Study On Analysis Methodology Of Brominated Flame Retardants Residues In Eggs And Pollution Survey In Beijing

Polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA) andhexabromocyclododecane (HBCD) are common brominated flame retardants (BFRs) which are widelyused in electronics, plastics, building materials, decoration materials, textiles and so on in the presenttimes. In recent years, people gradually noticed adverse effects of these BFRs on the environment andhuman health. Tetra-, penta-, hexa-, and hepta-BDE had been declared persistent organic pollutants(POPs)under the Stockholm Convention in2009. Then HBCD was forbidded by the organization. BFRshave endocrine toxicity, reproductive toxicity, liver toxicity and neurotoxicity in the present studies,threating human health and life safety. Despite the controversy of the origin of hydroxylatedpolybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers(MeO-PBDEs), a few studies provided that MeO-PBDEs and OH-PBDEs show greater toxicities thanPBDEs, and could be converted to each other. MeO-PBDEs were more than PBDEs in human blood. Soit is necessary to detect PBDEs, MeO-PBDEs and OH-PBDEs at the same time in organisms.This paper focused on the determination method of30brominated flame retardants, including12PBDEs,5MeO-PBDEs,9OH-PBDEs, TBBPA and3HBCD in the meantime. we carried out researchabout the remainess level of30BFRs in egg samples from Beijing’s wholesale markets, majorsupermarkets and rural area, the main contents and results are as follows:(1) A gas chromatography-negative chemical ionization mass spectrometry (GC-NCI-MS) methodwith gel permeation chromatography(GPC) and dispersive solid phase extraction (DSPE) had beendeveloped for17PBDEs and MeO-PBDEs in egg samples. In allusion to the tedious pretreatment, thepaper compared recoveries of different time quantum and different dispersive solid-phase extractionadsorbents of analytes, developed a GC-NCI-MS method for17PBDEs and MeO-PBDEs. The analyteswere extracted with mixture of hexane and dichloromethane (1:1，V/V) by accelerated solventextraction (ASE), and purified by100mg C18dispersive solid phase extraction (SPE) sorbentsfollowed with GPC by Bio-Beads S-X3(400×30mm) column, then analyzed by GC-NCI-MS. Therecoveries of analytes were64.5%~92.4%and65.6%~83.1%(except BDE85was54.8%) at5.0μg/kgin egg white and egg yolk, respectively. The relative standard deviation (RSD) was less than15.9%. Thelimits of quantitation (LOQ) for the object were0.01~0.1μg/kg.(2) A liquid chromatography tandem mass spectrometric (HPLC-MS/MS) method with gelpermeation chromatography(GPC) and dispersive solid phase extraction (DSPE) had been developedfor9OH-PBDEs, TBBPA and HBCD in egg samples. In allusion to no method of the determination forOH-PBDEs, TBBPA and HBCD in the meantime, the paper compared recoveries of different timequantum and different dispersive solid-phase extraction adsorbents of analytes, developed aHPLC-MS/MS method for OH-PBDEs, TBBPA and HBCD. The analytes were extracted with mixtureof hexane and dichloromethane (1:1，V/V) by accelerated solvent extraction (ASE), and purified by100mg C18dispersive solid phase extraction (SPE) sorbents followed with GPC by Bio-BeadsS-X3(400×30mm) column, then analyzed by HPLC-MS/MS. The recoveries of analytes were 69.0%~97.2%and61.3%~109.2%(except OH-BDE-137was47.4%) at1.0or5.0μg/kg in egg whiteand egg yolk, respectively. The relative standard deviation (RSD) was less than20.2%. The limits ofquantitation (LOQ) for the object were0.01~0.5μg/kg.(3) We carried out research about the remainess level of30BFRs in91egg samples fromBeijing’s wholesale markets, major supermarkets and rural area, comparing the difference of eggs fromdifferent feeding model.The detectablerates of PBDEs and MeO-PBDEs were12.31%and4.62%,respectively. The levels of total PBDEs detected in egg sampeles were1.02~41.88μg/kg, the levels oftotal MeO-PBDEs were3.76~16.93μg/kg. The kinds and levels of analyte in egg white were more thanthat in egg yolk. The detectablerates of TBBPA in egg white and egg yolk were50.55%and24.18%,respectively. The levelS of TBBPA detected in egg white and in egg yolk were0.17~9.02μg/kg and0.16~1.42μg/kg, respectively. The detectablerate and levels of analytes in egg yolk were more than thatin egg white. The detectablerates of α-HBCD, β-HBCD and γ-HBCD were97.70%,23.08%and97.80%, respectively. The levels of α-HBCD, β-HBCD and γ-HBCD were0.06~281.38μg/kg,0.12~7.93μg/kg and0.12~160.57μg/kg respectively. For HBCD, we foundα-HBCD>γ-HBCD>β-HBCD, and the level of α-HBCD in egg yolk was significantly more than eggwhite. There was no OH-PBDEs in egg samples.(4) The total daily intake of BFRs via eggs from the different gender and age group in Beijingwere investigated in this study. The results indicated that the exposure doses of7~14and above60weremore than others. For males, the ranking of daily intake exposure for BFRs in decreasing order was:seniors, adolescents, adults, children; for females, the ranking in decreasing order was: adolescents,seniors, children, adults. Males showed slightly higher exposure dose than females except children.