Simultaneous Determination by APCI-LC/MS/MS of Hydroxylated and Methoxylated Polybrominated Diphenyl Ethers Found in Marine Biota

Abstract

A method has been developed for the simultaneous analysis of hydroxylated and methoxylated analogs of tetrabromodiphenyl ethers (OH-tetraBDEs and MeO-tetraBDEs) and of hydroxylated and methoxylated analogs of tetrabromobiphenyl (diOH-tetraBB and diMeO-tetraBB) using high performance liquid chromatography/atmospheric pressure chemical ionization tandem mass spectrometry (APCI-LC/MS/MS) in negative ion mode. Chromatographic separation was performed on a 150 mm ODS column with acetonitrile:water (9:1, v/v) in mobile phase. Multiple reaction monitoring (MRM) was performed using the precursor [M-H]- ion for hydroxylated analogs, and the [M-Br+O]- ion for tetraBDEs and tetraBB, and their methoxylated analogs. The method was validated using cod liver oil samples spiked with nine analytes (100 ng/g) for linearity (r2 > 0.998), recovery (75-95%), repeatability (8-36% RSD), and sensitivity (limits of quantification (LOQ), 0.1-0.25 ng/g lipid for phenolic analytes and 6-80 ng/g lipid for neutral brominated compounds). The APCI-LC/MS/MS was applied to analyze tiger shark and bull shark liver samples, where their concentrations were up to 8 ng/g (lipid weight) for OH-BDEs, whereas they were up to 540 ng/g (lipid weight) for MeO-BDEs. The results were consistent with values determined by electron ionization (EI)-GC/MS. The first detection of 2,2'-dihydroxy-3,3',5,5'-tetrabromobiphenyl (2,2'-diOH-BB80) by this method was in marine sponge from Micronesia. The advantage of the LC/MS/MS method over GC/MS is that it provides rapid and simultaneous determination of OH-BDEs, MeO-BDEs, and their related analogs with a single preparation step and without the involvement of chemical derivatives. Although the method provides the different LOQ ranges between hydroxylated and neutral brominated analogs, future work could apply the method to the full range of PBDE-like contaminants present in the environment and in biota tissues.

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

“…Neither TBBPA AE nor TBBPA DBPE yielded Br − , which is different from that of other BFRs, such as polybrominated diphenyl ethers (PBDEs) and hydroxylated PBDE under MRM mode. 26,27 Thus, the ions at m/z 582.9 and 742.7 were chosen as the precursor ions (see Table S1 of the Supporting Information). For the second ionization, because of the breaking of the ether bond, the precursor ions of TBBPA AE and TBBPA BAE could form the product ions (m/z 526.5) (see Table S1 of the Supporting Information), which were also similar to the product ions of TBBPA AE and TBBPA BDBPE because of the same ionization mechanism (see Figure S5 of the Supporting Information).…”

Sample preparation method for the speciation of polybrominated diphenyl ethers and their methoxylated and hydroxylated analogues in diverse environmental matrices

“…In the published work, only 2-4 OHtetraBDE isomer were analyzed and the separating degree was not satisfied [29,33,34]. While using the improved methods in this work, six most frequently detected OH-tetraBDE isomer, including two ortho-hydroxylated PBDEs (6-OH-BDE47 and 2 -OH-BDE68), two para-hydroxylated PBDEs (4 -OH-BDE49 and 4-OH-BDE42), two meta-hydroxylated PBDEs (3-OH-BDE47 and 5-OH-BDE47) [36], can be simultaneously identified, which were shown in Fig.…”

“…Although some works used LC-MS/MS methods for the analysis of PBDEs and MeO-PBDEs [29][30][31], the high quantification limits made it unsuitable for the detection of trace PBDEs and MeO-PBDEs in environmental samples. OH-PBDEs can be determined by GC/MS as their MeOanalogues via a methylated derivatization using diazomethane [10,25,26,32], but the toxicity and easy explosive of diazomethane make the analysis difficult to handle.…”

“…OH-PBDEs can be determined by GC/MS as their MeOanalogues via a methylated derivatization using diazomethane [10,25,26,32], but the toxicity and easy explosive of diazomethane make the analysis difficult to handle. Therefore, atmospheric pressure chemical ionization (APCI)-LC/MS/MS [29,33] and ionspray ionization (ISP)-LC/MS/MS [34] methods have been developed for the analysis of OH-PBDEs without the time consuming step of derivatization. However, the selectivity and sensitivity of LC-MS/MS methods need to be further improved to make it more efficient in OH-PBDEs analysis.…”

“…Phenolic compounds were usually separated from neutral compounds by partitioning with potassium hydroxide after extraction. Thus the mentioned methods are always time-consuming and cause the loss of analytes [10,25,26] Kato et al [29] proposed a single cleanup procedure using gel permeation chromatography (GPC) for simultaneous collection of OH-PBDEs and MeO-PBDEs but limited to only some types of matrices such as biosamples.…”