Characteristics of major dioxin/furan congeners in melted slag of ash from municipal solid waste incinerators

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in slag of fly ash from three municipal solid waste (MSW) incinerators were analyzed to observe any changes in characteristics and distribution of their congeners by melting process. Actual concentration and Toxic Equivalent (TEQ) concentration profiles of 17 major congeners of PCDDs/PCDFs for gas, fly ash and melted slag were compared. The distributions of PCDDs/PCDFs in different streams macroscopically showed similarities with the generally known profiles for emission gas from a municipal waste incinerator. The total concentrations of PCDDs/PCDFs in off-gas and fly ash have been known to be a function of incineration conditions and of air pollution control device utilization; however, their normalized distributions were independent of such conditions. The concentrations of PCDDs/PCDFs in the melted slag of fly ash were not related to the concentrations of PCDDs/PCDFs congeners in fly ash but were rather a function of the melting furnace type and operation. The total amount of PCDDs/PCDFs in the melted slag of fly ash contained almost 150–27,000 times less dioxin than that in fly ash, however, the TEQ of dioxin in the slag was reduced by 435–43,500 times, which could enable them to be utilized as recycled construction materials. In normalized TEQ concentration profiles of 17 congeners of PCDDs/PCDFs, the ratio of PCDFs to PCDDs changed from 1.32 to 2.19 by melting, which showed relatively higher portion of furans left in melted slag than those in fly ash. By comparing reduction ratios of different congeners, PCDDs (dioxins) were relatively easier to destruct than PCDFs (furans) during melting process. The most difficult congener to destruct could be octa-chlorinated dibenzofuran (OCDF) among major congeners. For slag cooling methods, dioxin concentration in TEQ of slow cooled slag by air was four times higher than that of fast cooled slag by water. Thus cooling by water is more appropriate with the added beneficial effect of producing granules/particles, which can be utilized as roadbed materials.     

Selective determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin in the presence of a large excess of other polychlorinated dibenzodioxins and polychlorinated dibenzofurans

Summary A procedure is described for the selective separation of 2,3,7,8-TCDD from all other PCDDs and PCDFs. For this purpose the mixture of PCDDs and PCDFs is fractionated on Alumina Woelm B Super I in such a manner that all PCDDs and PCDFs are eluted prior to 2,3,7,8-TCDD. This procedure allows a more sensitive quantitative determination of 2,3,7,8-TCDD in samples which contain 2,3,7,8-TCDD only as a very minor fraction of the other TCDDs or PCDDs and PCDFs. Determination of 2,3,7,8-TCDD in pentachlorophenol and in a waste sample from 2,4-dichlorophenol production by this procedure is described.

---

Selektive Bestimmung von 2,3,7,8-Tetrachlordibenzo-p-dioxin in Gegenwart eines großen Überschusses anderer polychlorierter Dibenzodioxine und polychlorierter Dibenzofurane

Zusammenfassung Ein Verfahren wird beschrieben, das die selektive Abtrennung von 2,3,7,8-TCDD aus einer Mischung von allen PCDDs und PCDFs erlaubt. Dies geschieht durch Fraktionierung an Alumina Woelm B Super I, wodurch eine getrennte Elution aller PCDDs und PCDFs von 2,3,7,8-TCDD erreicht werden kann. Dieses Verfahren erlaubt die quantitative Bestimmung von 2,3,7,8-TCDD mit höherer Nachweisempfindlichkeit in Proben, die andere TCDDs bzw. PCDDs und PCDFs in extremen Überschüssen im Vergleich zu 2,3,7,8-TCDD enthalten. Am Beispiel der Bestimmung von 2,3,7,8-TCDD in Pentachlorphenol und in einem Produktionsrückstand von 2,4-Dichlorphenol wird die praktische Anwendbarkeit nachgewiesen.

