Organic contaminants in water - conceptual considerations for the production of liquid reference materials in support of the new water framework directive

The lack of suitable certified reference materials for the determination of organic pollutants in water has become a major problem within the framework of the new European water policy. This paper highlights approaches towards the production of certified reference materials and their drawbacks. On the basis of experience gained from proficiency-testing schemes, analytical practice, and reference material production a new concept for the production of liquid reference materials to be used in support of European legislation is presented and discussed briefly. The concept is based on a standard-addition approach and the simulation of effects interfering with the analytical process by use of individual matrix constituents or matrix-mimicking substances in combination with water-miscible solvents. The concept enables quantification of dissolved organic compounds in unknown water samples and evaluation of the analytical process with the help of a reconstituted sample. Open questions for further research are also outlined.     

The purpose and program of the IOC/UNEP/IAEA group of experts on standards and reference materials

Summary A Group of Experts on Standards and Reference Materials (GESREM) has been established by international agencies to improve the availability of standards and reference materials to marine scientists throughout the world. It functions by bringing together the users of such materials with their producers to discuss priorities and to seek resources to meet them. The GESREM has stimulated the production of a global catalog of available reference materials and has defined future actions to promote the availability and proper use of reference materials.     

Organic mass spectrometry in archaeology: evidence for Brassicaceae seed oil in Egyptian ceramic lamps

An analytical procedure based on alkaline hydrolysis and silylation followed by GC/MS analysis was employed to study the formation of characteristic acidic compounds and the development of a distinctive chromatographic pattern in the course of accelerated ageing tests on Brassicaceae seed oil. On the basis of mass spectra of trimethylsilyl derivatives, the main degradation products were identified as alpha,omega-dicarboxylic, omega-hydroxycarboxylic and dihydroxycarboxylic acids, including 11,12-dihydroxyeicosanoic acid and 13,14-dihydroxydocosanoic acid. The mass spectra of both these compounds are characterised by fragment ions arising from the alpha cleavage of the bond between the two vicinal trimethylsiloxy groups, resulting in fragments at m/z 215 and 345 for 11,12-dihydroxyeicosanoic acid, and at m/z 215 and 373 for 13,14-dihydroxydocosanoic acid. Other significant fragment ion-radicals from rearrangement process at m/z [M - 90](+*), [M - 142](+*), 204 as well as fragment ions at m/z [M - 15](+), [M - 105](+), 217 are present in the mass spectra of both the compounds. The results obtained for reference materials were compared with those relating to archaeological organic materials recovered in Egyptian pottery lamps. The occurrence of the same characteristic degradation products found in the reference materials subjected to accelerated ageing indicates an unambiguous origin for the organic archaeological remains and represents the chemical evidence for the use of oil from seeds of Brassicaceae as illuminant.     

Recent advances in the synthesis of fluoroalkylated compounds using fluoroalkyl anhydrides

Fluoroalkyl-containing organic compounds have exhibited wide applications in the field of pharmaceuticals, agrochemicals and materials science due to their outstanding properties such as biological activity, metabolic stability, lipophilicity, excellent chemical and thermal stability. Therefore, various synthetic strategies have been developed for the construction of fluoroalkyl-containing compounds, using highly active fluorinating reagents and fluorinated building blocks. Recently, the use of easily available and inexpensive trifluoroacetic anhydride (TFAA) and its anhydride analogues has attracted great attention to access numerous fluoroalkyl-containing compounds through cyclization and coupling reactions. In this review, we summarized the recent advances in the synthesis of fluoroalkylated compounds using fluoroalkyl anhydrides as reagents. This review aims to provide a reference for researchers on how to develop new synthetic straregies of fluorine-containing organic compounds and achieve kilograms or even tons preparation of fluorine-containing organic compounds using fluoroalkyl anhydrides.     

Reference Materials for the Analysis of Organic Compounds of Environmental and Occupational Concern

Summary

The requirements, preparation, purification, characterisation, determination and certification of purity, utilisation and handling of reference materials for the analysis of organic pollutants found in the environment and workplace are reviewed in relation to specific groups of organic compounds.     

