沉积物内多氯联苯测定中有机氯农药的排除及质量控制/质量保证研究

报道了沉积物样品中多氯联苯(PCBs)的分析方法及质量控制/质量保证(QA/QC)研究,结果表明多级复合硅胶柱对有机氯农药去除效果良好.采用25种PCBs同族体标样PCB25对分析方法进行了QA/QC研究,PCBs的平均回收率在97%～118%之间.用本方法测定25种多氯联苯同族体的检测限范围在0.5～1.4ng/g之间.     

土壤中重金属元素检测的质量认证

探讨了土壤中重金属检测能力验证的质量控制措施,为确保能力验证结果的准确性及不断提高实验室的检测技术水平提供参考.     

湿法程控消解-冷原子吸收方法测定微量汞的质量保证

对使用程序控制温度消解器和原子化发生、测定装置进行程序控制消解温度-湿法消解-氢化物发生-冷原子吸收方法测定微量汞的质量保证进行了研究,提出了人、样品、方法、仪器与器具、环境、试剂六方面的质量保证要点。     

标准物质在科研设备质量控制体系中的使用和管理

阐述了标准物质的应用和管理在科研设备质量控制体系中的重要性,指出了现阶段科研设备用标准物质存在的问题,并提出了对策。     

Identification of Phototoxic Polycyclic Aromatic Hydrocarbons in Sediments Through Sample Fractionation and QSAR Analysis

Abstract

The toxicity of certain polycyclic aromatic hydrocarbons (PAHs) can be greatly increased by simultaneous exposure of test organisms to ultraviolet (UV) wavelengths present in sunlight. This phenomenon, commonly termed photoinduced toxicity, had been evaluated extensively in laboratory settings where only one chemical of concern was present. However, more recent studies have demonstrated that complex mixtures of PAHs present, for example in sediments, also can cause phototoxicity to a variety of aquatic species when the samples are tested in simulated sunlight. Unfortunately, because these types of samples can contain thousands of substituted and unsubstituted PAHs it is difficult, if not impossible, to use conventional analytical techniques to identify those responsible for photoinduced toxicity. The objective of the present study was to link two powerful ecotoxicology tools, toxicity-based fractionation techniques and QSAR models, to identify phototoxic chemicals in a sediment contaminated with PAHs emanating from an oil refinery. Extensive chromatographic fractionation of pore water from the sediment, in conjunction with toxicity testing, yielded a simplified set of sample fractions containing 12 PAHs that were identified via mass spectroscopy. Evaluation of these compounds using a recently developed QSAR model revealed that, based upon their HOMO-LUMO gap energies, about half were capable of producing photoinduced toxicity. We further evaluated the phototoxic potential of the reduced set of PAHs by determining their propensity to bioaccumulate in test organisms, through calculation of octanol-water partition coefficients for the chemicals. These studies represent a novel linkage of sample fractionation methods with QSAR models for conducting an ecological risk assessment.     

多环芳烃的超临界流体色谱分离研究

烃中多环芳烃（晕苯和卵苯）的分离是极其困难的。研究了在不同极性毛细管填充ＳＦＣ柱上多环芳烃的分离条件。选用国产１５０ｍｍＣＮ填充柱,ＣＯ＿２为流动相,线性升压,ＦＩＤ检测,可在２６ｍｉｎ内将烃中三到十环多环芳烃分离,定量重复性良好。     

ASE/GC-MS法同时测定海洋沉积物中65种多氯联苯、多环芳烃与有机氯农药

建立了加速溶剂萃取/气相色谱-质谱法(ASE/GC-MS)同时测定海洋沉积物中28种多氯联苯(PCBs)、16种多环芳烃(PAHs)和21种有机氯农药(OCPs)的分析方法.结果表明,ASE的最佳萃取温度为100 ℃,最佳静态时间为5 min.GC-MS同时分析65种化合物时,PAHs的线性范围为0.05 ～5.00 ...     

