Chromatographic separation of marine organic pollutants.

A review and discussion of the chromatographic separation of marine organic pollutants is given, including sampling and clean-up procedures, fractionation and enrichment of marine pollutants, capillary gas chromatography (cGC) and high-performance liquid chromatography applying both classical and chiral stationary phases. The potential of multi-dimensional cGC for the analysis of marine organic trace pollutants is discussed for polychlorinated biphenyls (PCBs). The chromatographic separation of coplanar PCBs and of the enantiomers of chiral pollutants provides a further insight into the toxic potential of these marine organic pollutants.     

Analysis of industrial contaminants in indoor air: Part 1. Volatile organic compounds,carbonyl compounds,polycyclic aromatic hydrocarbons and polychlorinated biphenyls

This article reviews recent literature on the analysis of industrial contaminants in indoor air in the framework of the REACH project, which is mainly intended to improve protection of human health and the environment from the risks of more than 34 millions of chemical substances. Industrial pollutants that can be found in indoor air may be of very different types and origin, belonging to the volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) categories. Several compounds have been classified into the priority organic pollutants (POPs) class such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and furans (PCDD/PCDFs) and related polychlorinated compounds, and polycyclic aromatic hydrocarbons (PAHs). Many of these compounds are partially associated to the air gas phase, but also to the suspended particulate matter. Furthermore, settled dust can act as a concentrator for the less volatile pollutants and has become a matrix of great concern for indoors contamination. Main literature considered in this review are papers from the last 10 years reporting analytical developments and applications regarding VOCs, aldehydes and other carbonyls, PCBs, PCDDs, PCDFs, and PAHs in the indoor environment. Sample collection and pretreatment, analyte extraction, clean-up procedures, determination techniques, performance results, as well as compound concentrations in indoor samples, are summarized and discussed. Emergent contaminants and pesticides related to the industrial development that can be found in indoor air are reviewed in a second part in this volume.     

An improved clean-up strategy for simultaneous analysis of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and polychlorinated biphenyls (PCB) in fatty food samples

The study and extension of a simple automated clean-up method for polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) to a broad range of polychlorinated biphenyls (PCB) is described. The isolation of seven PCDD, ten PCDF, and three coplanar PCB (cPCB) is extended to eight monoortho substituted PCB and seven so-called "marker PCB" (Aroclor 1260) for fatty food samples. This enables quantification of 35 compounds - including all congeners with a WHO toxic equivalent factor (TEF)--in a single extraction and single purification step. The chromatographic behaviour of mono-ortho PCB and marker PCB on a variety of adsorbents, including basic alumina, has been studied. Partitioning of analytes through multi-column sequences is described and correlated with their structural and electronic properties, by use of molecular modelling calculations. The fractionation process available with the Power-Prep automated clean-up system enables rapid independent analysis of the different groups of compounds. Gas chromatography with high resolution mass spectrometry (GC-HRMS) is used for the PCDD/F and cPCB fraction and quadrupole ion-storage tandem in time mass spectrometry (GC-QISTMS) for analysis of the remaining PCB. A comparison study was performed on quality-control samples and real fatty food samples to evaluate the robustness of the new strategy compared with a reference method. On the basis of this simultaneous clean-up, a rapid simplified strategy for PCDD/F and selected PCB analysis determination is proposed for fatty food samples.     

Fast clean-up for polychlorinated dibenzo-p-dioxins, dibenzofurans and coplanar polychlorinated biphenyls analysis of high-fat-content biological samples

A fast clean-up procedure for the low level analysis of polychlorinated dibenzo-p-dioxins. polychlorinated dibenzofurans and coplanar polychlorinated biphenyls in highly fatty biological matrices using high capacity disposable multi-layer silica columns is presented. Results were compared with gel permeation chromatography for removal of lipids. Analytical criteria such as recovery rates, repeatability, reproducibility and robustness are evaluated through a broad range of biological matrices and reference materials analysis. The final proposed procedure for the complete analysis, including pressurized liquid extraction, Power-Prep system clean-up and GC-high-resolution MS analysis requires only 48 h, and allows the simultaneous preparation of up to 10 samples.     

