PCDD, PCDF, and PCB contamination of air and inhalable particulate in Rome

Summary The isomer specific determination of PCDD, PCDF and PCB was carried out on samples of air and inhalable particulate from Rome. Samples were taken daily for six months and pooled to yield two samples per month. Normal PCDD+PCDF concentrations expressed in TEQ ranged from 48 to 87 fg/m³, while total PCB ranged from 0.1 to 1.4 ng/m³. The 2, 3, 7, 8-substituted PCDD and PCDF congener pattern is shown together with the PCB congener pattern.     

Formation of polychlorinated dibenzodioxins and dibenzofurans by heating chlorophenols and chlorophenates at various temperatures

Summary Polychlorinated dibenzodioxins (PCDD) and polychlorinated dibenzofurans (PCDF) are formed by pyrolysis of chlorophenols and chlorophenates. Under certain conditions the PCDD pattern is completely governed by the chlorine substitution of the starting molecules. Pyrolyses of chlorophenols at elevated temperatures, however, lead to complex PCDD/PCDF mixtures. Nearly all trito heptachlorodibenzodioxin and -dibenzofuran congeners can arise simultaneously from a mixture of only two trichlorophenols. In this case the substitution pattern of the products is no longer influenced by that of the chlorophenols used.

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Bildung von polychlorierten Dibenzodioxinen und Dibenzofuranen durch Erhitzen von Chlorphenolen und Chlorphenolaten bei verschiedenen Temperaturen

Zusammenfassung Polychlorierte Dibenzodioxine (PCDD) und polychlorierte Dibenzofurane (PCDF) werden durch Pyrolyse von Chlorphenolen und Chlorphenolaten gebildet, wobei unter bestimmten Bedingungen das PCDD-Muster vollständig von der Chlorsubstitution der Ausgangsmoleküle bestimmt wird. Die Pyrolyse von Chlorphenolen bei höheren Temperaturen führt jedoch zu komplexen PCDD/ PCDF-Gemischen. Fast alle Tribis Heptachlordibenzodioxine und -dibenzofurane können gleichzeitig aus einer Mischung von nur zwei Trichlorphenolen hervorgehen. In diesem Fall wird das Substitutionsmuster der Produkte nicht mehr von dem der eingesetzten Chlorphenole beeinflußt.

     

Bestimmung polychlorierter Dibenzodioxine und polychlorierter Dibenzofurane in Motoren?len, Alt?len und Zweitraffinaten

Zusammenfassung Für die Bestimmung von polychlorierten Dibenzodioxinen (PCDD) und polychlorierten Dibenzofuranen (PCDF) in Motorenölen, Altölen und Zweitraffinaten wird ein Verfahren zur Anreicherung und Reinigung beschrieben, das für eine Nachweisgrenze von ca. 0,05 g/kg für die Einzelkomponenten untersucht wurde. Die Ölproben werden nacheinander über Alumina Woelm B Super I, eine gemischte Säule aus Kieselgel, Kieselgel/H₂SO₄, Kieselgel/NaOH und anschließend über Bio-Beads S-X3 chromatographiert und danach eine GC/MS-Analyse durchgeführt. Die Analyse von Motorenölen (Erstraffinaten) ergab, daß auch nach einer Laufleistung von 10 000 km in PKW-Motoren, die mit verbleitem Benzin betrieben wurden, keine PCDD/PCDF nachweisbar sind. Andererseits wurden in Altölen und daraus hergestellten Zweitraffinaten PCDD/ PCDF nachgewiesen, als deren Quelle das in der Mineralölindustrie eingesetzte Pentachlorphenol, das PCDD/PCDF als Nebenkomponenten enthält, identifiziert wurde. anderem in Motorenölen anreichern können. Außerdem wurde in den Medien mehrfach über den Nachweis von PCDD und PCDF in Altölen und Zweitraffinaten berichtet. Da in der Literatur für die Bestimmung von PCDD und PCDF in Ölen nach unserer Kenntnis kein Verfahren zur Anreicherung und Reinigung beschrieben ist, haben wir hierzu Untersuchungen durchgeführt. Im folgenden wird ein allgemein anwendbares Verfahren zur Bestimmung von PCDD und PCDF in Motorenölen, Altölen und Zweitraffinaten beschrieben.

