Study On Distribution Of Polybrominated Diphenyl Ethers(PBDEs)in Airborne Particles In Kunming

Flame retardants are chemicals added to the polymers,which are used in plastics,textiles,electronic circuitry and other materials to prevent fires(WHO 1994).Included among the different flame retardants are inorganic chemicals(such as antimony oxides),organic phosphate esters with or without halogens,and chlorinated and brominated organic compounds.The most used brominated flame retardants(BFRs)are polybrominated diphenyl ethers(PBDEs),hexabromocyclododecane(HBCD),tetrabromobisphenol-A(TBBP-A)and polybrominated biphenyls(PBBs).Similarly to other persistent organic pollutants(POPs),these BFRs(except TBBP-A)appear to be lipophilic and bioaccumulate in biota and humans.As a kind of the most used flame retardant,PBDEs mainly cause thyroid hormone disorder,the nerve poison and potential carcinogenic effects.Due to the observed increasing temporal trends in humans or biota,PBDEs are being determined in a growing number of laboratories.Analytical methods for the determination of BFRs have shown a rapid development over the last 5～6 years and were in most cases based on established methods for chlorinated pollutants,such as polychlorinated biphenyls(PCBs).But,up to now,for atmospheric particulates samples,only classical Soxhlet method was used as the extraction method.Using a high volume of organic solvents,a large amount of time and glassware were the disadvantages of Soxhlet method.After Soxhlet procedure,they almost use a multi-layer silica column(need a complex operations)to purify and concentrate the extracted samples.The aim of the present work is to develop and validate a fast and simple method based on MAE-SPE-GC-MS for the analysis of thirteen PBDEs(BDE-17,BDE-28,BDE-47,BDE-66,BDE-71,BDE-85,BDE-99,BDE-138,BDE-153,BDE-154,BDE-183,BDE-190 and BDE-209)in atmospheric particulates samples collected by ultra-fine glass filter.In this paper,four key conditions of MAE procedure(extraction solvent,solvent volume,extraction temperature and holding time),collection time of GPC procedure and three important conditions of SPE procedure(SPE cartridge,elution solvent,and pH)were carefully studied and developed.Finally,the optimized analytical method was used to analyze the PBDEs in atmospheric particulates collected from environment.For the instrument analysis process,Gas chromatography-mass spectrometry(GC-MS)has been widely used to determine PBDEs.The integrated method for the analysis of thirteen PBDEs in atmospheric particulates was developed by optimizing the MAE and SPE procedure.For MAE procedure,sufficient extraction was performed with 30 mL of acetone:n-hexane(1:1,v/v)as extraction solvent at 115℃ for 20 min,reducing the time and cost of analysis.For SPE procedure,sufficient isolation of the target compounds was obtained from the matrix by using Sep-PakC-18 cartridges with 15 mL of n-hexane:ethyl acetate(4:1,v/v)as the elution solvent when pH value of water samples was about 7.0.The method can achieve good repeatability and reproducibility with RSDs less than 15%for all target PBDEs in atmospheric particulates samples.A satisfactory recovery of the method was 74 to 112%.For the atmospheric particulates collected from environment.The results showed that the area has been polluted by PBDEs in different levels.13 PBDEs in TSP and PM2.5 samples were detected.From 2012 to 2014,the total concentration of PBDEs in TSP showed a trend of rise in eight sampling points.The distribution of PBDEs in PM2.5 was consistent with the TSP and PBDEs concentration showed the tendency of decrease from the city center to the outskirts.For industrial PBDEs,the concentration of DecaBDE more than PentaBDE and OctaBDE in Kunming,and in 2014 has increased than in 2012.From the point of present data,the toxicity risk was low about atmospheric particulate matter in Kunming.But with the rapid development of Kunming,the potential hazards of PBDEs in Kunming atmospheric particulate matter still cannot be ignored.