Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent

Molecular level characterization of dissolved organic sulfur (DOS) by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR MS) is necessary for further understanding of the role of DOS in the environment. Here, ESI spray solvent, a key parameter for ion production during ESI process, was investigated for its effect on the molecular characterization of DOS by ESI-FTICR MS. 100% MeOH as spray solvent was found for the first time to remarkably enhance the ionization efficiency of the majority of CHOS-molecules in NOM, which facilitated a total of 1473 CHOS-molecular formulas with one sulfur atom to be detected. The number of CHOS-molecular formulas obtained using 100%MeOH as spray solvent increased notably over 740 in comparison with those using 50% MeOH aqueous solution (731) or 50% ACN aqueous solution (653). Moreover, due to the enhancement of ionization efficiency of DOS during ESI processes, the tandem mass spectra of the NOM CHOS-molecules could be easily obtained using 100% MeOH as spray solvent, which were hardly obtained using 50% MeOH aqueous solution as spray solvent. The results of the tandem mass spectra suggested the first discovery of organosulfates or sulfonic acids in Suwannee River NOM sample. A simple method based on 100% MeOH as ESI spray solvent for advanced molecular characterization of DOS by ESI-FTICR MS was proposed and applied, and the results revealed more molecular information of DOS in sea DOM samples.     

土壤胡敏素对铜离子的吸附作用及其机理研究

以暗棕壤为供试土壤,研究了不同溶液pH值、离子强度、接触时间、反应温度和初始铜离子(Cu~(2+))浓度条件下,胡敏素对Cu~(2+)的吸附作用;利用扫描电子显微镜(SEM)、X-射线能量色散谱(EDS)、傅立叶变换红外光谱(FTIR)和X-射线光电子能谱(XPS),对胡敏素/胡敏素-Cu~(2+)复合物的表面形貌、元素分布和官能团组成进行了分析;应用延展X-射线吸收精细结构谱(EXAFS),对吸附态Cu~(2+)的局域配位结构进行了表征.结果表明:胡敏素对Cu~(2+)的吸附量随pH值、接触时间、反应温度和Cu~(2+)浓度的增加而增加,但随离子强度的增加而下降;吸附动力学符合准二级动力学方程,而吸附等温线用Langmuir方程的拟合效果较好;吸附过程需要能量,是自发、吸热和自由度增加的缔合反应;吸附Cu~(2+)之后,胡敏素表面产生了团聚现象,表面羧基、羟基、吡啶氮和N—O基团参与了Cu~(2+)的吸附作用,同时吸附态Cu~(2+)是以内层配位形式与胡敏素表面的O/N和C原子结合.     

重金属离子对肺表面活性物质单层膜的影响

为了探究重金属对肺表面活性物质（PS）膜的影响,利用Langmuir–Wilhelmy膜天平,研究了不同种类和浓度的重金属离子与PS单层膜的相互作用.发现Cr³⁺、Cu²⁺、Hg²⁺、Pb²⁺、Cd²⁺、Ni²⁺6种重金属离子均使PS单层的π-A等温线G-LE相变阶段外扩,而Fe³⁺可诱导单层缩合.随后,选取Cd²⁺,Cu²⁺,Hg²⁺,Fe³⁺4种离子进一步探究了重金属浓度对PS单层膜表面活性的影响规律,进行了可压缩模量分析,并结合红外光谱（FTIR）和原子力显微镜（AFM）探究其作用机理,发现Cu²⁺,Fe³⁺和Hg²⁺均会以浓度依赖的方式与PS单层的极性头部发生络合作用,形成复合物,改变膜的稳定性;而Cd²⁺的影响明显弱于其他3种金属离子,但也能使得PS单层有序性增强.     

SBR中联氨对亚硝化的影响

为了开发经济高效的生物脱氮工艺,研究了SBR中联氨对短程硝化反硝化的控制作用,考察了不同联氨投加量对短程硝化的影响。实验结果表明:在室温下,不控制溶解氧,p H为7.5~8.0时,投加7.5 mg/L联氨,亚硝氮积累效果最佳,其出水氨氮及亚硝氮浓度平均值分别为1.44,12.23 mg/L,均优于其他联氨投加量的监测结果;投加7.5 mg/L联氨的活性污泥中生物相种类和数量都优于未投加联氨的活性污泥,SEM图像显示活性污泥结构致密,紧凑,且菌落数量明显升高;从活性污泥的红外谱图可以看出,投加联氨与否,特征峰位置基本相同,但投加7.5 mg/L联氨的活性污泥EPS红外谱图峰强更高。     

Influence of Relative Humidity and Ozone on the Sampling of Volatile Organic Compounds on Carbotrap/Carbosieve Adsorbents