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Determination of polychlorinated dibenzodioxines and polychlorinated dibenzofurans in oil samples

Summary A clean-up procedure for the determination of polychlorinated dibenzodioxines (PCDDs) and polychlorinated dibenzofurans (PCDFs) in motor oil, used oil and recycled oil is described. The procedure was tested for a limit of detection of 0.05 g/kg for single isomers. The oil sample is chromatographed consecutively on Alumina Woelm B Super I, a mixed column of silica, silica/H₂SO₄, silica/ NaOH and finally on Bio-Beads S-X3. In motor oils, used for 10,000 km in cars run on leaded gasoline, no PCDDs or PCDFs could be detected. However, in used oil samples, collected from various sources, and in recycled oil produced from them, PCDDs and PCDFs were found. Pentachlorophenol, which is used in the mineral oil industry, and which contains PCDDs and PCDFs as side products, was identified as a source of these PCDDs and PCDFs.

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Die Untersuchungen wurden mit Unterstützung des Ministeriums für Ernährung, Landwirtschaft, Umwelt und Forsten Baden-Württemberg durchgeführt. Wir danken Herrn Kerzenmacher und Herrn Tichaczek für ihre sorgfältige Arbeit bei den Probenaufarbeitungen.     

Determination of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans in the Emission from Urban Incinerators

Summary An analytical procedure has been developed for analysis of emissions (ashes, fly ash, fumes and vapours) of urban waste incinerators in terms of their content of the most toxic chlorinated compounds such as polychlorinated dibenzodioxins (PCDD) and polychlorinated dibenzofurans (PCDF). It consists of a selective extraction, a careful clean-up with a silica gel and an alumina column, and gas Chromatographic analysis on high-resolution columns to separate individual constituents of the various classes and detect them with an E. C. detector. Peak identifications were made by comparison with the retention times of reference mixtures and were confirmed by GC-mass spectrometric analysis. It has been found that all emissions contain PCDDs and PCDFs with the more highly chlorinated species predominating. The highest concentration is found in the fly ash, in the range of about 1 ppm total PCDD, and 0.5 ppm total PCDF. It is shown that the formation of these compounds is due to thermal synthesis in the incineration process from precursors in the waste (phenols and chlorinated species).

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Bestimmung poly chlorierter Dibenzo-p-Dioxine und Dibenzofurane in den Emissionen städtischer Müllverbrennungsanlagen

Zusammenfassung Eine Methode zur Analyse von Emissionen städtischer Müllverbrennungsanlagen (Asche, Flugasche, Dämpfe und Abgase) wurde im Hinblick auf deren Gehalt an hochtoxischen chlorierten Verbindungen, wie PCDD (polychloriertes Dibenzodioxin) und PCDF (polychloriertes Dibenzofuran) entwickelt. Die Methode beruht auf einer selektiven Extraktion, einem Reinigungsschritt mit Hilfe einer Silicagel- und einer Aluminiumoxidsäule und letztlich einer gaschromatographischen Analyse. Die GC-Trennung erfolgte mit Hochleistungssäulen, um eine Trennung der zu analysierenden Komponenten für die Erfassung mit einem E.-C.-Detektor zu ermöglichen. Die Identifizierung der Peaks wurde durch Vergleich der Retentionszeiten von Referenzproben durchgeführt und durch GC-MS-Analyse bestätigt. In allen Emissionen wurden PCDDs und PCDFs bei Anreicherung der höher chlorierten Spezies gefunden. Höhere Konzentrationen traten in der Flugaschenprobe mit Gehalten von etwa 1 ppm Gesamt-PCDD und 0,5 ppm Gesamt-PCDF auf. Die Bildung dieser Verbindungen wird auf eine Synthese bei der thermischen Reaktion unter den Prekursoren beim Verbrennungsprozeß (u. a. Phenole und chlorierte Verbindungen) zurückgeführt.

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Presented at the 8th International Microchemical Symposium, Graz, August 25–30, 1980.     

