HPLC isolation and NMR structure elucidation of the most prominent octabromo isomer in technical octabromo diphenyl ether

The major octabromo isomer of technical octabromo diphenyl ether mixture (technical octaBDE) DE-79 was isolated by RP-HPLC. Three serially coupled columns (each 250 mm long) enabled a good separation of the target compound from other congeners using 100% ACN as eluent. Approximately 100 microg of the target compound was isolated with a purity of >90% and investigated by MS for confirmation of the degree of bromination. 1H-NMR and 2-D 1H-13C correlation NMR spectra unequivocally clarified that the octaBDE in question is 2,2',3,3',4,4',6,6'-octabromodiphenyl ether (BDE 197). Based on annual production rates of technical BDE products (1999/2001), approximately 380 tons of BDE 197 were annually produced which, on the long term, may enter the environment. Compared with other individual BDE congeners, BDE 197 has the seventh highest application rate. Reductive debromination of BDE 197 can lead to four hepta-, 15 hexa-, 23 penta-, and 28 tetra-BDE isomers, respectively. This variety includes all known major BDEs of environmental concern (BDE 47, 85, 99, 100, 153, 154, and 183). The identification of BDE 197 in technical octaBDE DE-79 strongly suggests that research on the environmental fate of BDEs should include this key-BDE congener.     

Fast sample preparation involving MASE and coupled column normal phase liquid chromatography for the rapid trace analysis of dioxins in air-dust samples from fire catastrophe emissions

A new approach has been developed and tested for the urgent analysis of dioxins in samples of air-dust filters originating from catastrophe emissions. The procedure consists of a fast extraction of the sample with microwave solvent extraction (MASE) and acetone as solvent followed by a fast cleanup of the extract with normal phase coupled column liquid chromatography (LC/LC).

The multi-dimensional LC/LC system employs a 50 mm×4.6 mm i.d. column packed with 3 μm silica and a 150 mm×4.6 mm i.d. column packed with 5 μm PYE as the first and second analytical column, respectively. Iso-hexane is used on both columns to perform cleanup and dichloromethane to perform efficient back-flush elution of the compounds from the second column. The obtained polarity-based separation in the first dimension and molecular-structure based separation in the second dimension provides a fast and powerful cleanup.

Validation was done by analysing samples of homemade RIVM air-dust with aged residues (n=8, spiking level about 15 pg mg⁻¹ per compound) of dioxins/furans and samples of reference Urban Dust SRM 1649a (n=4) with both the new approach and the existing conventional procedure and were instrumentally analyzed with capillary gas chromatography and high resolution mass spectrometric detection (GC/HRMS).

In comparison to the existing conventional procedure, the new approach reduces sample processing from several days to several hours per sample.

As regards the aged-residue air-dust samples, the new method shows a good accuracy, precision and high selectivity providing a performance in good agreement with the existing procedure. In SRM air-dust, the concentration of a few compounds obtained by the new method was below (10–50%) the certified value.     

低分子量溴代聚苯乙烯的制备及应用

用溶液法合成了一系列低分子量的聚苯乙烯，其溴化产物（Ｂｒ－ＰＳ）的溴含量和热稳定性与美国同类产品Ｐｙｒｏ－Ｃｈｅｋ ＬＭ相当，分别用作聚苯乙烯树脂的阻燃剂，极限氧指数测定结果表明，其阻燃性也达到了Ｐｙｒｏ－Ｃｈｅｋ ＬＭ的水平。     

Importance of REP values when comparing the CALUX bioassay results with chemoanalyses results Example with spiked vegetable oils

Differences between chemical activated luciferase gene expression (CALUX) bioassay and chemoanalyses results are observed.This paper shows that calculations of the TEQ values using REP values instead of WHO TEF values give different results. The REP values do affect the results obtained by the CALUX technique. These differences are more marked for the dioxin like PCB compounds (CALUX TEQ values are lower than WHO TEQ values) than for the dioxin compounds (CALUX TEQ values are higher than WHO TEQ values).The CALUX results were compared with the concentrations of the congeners’ spiked into the oil.     

