title: Microwave-assisted extraction combined with gel permeation chromatography and silica gel cleanup followed by gas chromatography-mass spectrometry for the determination of organophosphorus flame retardants and plasticizers in biological samples.
abstract: An analytical method for the determination of 14 organophosphorus flame retardants (OPFRs), including halogenated OPFRs, non-halogenated OPFRs and triphenyl phosphine oxide (TPPO) in biological samples was developed using gas chromatography-mass spectrometry (GC/MS). Biological samples were extracted using microwave-assisted extraction (MAE) with hexane/acetone (1:1, v/v) as the solvent; then, a two-step clean-up technique, gel permeation chromatography (GPC) combined with solid phase extraction (SPE), was carried out before GC/MS analysis. Experimental results showed that the developed method efficiently removed the lipid compounds and co-extract interferences. Moreover, using the relatively "narrow" column (with an i.d. of 10 mm) significantly decreased the elution volume and, therefore, prevented the loss of the most volatile OPFRs, especially trimethyl phosphate (TMP) and triethyl phosphate (TEP). The method detection limits (MDLs) for OPFRs in the biological samples ranged from 0.006 to 0.021 ng g(-1) lw, and the recoveries were in the range of 70.3-111%, except for TMP (38.9-55.6%), with relative standard deviations (RSDs) of less than 14.1%. The developed method was applied to determine the amount of the target OPFRs in biological samples (i.e., fish and domestic birds) that were collected from the Pearl River Delta (PRD) region in southern China. Of the 14 OPFRs, tri-n-butyl phosphate (TnBP), tris(2-chloroethyl) phosphate (TCEP), tris(chloropropyl) phosphate (TCPP) and tributoxyethyl phosphate (TBEP) were present in all of the biological samples that were analyzed, and dominated by TnBP, TCEP and TBEP. The concentrations of OPFRs in the biological samples that were collected from the PRD region were higher than those reported in other locations.
authors.affiliation: School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangdong, Guangzhou 510275, China.
authors.forename: Yongqing
authors.initials: Y
authors.lastname: Ma
authors.forename: Kunyan
authors.initials: K
authors.lastname: Cui
authors.forename: Feng
authors.initials: F
authors.lastname: Zeng
authors.forename: Jiaxin
authors.initials: J
authors.lastname: Wen
authors.forename: Hong
authors.initials: H
authors.lastname: Liu
authors.forename: Fang
authors.initials: F
authors.lastname: Zhu
authors.forename: Gangfeng
authors.initials: G
authors.lastname: Ouyang
authors.forename: Tiangang
authors.initials: T
authors.lastname: Luan
authors.forename: Zunxiang
authors.initials: Z
authors.lastname: Zeng
mesh_terms: D000818:Animals; D002397:Catfishes; D002645:Chickens; D002850:Chromatography, Gel / Q000379:methods* / Q000592:standards; D004372:Ducks; D005399:Fishes; D005411:Flame Retardants / Q000032:analysis*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods* / Q000592:standards; D008872:Microwaves; D009943:Organophosphorus Compounds / Q000032:analysis; D010968:Plasticizers / Q000032:analysis*; D058428:Silica Gel / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis
chemical_list: D005411:Flame Retardants; D009943:Organophosphorus Compounds; D010968:Plasticizers; D014874:Water Pollutants, Chemical; D058428:Silica Gel