Dioxin, patterns and source identification

Summary The primary sources of PCDD and PCDF are chemical, thermal, photochemical and enzymatic reactions. Most of the thermal sources result in emissions into the air. Analyses of air, soil and sediment samples indicate combustion processes as the major sources. Only 2,3,7,8-substituted congeners are found in higher animals such as fish and mammals. There is a discrepancy in profiles between sources and environmental reservoirs, which cannot fully be explained.     

Isomerenspezifische Bestimmung der Polychlordibenzodioxine (PCDD) und Polychlordibenzofurane (PCDF)

Ohne Zusammenfassung

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Isomer-specific determination of the polychlorinated dibenzodioxins (PCDD) and polychlorinated dibenzofurans (PCDF)

     

Evaluation of an automated clean-up system for the isotope-dilution high-resolution mass spectrometric analysis of PCB, PCDD, and PCDF in food

An automated clean-up system was evaluated for the simultaneous analysis of polychiorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF), and biphenyls (PCB) in different foods. In addition to the seventeen 2,3,7,8-substituted PCDDIPCDF and four non-ortho PCB, by use of the clean-up system studied, it was possible to collect the eight mono-ortho and two di-ortho PCB and the seven indicator PCB in two separate fractions during the same clean-up run. The study was first performed using standard mixtures containing PCDD, PCDF and PCB, and a certified reference material. The recoveries of the 13C-labeled compounds ranged from 51 to 90%, indicating that the PCDD, PCDF, and PCB clean-up worked satisfactorily. Next, the automated system for PCDD, PCDF, and PCB analysis was evaluated for foods such as milk, egg, meat (beef, chicken, and pork), mussel, and olive oil. The recoveries of the 13C-labeled compounds ranged from 40 to 120% for PCB and from 57 to 113% for PCDD/ PCDF, meeting the requirements of well accepted methods. Thus, the automated clean-up system studied is a suitable alternative to conventional clean-up methods.     

Levels of coplanar PCB in flue gases of high temperature processes and their occurrence in environmental samples

Summary Coplanar PCB (IUPAC nrs. 77, 126 and 169) have been determined in samples of flue gases and solid wastes from high-temperature processes, and soils and sediment.TEQ-levels of coplanar PCB present have been compared with those of PCDD/PCDF in the samples. It is found that, while in the flue gas samples coplanar PCB contribute less than 10% to the total TEQ level, soils and sediment may contain higher levels (up to 30% of the total TEQ for the samples analyzed).Moreover the pattern of PCB in the samples from high-temperature processes apparently differs considerably from that in the soils and sediment, in which PCB 77 constitutes >70% of the coplanar PCB.     

Extraction of a quality assurance sediment sample for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F)

An experimental design for two variables at three and four levels was used to investigate the Soxhlet extraction of polychlorinated dibenzo-p-dioxins/ dibenzofurans (PCDD/F) from a quality assurance sediment. The first variable was the solvent: toluene/methanol, toluene (both Soxhlet) and toluene in Soxhlet-Dean-Stark equipment. The second variable were four different bulks: silica, sulfuric acid treated silica, sodium carbonate and no bulk. Extractions with toluene/methanol and sulfuric acid provided only a small contribution to the overall extraction efficiency. Toluene/methanol preferably improved the extraction of PCDD, and the sulfuric acid improved the PCDF extraction. This was likely to reflect improved extraction efficiency of substructures in the sediment as pulp effluent remains (fiber) and fly-ash particulate. A previously found PCDD formation in extractions using toluene/methanol in presence of sodium carbonate was reproduced. A designed supercritical fluid extraction (SFE) experiment was also accomplished, however even under the best used conditions some PCDD/F were retained on the particulate compared to Soxhlet extraction. Variations in extraction efficiency in Soxhlet and SFE indicated that different subfractions of PCDD/F are connected to the matrix with different mechanisms, thus indicating that different PCDD/F fractions had different abilities to equilibrate also in the real environment.     