Developments in the use of chromatographic techniques in marine laboratories for the determination of halogenated contaminants and polycyclic aromatic hydrocarbons

Chromatography has been an important tool in marine laboratories. Since the 1960s, marine laboratories have been involved in the analysis of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and brominated flame retardants (BFRs). Column chromatography and liquid chromatography (LC) techniques have been used, mainly in the clean-up phase, while gas chromatography (GC) has been used extensively in the final determination of these contaminants. Developments have been observed from the use of packed GC columns, via capillary columns to the use of heart-cut multi-dimensional GC and comprehensive multi-dimensional GC. The progress made in interlaboratory studies and the availability of certified reference materials are discussed.     

Degradation-fragmentation of marine plastic waste and their environmental implications: A critical review

This review critically evaluates the plastic accumulation challenges and their environmental (primarily) and human (secondarily) impacts. It also emphasizes on their degradation and fragmentation phenomena under marine conditions. In addition, it takes into account the leachability of the various chemical substances (additives) embedded in plastic products to improve their polymeric properties and extend their life. Regardless of their effectiveness in enhancing the polymeric function of plastic products, these additives can potentially contaminate air, soil, food, and water. Several findings have shown that, regardless of their types and sizes, plastics can be degraded and/or fragmented under marine conditions. Therefore, the estimation of fragmentation and degradation rates via a reliable developed model is required to better understand the marine environmental status. The main parameter, which is responsible for initiating the fragmentation of plastics, is sunlight/UV radiation. Yet, UV- radiation alone is not enough to fragment some plastic polymer types under marine conditions, additional factors are needed such as mechanical abrasion. It should be also mentioned that most current studies on plastic degradation and fragmentation centered on the primary stages of degradation. Thus, further studies are needed to better understand these phenomena and to identify their fate and environmental effects.     

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.     

Performances and limitations of the HRMS method for dioxins, furans and dioxin-like PCBs analysis in animal feedingstuffs: Part I: Results of an inter-laboratory study

The European strategy for dioxin monitoring of the food chain has defined high-resolution gas chromatography coupled to high-resolution mass spectrometry (HRGC/HRMS) method as the confirmatory method that can provide reliable and comparable results at sub-parts per trillion (ppt) level. This paper describes the first inter-laboratory study on dioxins, furans and dioxin-like PCBs by HRGC/HRMS method in animal feedingstuffs. Two different statistical approaches (ISO 5725 and Cofino’s statistics) were used for the statistical evaluation. For this particular study, the performances of the HRGC/HRMS method seem to be congener-independent in repeatability and reproducibility conditions over a concentration range covering more than four orders of magnitude. Results clearly show the effect of precision loss below 0.1 ppt level per congener in repeatability conditions and below 0.2 ppt level per congener in reproducibility conditions. LODs reported by the laboratories give median values of 0.02 ng/kg for most of the toxic congeners. Relative standard deviation between the laboratories’ mean values using upper-bound approach for TEQ calculation is 6.2%, more than twice the maximum level set at 0.75 ng TEQ/kg of product.     

Method development for simultaneous analysis of HBCD,TBBPA, and dimethyl-TBBPA in marine biota from Greenland and the Faroe Islands

The brominated flame retardants hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) are high-production-volume chemicals. In recent years, their presence has been reported in sediment and biota from the marine environment. In this study, an analytical method was developed for the simultaneous determination of HBCD, TBBPA, and the possible metabolite dimethyl-TBBPA. The method was applied in a preliminary screening of egg, liver, and adipose tissue of marine biota from Greenland and the Faroe Islands. α-HBCD was detected in 35 of 36 analysed samples from the Arctic, indicating a ubiquitous presence of α-HBCD in the environment. β- and γ-HBCD were found in 10 and 14 samples, respectively. TBBPA and dimethyl-TBBPA were not detected in any of the samples indicating limited or no transport of these compounds to remote areas.     

The German bakery waste incident; use of a combined approach of screening and confirmation for dioxins in feed and food

During the last six years several incidents have occurred with dioxins in feed, stressing the need for rapid screening methods for these compounds. The most recent incident was the contamination of bakery waste used for animal feed due to the use of waste wood for drying of the material. In addition to Germany, the material was also shipped to the Netherlands. Levels up to 12 ng TEQ/kg have been detected, being about 15 times over the current limit of 0.75 ng TEQ/kg. In the Netherlands a combined strategy of screening with the CALUX-bioassay and the HRGC/HRMS confirmatory method was used to rapidly control the incident. Pigs were contaminated by the incident but only to a very limited extent. Despite the rather low limits for pig meat, the CALUX bioassay showed excellent performance, once again confirming the value of this assay.