原油空气氧化前后多环芳烃组分的气相色谱-质谱分析

采用柱层析法对空气氧化前后的原油进行族组分分离,利用气相色谱-质谱(GC-MS)分离测定其芳香烃组分,分析多环芳烃组分的变化.结果表明,随着氧化过程的进行,烷基化多环芳烃占多环芳烃的含量从氧化前的71.5%增加到92.0%(175℃)和90.2%(225℃).轻质组分萘和菲的优势逐渐被重质组分艹屈取代.侧链少的多环芳烃比侧链多的更易氧化.氧化后,其他稠环化合物蒽、萤蒽、芘、苯并蒽含量降低,苯并萤蒽含量增加;苯并芘在175℃氧化后含量降低,而在225℃氧化后含量增加.与此同时,175℃氧化后生成了原油所不含有的三芳甾烃、联苯和苯并呋喃.     

Mineral oil certified reference materials for the determination of polychlorinated biphenyls from the National Metrology Institute of Japan (NMIJ)

Four mineral oil certified reference materials (CRMs), NMIJ CRM 7902-a, CRM 7903-a, CRM 7904-a, and CRM 7905-a, have been issued by the National Metrology Institute of Japan, which is part of the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST), for the determination of polychlorinated biphenyls (PCBs). The raw materials for the CRMs were an insulation oil (CRM 7902-a and CRM 7903-a) and a fuel oil (CRM7904-a and CRM 7905-a). A solution of PCB3, PCB8, and technical PCB products, comprising four types of Kaneclor, was added to the oil matrices. The total PCB concentrations in the PCB-fortified oils (CRM 7902-a and CRM 7904-a) are approximately 6 mg kg⁻¹. In addition, the mineral oils which were not fortified with PCBs were also distributed as CRMs (CRM 7903-a and CRM 7905-a). Characterization of these CRMs was conducted by the NMIJ/AIST, where the mineral oils and the PCB solution were analyzed using multiple analytical methods such as dimethylsulfoxide extraction, normal-phase liquid chromatography, gel permeation chromatography, reversed-phase liquid chromatography, and chromatography using sulfoxide-bonded silica; and/or various capillary columns for gas chromatography, and two ionization modes for mass spectrometry. The target compounds in the mineral oils and those in the PCB solution were determined by one of the primary methods of measurement, isotope dilution–mass spectrometry (ID-MS). Certified values have been provided for 11 PCB congeners (PCB3, 8, 28, 52, 101, 118, 138, 153, 180, 194, and 206) in the CRMs. These CRMs have information values for PCB homologue concentrations determined by using a Japanese official method for determination of PCBs in wastes and densities determined with an oscillational density meter. Because oil samples having arbitrary PCB concentrations between respective property values of the PCB-fortified and nonfortified CRMs can be prepared by gravimetric mixing of the CRM pairs, these CRMs can be used for validation of PCB analyses using various instruments which have different sensitivities. Figure Preparation and certification processes of the mineral oil CRMs (example shown is polychlorinated biphenyls in insulation oil, high/low concentrations) Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A Method of Computing the PI Index of Benzenoid Hydrocarbons Using Orthogonal Cuts

The Padmakar–Ivan (PI) index of a graph G is defined as PI , where for edge e=(u,v) are the number of edges of G lying closer to u than v, and is the number of edges of G lying closer to v than u and summation goes over all edges of G. The PI index is a Wiener–Szeged-like topological index developed very recently. In this paper, we describe a method of computing PI index of benzenoid hydrocarbons (H) using orthogonal cuts. The method requires the finding of number of edges in the orthogonal cuts in a benzenoid system (H) and the edge number of H – a task significantly simpler than the calculation of PI index directly from its definition. On the eve of 70th anniversary of both Prof. Padmakar V. Khadikar and his wife Mrs. Kusum Khadikar.     

Quality assurance in biological monitoring of environmental exposure to pollutants: from reference materials to external quality assessment schemes