Occurrence and analytical methods of acrylamide in heat-treated foods. Review and recent developments

In early 2002, Swedish National Food Administration (SNFA) and University of Stockholm together announced that certain foods that are processed or cooked at high temperature contain relatively high levels of acrylamide. The occurrence of acrylamide is derived from heat-induced reactions between the amino group of asparagine and the carbonyl group of reducing sugars during baking and frying. Corresponding chromatographic methods are used to determine various structural groups present during this process. Gas chromatography (GC)-mass spectrometry (MS) and liquid chromatography with tandem mass spectrometry (LC-MS/MS) analysis are both acknowledged as the major useful and authoritative methods for the acrylamide determination and other chromatographic methods are also briefly introduced. The aim of this review is to summarize the state-of-the-art about the occurrence, analytical methods, and extraction and clean-up procedures of acrylamide. Special attention is given to chromatographic techniques applied for the occurrence and determination of acrylamide.     

Composition and analysis of liquid smoke flavouring primary products

Smoke flavourings are produced on a large scale and have been applied to a variety of food products for more than 30 years. The use of them has many advantages compared to traditional smoking techniques. Among others, the amount of (known) toxic compounds deriving from combustion processes can be more easily controlled in smoke flavourings. In order to ensure safe products, a new European Regulation requests data on the composition and lays down, in particular, the maximum permitted concentrations for selected polycyclic aromatic hydrocarbons (PAHs). This review compiles results published on the chemical composition of liquid smoke flavouring primary products, partly in relation to production process parameters, and the analytical methods involved. The methods cover chromatographic techniques for analysis of specific compounds including extraction methods and clean-up procedures. Analysis of sensorial and bulk parameters such as acidity and total phenolic compounds are described as well as they are used as standard methods for analysis of liquid smoke flavourings. A special section is devoted to discussing the analysis of PAHs.     

Automated clean-up procedure for the gas chromatographic-high-resolution mass spectrometric determination of polychlorinated dibenzo-p-dioxins and dibenzofurans in milk.

A highly automated extraction and clean-up method for polychlorinated dibenzodioxins and polychlorinated dibenzofurans is described. The method includes the use of gel permeation chromatography, alumina clean-up and porous graphitized carbon chromatography, followed by analysis by gas chromatography-high-resolution mass spectrometry. The procedure allows for the analysis of six milk samples per day in addition to two quality control samples and a blank. Detection limits on a fat basis for the individual congeners in milk samples are in the sub-ppt range. Long-term performance was investigated and data are given for reproducibility, precision and accuracy.     

Sample pretreatment method for the determination of polychlorinated biphenyls in bird livers using ultrasonic extraction followed by headspace solid-phase microextraction and gas chromatography-mass spectrometry

A simple and reliable sample methodology based on simultaneous ultrasonic extraction, sulfuric acid clean-up and headspace solid-phase microextraction (SPME)-gas chromatography-mass spectrometry has been developed as an advantageous analytical tool for the determination of seven polychlorinated biphenyl congeners in bird livers at low levels. The influence of several parameters on the efficiency of the proposed method was systematically investigated. The clean-up efficiency of sulfuric acid treatment was tested and compared with those of column chromatography (Flosiril, silica gel and alumina) and solid-phase extraction (SPE) (Supelclean ENVI-Carb cartridge) procedures. The use of sulfuric acid in the clean-up step prior to headspace solid-phase microextraction analysis allows the removal of interfering matrix compounds present in the liver extracts that would otherwise cause severe ionization suppression of the polychlorinated biphenyls (PCBs) during the ionization process. The optimized method had good linearity (R2>0.99) over the range studied (5-500 ng/g wet weight) and showed satisfactory level of precision, with RSD values lower than 10.6%. The obtained relative recoveries ranged between 63 and 94%. The limits of detection (0.06-0.63 ng/g wet weight) were low enough to check for harmful levels of polychlorinated biphenyls in biological samples, and were well below most of the restrictive limits established by European Union regulations. The method was found to be reliable under the operational conditions proposed and was applied successfully to the analysis of individual polychlorinated biphenyls in liver tissues. The results obtained from five bird species from Greece revealed the presence of the target compounds in all samples analyzed, at levels ranging between 0.54 and 39.45 ng/g wet weight.     

