Detection of tetrabromobisphenol A and its mono- and dimethyl derivatives in fish, sediment and suspended particulate matter from European freshwaters and estuaries

An analytical method was developed for the determination of tetrabromobisphenol A (TBBPA), 3,3',5,5'-tetrabromobisphenol-A-monomethyl ether (MM-TBBPA) and 3,3',5,5'-tetrabromobisphenol-A-dimethyl ether (DM-TBBPA), and its valid application on fish muscle matrix (bream and sole), suspended particulate matter (SPM) and surface sediment layer samples, using only 0.5 g sample material, is demonstrated. Here, for the first time, DM-TBBPA could be determined by an LC-MS/MS-based method applying atmospheric pressure photoionization (APPI), using the same sample extracts for all three analytes. Samplings covered freshwater fish (bream; annually, period 2007-2013) and SPM or sediment (every second year in the period 2008-2014) at selected European sites (rivers: Tees/UK, Mersey/UK, Western Scheldt/NL, Götaälv/SE, Rhône/FR; Lake Belau/DE). TBBPA could be quantified in 13 of 36 bream samples (range about 0.5-1.2 μg kg-1 ww) and 7 of 7 sole muscle samples (range about 0.5-0.7 μg kg-1 ww). Further, it could be quantified in 11 of the 14 SPM samples (range about 0.5-9.4 μg kg-1 dw) and in both of the surface sediment layer samples (2.3-2.6 μg kg-1 dw). MM-TBBPA could be quantified in 12 of 36 bream and 4 of 7 sole muscle samples (range about 0.8-1.8 μg kg-1 ww). Further, it could be quantified in 10 of the 14 river SPM samples (range about 2.3-4.5 μg kg-1 dw) and in both lake surface sediment layer samples (5.2-5.5 μg kg-1 dw). DM-TBBPA was rarely detectable and could not be quantified above the limit of quantification in any sample.