PBDEs production

Hardy ML. 2002a. A comparison of the properties of the major commercial PBDPO/PBDE product to those of major PBB and PCB products. Chemosphere 45(5) 717-728. 

Table 4 Composition (in % of total) of the three main PBDE products produced by Great Lakes Chemical Co. ...

Several countries have been given restrictions on the use of compounds because of potential toxic effects in humans. In the European Community, the use of tris(2,3-dibromopropyl) phosphate (EC Directive 76/769/EEC) and tris(l-aziridinyl)phosphine oxide (EC Directive 83/264/EEC) in textiles has been banned. In 1977, the U.S. Consumer Product Safety Commission banned the use of tris(2,3-dibromopropyl) phosphate in children s clothing (ICPS, 1995). The European Community has also banned the use of PBBs in textiles (EC Directive 83/264/EEC). Several countries have either taken or proposed regulatory actions on PBBs. In addition, controls on the emissions of dioxins and furans from municipal solid waste incinerators have been implemented in the United Kingdom under the Environmental Protection Act (1990). Germany has developed rules for the maximum content of selected 2,3,7, and 8 substituted polychlorinated dibenzo-pura-dioxins and dibenzofurans in products. Recently, the European Commission has issued a proposal to ban the production and use of PentaBDE. In U.S. A., on the other hand, there are currently no regulations on PBDE production or use. PBBs have not been used widely in Europe and also in U.S.A. the production of the main mixture, hexabromobiphenyl (Firemaster BP-6), ceased in 1974, after the Michigan disaster. ... 

Several methods for qualitative and quantitative analysis have been developed involving GC-NCT MS and GC-EI-MS. Until recently, quantitative work has been performed by using technical PBDE products, i.e., Bromkal 70-5DE (BK70), due to the lack of pure reference standards for most PBDE congeners. The major three components in BK70... 

Only in recent times has Albemarle, the source of Saytex brominated flame retardants, revealed more detail on the chemistry of some of their non-PBDE products. Saytex 8010 is ethane 1,2-bis (pentabromophenyl), or EBP, commercially available only from Albemarle. It was developed so that a brominated FR could be offered to the market that had a much-reduced likelihood to form dioxins or flirans during any subsequent combustion. 

In Tokyo, the Japan Environment Association changed its ecolabel criteria for copiers, printers and PCs. TTie change withdraws the exclusion of all BFRS to just PBBs and PBDEs, products that have little impact on the marketplace. Pressure for this change had filtered up from Japanese OEMs, who recognise the superior recyclability of BFR plastics and also the consumer demand for greater fire safety. 

For this purpose, the WEEE Directive has been complemented with an additional directive that limits the use of certain pollutants in these products. The EC Directive 2002/95/EC on the Restriction of the use of certain Hazardous Substances in electrical and electronic equipment (RoHS Directive) ([7], recast 2011 [9]) restricts the use of the six harmful substances/substance families lead, mercury, hexavalent chromium, polybrominated biphenyls (PBB), and polybrominated diphenyl ethers (PBDE) to 0.1% and cadmium to 0.01% w/w per homogenous material in equipment and components, but with several exemptions for a wide range of applications (Annex III and IV). 

It is expected that soil PBDEs and PCDD/Fs may also have stemmed from other sources than e-waste recycling processes, as only 3% of the global production of flame retardants is used in electronic products [36]. Apparently, only a small portion of BFRs occurring in the environments is derived from e-waste. 

PBDEs are a group of chemicals widely used as fire retardants in various commercial products. They have also been found in almost all environmental media around e-waste recycling sites, presumably due to unintended releases during primitive recycling operations. Herein a summary of the levels of PBDEs around e-waste recycling and reference sites is presented. 

PBDEs are a class of brominated flame retardants (BFRs) used in textiles, plastics and electronic products. The effects of BFRs are associated with three commercial mixtures of PBDEs decaBDE, octaBDE and pentaBDE. In laboratory animal experiments, the toxicity of PBDEs was linked to damage to liver function and,... 

BFRs are one of the last classes of halogenated compounds that are still being produced worldwide and used in high quantities in many applications. In order to meet fire safety regulations, flame retardants (FRs) are applied to combustible materials such as polymers, plastics, wood, paper, and textiles. Approximately 25% of all FRs contain bromine as the active ingredient. More than 80 different aliphatic, cyclo-aliphatic, aromatic, and polymeric compounds are used as BFRs. BFRs, such as polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), and tetrabromobisphenol A (TBBPA), have been used in different consumer products in large quantities, and consequently they were detected in the environment, biota, and even in human samples [26, 27]. 

Due to the toxicological effect of PBDEs, the production and use of penta-, octa-, and deca-BDE mixtures have been banned in Europe. Moreover, and in response to increasing international regulations on BFR formulations, alternative FRs for achieving commercial product fire safety standards are being developed and used. Some of these non-BDE BFRs are pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), and decabromodiphenylethane (DBDPE) [28],... 

HBCD is a brominated aliphatic cyclic hydrocarbon used as a flame retardant in thermal insulation building materials, upholstery textiles, and electronics. In 2001, the world market demand for HBCD was 16,700 tons, from which 9,500 tons was sold in the EU. These figures make HBCD the second highest volume BFR used in Europe [29], HBCD may be used as an alternative for PBDEs in some applications. To date, there are no restrictions on the production or use of HBCD. As a result of their widespread use and their physical and chemical properties, HBCD are now ubiquitous contaminants in the environment and humans [30, 31]. 

HBCD can be determined by GC-MS, using methods similar to those developed for PBDE determinations. As the response factors of the three diastereomers do not appear to differ very much, HBCD can be quantified as total HBCD. However, the different isomers have not so far been separated by this technique. Moreover, because isomers of HBCD are thermally labile (it is known that HBCD decomposition takes place between 240°C and 270°C), elution from a GC column usually results in a broad, diffuse peak. In addition, a number of chromatographic peaks corresponding to different breakdown products were detected. These peaks could interfere with some BFR congeners (e.g., BDE-99) [102,110]. TBBPA can be also determined by GC-MS however, a derivatization step must be carried out prior to injection on the GC system. 

There is a huge variety of PBDEs considering that there might be from one to ten bromine atoms bound to the diphenyl ether molecule. Among all the PBDEs, the commercial mixtures of decabromodiphenyl ether (deca-BDE), octabromodiphenyl ether (octa-BDE) and pentabromodiphenyl ether (penta-BDE) are the products that are most found in the environment. Related to octa-BDE and penta-BDE mixtures, their commercial use was banned in the European Union in 2004 and that year their leading manufacturers in North America stopped producing them on a voluntary basis [2], Regarding the deca-BDE mixture, since July 2008, its use has been... 

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