High-performance liquid chromatographic determination of Levetiracetam in human plasma: comparison of different sample clean-up procedures

An accurate and precise high-performance liquid chromatographic method using diode array detection for the determination of the novel antiepileptic, Levetiracetam, has been developed. Three clean-up procedures for the analysis of Levetiracetam in human plasma were implemented and evaluated, namely solid-phase extraction, deproteinization by addition of organic solvents and formation of insoluble salts. Adenosine was used as the internal standard for all three sample pretreatment procedures. Among the several cartridges used for solid-phase extraction, the hydrophilic-lypophilic balance (Oasis) HLB) phase provides the best extraction yield of Levetiracetam, together with high precision. With the two other clean-up procedures involving plasma deproteinization by addition of methanol or zinc sulphate, lower sensitivity and precision of the assays were obtained. However, they are cheaper and faster when compared with the solid-phase extraction procedure.     

Recent developments in the analysis of brominated flame retardants and brominated natural compounds

This article reviews recent literature on the analysis of brominated flame retardants (BFRs) and brominated natural compounds (BNCs). The main literature sources are reviews from the last five years and research articles reporting new analytical developments published between 2003 and 2006. Sample pretreatment, extraction, clean-up and fractionation, injection techniques, chromatographic separation, detection methods, quality control and method validation are discussed. Only few new techniques, such as solid-phase microextraction (SPME) or pressurized liquid extraction (PLE), have been investigated for their ability of combining the extraction and clean-up steps. With respect to the separation of BFRs, the most important developments were the use of comprehensive two-dimensional gas chromatography for polybrominated diphenyl ethers (PBDEs) and the growing tendency for liquid-chromatographic techniques for hexabromocyclododecane (HBCD) stereoisomers and of tetrabromobisphenol-A (TBBP-A). At the detection stage, mass spectrometry (MS) has been developed as well-established and reliable technology in the identification and quantification of BFRs. A growing attention has been paid to quality assurance. Interlaboratory exercises directed towards BFRs have grown in popularity and have enabled laboratories to validate analytical methods and to guarantee the quality of their results. The analytical procedures used for the identification and characterization of several classes of BNCs, such as methoxylated polybrominated diphenyl ethers (MeO-PBDEs) (also metabolites of PBDEs), halogenated methyl or dimethyl bipyrroles (DBPs), are reviewed here for the first time. These compounds were generally identified during the routine analysis of BFRs and have received little attention until recently. For each topic, an overview is presented of its current status.     

Determination of currently used pesticides in biota

Although pesticides enable control of the quantity and quality of farm products and food, and help to limit diseases in humans transmitted by insects and rodents, they are regarded as among the most dangerous environmental contaminants because of their tendency to bioaccumulate, and their mobility and long-term effects on living organisms. In the past decade, more analytical methods for accurate identification and quantitative determination of traces of pesticides in biota have been developed to improve our understanding of their risk to ecosystems and humans. Because sample preparation is often the rate-determining step in analysis of pesticides in biological samples, this review first discusses extraction and clean-up procedures, after a brief introduction to the classes, and the methods used in the analysis of pesticides in biota. The analytical methods, especially chromatographic techniques and immunoassay-based methods, are reviewed in detail, and their corresponding advantages, limitations, applications, and prospects are also discussed. This review mainly covers reports published since 2008 on methods for analysis of currently used pesticides in biota.     

