decrease in all of the growth parameters and changes in antioxidant enzyme activities. The activity of superoxide dismutase enhanced significantly by the increasing concentration of TiO₂-NPs. Enhancement of superoxide dismutase activity could be explained as promoting antioxidant system to scavenging the reactive oxygen species. In contrast, the activity of peroxidase was notably decreased in the treated plants. Reduced peroxidase activity could be attributed to either direct effect of these particles on the molecular structure of the enzyme or plant defense system damage due to reactive oxygen species.     

山西省CO2排放影响因素研究及情景分析

山西作为我国的能源大省,其碳排放强度更是持续位于全国最高水平,分析山西省CO₂排放影响因素,探究其发展模式,对于山西省的低碳发展意义重大.基于STIRPAT模型,将山西省能源CO₂排放的影响因素确定为人口、城镇化率、人均GDP、第二产业占GDP比重、能源强度.在岭回归拟合分析的基础上,利用灰色GM（1,1）模型对山西省CO₂排放驱动因素值进行预测,以提高能源CO₂排放预测的准确性,并结合情景分析方法,为山西省的CO₂减排设计了10种不同的发展情景.结果表明:①人口对山西省CO₂排放影响最大,其次是城镇化率和第二产业占GDP比重.②在当前经济发展阶段,能源强度和人均GDP等因素对山西省的CO₂排放影响不大,但能源强度对CO₂排放的抑制作用不可忽略.③山西省CO₂减排最佳的情景方案为适当控制人口数量和城镇化进程、加快产业结构的转型和技术的革新、降低第二产业占GDP比重和能源强度,并且大力推广新能源和清洁可再生能源的开发使用以优化能源消费结构.在该情景下,山西省2020年的CO₂排放量可以控制在5.16×108 t.      

铁纳米线对水中Cu2+的吸附性能及机理

为研究nZVI（纳米零价铁）材料对水中Cu2+的吸附性能,采用液相还原法合成核壳结构的nZVI,即FSCNs（铁纳米线,Fe@Fe₂O₃ core-shell nanowires）.通过批处理吸附试验研究pH、离子强度、FSCNs投加量、反应时间、初始ρ（Cu2+）、反应温度等因素对Cu2+去除率的影响,运用动力学模型、等温吸附模型和吸附热力学模型分析FSCNs对Cu2+的吸附特性,并利用SEM（扫描电镜）、XRD（X射线衍射）和XPS（X射线光电子能谱）等表征手段探讨FSCNs对Cu2+的吸附机制.结果表明:①在pH为5、离子强度为0.01 mol/L、FSCNs投加量为0.5 g/L、反应温度为318 K条件下,FSCNs对Cu2+产生的吸附容量最大,为387.6 mg/g.②FSCNs对Cu2+的吸附反应在30 min内达到吸附平衡,此时的最大吸附率可达96%;FSCNs对Cu2+的吸附更符合准二级动力学模型（R2≥0.992）,表明化学吸附可能为该反应的限制步骤;Langmuir和Freundlich等温吸附模型均能较好地拟合吸附结果（R2≥0.992）;该吸附过程是自发的吸热反应〔ΔG0（吉布斯标准自由能） < 0,ΔH0（标准焓变）>0〕.③大部分Cu2+在加入FSCNs后转化为Cu、Cu₂O和CuO,被吸附在FSCNs表面,吸附、还原与共沉淀可能是FSCNs去除水中Cu2+的主要机理.研究显示,FSCNs对Cu2+的最大吸附容量为387.6 mg/g,能快速高效吸附水中的Cu2+,应用前景良好.      

Long-term observations of tropospheric NO2, SO2 and HCHO by MAX-DOAS in Yangtze River Delta area, China

Yangtze River Delta(YRD) area is one of the important economic zones in China. However,this area faces increasing environmental problems. In this study, we use ground-based multi-axis differential optical absorption spectroscopy(MAX-DOAS) network in Eastern China to retrieve variations of NO_2, SO_2, and formaldehyde(HCHO) in the YRD area. Three cities of YRD(Hefei, Nanjing, and Shanghai) were selected for long-term observations. This paper presents technical performance and characteristics of instruments, their distribution in YRD, and results of vertical column densities(VCDs) and profiles of NO_2, SO_2, and HCHO.Average diurnal variations of tropospheric NO_2 and SO_2 in different seasons over the three stations yielded minimum values at noon or in the early afternoon, whereas tropospheric HCHO reached the maximum during midday hours. Slight reduction of the pollutants in weekends occurred in all the three sites. In general trace gas concentrations gradually reduced from Shanghai to Hefei. Tropospheric VCDs of NO_2, SO_2, and HCHO were compared with those from Ozone Monitoring Instrument(OMI) satellite observations, resulting in R~2 of 0.606, 0.5432, and 0.5566, respectively. According to analysis of regional transports of pollutants, pollution process happened in YRD under the north wind with the pollution dissipating in the southeast wind. The feature is significant in exploring transport of tropospheric trace gas pollution in YRD, and provides basis for satellite and model validation.     

