Environmental Determination of Alkylphenol Polyethoxylate Refractory Residues Using Mass Spectrometric Techniques

Abstract

The use of methane chemical ionisation GC/MS gave satisfactory results when applied to environmental analysis of halogenated octylphenol polyethoxylates residues. In addition the selected ion monitoring GC/MS technique has been successfully applied for simulataneous qualitative and quantitative determination of some refractory metabolites of nonylphenol polyethoxylates in secondary sewage effluent and surface waters.     

Handling of Environmental and Biological Samples via Pre-Column Technologies

Abstract

Sample handling is still a weak point in chromatography and in analytical chemisty in general. One consideration is the automation potential of new procedures. Solid-liquid extraction techniques in combination with pre-column technology are particularly promising in this regards. The construction and geometry of pre-columns both for conventional and narrow-bore HPLC are of major importance, since band broadening should be kept at a minimum for an optimal functioning of the analytical system. The various operations that can be carried out with such a pre-column are trace-enrichment, clean-up of the sample which depends on the type of adsorbents used in the precolumn, i.e., polar or apolar materials, ion exchangers or metal covered surfaces, etc., protection of the analytical column, field sampling and storage of samples and as a substrate for on-column chemical derivatizations. These various operations are demonstrated with practical examples from the fields of environmental and biological analysis. The selectivity can be further enhanced by coupling precolumn technology with selective detection modes such as diode array UV, electrochemical or fluorescence detection. This enables the construction of optimal and integrated analysis sytems which are fully automated and microprocessor controlled. They can also be made compatible with miniaturized LC-technology.     

A Quality Assurance Study for the Analysis of Hydrocarbons in Sediments

Abstract

Two exercises (MEDCAL I and II) were conducted in our Department during November 1984 and October 1986, with participants from the Mediterranean region, for testing the IOC Manual for the determination of petroleum hydrocarbons in sediments (IOC, Manuals and Guides, No. 11).

The gas chromatographic analysis of the saturated hydrocarbon fraction provided, at the best, a precision of 60% (relative standard deviation RSD) for n-alkanes (mean conc. 0.89 μg/g) and 56 % for the unresolved complex mixture (UCM) (mean conc. 16μg/g). The CPI and the pristane/phytane ratio provided better results (13% RSD). The aromatic fractions, analysed by UV-fluorescence, yielded in total a mean concentration of 10μg/g of chrysene equivalents with a 49% RSD.

The extraction-partition step was confirmed to be the main source of error in the analysis because when the results were corrected for recoveries, the RSD were reduced to 17, 30 and 6% for n-alkanes, UCM and total aromatics, respectively. Our reference intra-laboratory precision was, respectively, 18, 14 and 14%.     

Antarctic Environmental Specimen Bank-First 5 Years of Experience

Abstract

The Project on an Antarctic Environmental Specimen Bank (Banca Campioni Ambientali Antartici—BCAA) began in 1994 in order to collect and classify samples from the Antarctic ecosystem to be used for future studies.

The objectives of the project are similar to the general aims of the Environmental Specimen Banks, but they specifically focus on the chemical aspects concerning the research activities of the Italian Project on the “Micropollutants Chemistry” (Sector “Chemical Contamination” of the Italian Antarctic Research Programme—PNRA).

During these first years the facilities suitable for storing a significant number of specimens (now over 2,000) at different temperatures (from ?30°C to ?150°C) and a database system, specifically designed for managing and consulting information concerning both the storage of samples and data on their chemical characterisation, have been developed.

In addition, a programme for validating the procedures of Antarctic organisms storage by checking the stability of some chemical parameters both in fresh and freeze-dried specimens has been developed.     

Retention profile of Fe,Mn and Cu onto chemically treated polyurethane with carbon disulfide

Dithiocarbamate modified polyurethane foam (DTC-PUF) was synthesized as a new solid-phase extraction sorbent for the preconcentration and determination of Fe(II), Mn(II) and Cu(II) in environmental samples using flame atomic absorption spectrometry. Maximum extraction of the elements was achieved at pH 5–7 and flow rate 3 mL min^?1. Quantitative desorption was achieved by 10 mL from 1.0 mol L^?1 HCl solution. The capacity of the sorbent was 149.2 ± 0.5, 237.5 ± 0.2, 200.2 ± 0.1 μg g^?1 and the limit of detection was of 0.015, 0.015 and 0.012 μg mL^?1for Fe(II), Mn(II) and Cu(II), respectively. A preconcentration factor of 100 was obtained for all elements. The developed method was successfully applied to the determination of the tested elements in water (tap and lake) and plant (spinach and parsley leaves) samples and showed good recovery values from 98 to 111% with corresponding RSD values ranged from 0.6 to 8.6%.     