Measurement of PCDDs, PCDFs, and non-ortho-PCBs by comprehensive two-dimensional gas chromatography-isotope dilution time-of-flight mass spectrometry (GC x GC-IDTOFMS)

Comprehensive two-dimensional gas chromatography with isotope-dilution time-of-flight mass spectrometry (GC × GC-IDTOFMS) was used to measure polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), and coplanar polychlorinated biphenyl (cPCB) concentrations in ash, sediment, vegetation, and fish samples. The GC × GC capability was achieved by using a quad jet, dual stage, thermal modulator. Zone compression of the GC peaks from modulation resulted in a significant increase of the signal intensity over classical GC-IDTOFMS. The GC × GC column set used an Rtx-Dioxin 2 phase as the first dimension (¹D) and an Rtx-500 as the second dimension (²D). The chromatographic separation of the 17 PCDD/Fs and the 4 cPCBs was attained in ¹D except for 2,3,7,8-TCDD and CB126 for which deconvoluted ion currents (DIC) were required to be reported separately. The Rtx-500 phase separated the bulk matrix interfering compounds from the target analytes in ²D. The instrumental limit of detection (iLODs) was 0.5 pg for 2,3,7,8-TCDD. The calibration curves showed good correlation coefficients for all the compounds investigated in the concentration range of 0.5–200 pg. GC × GC-IDTOFMS results compared favorably to those from conventional isotope-dilution one-dimensional gas chromatography-high resolution mass spectrometry (GC-IDHRMS). The comprehensive mass analysis of the TOFMS further permitted the identification of other contaminants of concern in the samples.     

Determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin in commercial chlorophenols and related products

Summary We have recently published a procedure [1] which allows the selective determination of 2,3,7,8-TCDD in the presence of a large excess of other polychlorinated dibenzodioxins (PCDD) and polychlorinated dibenzofurans (PCDF). This method was applied for the determination of 2,3,7,8-TCDD in several samples of chlorophenols and related products.Analytical results are reported for pentachlorophenol, sodium pentachlorophenate, 2,3,4,5-tetrachlorophenol, 2,4-dichlorophenoxyacetic acid, hexachlorophene, and chloranil. While 2,3,7,8-TCDD could not be detected at a limit of detection of about 0.03 ng/g (ppb) in pentachlorophenol and chloranil, 2,3,7,8-TCDD could be shown to be present in all samples of sodium pentachlorophenate and also in the samples of 2,3,4,5-tetrachlorophenol, 2,4-D, and hexachlorophene. With the exception of 2,4-D, the concentration of 2,3,7,8-TCDD in these samples was below 1 ng/g (pbb).

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Bestimmung von 2,3,7,8-Tetrachlordibenzo-p-dioxin in handelsüblichen Chlorphenolen und verwandten Produkten

Zusammenfassung Ein von uns beschriebenes Verfahren [1] erlaubt die selektive Abtrennung von 2,3,7,8-TCDD von den übrigen PCDD und PCDF durch Fraktionierung an Alumina Woelm B Super I. Diese Methode wurde nun zur Bestimmung von 2,3,7,8-TCDD in verschiedenen Proben von Chlorphenolen und verwandten Produkten angewandt.Analysenergebnisse für Pentachlorphenol, Pentachlorphenol-Natrium, 2,3,4,5-Tetrachlorphenol, 2,4-Dichlorphenoxyessigsäure, Hexachlorophen und Chloranil werden berichtet. Während in Pentachlorphenol und Chloranil 2,3,7,8-TCDD bei einer Nachweisgrenze von ca. 0,03 ng/g (ppb) nicht nachgewiesen werden konnte, wurde 2,3,7,8-TCDD in allen übrigen Proben nachgewiesen. Mit Ausnahme von 2,4-Dichlorphenoxyessigsäure lagen die Konzentrationen an 2,3,7,8-TCDD unter 1 ng/g (ppb).

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This work was supported by the Ministerium für Ernährung, Landwirtschaft, Umwelt und Forsten, Baden-Württemberg. The skilful technical assistance of Roland Kerzenmacher and Heinz Tichaczek is acknowledged.     

