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.     

Rapid and sensitive liquid chromatography-tandem mass spectrometry for the quantitation of epirubicin and identification of metabolites in biological samples

A highly sensitive and selective liquid chromatography-mass spectrometry (LC-MS) method has been developed for the determination of epirubicin in serum and cell specimens using daunorubicin as an internal standard. Using atmospheric pressure chemical ionisation (APCI), the epirubicin metabolites were readily distinguishable by their fragmentation pattern in the mass spectrometer. Selected reaction monitoring (SRM) mode was employed for quantitation of epirubicin and the metabolites. Following extraction, chromatography was performed on a C18 column with a mobile phase consisting of water-acetonitrile-formic acid, pH 3.2, with a flow rate of 200 μl/min. The limit of detection (LOD) and the limit of quantitation (LOQ) of this method in serum were determined to be 1.0 and 2.5 ng/ml, respectively. Linearity of the method was verified over the concentration range of 2.5-2000 ng/ml, with a high correlation coefficient (R² ≥ 0.998). For the extraction procedure, an aliquot of 500 μl serum, spiked with internal standard, was extracted using a chloroform-2-isopropanol (2:1, v/v) mixture. The method has been applied to the analysis of epirubicin in cancer cell samples and the identification of known and unknown metabolites in clinical trial patient serum samples.     

Local and non-local sources of airborne particulate pollution at Beijing--The ratio of Mg/Al as an element tracer for estimating the contributions of mineral aerosols from outside Beijing

A new element tracer technique has firstly been established to estimate the contributions of mineral aerosols from both inside and outside Beijing. The ratio of Mg/Al in aerosol is a feasible element tracer to distinguish between the sources of inside and outside Beijing. Mineral aerosol, inorganic pollution aerosol mainly as sulfate and nitrate, and organic aerosol are the major components of airborne particulates in Beijing, of which mineral aerosol accounted for 32%―67% of total suspended particles (TSP), 10%―70% of fine particles (PM2.5), and as high as 74% and 90% of TSP and PM2.5, respectively, in dust storm. The sources from outside Beijing contributed 62% (38%―86%) of the total mineral aerosols in TSP, 69% (52%―90%) in PM10, and 76% (59%―93%) in PM2.5 in spring, and 69% (52%―83%), 79% (52%―93%), and 45% (7%―79%) in TSP, PM10, and PM2.5, respectively, in winter, while only ～20% in summer and autumn. The sources from outside Beijing contributed as high as 97% during dust storm and were the dominant source of airborne particulates in Beijing. The contributions from outside Beijing in spring and winter are higher than those in summer, indicating clearly that it was related to the various meteorological factors.     

高脂饮食对小鼠脂肪代谢和矿物元素代谢的影响

为探讨高脂饮食对小鼠脂肪代谢和矿物元素代谢的影响,用昆明(KM)小鼠24只,出生28 d后随机分成2组,各12只,分别给予高脂饲料与普通饲料,饲养至第9周眼球取血处死,取皮下、腹腔、肠系膜脂肪,毛,肝,血,计算体质量脂肪质量比,测定毛、肝、血中Zn、Ca、Cu、Mn、Mg、Fe含量。结果表明,高脂饮食小鼠体质量增加(P<0.05),单位腹腔脂肪及血Ch显著性增加(P<0.01)。肝Zn、Cu、Mg、Fe、Mn显著降低(P<0.01),血凝块Zn升高(P<0.05),Cu降低(P<0.05),毛Mg降低(P<0.05)。提示高脂饮食引起体质量与血脂增加,脂肪堆积,矿物元素代谢紊乱;不同器官矿物元素的代谢紊乱有差异,以肝脏最显著。     

运动对去卵巢大鼠骨元素代谢的影响

用测定骨元素含量的方法，分析了运动对正常大鼠和切除双侧卵巢后的大鼠骨元素代谢的影响。将健康4个月龄雌性SD大鼠44只随机分成5组：（1）非去势非运动组；（2）非去势＋运动组；（3）假去势非运动组；（4）去势非运动组；（5）去势＋运动组。运动组用大鼠专用跑台中等运动强度训练，持续10周。结果表明，去卵巢大鼠骨Ca,Mg,S,Mn,Zn等含量显著降低，P含量显著增加。运动训练可使去卵巢大鼠降低的骨Ca,Mg,S,Mn,Zn等含量显著回升，骨P含量显著回降。提示中等强度运动训练可对抗由于去卵巢所引起的骨元素代谢紊乱。     

Hydride generation atomic fluorescence spectrometric determination of As, Bi, Sb, Se(IV) and Te(IV) in aqua regia extracts from atmospheric particulate matter using multivariate optimization