---

---

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

A direct method for the decontamination of a fly ash amended wet soil,artificially polluted with dioxins

We report hereby the first method of direct treatment of a wet soil containing toxic polychloroderivatives. Using a system with metallic Ca and 5% Rh fixed on charcoal in methanol, soil samples artificially polluted with fly ash containing polychloro-dibenzodioxins (PCDDs), polychloro-dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (co-PCBs), and having 69.2% to 84.6% moisture content, were successfully treated and decontaminated. This treatment afforded excellent hydrodechlorination yields for the 29 most toxic congeners of PCDDs, PCDFs and PCBs (98.3% degradation yield based on toxic equivalent quotient — or TEQ) after a 24 h treatment, at room temperature.      

Separation of polychlorinated dibenzothiophenes from polychlorinated dibenzodioxins and -furans

Polychlorinated dibenzothiophenes (PCDT) have recently been identified in a series of environmental samples. Since their masses are very close to those of the polychlorinated dibenzodioxins (PCDD), low resolution mass selective detection cannot be used to distinguish between these two classes of compounds. A method is presented which may allow this, involving the oxidation of the PCDTs to the corresponding sulfones which have a higher mass than the PCDDs. If needed, the PCDTO₂s can easily be separated from the PCDDs and the polychlorinated dibenzofurans (PCDFs) by simple chromatographic techniques. The PCDDs/Fs are apparently stable under the oxidative conditions so that now a determination of PCDDs and PCDFs becomes possible without interference from PCDTs.     

Group separation of ortho-PCBs, coplanar non-ortho-PCBs and PCDDs/PCDFs using an alumina column as an one-step clean-up procedure

 A novel, simple inexpensive and rapid clean-up procedure is presented for the separation and quantitative determination of polychlorinated biphenyls (ortho-PCBs), coplanar non-ortho-PCBs (PCB No. 77, 126, 169) and polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in environmental samples. This clean-up procedure is the first method separating ortho-PCBs, non-ortho-PCBs and PCDD/PCDFs in one step with a single activated alumina column. Firstly, the ortho-PCBs are eluted from the activated alumina with a non-polar solvent. The non-ortho-PCBs are isolated in the second fraction with a more polar solvent-mixture, and finally the PCDD/PCDFs are collected in a polar fraction. This clean-up procedure was used to determine the congener-specific concentrations of ortho-PCBs, non-ortho-PCBs 77, 126 and 169 and PCDD/PCDFs in two different seepage waters and in one sewage sludge by HRGC and HRMS. The toxic equivalent quantities (TEQs) of the individual PCDD/PCDF-congeners and some toxic coplanar PCB-congeners were estimated. Received: 26 June 1996/Revised: 11 September 1996/Accepted: 14 September 1996     

Recoveries of organochlorine compounds (polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) in water using steam distillation-solvent extraction at normal pressure

A simultaneous steam distillation-solvent extraction (SDE) procedure was used for determining polychrlorinated biphenyls, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCBs, PCDDs and PCDFs) at sub-ppb levels in water samples. Recoveries of 39.8–138.7% and a standard deviation of lower than 10% were achieved for the individual coplanar PCB and the 2,3,7,8-substituted PCDD/F congeners. SDE is a fast, clean, inexpensive and reproducible procedure for the determination of individual PCBs, PCDDs and PCDFs in waters at very low concentrations.     

Clean-up by high-performance liquid chromatography of polychlorodibenzo-p-dioxins and polychlorodibenzofurans on a pyrenylethylsilica gel column

A clean-up step prior to the determination of polychlorodibenzo-p-dioxins (PCDDs) and polychlorodibenzofurans (PCDFs) based on normal- phase HPLC on a 2-(1-pyrenyl)ethyldimethyl silylated silica column is presented. With hexane as mobile phase, polychlorobiphenyls (including highly chlorinated non-ortho isomers) and organochlorine pesticides are eluted in the first fraction. The total fraction of PCDDs and PCDFs can be eluted by backflushing. By application of a gradient, all congeners are eluted within 75 min. The retention order of the PCDDs and PCDFs is predominantly governed by the degree of chlorination, but the substitution pattern also has a strong influence. Subtractions of the PCDD/PCDF fraction can be taken. The fraction containing 2,3,7,8-tetrachlorodibenzo-p-dioxin was isolated. The three tetrachlorodibenzo- p-dioxin isomers of this fraction were baseline separated on a non-polar capillary GC column.     