Extraction of a quality assurance sediment sample for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F)

An experimental design for two variables at three and four levels was used to investigate the Soxhlet extraction of polychlorinated dibenzo-p-dioxins/ dibenzofurans (PCDD/F) from a quality assurance sediment. The first variable was the solvent: toluene/methanol, toluene (both Soxhlet) and toluene in Soxhlet-Dean-Stark equipment. The second variable were four different bulks: silica, sulfuric acid treated silica, sodium carbonate and no bulk. Extractions with toluene/methanol and sulfuric acid provided only a small contribution to the overall extraction efficiency. Toluene/methanol preferably improved the extraction of PCDD, and the sulfuric acid improved the PCDF extraction. This was likely to reflect improved extraction efficiency of substructures in the sediment as pulp effluent remains (fiber) and fly-ash particulate. A previously found PCDD formation in extractions using toluene/methanol in presence of sodium carbonate was reproduced. A designed supercritical fluid extraction (SFE) experiment was also accomplished, however even under the best used conditions some PCDD/F were retained on the particulate compared to Soxhlet extraction. Variations in extraction efficiency in Soxhlet and SFE indicated that different subfractions of PCDD/F are connected to the matrix with different mechanisms, thus indicating that different PCDD/F fractions had different abilities to equilibrate also in the real environment. Received: 5 December 1997 / Revised: 9 February 1998 / Accepted: 15 February 1998     

Determination of PCDD/PCDF in motor oil and air particulates. A modular approach in clean-up

Summary In trace analysis of the polychlorinated dibenzodioxins (PCDD) and -furans (PCDF) simple adsorption Chromatographic procedures for matrix removal are shown to be highly successful. In the case of a complex matrix a combination or even a repetition of different separation steps is necessary. The independent, flexible combination of separation steps (modular approach) makes it possible to find the optimum conditions for the removal of extremely divergent matrices in an easy way. A combination of classical separation steps in organic trace analysis has been successfully applied to the investigation of used motor oil and urban particulates: hexane/DMF partition, adsorption chromatography on various adsorbents (silica, alumina, Mg-silicate) as well as the extractive digestion procedure with concentrated sulfuric acid. In this way it became possible to inject the mass equivalent of 3 g of oil in HRGC/ MSD-analysis.

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Bestimmung von PCDD und PCDF in Motorenöl und Straßenstaub. Ein modularer Ansatz für die Matrixabtrennung

     

Comparison of sample preparation (extraction) techniques for phthalocyanine blue pigment types

Summary Two sample preparation methods, Soxhlet extraction and the perforation of solutions in conc. sulphuric acid were used and compared for PCDD and PCDF determination in phthalocyanine blue (Heliogen ® Blue) pigments. The Soxhlet extraction method gave lower recoveries for the penta to octachloro homologues. The PCDD/F-values (of isomers) determined with the perforation method were in the range of 0.1 to 3 ppb, mainly hexa, hepta and octachloro-homologues. The results for the tetrachloro-isomers were comparable in the range of precision obtained. Artefact formation during Soxhlet-extraction cannot be excluded. All the analyzed Heliogen Blue-Pigments showed PCDD and PCDF values below the values of the German Regulations (GefStoffV).Dedicated to Professor Dr.Dr. h.c. mult. E. O. Fischer on the occasion of his 75th birthday     

Computer-assisted peak recognition for polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in environmental samples

A software has been developed for the peak recognition of 136 polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) after high resolution gas chromatography coupled with mass spectrometry (HRGC/HRMS). Based on the retention times of ¹³C labelled 2,3,7,8-substituted PCDD/F internal standards, the retention times of all PCDD and PCDF can be calibrated automatically and accurately. Therefore, it is very convenient to identify the peaks by comparing the retention of samples and the calibrated retention times of their chromatograms. Hence, this approach is very significant because it is impossible to obtain always a standard chromatogram and PCDD/F analysis are very expensive and time consuming. The calibration results can be transferred to Excel for calculation. The approach is a first step to store costly and environmentally relevant data for future application.     

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.     

PCDD, PCDF, AND DL-PCB analysis in food: performance evaluation of the high-resolution gas chromatography/low-resolution tandem mass spectrometry technique using consensus-based samples