The presence of chemicals in the environment is a matter of concern in that it poses potential health risks. At present, exposure to toxic chemicals and their biological and biochemical effects can be better estimated by biological monitoring, through the systematic collection of specimens from potentially exposed humans. Biological monitoring of human exposure to environmental pollutants is hampered by the difficulty to assess data reliability. As a consequence, the validity of biological monitoring should depend on the strict implementation of a quality assurance (QA) program, which includes a series of procedures aiming to ensure that laboratory results meet defined standards of quality and are reliable. For the validation and monitoring of methods’ performance, to ensure the trueness of measurements and to warrant the traceability to international standards, reference materials (RMs) and certified reference materials should be used. Internal quality control and external quality assessment (EQA) are part of overall QA and are carried out to verify that analytical errors are compatible with the specific requirements or needs of the user. In particular EQA schemes (EQAS) allow to test independently the analytical performance of participating laboratories. In the last decades, increasing concern has been raised by urban air pollution; lead and benzene, two gasoline components released by motor vehicle exhausts, are known to be toxic to humans. For biological monitoring of lead exposure of the general population, screening campaigns, utilizing lead in blood as a biomarker, have been carried out since the 1970s. Strict strategies were adopted to ensure data comparability, including the preparation of RMs, the organization of EQAS and the cross-exchange and analysis of blood samples between laboratories. Biological monitoring of benzene exposure could be carried out by means of various biomarkers such as benzene in blood and benzene, trans,trans-muconic acid (t,t-MA) and S-phenylmercapturic acid (S-PMA) in urine. At present, few RMs and EQAS are available for these biomarkers. A pilot EQAS for t,t-MA in urine, adopted to assess the reliability of data regarding benzene exposure, has been organized and carried out between 1996 and 1997 in Italy. From the accrued experience, it clearly emerges the importance of strategies designed to guarantee the quality of biological monitoring data. The use of RMs and the participation in EQAS are highly recommended in order to improve the global performance of methods and laboratories involved in biological monitoring.     

判别分析用于烃类化合物分类及汽油样品的族组成分析

研究了判别分析用于烃类化合物分类的可行性，以198个烃类化合物在BD－1和BD－5固定相上同一柱温下的保留指数差及其在各柱上的温度系数为判别变量，成功地建立了烷烃、环烷烃、芳烃和烯烃的判别函数，以此对裂化汽油，重整生成汽油、石脑油和蒸馏常顶汽油进行了族组成分析，经气相色谱－质谱分析验证了结果的正确性，为汽油产品的族组成分析提供了一种新的方法。     

Thermal Analysis as Part of the Quality System within Industrial Laboratories

The use of thermal analysis as part of a quality system in industry can be effective only if the techniques are made to conform to high standards of quality assurance. Achieving these high standards is not problem free and there remain many issues which require the attention of thermal analysts in industry and academe. Fundamental aspects which have been considered include limitations due to instrument design, problems in computerised control and analysis. A key aim is towards validation of data at international level. This revised version was published online in August 2006 with corrections to the Cover Date.     

Adoption of Common Schemes for Single and Sequential Extractions of Trace Metal in Soils and Sediments

Abstract

The various methods for determining the mode of occurrence of trace metals in sediments and soils have a long history which dates back to the determinations of the availability of metals for plant nutrition performed earlier. Various methods have been developed in the 70′s and 80′s dealing with both single and sequential extraction schemes. Although some schemes received wide acceptance, none of them developed into a commonly accepted procedure. As a result, the information obtained was site-specific and the interpretation of the results scientist-specific. The workshop on single and sequential extraction in sediments and soils held at Sitges     

A Mid-Infrared Sensor for Monitoring of Chlorinated Hydrocarbons in the Marine Environment

Abstract

As part of the European research project SOFIE - “Spectroscopy using Optical Fibres in the Marine Environment”, a portable sensor system for chlorinated hydrocarbons in seawater is being developed. This novel analytical tool for real-time in-situ monitoring of a particularly important class of seawater pollutants consists of a robust, miniaturised FT-IR spectrometer in a sealed aluminium pressure vessel and a fibre optic sensor head. In a laboratory set-up using an ATR-crystal as a simplified sensor head, the effect of potentially interfering substances, both of natural and anthropogenic origin, on the sensor response was tested. It was found that the sensor readings for a specific analyte are not susceptible to aliphatic and aromatic components as well as other chlorinated hydrocarbons up to concentrations well above the average levels to be encountered in the oceans. The same applies for the parameters salinity and turbidity. Consequently, the proposed sensor system should be well suited for real-world sub-sea applications.     

