DOAS监测排放烟气浓度时谱线漂移处理方法研究

差分吸收光谱法(DOAS)是利用气体在紫外可见光波段对光具有选择吸收的特性来测量气体浓度的一种方法。DOAS法连续监测系统的核心是软件部分,由于吸收谱线漂移现象的存在,光谱解析算法的改进对污染气体浓度的计算带来很大的影响。基于DOAS法研究监测排放烟气浓度时谱线漂移对浓度计算的影响,并提出将相关函数和相关系数结合参与浓度计算,实验的结果表明,可以有效地减小谱线漂移时浓度计算的误差。     

牛粪发酵沼液DOM与Fe (III)离子络合机制研究

采用荧光光谱、红外光谱、平行因子（PARAFAC）分析及二维相关光谱（2D-COS）分析来解释Fe （III）与牛粪发酵DOM的络合异质性及机制.结果表明,PAFAFAC能够识别6个荧光组分,包括类蛋白（C2）、类富里酸（C1）、类腐殖酸（C4、C5）、类蛋白与类富里酸和类腐殖酸结合的荧光组分（C3、C6）.2D-SYS-COS分析仅能识别类蛋白和类富里酸荧光物质,DOM中类蛋白荧光为主要的荧光组分.2D-COS分析表明,在334nm处的类富里酸荧光组分优先与Fe （III）离子发生络合作用,络合次序为334nm→306nm.DOM中能够优先与Fe （III）发生络合作用的为仲铵盐-NH₂基团,各官能团组分与Fe （III）发生络合作用次序为2265→2771→1528→1310→1805→1479cm^-1.双对数模型计算结果表明牛粪发酵沼液DOM能够与Fe （III）形成高化学稳定性的络合物,其络合常数在4.34~7.03之间,研究结果能够为沼液施用土壤金属离子的形态分布和迁移转化提供理论指导.     

气相分子吸收光谱法测定海水中氨氮的干扰因素识别及预处理方法研究

采用气相分子吸收光谱法测定海水样品中的氨氮,重点考察海水中共存离子对氨氮测定结果的影响规律,识别测定过程中主要的干扰因素,并提出消除干扰的预处理方法.研究结果表明,碘离子会对氨氮的测定产生负干扰,当样品中碘离子质量浓度达到0.0765 g/L时,氨氮的测定结果与标准值相比明显降低,且在碘离子质量浓度达到0.1910 g...     

Tracing the impact of stack configuration on interface resistances in reverse electrodialysis by in situ electrochemical impedance spectroscopy

• RED performance and stack resistance were studied by EIS and LSV. • Interface resistance were discriminated from Ohmic resistance by EIS. • Impacts of spacer shadow effect and concentration polarization were analyzed. • Ionic short current reduced the power density for more cell pairs. • The results enabled to predict RED performance with different configurations. Reverse electrodialysis (RED) is an emerging membrane-based technology for the production of renewable energy from mixing waters with different salinities. Herein, the impact of the stack configuration on the Ohmic and non-Ohmic resistances as well as the performance of RED were systematically studied by using in situ electrochemical impedance spectroscopy (EIS). Three different parameters (membrane type, number of cell pairs and spacer design) were controlled. The Ohmic and non-Ohmic resistances were evaluated for RED stacks equipped with two types of commercial membranes (Type I and Type II) supplied by Fujifilm Manufacturing Europe B.V: Type I Fuji membranes displayed higher Ohmic and non-Ohmic resistances than Type II membranes, which was mainly attributed to the difference in fixed charge density. The output power of the stack was observed to decrease with the increasing number of cell pairs mainly due to the increase in ionic shortcut currents. With the reduction in spacer thickness from 750 to 200 µm, the permselectivity of membranes in the stack decreased from 0.86 to 0.79 whereas the energy efficiency losses increased from 31% to 49%. Overall, the output of the present study provides a basis for understanding the impact of stack design on internal losses during the scaling-up of RED.     

基于傅里叶红外光谱法测定燃煤电厂烟气中SO3与H2SO4

基于傅里叶红外光谱法(FTIR)监测燃煤电厂烟气处理流程中的SO3与H2 SO4.结果表明,布袋除尘进口、出口和烟囱出口的SO3与H2SO4之和(SO3+H2SO4)分别为(29.33±2.30)mg/m3、(25.15±1.63)mg/m3和(12.13±1.26)mg/m3;布袋除尘与湿法脱硫对SO3+H2 SO4...     

气相分子吸收光谱法测定水中氨氮干扰因素的研究

气相分子吸收光谱法测定成分复杂氨氮实际样品时,干扰因素造成测定结果不准确,而现有的标准方法和文献对干扰物质的研究不全面,制约了仪器的应用。该文系统地开展干扰因素的研究,提出干扰因素的消除方法,用加标回收率验证消除的有效性。结果表明,亚硫酸盐、硫化物等还原性物质对测定产生负干扰;石油烃、N,N-二甲基甲酰胺(DMF)等挥发性有机物、有机胺类以及亚硝酸盐对测定产生正干扰。根据不同干扰类型,通过加入适量酸性重铬酸钾溶液、在酸性条件下加热煮沸、预蒸馏等方法可消除干扰,消除干扰后加标回收率为84%~120%。生活污水、石化企业废水等6种典型水样消除干扰后,气相分子吸收光谱法和纳氏试剂分光光度法测定氨氮有较好的可比性,干扰消除方式有效。     

Spectroscopic characterization and photochemistry of the Criegee intermediate CF3C(H)OO

Criegee intermediates (CIs), also known as carbonyl oxide, are reactive intermediates that play an important role in the atmospheric chemistry. Investigation on the structures and reactivity of CIs is of fundamental importance in understanding the underlying mechanism of their atmospheric reactions. In sharp contrast to the intensively studied parent molecule (CH₂OO) and the alkyl-substituted derivatives, the knowledge about the fluorinated analogue CF₃C(H)OO is scarce. By carefully heating the triplet carbene CF₃CH in an O₂-doped Ar-matrix to 35 K, the elusive carbonyl oxide CF₃C(H)OO in syn- and anti-conformations has been generated and characterized with infrared (IR) and ultraviolet-visible (UV-vis) spectroscopy. The spectroscopic identification is supported by ¹⁸O-labeling experiments and quantum chemical calculations at the B3LYP/6-311++G(3df,3pd) and MP2/6-311++G(2d,2p) levels. Upon the long-wavelength irradiation (λ > 680 nm), both conformers of CF₃C(H)OO decompose to give trifluoroacetaldehyde CF₃C(H)O and simultaneously rearrange to the isomeric dioxirane, cyclic-CF₃CH(OO), which undergoes isomerization to the lowest-energy carboxylic acid CF₃C(O)OH upon UV-light excitation at 365 nm. The O₂-oxidation of CF₃CH via the intermediacy of CF₃C(H)OO and cyclic-CF₃CH(OO) might provide new insight into the mechanism for the degradation of hydro-chlorofluorocarbon CF₃CHCl₂ (HCFC-123) in the atmosphere.