Dual-column high-performance liquid chromatographic cleanup procedure for the determination of polychlorinated dibenzo-p-dioxins and dibenzofurans in fish tissue

A high-performance liquid chromatographic cleanup procedure employing normal-phase alumina and carbon--silica separations was developed for isolating polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) from other polychlorinated pollutants present in fish tissue. The method utilizes a column-switching step where the dioxins and furans are trace enriched onto a carbon-silica column as they are eluted from the alumina column. Interfering components such as polychlorinated biphenyls and chlorinated diphenyl ethers elute through the carbon--silica column. The PCDDs and PCDFs are subsequently recovered by backflushing the carbon--silica column using toluene.     

Comparison of immunoaffinity column recovery patterns of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans on columns generated with different monoclonal antibody clones and polyclonal antibodies

Evaluation of immunoaffinity columns (IACs) for dioxin serum sample clean-up requires a determination of the recovery of various dioxin congeners. We compared the IAC performance of different monoclonal and polyclonal anti-dioxin antibodies, measuring the recovery of congeners of polychlorinated dibenzo-p-dioxins (PCDDs). In addition, we measured the recovery of congeners of the structurally related polychlorinated dibenzofurans (PCDFs).The polyclonal antibody based IACs evaluated had lower recovery for highly chlorinated dioxin congeners, but were more specific toward 2,3,7,8-TCDD. The resemblance of the hapten to 2,3,7,8-TCDD appeared to play a clear role, but chlorines in the 2-, 3- and 7-positions of the hapten were essential. Recovery of 2,3,7,8-TCDD from the IAC showed some relation to the affinity for the antibody measured by either the K_a from accelerator mass spectrometry (AMS) or with 50% inhibition of color activity (IC₅₀) determined from an ELISA analysis.The IACs prepared from four monoclonal antibodies (Mabs) derived from a common hapten showed differences in their retention patterns of PCDDs/PCDFs. Comparison of IC₅₀ from ELISA with recovery from the IACs indicated that a minimum IC₅₀ of 100 ppb was required for satisfactory recovery from the IAC, but the correlation was poor, indicating other factors were involved. Mab DD3 showed the broadest spectrum of the Mabs and showed satisfactory recoveries of all of the dioxin congeners, except OCDD. In addition, DD3 showed good recovery toward 2,3,4,8-TCDF, 2,3,4,7,8-PeCDF and 2,3,4,6,7,8-HxCDF but has poor recovery when PCDFs have a chlorine substitution in the 1-position.     

Development of a reference material for routine performance monitoring of methods measuring polychorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and dioxin-like polychlorinated biphenyls

Matrix–matched environmental certified reference materials (CRMs) are one of the most useful tools to validate analytical methods, assess analytical laboratory performance and to assist in the resolution of data conflicts between laboratories. This paper describes the development of a lake sediment as a CRM for polychorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DLPCBs). The presence of DLPCBs in the environment is of increased concern and analytical methods are being developed internationally for monitoring DLPCBs in the environment. This paper also reports the results of an international interlaboratory study involving thirty-five laboratories from seventeen countries, conducted to characterize and validate levels of a sediment reference material for PCDDs, PCDFs and DLPCBs.     

Development of supercritical fluid extraction with a solid-phase trapping for fast estimation of toxic load of polychlorinated dibenzo-p-dioxins-dibenzofurans in sawmill soil

A method consisting of automated supercritical fluid extraction (SFE) with simultaneous cleanup by a solid-phase trap was developed for fast analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in soil. SFE was optimised to replace conventional liquid-based methods in routine analyses of PCDD/PCDFs in sawmill soil contaminated by a chlorophenol formulation. PCDD/PCDFs were quantitatively extracted in 60 min using CO2 at 400 atm and 100 degrees C without a modifier. A trap containing a small amount of activated carbon mixed with Celite efficiently collected PCDD/PCDFs after SFE. After SFE co-extracted impurities were eluted out from the trap with 4 ml of hexane and PCDD/PCDFs were eluted with 10 ml of toluene. The concentrations and TCDD-equivalent of PCDD/PCDFs corresponded to the results of traditional solvent extraction method (Soxhlet) in six sawmill soils tested. The performance of the trap was maintained over a long period of time (nearly 100 extractions).     

