Hydroxylated transformation products obtained after UV irradiation of the current-use brominated flame retardants hexabromobenzene, pentabromotoluene, and pentabromoethylbenzene.

Hexabromobenzene (HBB), pentabromotoluene (PBT), and pentabromoethylbenzene (PBEB) are current-use brominated flame retardants (cuBFRs) which have been repeatedly detected in environmental samples. Since information on hydroxylated transformation products (OH-TPs) was scarcely available, the three polybrominated compounds were UV irradiated for 10 min in benzotrifluoride. Fractionation on silica gel enabled the separate collection and identification of OH-TPs. For more insights, aliquots of the separated OH-TPs were UV irradiated for another 50 min (60 min total UV irradiation time). The present investigation of polar UV irradiation products of HBB, PBT, and PBEB was successful in each case. Altogether, eight bromophenols were detected in the case of HBB (three Br3-, four Br4-, and one Br5-isomer), and nine OH-TPs were observed in the case of PBT/PBEB (six Br3- and three Br4-congeners). In either case, Br➔OH exchange was more relevant than H➔OH exchange. Also, such exchange was most relevant in meta- and ortho-positions. As a further point, and in agreement with other studies, the transformation rate decreased with decreasing degree of bromination. UV irradiation of HBB additionally resulted in the formation of tri- and tetrabrominated dihydroxylated compounds (brominated diphenols) that were subsequently identified. These dihydroxylated transformation products were found to be more stable than OH-TPs.

Synthesis and evaluation of hydroxy­ and dihydroxy brominated benzenes, methyl- and ethylbenzenes: Potential metabolites of current-use brominated flame retardants.

Knowledge on the presence of occurrence of oxygen containing transformation products (OxyTPs) of the current-use flame retardants hexabromobenzene (HBB), pentabromotoluene (PBT) and pentabromoethylbenzene (PBEB) is limited due to the lack of standard compounds. For this purpose, we investigated the structures of tri- and tetrabrominated phenols, diphenols, methylphenols and ethylphenols. First, 13 non-brominated or partly brominated (alkyl) phenols and diphenols were brominated with the goal to generate all possible tri- and tetrabrominated isomers. Instead of compound isolation and spectroscopic analysis, the resulting products were interpreted by combinatoric evaluation of GC/MS data, data from undirected syntheses and UV transformation studies as well as theoretical considerations. Altogether, all 44 tri- to tetrabrominated OxyTPs existing in theory could be assigned and fed in a data base.

Full Characterization of the UV Hydrodebromination Products of the Current-Use Brominated Flame Retardants Hexabromobenzene, Pentabromotoluene, and Pentabromoethylbenzene.

UV transformation was studied with three structurally closely related current-use brominated flame retardants (cuBFRs), i.e., hexabromobenzene (HBB), pentabromotoluene (PBT), and pentabromoethylbenzene (PBEB). Irradiation in toluene and benzotrifluoride (BTF) showed pseudo-first-order kinetics. Repeated high-performance liquid chromatographic (HPLC) fractionation, available reference standards, dedicated syntheses, gas chromatography with mass spectrometry (GC/MS), GC separation on two different phases including retention time rules based on dipole interactions, and proton magnetic resonance spectroscopy (1H NMR) evaluation enabled a full structural characterization of all 22 transformation products formed by hydrodebromination. In addition to pentabromobenzene (only transformation product with five bromine), tetra- and tribrominated transformation products were predominantly formed in the case of all three cuBFRs. Hydrodebromination was favored by bromine removal from positions with a high Br density. Br → H exchange was about 3 times faster in positions flanked by two vicinal Br atoms. This favored pathway explained why hydrodebromination sharply dropped at the level of tribrominated cuBFRs because readily degradable precursors were no more available at this point. Hence, a full degradation of tribrominated and lower-brominated transformation products may only be achieved in combination with a different process such as microbial transformation.

Photolytic Transformation Products of Decabromodiphenyl Ethane (DBDPE).

The photolytic transformation of decabromodiphenyl ethane-a current-use brominated flame retardant and major substitute of the structurally related decabromodiphenyl ether-was investigated in different solvents (toluene, dichloromethane, chlorobenzene, and benzyl alcohol). The transformation rate followed pseudo first order kinetics, with increasing half-life ( t1/2) in the order of toluene ( t1/2 = 4.6 min), chlorobenzene ( t1/2 = 14.0 min), dichloromethane ( t1/2 = 27.9 min), and benzyl alcohol ( t1/2 ≈ 60 min). Formation and amount of transformation products varied depending on the solvent used. A detailed study of the hydrodebromination products allowed us to tentatively assign all three possible nonaBDPEs (BDPE 207, 208, and in benzyl alcohol only BDPE 206) and three predominant octaBDPE congeners (BDPE 197, 201, and 202). Next to the reported BDPEs, formation of several oxygen containing transformation products (OxyTPs), dominated by octabrominated OxyTP, was verified by GC-Orbitrap-HRMS analysis. Use of HPLC and Florisil column enabled the separation of OxyTPs and BDPEs, and the polybrominated OxyTPs were most likely tricyclic compounds with almost planar structure.

Comparison of food colour regulations in the EU and the US: a review of current provisions.

This review describes the European Union and the US regulations applicable to food colours. Despite the different regulatory frameworks, the overall approach is similar, based on well-established risk-assessment procedures and risk-management measures. However, differences impacting free movement of goods can be found in the details and implementation of regulations. Using additives approved only in the US or in the EU implies that producers aiming to export need to adjust their product composition to the export market. Failure to comply may give rise to claims of adulteration, misbranding or non-compliance and rejection at the border or recall from the market. A careful comparison of the level of protection provided by the two sets of regulations, the criteria of good manufacturing practice (GMP) inspections and the certification requirements could be key to aligning the rules and to negotiating mutual recognition agreements. This review provides an extensive overview of the similarities and differences in regulating food colours in the EU and the US.