Comprehensive Analysis for Organo-bromine Compounds in Environmental Samples with GC/MS (EI/NCI)

Introduction. Brominated flame retardants (BFRs) are chemicals that are added to polymers that are used in plastics, rubber, textiles and other materials to prevent fires. Similarly to other organic pollutants, BFRs have persistence and bioaccumulation potential in organisms. Recently, BFRs have become of increasing concern in environmental samples, due to the increase of the concentration of BFRs in contrast to that of organo-chlorine compounds such as PCDDs/DFs and PCBs. PBDEs have been emerged the level of contamination in environment (water, air, sediment, sewage sludge, organism) and human (blood, milk, tissue) at great endeavor by a large number of researchers. However, other BFRs scarcely emerge the actual circumstances of contamination, although tribromophenol has acute toxicity against aquatic organisms, tetrabromobisphenol A (TBBPA) has persistence and endocrine disruption potential, and hexabromocyclododecane (HBCD), bis(tribromophenoxy)ethane (BTBPE), and Decabromodiphenylethane (DBDPE) have persistence and bioaccumulation potential similarly to PBDEs. Moreover, as one of the actual circumstances of contamination by BFRs, it has reported that some BFRs are transformed to organo-bromine compounds that have a higher bioaccumulation potential than their parent compounds in environment. For example, dimethylated derivative of TBBPA may have some use as a flame retardant, but may also be the result of methylation of TBBPA in sediment, or in organism. Similarly, tribromoanisole may be the result of methylation of tribromophenol. And PBDEs are transformed to hydroxylated and methoxylated PBDEs through metabolism in vivo. Considering these facts, in products such as plastics, in environment such as water, sediment, and organisms, it is supposed that various pieces of organo-bromine compounds are contained, which are 1) known BFRs such as PBDEs, tribromophenol, TBBPA, HBCD, BTBPE, and DBDPE, 2) unknown BFRs, 3) organo-bromine compounds transformed from BFRs, and 4) natural organo-bromine compounds. Therefore, investigation of various organo-bromine compounds is required to evaluate the actual circumstances of contamination by BFRs in products and environmental samples. In previous study, we developed the comprehensive analytical method for various organo-bromine compounds by gas chromatography/mass spectrometry (GC/MS) with electron impact (EI) or negative ion chemical ionization (NCI), established suitable clean-up method, and these GC/MS and clean-up techniques were applied for blubber of finless porpoise sample. In the present study, we analyzed plastic products and blubber of finless porpoise samples, identified known or unknown organo-bromine compounds, investigated the level of contamination in various pieces of organo-bromine compounds, and quantified organo-bromine compounds which C-labelled internal standard were available, such as PBDEs, HBCD, TBBPA and TBBPA dimethyl ether that is the metabolite of TBBPA, tribromophenol and tribromoanisole that is the metabolite of tribromophenol, BTBPE, DBDPE.