Identification of Tetrabromobisphenol A Allyl Ether and Tetrabromobisphenol A 2,3-Dibromopropyl Ether in the Ambient Environment near a Manufacturing Site and in Mollusks at a Coastal Region

Abstract

Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants (BFRs) and has been frequently detected in the environment and biota. Recent studies have found that derivatives of TBBPA, such as TBBPA bis(allyl) ether (TBBPA BAE) and TBBPA bis(2,3-dibromopropyl) ether (TBBPA BDBPE) are present in various environmental compartments. In this work, using liquid chromatography coupled with tandem mass spectrometry (LC−MS/MS) and liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (LC−Q-TOF-MS), TBBPA allyl ether (TBBPA AE) and TBBPA 2,3-dibromopropyl ether (TBBPA DBPE) were identified in environmental samples and further confirmed by synthesized standards. Soil, sediment, rice hull, and earthworm samples collected near a BFR manufacturing plant were found to contain these two compounds. In sediments, the concentrations of TBBPA AE and TBBPA DBPE ranged from 1.0 to 346.6 ng/g of dry weight (dw) and from 0.7 to 292.7 ng/g of dw, respectively. TBBPA AE and TBBPA DBPE in earthworm and rice hull samples were similar to soil samples, which ranged from below the method limit of detection (LOD, <0.002 ng/g of dw) to 0.064 ng/g of dw and from below the LOD (<0.008 ng/g of dw) to 0.58 ng/g of dw, respectively. Furthermore, mollusks collected from the Chinese Bohai Sea were used as a bioindicator to investigate the occurrence and distribution of these compounds in the coastal environment. The detection frequencies of TBBPA AE and TBBPA DBPE were 41 and 32%, respectively, and the concentrations ranged from below LOD (<0.003 ng/g of dw) to 0.54 ng/g of dw, with an average of 0.09 ng/g of dw, for TBBPA AE, and from below LOD (<0.008 ng/g of dw) to 1.41 ng/g of dw, with an average of 0.15 ng/g of dw, for TBBPA DBPE.

Tetrabromobisphenol-A/S and Nine Novel Analogs in Biological Samples from the Chinese Bohai Sea: Implications for Trophic Transfer

“…The concentration levels and detection frequencies of TBBPA-MAE, TBBPA-MDBPE, TBBPS-MAE, TBBPS-MBAE, and TBBPS-MDBPE were higher in this study than those in mollusk samples collected from coastal areas of the Chinese Bohai Sea. 14,15 The detection frequencies of TBBPA, TBBPS and the monomodified byproducts were comparable to other BFRs that were detected in the same area, such as PBDEs and hexabromocyclododecane (HBCD). 31 With the wide use of TBBPA/S, these byproducts have become the prevailing contaminants in this regions and their concentrations are gradually increasing.…”

“…14 Meanwhile, the MDL and MQL for TBBPA-BDBPE in biological samples, which benefiting from the optimized pretreatment method, were 6000 pg/g dw and 20 000 pg/g dw, much lower than the previously reported values of 50 000 pg/g dw and 180 000 pg/g dw. 14 Thus, it appears optimized pretreatment method can compensate for insufficient sensitivity of the detector.…”

“…These relationships indicated TBBPA and TBBPS analogs were likely accumulated from similar sources, which are assumed to be located around the south costal area of the Chinese Bohai Sea. 14 The incomplete reaction for the commercial products resulted in the occurrence of byproducts. For the TBBPA/S derivatives, the ether bond linked structures account for most products.…”

“…16−18,39−42 Currently, TBBPA-MAE and TBBPA-MDBPE have been identified as degradation products of TBBPA-BAE and TBBPA-BDBPE according to the results of UM-PPS (http://umbbd.msi.umn.edu/predict/). 8,14 TBBPA-MAE, TBBPA-MDBPE, and TBBPS-MDBPE can be generated as the degradation products through the cleavage of a single ether bond in TBBPA-BAE, TBBPA-BDBPE, and TBBPS-BDBPE, respectively. 13−15 TBBPA and TBBPS are common degradation products that occur with the cleavage of two ether bonds in TBBPA and TBBPS derivatives.…”

“…14,15 However, the bioaccumulation and trophic transfer properties of these novel TBBPA/S analogs in the aquatic food web have never been studied and much about them remains unknown. Moreover, further study of novel TBBPA/S analogs in complex biota matrices has also been impeded by a lack of available methods and pure standards.…”