Sample preparation for chromatographic separations: an overview

Chromatographic methods dominate the field of organic analysis. However, many samples are too dilute, too complex or incompatible with the chromatographic system to render separation or detection possible without preliminary matrix simplification and/or preconcentration. A broad selection of the most common, recent and emerging isolation, clean-up and concentration techniques used to prepare samples for chromatographic separations are reviewed.     

Liquid chromatographic-tandem mass spectrometric determination of nonylphenol polyethoxylates and nonylphenol carboxylic acids in surface water

Various liquid chromatographic methods used in the analysis of mycotoxins (zearalenone, trichothecenes and fumonisins) produced by Fusarium species were compared in this work. The results demonstrate the suitability of modern clean-up procedures employing multifunctional MycoSep and immunoaffinity columns although these methods are more expensive than conventional methodologies for clean-up. HPLC with both fluorescence and photodiode array detection is a suitable technique for the analysis of toxic secondary metabolites produced by Fusarium species; different derivatisation strategies have been studied to improve the sensitivity of the technique because of the low concentration of these metabolites in contaminated food. The utility of the proposed methodology was assessed in cereal cultures of various Fusarium strains.     

Development of new-type rapid analysis technology of polychlorinated biphenyls by using liquid chromatographic clean-up material (polyvinyl alcohol gel)

We developed a new-type rapid polychlorinated biphenyl (PCB) analysis technology on the basis of a liquid chromatographic clean-up system combined with a large-volume injection GC-LRMS. Among 18 kinds of materials such as polymer gels, normal-phase silica gels, reversed-phase silica gels, carbon material and ion-exchange material, polyvinyl alcohol (PVA) gel and poly (hydroxylmethacrylate) gel were found to give rather good separation performance for insulating oil. Especially, PVA gel was confirmed to be the most suitable for rapid PCB analysis because of its least required quantity of fraction liquid as well as the highest resolution. Then, we confirmed elution characteristics of all PCB isomers and removal efficiency of insulating oil on PVA gel under an optimized condition, and established high-performance clean-up system using a combination of octadecyl silica gel (ODS), porous graphite carbon (PGC) and PVA gel. In this system, we applied newly valve-switching method that could remove other impurities. In addition, it was demonstrated that the proposed clean-up system could become highly sensitive and rapid PCB analysis technology with 2-h analysis time, lower measurement limit of less than 0.05 mg/kg, and a variation coefficient of less than 5%, by coupling with a large-volume injection type GC-LRMS. Thus, we can conclude that this rapid PCB analysis technology has not only good correlativity (R2>0.999) with standard analysis method but also high durability and can be fully applied to actual PCB-treatment plants.     

Hyphenation of gas chromatography and resonance-enhanced laser mass spectrometry (REMPI-TOFMS): A multidimensional analytical technique

Analysis of environmental samples usually requires time consuming sample preparation and clean-up procedures prior to instrumental detection. Faster analysis requires an enhanced instrumental selectivity in order to reduce the necessary clean-up effort. In this context we present a novel concept for coupling gas chromartography/mass spectrometry (GC-MS) with high resolution UV spectoscopy to increase selectivity. We use UV-laser induced, resonance-enhanced multi-photon ionization (REMPI)as a compound specifie ion source for time-of-flight mass spectrometry (TOFMS). The REMPI ionization involves the UV absorption spectroscopy into the ionization process as an aditional analytical dimension. The heart of the GC-REMPI-TOFMS coupling is a specially designed valve, which repetitively (20 Hz) expands the chromatographic eluent as short supersonic jet gas pulses (≈ 150 μs duration) into the vacuum of the mass specrtrometer. The sample molecules are cooled down to temperatures of 10-40 K within the jet expansion. Under these conditions, UV absorption spectriscopy (i.e. REMPi spectroscopy) becomes highly compound selective, even able to distinguish isomeric compounds. The ions formed by REMPI ionization are mass analyzed in the TOFMS. Thus the GC-REMPI-TOFMS coupling presented here is actually a three-dimensional analytical instrument, providing gas chromatographic (retention time) as well as mass spectrometric (molecular mass) and UV -spectroscopic (excitation laser wavelength) selectivity. In combination with gas phase sampling and concentration techniques for semi-volatile organic air pollutants based, e.g., on silicone rubber traps the GC-LAMS technique can be a powerful tool for fast environmental target analysis, e.g. for industrial emission control purposes.     

