Concentration and clean-up of trace hydrocarbons from atmospheric particulate matter

Summary The aim of this work is to establish the best conditions for concentration and purification steps in the trace analysis of aliphatic and polycyclic aromatic hydrocarbons (PAH) from atmospheric particulate matter by gas chromatography-flame ionisation detection (GC-FID) and high performance liquid chromatography with ultraviolet and fluorescence detection (HPLC-UV-FL). The best results for the more volatile compound were obtained with a combination of rotary evaporation and a stream of nitrogen (near to 100% for aliphatic hydrocarbons and from 70 to 105% for PAH). Two types of solid phase extraction (SPE)cartridges (Supelclean ^tm LC-Silica SPE tubes and Sep-Pak^? Plus silica cartridges) and glass column were examined for the purification and fractionation step. Blank chromatograms of both types of cartridges analysed by GC-FID made this study difficult, because a PSS (programmed split-splitless) injector was employed thereby increasing the sensitivity. This problem was not observed in the HPLC-UV-FL blank chromatograms of these cartridges. Glass columns filled with silica and alumina were chosen because no interference was found in the GC-FID blank chromatograms and the best recoveries in the fractionation of both aliphatic hydrocarbons and PAH were achieved. This is especially important when aliphatic hydrocarbons concentrations are lower than 1 μg mL⁻¹. Finally, the selected conditions were applied to the analysis of hydrocarbons in real atmospheric particulate samples.     

毛细管电泳中样品在线预富集方法

本文对高效毛细管电泳中样品在线预富集方法作了评述，包括瞬间等速电泳，反流速电泳，场放大进样，场放大排除基体和固相萃取等技术，引用文献81篇。     

A method for the determination of histamine in wine by HPLC with precolumn derivatization with phenylisothiocyanate

Summary A method for determining histamine in wine by precolumn derivatization with PITC (phenylisothiocyanate) with reversed-phase HPLC and UV detection is reported. Histamine can be determined together with the 24 amino acids within 40 min, or separately in a shorter time (less than 4 min) if a prior solid phase extraction clean-up is used.     

高聚物固体电解质聚氧化乙烯－溴化铜复阻抗谱及介电常数的静水压效应

采用分子量５００万的聚氧化乙烯和无水溴化铜，通过混溶蒸发法制备成高聚物固体电解质Ｐ（ＥＯ）ｎ－ＣｕＢｒ２薄膜，并在０．１～３００ＭＰａ范围不同的流体静水压下详细测量其复平面阻抗谱，分别得到在不同压力下离子电导率和介电常数与测量频率的关系．进一步解谱准确地求出Ｐ（ＥＯ）ｎ－ＣｕＢｒ２（ｎ＝１２、１６）薄膜离子电导率和介电常数的静水压效应，并结合Ｘ－光物相分析，根据离子迁移通道的物理图象和高聚物的极化机构进行了初步的讨论．添加２０％的增塑剂碳酸丙烯酯，较大改进了压力下的导电性．１２０～３００ＭＰａ的离子电导率提高一个数量级     

固相微萃取/二氧化锡气体传感器联用技术对果蔬中有机磷农药残留的快速检测

研究了固相微萃取(SPME)和二氧化锡气体传感器的联用技术对果蔬中有机磷农药残留乐果、氧乐果、甲胺磷、乙酰甲胺磷、马拉硫磷、敌百虫等的快速检测。结果表明，在85℃下，解吸8min，二氧化锡气体传感器在2min内完成对有机磷农药残留的快速检测。零解吸时间测量的甲胺磷的动态响应曲线表明。SPME／二氧化锡气体传感器联用技术对分析SPME的解吸平衡非常有利。     

Feasibility of using solid sampling graphite furnace atomic absorption spectrometry for speciation analysis of volatile and non-volatile compounds of nickel and vanadium in crude oil