Optimization of pressurized liquid extraction (PLE) of dioxin-furans and dioxin-like PCBs from environmental samples

Pressurized liquid extraction (PLE) applying three extraction cycles, temperature and pressure, improved the efficiency of solvent extraction when compared with the classical Soxhlet extraction. Polychlorinated-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like PCBs (coplanar polychlorinated biphenyls (Co-PCBs)) in two Certified Reference Materials [DX-1 (sediment) and BCR 529 (soil)] and in two contaminated environmental samples (sediment and soil) were extracted by ASE and Soxhlet methods. Unlike data previously reported by other authors, results demonstrated that ASE using n-hexane as solvent and three extraction cycles, 12.4 MPa (1800 psi) and 150 degrees C achieves similar recovery results than the classical Soxhlet extraction for PCDFs and Co-PCBs, and better recovery results for PCDDs. ASE extraction, performed in less time and with less solvent proved to be, under optimized conditions, an excellent extraction technique for the simultaneous analysis of PCDD/PCDFs and Co-PCBs from environmental samples. Such fast analytical methodology, having the best cost-efficiency ratio, will improve the control and will provide more information about the occurrence of dioxins and the levels of toxicity and thereby will contribute to increase human health.     

Development of a reference material for routine performance monitoring of methods measuring polychorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and dioxin-like polychlorinated biphenyls

Matrix-matched environmental certified reference materials (CRMs) are one of the most useful tools to validate analytical methods, assess analytical laboratory performance and to assist in the resolution of data conflicts between laboratories. This paper describes the development of a lake sediment as a CRM for polychorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DLPCBs). The presence of DLPCBs in the environment is of increased concern and analytical methods are being developed internationally for monitoring DLPCBs in the environment. This paper also reports the results of an international interlaboratory study involving thirty-five laboratories from seventeen countries, conducted to characterize and validate levels of a sediment reference material for PCDDs, PCDFs and DLPCBs.     

Glycosides from <Emphasis Type="Italic">Stevia rebaudiana</Emphasis>

A new laboratory method for isolating the glycosides stevioside and rebaudiosides A and C from leaves of Stevia rebaudiana was proposed. According to HPLC, the glycoside contents in plants grown in Russia (Voronezh Oblast’) and Ukraine (Crimea) were 5–6% (stevioside) and 0.3–1.3% (rebaudiosides A and C). __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 68–71, January–February, 2007     

World-wide comparison on the quality of analytical determinations of PCDDs/PCDFs and dioxin-like PCBs in food

Interlaboratory comparsion exercises on the determination of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs) and dioxin-like polychlorinated biphenyls (PCBs) in three natural foodstuffs have been performed annually since 2000 by the Norwegian Institute of Public Health. Up to 77 laboratories from 24 countries world-wide have reported results. The data have been statistically analysed in order to assess the comparability of both the reported individual congener concentrations and the calculated toxic equivalents (TEQ). Due to the low concentrations of PCDDs/PCDFs and dioxin-like PCBs in food, the treatment of congeners reported as “not detected” and the identification of outliers, influence the estimation of the consensus values considerably. Based on the experiences from the first two rounds, an approach for calculation of the consensus values was established, resulting in a non-skewed distribution of data. The relative standard deviation of consensus TEQs was 13–32% for PCDDs/PCDFs and 11–45% for PCBs. Z-scores were calculated for PCDD/PCDF-TEQs using a target value of ±20% for the deviation. For food samples with a PCDD/PCDF contamination of more than half of the EU maximum level, 63–87% of the participants achieved Z-scores ±1, while for low contaminated foodstuffs about 60% of the participants had Z-scores of ±2. After four rounds of interlaboratory comparisons it can be concluded that there is a good comparability of the analytical data for dioxins and dioxin-like PCBs in food at higher contamination levels. However, the laboratories need to improve their performance when determining levels in food with low contamination of dioxin-like compounds, due to the increasing demand for analyses of such food items. The importance of determining dioxin-like PCBs is demonstrated by their large contribution to the total TEQ, especially in food from the marine environment.     

