城市雾天单个矿物颗粒物理和化学特征

应用场发射扫描电镜(FESEM)和带能谱的扫描电镜(SEM-EDX)对北京冬季雾天和正常天气下收集的4个样品进行研究.雾天中矿物颗粒的数量-粒度分布的峰值出现在0.1～0.3 μm和1～2.5 μm之间,并且发现雾天出现的二次矿物颗粒的数量百分含量(4.67%)高于正常天气条件(0.12%).单个矿物颗粒的EDX能谱显示,雾天和正常天气中单个矿物颗粒的主要化学成分有一定的差别,尤其是S元素.矿物颗粒分为9种不同类型:"富Si"、"富Ca"、"富S"、"富Fe""富Mg"、"富Al"、"富Ti"、"富K"和"富Cl",其中雾天"富Ca"中55%的颗粒含有Ca(50%±1.2%)和S(37%±1.6%),"富S"中72%的颗粒含有S(44%±1.5%)和Ca(33%±2%),说明了雾天中绝大部富集S的颗粒物中同时富集Ca,这在一定程度上说明了北京市大气中这些含Ca的碱性矿物对雾水酸性有一定的缓冲作用.雾天样品中S/Ca的平均比值为6.11,如果以冬季正常天气条件下S/Ca的均值0.73为背景值,雾天中S/Ca的比值是冬季正常天气的8倍,可见雾天中颗粒物表面的硫化现象相当严重,同时也显示出雾天SO2向硫酸盐的转化率比较高.     

飞行时间二次离子质谱法在一次污染过程中PM2.5表面组分分析中的应用

团簇离子源的发明和使用，使飞行时间二次离子质谱（TOF-SIMS）法成为材料表面化学分析越来越重要的手段，TOF-SIMS法的主要测试功能包括表层质谱、化学成像及深度剖析3种。采用TOF-SIMS法对一次污染过程中的大气细颗粒物（PM_2.5）的表层进行检测，得到了PM_2.5表面成分的质谱及成像信息。结果表明：PM_2.5表层存在多种金属离子，通过扫描电子显微镜能谱仪的形貌与飞行时间二次离子质谱仪的成像亮度分析可知，K⁺、Na⁺、Mg²⁺响应强度相对较强，含量较高；通过原子吸收光谱仪进行金属离子定量可知，2018年11月4日和12月24日的K⁺、Na⁺、Mg²⁺的平均质量分别为1.809 5、0.443 8、1.526 2 mg；从形态分布上看，PM_2.5表面烟尘集合体含量较多，其次为燃煤飞灰、矿物颗粒和超细未知颗粒；PM_2.5表层的有机物离子C_xH_y片段也较多，经过m/z的测试数据进一步确定，表明颗粒物表层含有大量的脂肪烃和芳香烃；除此之外，还存在含N、O、S等的有机物和无机物。     

Reaction hazard and mechanism study of H2O2 oxidation of 2-butanol to methyl ethyl ketone using DSC,Phi-TEC II and GC-MS

Methyl ethyl ketone (MEK) oxidation via H₂O₂ with tungsten-based polyoxometalate catalysts has gained much attention with an ever-growing body of knowledge focusing on the development of environmentally benign processes in chemical industry. In this study, two calorimetry techniques, differential scanning calorimetry (DSC) and Phi-TEC II adiabatic calorimetry, were employed to analyze the thermal hazards associated with the 2-butanol oxidation reaction system. Hydrogen peroxide was the oxidant and a tungsten-based polyoxometalate as the catalyst. Gas chromatography-mass spectrometry was used for identification of the organic products. Important thermal kinetic data were obtained including “onset” temperature, heat of reaction, adiabatic temperature rise and self-heat rate. From DSC results, three exothermic peaks were detected with a total heat generation of approximately 1.26 kJ/g sufficiently to induce a thermal runaway. Possible reaction pathway for three stages were proposed based on both DSC and GC-MS results. One exotherm was detected by Phi-TEC II calorimeter and the pressure versus temperature profile together with the DSC and GC-MS data demonstrate the complexity of 2-butanol reaction system under both thermal screening and adiabatic conditions.     

土壤腐殖酸慢热解表征实验影响因素研究

以土壤提取的腐殖酸为研究对象,进行了差式量热扫描(DSC)和热重分析(TGA)的可重复性实验、样品质量对比实验和预处理对比实验。综合分析了影响慢热解特征温度参数的因素和效应,并根据作用原理将其总结为热滞后效应和反应平衡滞后效应。结果表明,高级热分析技术用于土壤慢热解表征可重复性良好,差式量热扫描与热重分析结果可比性强,然而热分析曲线和热特征参数对实验条件的响应灵敏,其中样品质量和升温速率的影响尤其显著。研究结果表明,慢热解技术用于土壤有机质分析具有良好的准确性和重现性,提出了保障土壤腐殖酸慢热解质量控制的最佳样品量[DSC为(10±0.1)mg]、最佳气体氛围(He)和最佳升温速率(10℃/min)、精确压实程度等实验条件。     

Comparisons of TGA and DSC approaches to evaluate nitrocellulose thermal degradation energy and stabilizer efficiencies

This study investigated the thermal degradation energy (activation energy, E_a) for nitrocellulose (NC) with low nitrogen content of 11.71 mass%, so-called NC3, by using two different kinds of thermal analysis instruments: thermogravimetric analyzer (TGA) and differential scanning calorimetry (DSC). A comparison of E_a for various nitrogen content NC samples at two scanning rates (5 and 10 °C min^?1) tested by TGA and DSC is also discussed in this paper. Meanwhile, our aim was to analyze the anti-degradation of E_a for NC with high nitrogen content, as so-called NC1. Thermal stability for NC1 with diphenylamine (DPA) was tested via DSC with 10 DPA concentrations in weights of 0, 0.25, 0.50, 0.75, 1.0, 1.25, 1.50, 1.75, 2.0, and 3.0 mass%. Experimental results indicated that E_a of NC3s was 319.91 kJ mol^?1. Moreover, that while dosing DPA into NC1 the best recipe could be employed to avoid any violent NC1 runaway and also can be used to distinguish the differences of thermal decomposition E_a between NC with different nitrogen contents. This study established a fast and efficient procedure for thermal decomposition properties of NC, and could be applied as an intrinsically safer design during relevant operations.     