A highly sensitive and simple method, based on hydride generation and atomic fluorescence detection, has been developed for the determination of As, Bi, Sb, Se(IV) and Te(IV) in aqua regia extracts from atmospheric particulate matter samples. Atmospheric particulates matter was collected on glass fiber filters using a medium volume sampler (PM1 particulate matter). Two-level factorial designs have been used to optimise the hydride generation atomic fluorescence spectrometry (HG-AFS) procedure. The effects of several parameters affecting the hydride generation efficiency (hydrochloric acid, sodium tetrahydroborate and potassium iodide concentrations and flow rates) have been evaluated using a Plackett-Burman experimental design. In addition, parameters affecting the hydride measurement (delay, analysis and memory times) have been also investigated. The significant parameters obtained (sodium tetrahydroborate concentration, sodium tetrahydroborate flow rate and analysis time for As; hydrochloric acid concentration and sodium tetrahydroborate flow rate for Se(IV); and sodium tetrahydroborate concentration and sodium tetrahydroborate flow rate for Te(IV)) have been optimized by using 2ⁿ + star central composite design. Hydrochloric acid concentration and sodium tetrahydroborate flow rate were the significant parameters obtained for Sb and Bi determination, respectively. Using a univariate approach these parameters were optimized. The accuracy of methods have been verified by using several certified reference materials: SRM 1648 (urban particulate matter) and SRM 1649a (urban dust). Detection limits in the range of 6 × 10⁻³ to 0.2 ng m⁻³ have been achieved. The developed methods were applied to several atmospheric particulate matter samples corresponding to A Coruña city (NW Spain).     

The discovery of polymer‐clay hybrids

The first successful example of a polymer‐clay hybrid was nylon‐clay hybrid (NCH), which is a nano‐meter‐sized composite of nylon‐6 and 1‐nm‐thick exfoliated aluminosilicate layers of the clay mineral. NCH was found and developed at Toyota Central Research and Development Laboratories over 17 years ago. The NCH containing a few weight percentages of clay exhibits superior properties such as high modulus, high strength, and good gas‐barrier properties. The key for the discovery of NCH was the polymerization of a nylon monomer in the interlayer space of the clay. This highlight presents the development of NCH from its discovery to its commercialization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 819–824, 2004     

Studies of the soluble part of oxidised coals

Soluble products obtained from the oxidation of four types of coal, each characterised by different degree of coalification and different degree of sulphur content, are studied. The coals are oxidised with peracetic acid (PAA) and nitric acid. Analyses are performed by Atmospheric Pressure-Temperature Programmed Reduction (AP-TPR) and Fourier Transform Infrared Spectroscopy (FTIR). The soluble products contain much more sulphur than the insoluble products of oxidation. The products obtained from the reaction with HNO₃ contain higher amounts of inorganic sulphur compounds, while those obtained from the reaction with PAA are characterised by an increased content of organic sulphur species.     

人中白矿物元素含量分析

用原子吸收分光光度法测定了中药人中白中 1 2种矿物元素含量。结果表明 ,人中白中Ca、Mg、Ba、K和Na的含量在 1× 1 0 3以上 ,而Fe、Cr、Mn的含量在 1 0× 1 0 6 ～ 1 0 0 0× 1 0 6 范围内 ;Ni、Se浓度也超过 1 0× 1 0 6 ,Cu、Co的含量也在 5× 1 0 6 以上。     

Quantitative millimetre wavelength spectrometry at pressures approaching atmospheric: II. Determination of oxygen at atmospheric pressure

A millimetre wavelength (MMW) Fabry-Perot cavity spectrometer described in earlier work has been applied to the measurement of oxygen absorption at 60 GHz and atmospheric pressure in a gas matrix of nitrogen. The spectrometer has also been modified such that the MMW source is stabilised by a sub-harmonic microwave signal transmitted by an infrared carrier on a single mode telecommunications fibre optic. This is a step towards developing an instrument comprising minimal electronic components that can perform MMW spectrometry remotely. Oxygen determinations were achieved by monitoring the change in the quality factor (Q) of a resonant Fabry-Perot cavity due to the presence of an absorbing sample. The MMW absorption of the sample was determined by incrementing the frequency modulation (FM) deviation of the source frequency scanning the cavity resonance profile. The response curve of absorption signal versus fraction of oxygen in nitrogen was found to be linear throughout the working range of 1-100% O₂ (v/v) in N₂ with a slope of (1.407±0.007)×10⁻⁴ m⁻¹ (% O₂)⁻¹. The detection limit (3× standard deviation of the background) was found to be ∼0.8% (v/v). The MMW technique employed is advantageous since, unlike common MMW techniques, there is no vacuum requirement. Application of this method, to the monitoring of oxygen in gas mixtures of practical importance, is proposed. Values of the oxygen spectral absorption coefficients of lines between 55 and 60 GHz were measured at reduced pressure and found to be within ±2% of previous literature values. A pressure correction coefficient for O₂ absorption at 60 GHz in the 45-121 kPa range was obtained and found to be (1.354±0.014)×10⁻⁴ m⁻¹ kPa⁻¹.