“Do it yourself” reference materials for δ 13C determinations by isotope ratio mass spectrometry

A method is described to prepare inexpensive organic reference materials for routine stable isotope work. The method blends isotope-enriched and isotope-depleted materials to match closely international measurement standards. Examples are presented showing how ¹³C-enriched and ¹³C-depleted glucose were blended to match the isotopic compositions of the international carbon isotope standards, NBS 19 and L-SVEC. Preparation of the blended standards was straightforward, and the prepared solutions proved easy to dispense into tin capsules and easy to combust in a conventional isotope analysis system. The blended materials allow a laboratory to perform a two-point calibration for isotopic composition on a daily basis, with the use of an international reference material recommended for routine quality assurance. The blending method can be applied widely to make isotope standards for other elements and compounds.     

Development of certified reference materials of high-purity volatile organic compounds: purity assay by the freezing-point depression method

For accurate measurement of concentrations of substances by instrumental analysis, reliable calibration standards are needed. In Japan, national reference materials are supplied under the national standards dissemination system named the Japan Calibration Service System (JCSS). In JCSS, calibration standards for the analysis of environmental pollutants are supplied. For the traceability to the SI of reference materials for calibration in JCSS, the National Metrology Institute of Japan (NMIJ) is developing high-purity reference materials of volatile organic compounds (VOCs) as NMIJ CRMs. The freezing-point depression method, which has potential as a primary method of measurement, is employed for the determination of property value. In this paper, a development scheme of certified reference materials of high-purity VOCs is described. Presented at BERM-11, October 2007, Tsukuba, Japan.     

Organometallic chemistry related to applications for microelectronics in Japan

This is meant to be a brief overview of the developments of research activities in Japan on organometallic compounds related to their use in electronic and optoelectronic devices. The importance of organometallic compounds in the deposition of metal and semiconductor films for the fabrication of many electronic and opto-electronic devices cannot be exaggerated. Their scope has now extended to thin-film electronic ceramics and high-temperature oxide superconductors. A variety of organometallic compounds have been used as source materials in many types of processing procedures, such as metal–organic chemical vapor deposition (MOCVD), metalorganic vapor-phase epitaxy (MOVPE), metal–organic molecular-beam epitaxy (MOMBE), etc. Deposited materials include silicon, Group III–V and II–VI compound semiconductors, metals, superconducting oxides and other inorganic materials. Organometallic compounds are utilized as such in many electronic and optoelectronic devices; examples are conducting and semiconducting materials, photovoltaic, photochromic, electrochromic and nonlinear optical materials. This review consists of two parts: (I) research related to the fabrication of semiconductor, metal and inorganic materials; and (II) research related to the direct use of organometallic materials and basic fundamental research.     

Reference materials for domoic acid, a marine neurotoxin

Summary Domoic acid was recognized recently [1, 2] to be a marine neurotoxin associated with shellfish harvested or cultured for use as human food. Evidence about the occurrence of domoic acid and its importance to shellfish industries is reviewed. The preparation and certification of two reference materials for the determination of domoic acid, an instrument calibration solution (DACS-1, released by the Marine Analytical Chemistry Standards Program [MACSP] in May, 1989), and a tissue reference material (MUS-1, homogenized soft tissues of Mytilus edulis, released by the MACSP in August, 1989) are described. We believe these are the first certified standards or reference materials to be available for the determination of shellfish toxins, a problem of increasing importance to aquaculturists and the seafood industry, as well as to agencies concerned with the safety of food. The tissue homogenate preparation techniques we have developed and used may be of general interest for the preparation of other tissue reference materials for the determination of other organic compounds, since the sealed, fluid homogenate samples seem acceptably stable without being continuously frozen or refrigerated.NRCC No. 31925     

Differential scanning calorimetry to measure the purity of polycyclic aromatic hydrocarbons

The application of differential scanning calorimetry (DSC) for purity determination is well documented in literature and is used amongst others in the analysis of pure organic crystalline compounds. The aim of this work is to examine whether the DSC method for purity determination consistently produces values for the purity of polycyclic aromatic hydrocarbons (PAHs) which are sufficiently accurate as required for the certification of reference materials. For this purpose, 34 different existing PAH certified reference materials were tested. The DSC results are shown to be consistent with the results obtained by other methods assessing the organic impurities content in PAHs, like gas chromatography (GC), high performance liquid chromatography (HPLC) and mass spectrometry. Significant differences between the measured values and the certified purity values were observed only in a limited number of cases.     