Application of a new focused microwave technology with species-specific isotope dilution analysis for the quantitative extraction of organometallic contaminants in solid environmental matrices

A new self-tuning single-mode-focused microwave technology has been evaluated in this work to perform the quantitative routine extraction of organometallic species from solid matrices of environmental interest. Species-specific isotope dilution analysis has been employed to better investigate the real influence of the microwave-assisted extractions on the final results. The advantages of such methodology in comparison with other established microwave units for the routine speciation analysis of organomercury and organotin compounds are discussed (such as the capability of using disposable glass vials, a self-tuning mode to provide an accurate control of the temperature and pressure inside of the vials, and the possibility of performing automated sequence of extractions with low sample size). The results obtained in this work demonstrated that such technology provides a fast and reliable quantitative extraction of the organometallic species in a wide range of extraction conditions even when the multi-elemental (Sn and Hg) species-specific determination is carried out.     

18O同位素标记定量肽段串联体蛋白质结合同位素稀释-多反应监测质谱的蛋白质绝对定量新方法

建立了定量肽段串联体蛋白质(concatamers of Q peptides, QconCATs)结合¹⁸O同位素标记-多反应监测质谱的蛋白质绝对定量新方法。首先对QconCAT重组蛋白质进行了纯度表征,十二烷基硫酸钠-聚丙烯酰胺凝胶电泳(SDS-PAGE)表征结果表明重组蛋白质的纯度在99%以上,相对分子质量约为63.4 kDa。对QconCAT重组蛋白质酶切后的肽段混合物进行质谱分析,并经pFind和pLabel软件处理,验证了目标肽段。还考察了QconCAT重组蛋白质的酶切效率和¹⁸O标记效率,并对QconCAT蛋白质结合¹⁸O标记-同位素稀释-多反应监测质谱方法进行了评价。实验结果表明,采用该方法对腾冲嗜热厌氧菌(Thermoanaerobacter tengcongensis, TTE)中选定蛋白质的肽段进行绝对含量测定时,相对标准偏差小于20%,准确度较高,说明该方法可用于复杂生物样本中蛋白质的绝对定量。更重要的是所建方法不仅解决了细胞培养氨基酸稳定同位素标记(SILAC)技术的重标试剂价格昂贵的问题,也为定量蛋白质组学提供了一种新的方法。     

基于ARM11的热力站远程水质监控系统设计

为实现对循环水水质的远程监测,设计并开发了一种基于嵌入式技术的热力站远程水质监测系统的监测终端。监测终端由水质传感器、GPRS模块、通信转换模块及嵌入式开发板组成。嵌入式开发板以ARM11系列的Tiny6410为硬件基础,并嵌入WinCE系统作为软件平台,同时加入SQLite数据库以实现将水质传感器采集到的氯离子、PH值、溶解氧等参数的本地存储、查询及图表显示。最后监测终端通过GPRS模块与数据中心建立无线连接,接收数据中心的配置命令,并将现场测得数据发送到远端数据中心。调试结果表明：远程监测终端实现了循环水水质远程监测的功能要求,对于实现水质自动化监测具有一定的理论意义和实用价值。     

Cyanide ion colorimetric chemosensor based on protonated merocyanine in EtOH

This Letter aimed to develop an efficient method for the determination of cyanide ion (CN⁻). A novel colorimetric chemosensor 4-[(1E)-2-(4-hydroxyphenyl)ethenyl]-1-allylpyridinium bromide (HPEAPB) was synthesized. HPEAPB displayed good selectivity toward CN⁻ over other competing anions in ethanol. A color change from yellow to red was immediately observed upon the addition of CN⁻ and the limit of detection (LOD) was 3.4 × 10⁻⁶ mol L⁻¹. The sensing mechanism was discussed by UV–vis, ¹H NMR titration, and a comparison study. Colorimetric test paper for CN⁻ was prepared by attaching HPEAPB to a chromatography paper, which could be used to detect CN⁻ in environmental samples as simply as a pH-indicator paper for pH value. The LOD of the test paper for CN⁻ was 2.0 × 10⁻⁴ mol L⁻¹. This detection method for CN⁻ has potential applications in cyanide ion containing fields by combination of rapid and real-time advantages.     

新型污染物的环境质谱技术研究进展

随着科学技术的飞速发展,质谱检测及其联用技术方法正以前所未有的速度、广度和深度全面渗透到环境分析化学中,其在环境监测中的使用已经或正在日常化.近年来,一些高分辨质谱及其与色谱等的联用技术在目标污染物和非目标污染物的同时甄别鉴定和分析中发挥了重要作用,其对于阐明污染物在环境的归趋具有重要意义.本文对质谱技术及其与气相色谱和液相色谱的联用技术在污染物尤其是新型污染物分析中的进展进行了总结,并对高分辨质谱技术的环境应用研究给于关注,对环境质谱技术的发展方向进行了展望.