A method for the direct determination of volatile and non-volatile nickel and vanadium compounds in crude oil without previous treatment using direct solid sampling graphite furnace atomic absorption spectrometry is proposed. The crude oil samples were weighed directly onto solid sampling platforms using a microbalance and introduced into a transversely heated solid sampling graphite tube. In previous work of our group losses of volatile nickel and vanadium compounds have been detected, whereas other nickel and vanadium compounds were thermally stable up to 1300 and 1600 °C, respectively. In order to avoid this problem different chemical modifiers (conventional and permanent) have been investigated. With 400 μg of iridium as permanent modifier, the signal started to drop already after two atomization cycles, possibly because of an interaction of nickel (which is a catalyst poison) with iridium. Twenty micrograms of palladium applied in each determination was found to be optimum for both elements. The palladium was deposited on the platform and submitted to a drying step at 150 °C for 75 s. After that the sample was added onto the platform and submitted to the furnace program. The influence of sample mass on the linearity of the response and on potential measurement errors was also investigated using four samples with different nickel content. For the sample with the lowest nickel concentration the relationship between mass and integrated absorbance was found to be non-linear when a high sample mass was introduced. It was suspected that the modifier had not covered the entire platform surface, which resulted in analyte losses. This problem could be avoided by using 40 μL of 0.5 g L⁻¹ Pd with 0.05% Triton X-100. Calibration curves were established with and without modifier, with aqueous standards, oil-in-water emulsions and the certified reference material NIST SRM 1634c (trace metals in residual fuel oil). The sensitivity for aqueous standards and emulsions was close to that for SRM 1634c, making possible the use of aqueous standards for calibration. The limits of detection and quantification obtained for nickel and vanadium under this condition were found to be 0.02 and 0.06 μg g⁻¹, respectively, for both elements, based on 10 mg of sample. Nickel and vanadium were determined in the samples with (total Ni and V) and without the use of Pd (thermally stable compounds), and the concentration of volatile compounds was calculated by difference. The results were compared with those obtained by high-resolution continuum source graphite furnace atomic absorption spectrometry by emulsion technique; no significant differences were found for total Ni and V at the 95% confidence level according to a Student's t-test.     

Effect of Ba and Bi doping on the synthesis and sintering of Ge-based apatite phases

Recently, high oxide ion conduction has been observed in the apatite-type systems La_9.33+x(Si/Ge)₆O_26+x/2, with conductivities approaching and even exceeding that of yttria-stabilized zirconia. The Ge-based phases have been reported to suffer from Ge loss and undergo irreversible structural changes on sintering at the high temperatures required to obtain dense pellets. In this paper we discuss doping studies (Ba, Bi for La) aimed at stabilizing the hexagonal apatite lattice to high temperature, and/or lowering the synthesis and sintering temperatures. The results show that doping with Ba helps to stabilize the hexagonal lattice at high temperatures, although Ge loss appears to still be a problem. Conductivity data show that, as previously reported for the Si-based systems, non-stoichiometry in the form of cation vacancies and/or oxygen excess is required to achieve high oxide ion conduction in these Ge-based systems. Neutron diffraction structural data for the fully stoichiometric phase La₈Ba₂Ge₆O₂₆ shows that the channel oxygen atoms show little anisotropy in their thermal displacement parameters, consistent with the low oxide ion conductivity of this phase. Bi doping is shown to lower the synthesis and sintering temperatures, although the presence of Bi means that these samples are not stable at high temperatures under reducing conditions.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, April 10–12, 2003     

含双键侧基的聚氧乙烯与苯乙烯的接枝共聚物及其产物的性质

由环氧乙烷及烯丙基缩水甘油醚合成含双键侧基的聚氧乙烯用苯乙烯接枝共聚,接枝效率可达50％左右.接枝产物经纯化,用IR及~1H NMR表征.该产物与LiClO_4的络合物有较高的室温导电率,其PEO含量在70％及EO/Li=20/1时,25℃的导电率接近10~(-4)S/cm.此外,该接枝共聚物有较高的乳化能力.在Williamson固液反应中具有良好的相转移催化作用.     

共沉淀CuO-ZrO2复合氧化物分散态结构研究

用XRD、EXAFS、XPS表征了共沉淀法制备的CuO-ZrO2复合氧化物的分散态结构. 500 ℃焙烧的样品在一定组成范围内形成大体均匀的无定形态固溶体. CuO含量超过其在ZrO2中溶解度时，多余的CuO以CuO晶体形式存在；当ZrO2含量超过其在CuO中溶解度时，多余的ZrO2以四方相ZrO2晶体形式存在.焙烧温度达到800 ℃时，样品由单斜相ZrO2和CuO晶体组成.