Due to safety concerns regarding dietary exposure to POPs, regulatory bodies are issuing detailed guidelines for testing for polychlorodibenzodioxins (PCDDs) and polychlorodibenzofurans (PCDFs) ('dioxins') and dioxin‐like (DL)‐PCBs in foods of animal origin. Determination of the aforesaid chemicals at regulatory levels requires highly selective and sensitive testing techniques. The new generation of low‐resolution mass spectrometers (triple quadrupoles) allows very low levels of quantification to be reached (in the order of tens of femtograms), thus suggesting a potential for their application in food and feed analysis. The performance of the low‐resolution tandem mass spectrometry (LRMS/MS) approach with triple quadrupoles was assessed on a qualified set of food samples from proficiency tests (PTs) and defense analysis. Accuracy was tested comparing the results with data from high‐resolution mass spectrometry (HRMS) and with consensus values from PTs. The cumulative TEQ results were characterized by deviations not exceeding 15% of PCDD + PCDF, DL‐PCB, and PCDD + PCDF + DL‐PCB (TEQ_TOT) reference consensus values (sample TEQ_TOT range, 2.29–25.1 pgWHO‐TEQ₉₇/g fat). Congener analytical variabilities did not influence significantly the WHO‐TEQ₉₇ outcome of the corresponding sample. This preliminary performance evaluation highlights the potential of LRMS/MS as a routine technique for quantitative analysis of PCDDs, PCDFs, and DL‐PCBs in food. Copyright © 2011 John Wiley & Sons, Ltd.     

Heavy Metal Concentrations in Water,Sediment and Fish from Izmit Bay,Turkey

Abstract

Mercury, cadmium and lead levels in water, sediment and fish samples from Izmit Bay, Turkey have been determined. Sampling and analysis methods are described. Variations of heavy metal concentrations from different sampling stations are discussed. Results indicate that the levels of mercury and cadmium were highest in the vicinity of a chlor-alkali plant while the highest concentration of lead was near a metallic pipe factory. The amounts of heavy metals found in the shoreline sediment samples were similar to those found in fish species from the bay.     

Maternal body burden of organochlorine pesticides and dioxins.

To investigate the body burden of organochlorine pesticides and dioxins in Japanese women, 125 milk samples were collected from 41 mothers in 1994, 42 in 1995, and 42 in 1996. Of the 125 samples, 82 were from primipara mothers (first delivery) and 43 were from multipara mothers (second or later delivery). By using capillary gas chromatography with electron capture detection, beta-HCH and p,p'-DDE were detected as the major chlorine pesticides in human milk. Average levels of beta-HCH and p,p'-DDE were 475 and 368 ng/g lipid, respectively, in primipara breast milk, 314 and 259 ng/g lipid in multipara breast milk, and 420 and 330 ng/g lipid in total breast milk. Dieldrin, heptachor epoxide, oxychlordane, trans-chlordane, and cis-chlordane were detected at lower average levels of 3, 4, 34, 41, and 5 ng/g lipid, respectively. By using high-resolution gas chromatography with mass spectrometric detection, dioxins were detected in all samples. Average levels of total polychlorinated dibenzo-p-dioxin (PCDD), total polychlorinated dibenzofuran (PCDF), total PCDD + PCDF, total coplanar polychlorinatedbiphenyl (CoPCB), and total dioxin were 10.0, 7.8, 17.7, 9.9, and 27.5 TEQ (toxic equivalent) pg/g lipid, respectively, in primipara breast milk; 7.0, 5.8, 12.8, 7.3, and 20.1 TEQ pg/g lipid in multipara breast milk; and 8.9, 7.1, 16.1, 8.9, and 25.0 TEQ pg/g lipid in total breast milk. In primipara breast milk, significant correlations were found among levels of beta-HCH, p,p'-DDE, total PCDD-TEQ, total PCDF-TEQ, total CoPCB-TEQ, and total TEQ except for less correlation between p,p'-DDE and total PCDF-TEQ. Levels of these analytes also significantly increased depending on mother's age, except for total Co-PCB-TEQ. For the correlation with food habit, the only positive correlation was between total PCDF-TEQs and fish intake.     

Advances in analytical techniques for polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and dioxin-like PCBs

Analytical techniques for the determination of polychorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and dioxin-like PCBs (DLPCB) are reviewed. The focus of the review is on recent advances in methodology and analytical procedures. The paper also reviews toxicology, the development of toxic equivalent factors (TEF) and the determination of toxic equivalent quantity (TEQ) values. Sources, occurrence and temporal trends of PCDD/PCDF are summarized to provide examples of levels and concentration ranges for the methods and techniques reviewed.