Determination of pesticides and other physiologically active compounds by capillary gas chromatography with an atomic-emission detector without using standard reference materials

It was shown that organic substances can be determined by gas chromatography with an atomicemission detector without using standard reference materials of these substances or information on their toxicity, but using reference materials of other compounds containing similar hetero-atoms     

Precise and traceable carbon isotope ratio measurements by multicollector ICP-MS: what next?

This article reviews recent developments in the use of multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) to provide high-precision carbon isotope ratio measurements. MC-ICP-MS could become an alternative method to isotope ratio mass spectrometry (IRMS) for rapid carbon isotope ratio determinations in organic compounds and characterisation and certification of isotopic reference materials. In this overview, the advantages, drawbacks and potential of the method for future applications are critically discussed. Furthermore, suggestions for future improvements in terms of precision and sensitivity are made. No doubt, this is an exciting analytical challenge and, as such, hurdles will need to be cleared.     

Study of applicability of various solid-phase extraction materials for sample handling in screening analysis of organic micropollutants in water.

At present, solid-phase extraction (SPE) has become an often preferred preconcentration technique in the screening for a wide range of organic micropollutants in water. A wide choice of materials available on the market makes SPE a suitable tool to cope with an increasing variability of organic compounds entering the hydrosphere. However, the interactions of various sorbent materials with compounds having different physico-chemical properties leads inevitably to large differences in preconcentration efficiency. The aim of this paper was to investigate the efficiency of preconcentration of selected organic compounds from aqueous solutions on various SPE materials. Simultaneously, the potential of newly emerging SPE procedures was compared to results of traditional liquid-liquid extraction methods. The group of 19 tested analytes was selected so as to represent different classes of organic compounds which may occur in waters. The results obtained showed that most of the tested materials were suitable for sufficient preconcentration of a substantial part of the tested analytes. However, specific differences in recovery of one or more analytes were found for almost each sorbent even in the case when the materials had similar composition. This behaviour clearly indicates the need for a thorough testing of capabilities of any SPE material intended for the use in a wide range screening method for the identification of unknown organic micropollutants in water.     

二嗪类有机光电功能材料的应用进展

在过去的几十年里,有机电子学作为一个新兴领域迅猛发展,为科学技术的进步作出了巨大的贡献.有机材料被应用在各种电子器件中,并取得了卓越的成效.作为使用在电子器件中最基本的组分,有机光电材料更是备受瞩目.二嗪类化合物具有优异的光电性能,是光电材料领域最活跃的研究方向之一.两个N原子相对位置的不同,可以构成三种异构体,分别为哒嗪(1,2-二嗪)、嘧啶(1,3-二嗪)和吡嗪(1,4-二嗪),从而有效地调控材料的电子结构,且可以影响二嗪化合物不同位置的修饰,从而得到了广泛关注.本文对近年来二嗪类化合物在光伏材料、薄膜半导体材料、液晶材料、传感材料和电致发光材料等领域的研究进展进行了较全面的总结和评述,指出目前基于二嗪类化合物的光电材料所面临的困难以及未来的发展方向,最后展望了二嗪类化合物作为杂环类有机光电功能材料的应用前景.     

Four-coordinate organoboron compounds with a π-conjugated chelate ligand for optoelectronic applications

Four-coordinate organoboron compounds with a π-conjugated chelate backbone have emerged recently as highly attractive materials for a number of applications including use as emitters and electron-transport materials for organic light-emitting diodes (OLEDs) or organic field transistors, photoresponsive materials, and sensory and imaging materials. Many applications of this class of boron compounds stem from the electronic properties of the π-conjugated chelate backbone. Charge-transfer transitions from an aromatic substituent attached to the boron center of the π-conjugated chelate backbone and steric congestion have also been found to play important roles in the luminescent and photochromic properties of the four-coordinate boron compounds. This article provides an update-to-date account on the application aspects of this important class of compounds in materials science with the emphasis on OLED applications and photochromic switching.     

