Determination of non-halogenated, chlorinated and brominated organophosphate flame retardants in herring gull eggs based on liquid chromatography-tandem quadrupole mass spectrometry.

Numerous triester organophosphate flame retardants (OPFRs) have been used for several decades and continue to be used in a variety of commercial products. We developed a sensitive quantitative method for the analysis of, seven non-halogenated, three chlorinated and two brominated OPFRs of known or possible environmental relevance in herring gull eggs. This method is based on a simple two-step sample extraction followed by liquid chromatography-electrospray ionization(+)-tandem mass spectrometry. Instrumental detection limits and method limits of quantification (MLOQs) among the 12 OPFRs ranged from 0.01 to 0.12 ng/mL and 0.06 to 0.20 ng/g, respectively. The mean OPFR recovery efficiencies of replicate analyses (n=6) were very quantitative and ranged from 89% to 104%, with the two brominated OPFRs being somewhat lower but reproducible, i.e., 67% and 72%, respectively. Essentially negligible matrix effects were indicated by a standard addition approach that revealed mean percent signal recoveries (n=5 replicates) of 89-106% for most OPFRs. In the analysis of n=13 herring gull eggs from the Channel-Shelter Island colony (Lake Huron), tris(2-chloroisopropyl) phosphate (<MLOQ - 4.1 ng/g wet weight, ww), tris(2-chloroethyl) phosphate (<MLOQ - 0.6 ng/g ww) and tris(2-butoxyethyl) phosphate (<MLOQ - 2.2 ng/g ww) were detected and/or quantified.