Soot reduction by addition of dimethyl carbonate in normal and inverse ethylene diffusion flames: Nanostructural evidence

Oxygenated fuel represents an attractive alternative as an additive for reducing soot emissions.Dimethyl carbonate(DMC) is an oxygenated compound which is a good option to reduce soot,but the detailed characteristics of soot produced from combustion of hydrocarbon fuels blended with DMC are still lacking. The present research studied the nanostructure and reactivity of soot particles in ethylene/DMC normal and inverse diffusion flames. High resolution transmission electron microscopy(HRTEM), X-ray diffraction(XRD), and thermogravimetric analysis(TGA)were used to analyze the nanostructure and reactivity of soot. It was found that DMC addition was effective in decreasing the average weights of soot formed in flames. The results of HRTEM images showed that soot particles obtained with DMC addition showed liquid-like material and tight bonding, and exhibited more highly disorganized layers, which give it higher reactivity than soot obtained without DMC addition. Furthermore, HRTEM was used to analyze soot fringe characteristics consisting of fringe tortuosity, fringe length, and fringe separation. XRD was used to crosscheck the results for fringe separation, and was consistent with HRTEM results. In addition, the mass loss curve of TGA experiments showed that DMC addition could enhance the reactivity of soot particles.     

Alkali resistance promotion of Ce-doped vanadium-titanic-based NH3-SCR catalysts

The effect of K deactivation on V_2O_5/WO_3-TiO_2 and Ce-doped V_2O_5/WO_3-TiO_2 catalysts in the selective catalytic reduction(SCR) of NOxby NH_3 was studied.Ce-doped V_2O_5/WO_3-TiO_2 showed significantly higher resistance to K deactivation than V_2O_5/WO_3-TiO_2.Ce-doped V_2O_5/WO_3-TiO_2 with K/V = 4(molar ratio) showed 90% NOxconversion at 350°C,whereas in this case V_2O_5/WO_3-TiO_2 showed no activity.The fresh and K-poisoned V_2O_5/WO_3-TiO_2 and Ce-doped V_2O_5/WO_3-TiO_2 catalysts were investigated by means of in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS),NH_3-temperature progress decomposition(NH_3-TPD),X-ray photoelectron spectroscopy(XPS) and H2-temperature program reduction(H_2-TPR).The effect of Ce doping on the improving resistance to K of V_2O_5/WO_3-TiO_2 were discussed.     

利用集合均方根卡尔曼滤波反演重庆地区SO2源排放

传统的"自下而上"清单方法估算的排放清单,其数据的准确性和时效性存在较大局限.基于集合均方根卡尔曼滤波的源清单反演方法,结合WRF-CMAQ（天气研究和预报模式-公共多尺度空气质量模型）被用于对以清华大学编制的2010年MEIC（中国多尺度排放清单模型）排放清单为基础制作的重庆地区SO₂排放源进行反演试验以解决准确性和时效性问题,试验时间段为2014年10月15-31日,重庆主城17个环境空气质量国控监测点ρ（SO₂）小时观测资料用于反演及检验.结果表明:该方法能够反演重庆地区SO₂源排放量,随着反演次数增加,基于反演排放源预报的ρ（SO₂）预报误差持续减小,反演4次后预报误差达到比较低的稳定的水平,其均方根误差均低于20 μg/m3. 5次反演后SO₂源排放量用于2014年10月24-29日每天起始预报,其预报的站点、时间平均的均方根误差从100~400 μg/m3降至30 μg/m3以下.反演中应用局地化尺度减少集合取样误差影响,54与81 km两个局地化尺度反演结果对预报改善效果相当,表明主要影响重庆主城ρ（SO₂）的源排放位于主城及周边地区,也说明内源排放对重庆主城ρ（SO₂）起主要影响.反演后面源排放量主城区降幅约为30 kg/（d·km2）,周边地区减少10~20 kg/（d·km2）,主城区部分SO₂点源排放量降幅约为25 kg/（d·km2）,说明2010年MEIC排放清单高估了试验时段重庆地区的SO₂排放.      

Seasonal variation and chemical composition of particulate matter: A study by XPS, ICP-AES and sequential microanalysis using Raman with SEM/EDS

During the winter period (January–March 2016), the total suspended particles (TSP) and particulate matter smaller than 2.5 μm (PM_2.5) were characterized by the application of various analytical techniques in four zones of the Metropolitan Area of Monterrey in Mexico. To evaluate the seasonal variation of some elements in the particulate matter, the results of this study were compared with those obtained during the summer season (July–September 2015). The speciation of the C_1s signal by X-ray photoelectron spectroscopy revealed the contribution of aromatic and aliphatic hydrocarbons as the main components in both seasons. Conversely, carboxylic groups associated with biogenic emissions were detected only in winter. The percentages of SO₄^2 ? ions were lower in winter, possibly caused by the decrease in the solar radiation, and relative humidity recorded. The results of the ICP analysis revealed that Fe, Zn and Cu were the most abundant metals in both TSP and PM_2.5 in the two seasons. There were significant seasonal variations for concentrations of As, Ni and Zn in the urban area and for Fe, As, Cd, Ni and Zn in the industrial zone. This was attributed to the greater burning of fuels as well as to an increase in vehicular traffic, the effect of thermal inversion and changes in some meteorological parameters. The results of the sequential microanalysis by Raman spectroscopy and SEM/EDS allowed observation of deposits of carbonaceous material on the particles and to perform the speciation of particles rich in Fe and Pb, which helped infer their possible emission sources.