Determination Of Brominated Flame Retardants In Typical Environmental Water

Brominated flame retardants(BFRs)have been used since the 1970 s and are one of the most widely used flame retardants in the world.However,many traditional brominated flame retardants,such as commercial pentabromodiphenyl ether(Penta-BDE),commercial octabromodiphenyl ether(Octa-BDE),commercial decabromodiphenyl ether(Deca-BDE),hexabromocyclododecane(HBCD)have been listed as Persistent Organic Pollutants(POPs)by the Stockholm Convention due to their toxicity,long-distance transport and bioaccumulation.The restriction on the production and use of traditional BFRs has led to the gradual use of novel brominated flame retardants(NBFRs)as substitutes in materials and commodities.At present,the distribution data on NBFRs in water are relatively limited.Therefore,this article carried out the research on the quantitative analytical methods and water distribution of the NBFRs,which was mainly divided into the following three parts:1.The establishment of analytical methods for the determination of the concentration of NBFRs in water.The extraction efficiencies of solid phase extraction and liquid-liquid extraction as pretreatment methods for 10 NBFRs as the target analytes were compared.The results showed that liquid-liquid extraction had the characteristics of low material cost,time-saving,easy to operate,and high recovery rate.Through the selection of extraction solvent,optimization of extraction dosage,pH adjustment and other steps,the final recovery rate of liquid-liquid extraction method was 79.0%-123.0%.UPLC-MS/MS was used to quantitatively analyze NBFRs.After optimization of the liquid chromatography conditions and mass spectrometry parameters,the results showed that the method standard curves were within the range of2.0-20.0 ng/L or 0.2-20.0 ng/m L.The correlation coefficients were all over 0.99.The detection limit of the method was 0.2 ng/L or 2.0 ng/L.In this article,a method for quantitative analysis of NBFRs with liquid-liquid extraction combined with UPLC-MS/MS was established.This method has the advantages of high sensitivity,good reproducibility,and low matrix interference.2.Quantitative research of NBFRs in typical environmental water.The above method was applied to the analysis of the concentrations of NBFRs in water of wastewater treatment plants,landfills,and a river.The results show that some NBFRs can be detected in the selected water.The types and concentrations of NBFRs in different water were different,but the differences were not obvious.The concentrations of NBFRs detected were between N.D.-5.27 ng/L.In addition,the concentration of hexabromobenzene(HBB)in the Qiantang River illustrated the downstream dilution and the absence of pollution sources near the downstream.The changes of the concentrations of tribromophenol(TBP)in influent and effluent of the wastewater treatment plant indicated that biodegradation method may eliminate it.3.Quantitative study of BFRs in seawater.UPLC-MS/MS was used to analyze the concentrations of BFRs in the South China Sea.Experimental results show that for traditional BFRs,only BDE-209 can be detected in all the seawater samples,while most of them cannot be detected.The concentration of BDE-209 was relatively low(0.76-3.82 ng/L);for NBFRs,TBP can be detected(1.55-17.72 ng/L)in all the seawater samples.The obtained results prove that the concentrations of NBFRs were much higher than that of the traditional BFRs,and the results also effectively supplemented the research on BFRs in seawater.