Application of mass spectrometry in the analysis of polybrominated diphenyl ethers

Abstract

This review summarized the applications of mass spectrometric techniques for the analysis of the important flame retardants polybrominated diphenyl ethers (PBDEs) to understand the environmental sources, fate and toxicity of PBDEs that were briefly discussed to give a general idea for the need of analytical methodologies. Specific performance of various mass spectrometers hyphenated with, for example, gas chromatograph, liquid chromatograph, and inductively coupled plasma (GC/MS, LC/MS, and ICP/MS, respectively) for the analysis of PBDEs was compared with an objective to present the information on the evolution of MS techniques for determining PBDEs in environmental and human samples. GC/electron capture negative ionization quadrupole MS (GC/NCI qMS), GC/high resolution MS (GC/HRMS) and GC ion trap MS (GC/ITMS) are most commonly used MS techniques for the determination of PBDEs. New analytical technologies such as fast tandem GC/MS and LC/MS become available to improve analyses of higher PBDEs. The development and application of the tandem MS techniques have helped to understand environmental fate and transformations of PBDEs of which abiotic and biotic degradation of decaBDE is thought to be one major source of Br(1-9)BDEs present in the environment in addition to direct loading from commercial mixtures. MS-based proteomics will offer an insight into the molecular mechanisms of toxicity and potential developmental and neurotoxicity of PBDEs.

Novel Analytical Approach for Brominated Flame Retardants Based on the Use of Gas Chromatography-Atmospheric Pressure Chemical Ionization-Tandem Mass Spectrometry with Emphasis in Highly Brominated Congeners

“…The bromination degree affected to the behavior of the compound under APCI. In the case of Br [3][4] Cone voltage between 5 and 50 V was tested in order to select the optimum value for each compound considering the possibility that in-source fragmentation can occur, especially at higher cone voltages. No significant differences on in-source fragmentation pattern were observed, but voltages higher than 40 V generally led to a loss of abundance of the molecular ion and/or protonated molecule without increasing the abundance of mass fragments.…”

“…As a result of bans, the use of novel BFRs, such as decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), used in replacement of Deca-BDE and Octa-BDE mixtures, respectively, and the use of organophosphorus flame retardants is increasing [1][2][3] . Several reviews have reported the analytical methods commonly used for the determination of PBDEs in environmental and biological matrices [4][5][6][7][8][9][10] . Gas chromatography (GC) coupled to mass spectrometry (MS) operating in both electron ionization (EI) and electron capture negative ionization (ECNI) modes using quadrupole (Q), triple quadrupole (QqQ) or ion trap (IT) analyzers are the techniques most widely used 2,[11][12][13][14][15] .…”

“…Gas chromatography (GC) coupled to mass spectrometry (MS) operating in both electron ionization (EI) and electron capture negative ionization (ECNI) modes using quadrupole (Q), triple quadrupole (QqQ) or ion trap (IT) analyzers are the techniques most widely used 2,[11][12][13][14][15] . GC-EI-MS methods are readily suitable for quantifying Br [1][2][3][4][5][6][7] BDEs in environmental and biological samples, but are not on purpose for higher brominated analogues (Br [8][9][10] BDEs), and further research should be directed towards the improvement of accuracy and sensitivity for highly brominated BDE congeners. GC-EI-MS is prone to interferences from other chemicals with similar structures (especially polychlorinated biphenyls, PCBs), which may affect the quality of analytical data.…”

“…In addition, EI ionization produces high fragmentation of compounds making difficult to select specific and/or abundant precursor ions. This fact compromises the selectivity and sensitivity of the MS/MS method 4 .…”

“…To this aim is necessary increasing the resolution until 24000 FWHM, which is not appropriate from the sensitivity point of view due to the significant loss of sensitivity. Moreover, the high acquisition and maintenance costs of these instruments make this technique not much accessible for most laboratories 4 .…”