HRGC-LRMS测定垃圾焚烧炉布袋飞灰中的二噁英类物质

利用高分辨气相色谱-低分辨质谱(HRGC-LRMS)测定了某垃圾焚烧厂布袋飞灰中的二(口恶)英类物质,结果表明对于测定二(口恶)英类浓度相对较高的垃圾飞灰而言,采用HRGC-LRMS是一种可行的方法,回收率在74％～114％之间。该飞灰样品中以二(口恶)英为主,呋喃的含量相对较低,二(口恶)英／呋喃值为4.6,二(口恶)英类物质总量为211.7ng／g,折算到毒性当量为0.69ngI-TEQ／g。     

Rapid and cost-effective analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in soil, fly ash and sediment certified reference materials using pressurized liquid extraction with an integrated carbon trap

Pressurized liquid extraction with an integrated carbon trap (PLE-C) has recently been developed for fast and efficient analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in food and feed. The method has also been tested, but not verified, for use on more complex soil samples, such as soil, sediment and fly ash. Hence, the primary aim of this study was to verify that PLE-C can produce reliable data for PCDDs/PCDFs in various abiotic matrixes. A second aim was to find a replacement for the previously used AX21 active carbon that is currently not commercially available. The performance of the PLE-C was evaluated using both single congener concentrations and toxic equivalency potentials (TEQ-pot) of three (soil, sediment and fly ash) certified reference materials. The results clearly show that PLE-C can be used for abiotic samples and that a commercially available carbon (Norit SA 4PAH HF) can replace the AX-21 carbon in the carbon trap. The TEQ-pot values obtained for the soil and sediment samples were within the uncertainty limits of the corresponding certified values, as were the determinations of single congener concentrations. PLE-C therefore has great potential for determination of PCDDs/PCDFs in soil and sediment samples. The TEQ-pot result for the fly ash was slightly lower than the certified TEQ-pot value, but it is still within the uncertainty limits of the certified value. Out of the single congener concentrations all but four (out of 17) agreed well with the values. Hence, PLE-C may potentially be used also for fly ash—after slight modifications. The integrated PLE-C and cleanup procedure is less labour-intensive than traditional methods such as Soxhlet extraction followed by a multistep cleanup, and consumes smaller quantities of ultrapure solvents than the commonly used Power-Prep system. In addition, PLE-C is capable of larger sample throughputs than the conventional methods. Thus, PLE-C is a promising alternative to the currently used sample preparation procedures for dioxins in abiotic samples. Figure PLE with integraded carbon trap for rapid PCDD/Fs analysis Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Two New Anti-Tobacco Mosaic Virus Alkaloids from the Whole Plants of Thalictrum microgynum

Chemistry of Natural Compounds - Two new (1 and 2), together with four known (3–6) alkaloids were isolated from the whole plants of Thalictrum microgynum. Compounds 1–6 were tested for...     

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.

---

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.

---

---

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.     

Preparation and evaluation of OV-240-OH coated glass capillary columns for isomer specific determination of PCDDs and PCDFs

Glass capillaries were leached, dehydrated, persilylated with 1, 3-bis (3-cyanopropyl) tetramethyldisiloxane, and coated with OV-240-OH. After crosslinking and binding the phase to the glass surface the columns showed high separation efficiency, high temperature stability, and inertness comparable to persilylated apolar columns. Column performance is shown to be superior to liquid phase cyanopropyl columns such as SP 2330. The excellent separation capabilities together with the selectivity of the phase makes OV-240-OH coated columns a valuable tool for the determination of toxic isomers in complex mixtures of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The order of elution of individual TCDD isomers was found to be similar to that described for SP 2330 or Silar 10c. The detection of PCDDs and PCDFs in a fly ash extract further illustrates the utility of OV-240-OH coated columns. The high temperature limit of these columns opens the way for the analysis of high boiling compounds such as mixed brominated/chlorinated dibenzo-p-dioxins and dibenzofurans.