Processing of whey from dairy industry waste

An investigation carried out in 11 dairies in Serbia has shows that 78.75 % of whey, a by-product of cheese industry, is emitted into river systems, thus contributing to the organic pollution of the environment. This pollution can be avoided by processing of whey into food and pharmaceuticals. It is shown that low-temperature regime of whey concentration and fractionation, based on vacuum concentration and diafiltration, preserves whey proteins undenaturated, as proved by differential scanning calorimetry method. Functional native whey proteins based food products, with potentially high immunomodulatory activity, are obtained.     

Investigation of the role of biopolymer clusters in MBR membrane fouling using flash freezing and environmental scanning electron microscopy

The technique that employs flash freezing and environmental scanning electron microscopy (ESEM) was utilised for detailed investigation of the fouling materials in a membrane bioreactor (MBR). The method involves the flash freezing of a wet sample in liquid nitrogen for 10 s to preserve its structure for direct ESEM observation with a high image resolution. ESEM images show that the sludge cake formed by simple filtration of the MBR bulk sludge has a highly porous, sponge-like structure with a fairly low resistance. However, the fouling layer attached to the membrane surface contains a thin gel layer under the main body of the sponge-like sludge cake, which is similar to that formed by filtration of a dispersion of biopolymer clusters (BPCs). It is apparent that BPCs tend to accumulate on the membrane surface, and the gel layer is largely responsible for the high filtration resistance of the cake layer on the fouled membranes.     

悬浮载体生物膜内硝化菌群空间分布规律

利用16S rRNA寡核苷酸探针荧光原位杂交和共聚焦激光扫描显微镜联用技术,对悬浮载体生物膜内硝化菌群的空间分布规律进行了分析.试验采用3组结构完全相同的悬浮载体生物膜反应器,每个反应器的曝气区为6L,沉淀区为2L,水力停留时间为1.0h,3个反应器的进水COD/NH₄⁺-N分别为15、10和5,从反应器中取出载体颗粒表面的生物膜进行分析,研究各反应器中生物膜的微生物群落结构的变化规律.结果表明,SCBR内载体表面生物膜的总体厚度在80～120μm左右,氨氧化菌和亚硝酸盐氧化菌主要分布在生物膜表面的20～30μm左右范围内.随着进水中COD/NH₄⁺-N的增加,氨氧化菌和亚硝酸盐氧化菌在整个生物膜中所占的比例逐步下降.     

Quantification, morphology and source of humic acid, kerogen and black carbon in offshore marine sediments from Xiamen Gulf, China

Three types of macromolecular organic matters (MOMs), i.e. humic acid (HA), kerogen+black carbon (KB), and black carbon (BC) were extracted from marine sediments of Xiamen Gulf, southeast of China. The chemical composition, morphological property and source of the three extractions were characterized by elemental analyzer/isotope ratio mass spectrometry (EA/IRMS) and scanning electron microscope (SEM). The results showed that KB was the predominant fraction in MOMs, which accounted for 61.79%-89.15% of the total organic content (TOC), while HA consisted less than 5%. The relative high contents of kerogen and BC, and low contents of HA in the samples indicated that anthropogenic input might be the major source of organic matter in marine sediments near the industrial regions. The characterization of SEM, not only revealed morphological properties of the three fractions, but also allowed a better understanding of the source of MOMs. The δ 13 C values of the three fractions suggested that materials from terrestrial C 3 plants were predominant. Furthermore, the anthropogenic activities, such as the discharge of sewage, coal and biomass combustion from industry nearby and agricultural practices within drainage basin of the Jiulong River, were remarkably contributed to the variations in δ 13 C values of MOMs in the offshore marine sediments.     

Characterization of cake layer structure on the microfiltration membrane permeability by iron pre-coagulation

A cake layer is formed by coagulation aggregates under certain transmembrane pressure in the coagulation-microfiltration (MF) process. The characteristics of humic acid aggregates coagulated by different iron-based coagulants, such as charge, size, fractal dimension and compressibility, have an effect on the cake layer structure. At the optimum iron dose of 0.6 to 0.8 mmol/L for ferric chloride (FC) and polymer ferric sulfate (PFS) pre-coagulation, at the point of charge neutralization for near zero zeta potential, the aggregate particles produced possess the greatest size and highest fractal dimension, which contributes to the cake layer being most loose with high porosity and low compressibility. Thus the membrane filterability is better. At a low or high iron dose of FC and PFS, a high negative or positive zeta potential with high charge repulsion results in so many small aggregate particles and low fractal dimension that the cake layer is compact with low porosity and high compressibility. Therefore the membrane fouling is accelerated and MF permeability becomes worse. The variation of cake layer structure as measured by scanning electric microscopy corresponds with the fact that the smaller the coagulation flocs size and fractal dimension are, the lower the porosity and the tighter the cake layer conformation. This also explains the MF membrane flux variation visually and accurately.