Survey of reference materials for trace elements, nuclides and organic microcontaminants

The International Atomic Energy Agency (IAEA), in co-operation with the United Nations Environment Programme (UNEP), has recently prepared a survey on internationally available analytical reference materials for trace elements, nuclides and organic contaminants in biological, environmental and related matrices. The purpose is to help analysts to select reference materials for quality assurance that match as closely as possible, with respect to matrix type and concentrations of the measurands of interest, the “real” samples that are to be measured. The present version of the survey, which is available in the form of two cost-free printed volumes [1], contains over 10,000 certified and information values in 650 reference materials from 27 different producers. The 455 measurands listed include trace elements, major and minor elements, organic contaminants, organometallic compounds, radionuclides and stable isotopes. Currently, the database from which the survey has been produced is being modified and extended so as to make the data available in electronic form via the Internet. Received: 11 June 1997 / Revised: 7 July 1997 / Accepted: 9 July 1997     

Utilisation of certified reference materials in monitoring common environmental pollutants (PAHs, Nitro-PAHs, PCBs)

Summary Monitoring of the concentration levels of certain environmental organic pollutants which pose potential health hazards is examined. The use of reference materials in the quantitative measurement of common pollutants such as polycyclic aromatic hydrocarbons (PAHs), polycyclic heteroaromatic compounds, nitro-polycyclic aromatic hydrocarbons, and polychlorinated biphenyls (PCBs) is reviewed within the context of achieving optimum precision sand accuracy of the measurements.

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Verwendung zertifizierter Referenzmaterialien bei der Messung von Umweltverunreinigungen (PAHs, Nitro-PAHs, PCBs)

     

Purity assessment for avoparcin

Well-characterized pure-substance reference materials for the use as calibrants are essential to establish the metrological traceability of the results of chemical measurements. Normally, the characterization of this type of reference material is conducted through a thorough purity assessment of the compound concerned. For this reason, studies on purity assessment, especially for neat organic compounds, continues as an important part of work being undertaken by metrological institutions around the world. Among others, the need for certified pure reference standards continues to increase for residues analysis in foods, particularly for those compounds which have been banned for food safety reasons, but their residues in foods are still monitored under food surveillance program in many countries. In this respect, avoparcin serves as a very good example where testing laboratories have difficulties in obtaining traceable and comparable results on determination of avoparcin in food matrix samples due, in part, to the unavailability of certified pure-substance reference material as calibrant. In this study, it was attempted to assess the purity of a commercially available test material of avoparcin using the mass balance approach. The objective of this paper is to share the difficulties encountered during the course of purity assessment and how they were addressed. As expected, the most challenging part of work was to identify and estimate the amount of unknown impurities, both organic and inorganic-related ones, given the chemical structure and properties of avoparcin. For instance, avoparcin exists in two forms in the test material, i.e., α- and β-avoparcin, and they were found to be susceptible to hydrolysis under certain conditions.     

Enhanced Room-Temperature Phosphorescence through Intermolecular Halogen/Hydrogen Bonding

Room-temperature phosphorescence (RTP) materials with high efficiency have attracted much attention because they have unique characteristics that cannot be realized in conventional fluorescent materials. Unfortunately, efficient RTP in metal-free organic materials is very rare and it has traditionally been considered as the feature to divide purely organic compounds from organometallic and inorganic compounds. There has been increasing research interest in the design and preparation of metal-free organic RTP materials in recent years. It has been reported that intermolecular interactions make a big difference to the photophysical behavior of organic molecules. In this regard, herein, the parameters that affect RTP efficiency are discussed, and a brief review of recent intermolecular halogen-/hydrogen-bonding strategies for efficient RTP in metal-free organic materials are provided. The opportunities and challenges are finally elaborated in the hope of guiding promising directions for the design and application of RTP materials.