土壤中多环芳烃和酞酸酯类有机污染物气相色谱-质谱测定方法中的质量控制与质量保证

建立了气相色谱-质谱(GC-MS)测定土壤中多环芳烃(PAHs)和酞酸酯类(PAEs)有机污染物的方法。样品经加速溶剂萃取和超声萃取处理后,通过固相萃取或凝胶渗透色谱法进行净化,在选择离子监测模式下进行定量。通过全程序空白、空白加标回收、清洁土壤基质加标回收及有证标准参考物质比对等方式,对所建立的方法进行严格的质量控制和保证。16种PAHs和7种PAEs的方法检出限分别为0.13～2.2 μg/kg和0.19～0.52 μg/kg,平均加标回收率分别为41.5%～116.9%和90.7%~107.1%。本研究所建立的土壤中PAHs和PAEs的GC-MS快速分析方法及其质量控制措施可以为全国性土壤污染状况调查数据的科学性和准确性提供技术保障。     

GC-MS法测定大气样品的前处理研究--碳化纤维树脂捕集大气中痕量多环芳烃

研究了碳化纤维树脂吸附载体采集大气中多环芳烃(PAHs)的性能、样品前处理条件和毛细管气相色谱－质谱联用仪检测PAHs的,地具有代表性的多个采样点进行了实地采样、分析,证明碳化纤维树脂吸附载体是一种性能独特的固相吸附剂,建立的样品前处理方法可行,分析数据可靠,可用于大气中PAHs的检测。     

银离子固相萃取-程序升温大体积进样-气相色谱法定量分析市售巧克力中的饱和烷烃矿物油

建立了银渍硅胶固相萃取柱离线(Ag-SPE)净化,程序升温进样-气相色谱-氢火焰离子化检测器(PTV-GC-FID)定量分析巧克力中饱和烷烃矿物油(MOSH)的方法.以正己烷浸泡提取巧克力中的MOSH,离心后取1 mL上清液,过0.3％ Ag渍硅胶SPE柱净化,氮吹浓缩,定容至0.2 mL,注入GC分析; GC的进样口程序升温过程:初始温度45℃,保持1 min(分流比200∶1),以250℃/min升温至360℃(分流阀关闭2 min),并保持27 min(分流比100∶1); 进样量40 μL; 柱温箱升温程序为:35℃保持3 min,以25℃/min升温至350℃,以5℃/min升温至370℃,保持10 min,载气为高纯氮气,流速1.3 mL/min(压力60 kPa); FID温度为380℃.结果表明,本方法的MOSH定量限为0.5 mg/kg,加标回收率为84.9％～108.6％,相对标准偏差(RSD)为0.2％～1.5％.运用本方法对25个市售巧克力样品中的MOSH含量进行了测定,3个样品未检出,其余22个样品中MOSH含量为1.09～8.15 mg/kg(其中C16～C35 的含量为0.56～4.43 mg/kg),有3个样品含量高于5.00 mg/kg,为严重污染样品.本方法操作简便,检出限低,适用于巧克力中MOSH的定量测定.     

轻烃中痕量硫的紫外荧光分析系统的改进

开发了一种新的０．１－１．０ｍｇ／Ｌ痕量硫的分析系统及方法，方法以Ａｎｔｅｋ７０００氧化裂解－紫外荧光定硫仪为基础，通过对进样系统、裂解管、及检测限等方面的改进、使单次分析样品最大进样量增加到５０μＬ。方法的检测限达到０．１ｍｇ／Ｌ，满足了科研及生产工艺的需要。     

Origin of Polycyclic Aromatic Hydrocarbons (PAH) in Recent Sediments from the Continental Shelf of the “Golfe de Gascogne” (Atlantic Ocean) and in the Gironde Estuary

Abstract

Several aromatic series have been analysed on sediment extracts by high performance liquid chromatography coupled (HPLC) and by high resolution Shpol'skii spectroscopy. HPLC coupled to a programmable spectrofluorometer as detector has been used for the detection of the sixteen PAH priority pollutants recommended by the US Environmental Protection Agency. Relative distribution in methylated phenanthrene, chrysene, and pyrene series have been examined by high resolution spectrofluorometry in Shpol'skii matrices for the determination of the sources of aromatic matter in the sediments. These complementary studies would provide useful information on the origin of PAH in marine sediments.