By using a dynamic dilution system, the atmospheric measurement of 11 selected toxics VOCs (ethylene, acetylene, propene, 1-butene, 1,3-butadiene, 1-pentene, 1-hexene, benzene, toluene, ethylbenzene, m+p-xylene) from the list WHO of 1996 and TO-14 method of US EPA by preconcentration by thermal desorption (TD), analysis by gas chromatography (GC), identification and quantification with a flame ionisation detector (FID) was developed and validated in term of metrology, especially the techniques of sampling of these VOCs with adsorbents cartridges "Air Toxics" when used with an "UMEG sampler" equipped in the inlet with a nafion membrane. In particular the influence of climatic conditions (temperature and relative humidity) and the influence of chemical factors like ozone, on the representativity of sampling were studied. Experiments made with various humidities showed that the addition of a nafion membrane in the inlet of the sampling system was required. Without this membrane, losses of compounds were observed for RH >50%. With this membrane, storage for 2 weeks in a refrigerator, as for canisters, did not induce a loss of compounds. No significative decrease of concentrations of the studied VOCs after 14 days storage, which are known to react with ozone, were observed with an ozone concentrations of 55 ppb. One explanation is that nafion membrane, placed in the inlet of the sampler, will neutralize ozone before entering the sampling tubes. This observation is in accordance with literature which states that the sampling of VOCs on Carbotrap cartridges without ozone scrubber induce a loss of compounds.     

脉动风速功率谱与随机Fourier幅值谱的关系研究

功率谱密度函数是随机过程在频域内的重要特征量,但由于其本质上是平稳过程的频域数值特征,致使其很难全面反映原始随机过程的概率信息,这就需要从更本源的意义上考察随机过程。本文试图从Fourier随机函数的角度反映随机过程,将经典的功率谱密度函数中具有物理意义的可测变量看作随机变量,利用功率谱与Fourier幅值谱的关系,定义了随机Fourier幅值谱;以Davenport谱为例,证实当地面粗糙度服从对数正态分布、10m高度基本风速服从极值Ⅰ型分布时,可通过功率谱构造具有物理意义的随机Fourier幅值谱。通过实测风速Fourier谱与随机Fourier幅值谱的比较,证明随机Fourier幅值谱的概念具有合理性。     

TA-FTIR/MS用于硝酸铵及其混合物的热化学行为研究

为评价物料混合对危险化学品热化学行为的影响,采用热分析-红外/质谱联用技术(TA-FTIR/MS)研究硝酸铵、柠檬酸和蔗糖的混合物的热化学行为。通过对硝酸铵及其混合物的分解温度和分解过程中逸出气体的分析,发现硝酸铵、柠檬酸和蔗糖的混合物热分解温度分别降低至135℃和153℃,而硝酸铵与甲基纤维素的混合物分解温度与硝酸铵基本相同为201℃,且各混合体系的气相分解产物均有氮氧化物(NOX),H2O和CO2。结果表明,混合物受热后其中的硝酸铵首先分解为硝酸和氨气;酸性物质和还原性物质由于对硝酸的分解反应有催化作用,使得混合物的热稳定性下降。     

ACCURACY OF LAKE AND STREAM TEMPERATURES ESTIMATED FROM THERMAL INFRARED IMAGES1

Emitted thermal infrared radiation (TIR, λ= 8 to 14 μm) can be used to measure surface water temperatures (top approximately 100 μm). This study evaluates the accuracy of stream (50 to 500 m wide) and lake (300 to 5,000 m wide) radiant temperatures (15 to 22°C) derived from airborne (MASTER, 5 to 15 m) and satellite (ASTER 90 m, Landsat ETM+ 60 m) TIR images. Applied atmospheric compensations changed water temperatures by ?0.2 to +2.0°C. Atmospheric compensation depended primarily on atmospheric water vapor and temperature, sensor viewing geometry, and water temperature. Agreement between multiple TIR bands (MASTER ‐ 10 bands, ASTER ‐ 5 bands) provided an independent check on recovered temperatures. Compensations improved agreement between image and in situ surface temperatures (from 2.0 to 1.1°C average deviation); however, compensations did not improve agreement between river image temperatures and loggers installed at the stream bed (from 0.6 to 1.6°C average deviation). Analysis of field temperatures suggests that vertical thermal stratification may have caused a systematic difference between instream gage temperatures and corrected image temperatures. As a result, agreement between image temperatures and instream temperatures did not imply that accurate TIR temperatures were recovered. Based on these analyses, practical accuracies for corrected TIR lake and stream surface temperatures are around 1°C.     

红外和热分析联用在化工产品研究中的应用

运用实例论述了红外光谱分析与热分析联用在化工产品的产品开发和检测方面的应用。     

估计近场地震动的统计—经验格林函数法

本文提出统计-经验格林函数法,用以估计缺乏小震记录场点在大震时的地震动时程。统计-经验格林函数的富里哀幅值谱从其它类似场地获得的小震记录的富里哀谱的衰减关系中得到,其相位谱则直接取自小震记录的相位谱。本文分别用经验格林函数法和统计-经验格林函数法,用迁安台记录到的1976年唐山地震的三次余震(M_L 5.8、M_L 5.7和M_L 5.4)的加速度记录,合成唐山地震的最大余震滦县地震(M_s 7.1)时迁安台的加速度时程曲线,合成结果说明了所提方法的可行性。