Sample preparation methods in the analysis of pesticide residues in baby food with subsequent chromatographic determination

Pesticides are widely utilized at various stages of cultivation and during postharvest storage to protect plants against a range of pests and/or to provide quality preservation. Reliable confirmatory methods are required to monitor pesticide residues in baby foods and to ensure the safety of baby food supply. This review covers methods in which pesticide residues have been determined in baby food by the use of a wide range of chromatographic techniques after various sample preparation steps. The main attention is paid to the evaluation and improvement of sample extraction and clean-up methods (liquid extraction, solid-phase extraction (SPE), dispersive SPE (DSPE), microextraction procedures, matrix solid-phase dispersion (MSPD) and supercritical fluid extraction (SFE)) considering low concentration levels of pesticide residues in baby food resulting from stringent European Union (EU) legislation. Instrumental aspects together with the matrix effects significantly contributing to the most important parameters considered in pesticide residues analysis of baby food--limits of detection (LODs) and limits of quantification (LOQs) were included within the scope of this overview. Paper involves also monitoring studies.     

An off-line two-dimensional analytical procedure for determination of polycyclic aromatic hydrocarbons in smoke aerosol

Smoke aerosol from stoves consists of a wide variety of chemical substances of which a number have toxic properties. To study the impact of aerosol emissions on health and environment reliable analytical procedures must be available for these samples. An off-line two-dimensional HPLC method is described for the determination of a number of polycyclic aromatic hydrocarbons (PAH). The method consists of a HPLC clean-up step yielding distinct fractions on activated silica and followed by analysis of each of the fractions by isocratic reversed phase HPLC. Detection is by UV and fluorescence monitors in series. Combination of the chromatographic data obtained from both the clean-up and analytical step provides additional qualitative information.     

Micropore-free surface-activated carbon for the analysis of polychlorinated dibenzo-p-dioxins-dibenzofurans and non-ortho-substituted polychlorinated biphenyls in environmental samples

2,3,7,8-Substituted polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs) and non-ortho-substituted polychlorinated biphenyls (PCBs) account for almost all of the total toxic equivalents (TEQ) in environmental samples. Activated carbon columns are used to fractionate the samples for GC-MS analysis or bioassay. Micropore-free surface-activated carbon is highly selective for PCDD/Fs and non-ortho-PCBs and can improve the conventional activated carbon column clean-up. Along with sulfuric acid-coated diatomaceous earth columns, micropore-free surface-activated carbon provides a rapid, robust, and high-throughput sample preparation method for PCDD/Fs and non-ortho-PCBs analysis.     

Chromatographic methods for the determination of mycotoxins in food products

Chromatographic methods for the determination of mycotoxins from different classes in food products of plant and animal origins are surveyed. The procedures of sample preparation and extract purification and the use of various chromatographic analysis techniques are considered.     

Solid-phase extraction of sugar cane soot extract for analysis by gas chromatography with flame ionisation and mass spectrometric detection

The incomplete combustion of biomass is one of the most important sources of emissions of organic compounds into the atmosphere, like polycyclic aromatic hydrocarbons (PAHs) which show genotoxic activity. Since environmental samples generally contain interferents and trace amounts of PAHs of interest, concentration and clean-up procedures are usually required prior to the final chromatographic analysis. This paper discusses the performance of Sep-Pak cartridges (silica gel and RP18) on clean-up of sugar cane soot extract. The best results were obtained with a silica Sep-Pak cartridge. The recoveries ranged from 79% (benzo[b]fluoranthene) to 113% (benzo[e]pyrene).