High Throughput Extraction Strategy For Simultaneous Analysis Of Emerging Halogenated Organic Contaminants In Marine Environment

Halogenated organic contaminant(HOC)is one of the largest persistent organic pollutants(POPs)groups of marine environments.These emerging HOCs are difficult to degrade in the environment and have strong lipophilic properties.HOCs often exhibit toxic effects on marine organisms,especially the long-lived organisms due to bio-magnifications through the food chain and maternal transfer.Tetrabromobisphenol A(TBBPA),polyhalocarbazoles(PHCZs),and their analogs are the emerging HOCs invading the marine environment.They are widely detected in seawater,sediment and seafood,and they have POP-like properties,show potential health risks to marine organisms and human.So far,a few methods have been reported for the simultaneous analysis of these pollutants due to their large polarity difference.As a result,the study on the environmental source,distribution,return and toxicity of emerging HOCs is slow,which limits the comprehensive assessment of environmental risks of HOCs.In view of the fact that there are few simultaneous analysis strategies for emerging HOCs,an extraction and cleanup strategy coupled with high performance liquid chromatography(HPLC)was developed for simultaneous determination of 19 emerging HOCs in marine environment,including carbazole(CZ),PHCZs,bisphenol A(BPA),and its brominated analogs(e.g.,monobromobisphenol A(MBBPA),dibromobisphenol A(DBBPA),TBBPA,and other derivatives).The details are as follows:1)High-throughput analysis of 19 emerging HOCs in seawater samples.Liquid-liquid extraction(LLE)was performed for seawater samples using dichloromethane as the extraction solvent,and then analyzed by HPLC.The method detection limit(MDLs)and method quantification limit(MQLs)were 0.020-0.100 ng/m L and 0.200-2.000 ng/m L,respectively.The relative spiked recovery was in range of 78.8-110.9%,SD < 8.8%.The relative standard deviation(RSD)of intra-day and inter-day test were 0.1-1.3% and 0.1-2.6%,indicating good precision.The matrix effects ranged from-12.7% to 9.8%,indicating that the matrix effect of the strategy was negligible.The method is simple,easy to operate,and have good reproducibility,can be used for simultaneous extraction of various emerging HOCs from marine water.2)High-throughput analysis of 19 emerging HOCs in seafood samples.The target analytes were analyzed through HPLC after ultrasound-assisted extraction(UAE)and cleanup(gel permeation chromatography(GPC)and solid phase extraction).The acceptable spike-recoveries were within 65.7–118.3%,SD < 12.1%;the precision was intra-/inter-day RSDs: 0.0–6.7% / 0.0–8.5%;and the matrix effects were between-14.1%to 12.4%.MDLs and MQLs were 0.002–0.014 and 0.020–0.200 ?g/g dw,respectively.The validation of the method shows that this strategy has good performance and meets the basic requirements of seafood analysis experiment.Additionally,GPC was used in the analysis of biological samples with good recovery rate,effective removal of interfering substrate,and good reproducibility,so this method was successfully used for analyzed the seafood samples and the concentrations of these analytes were in range of nd–5.4 ?g/g dw and the recovery were in range of 54.2–144.0% in actual samples.The method has good practicability.3)High-throughput analysis of 19 emerging HOCs in marine sediment samples.The19 analytes could be directly analyzed through HPLC after UAE and GPC cleanup.The recovery was within 58.4-110.4%,with SD < 11.9%.The intra-day and inter-day precisions were 0.1-1.4% and 0.3-4.8%,respectively.The matrix effect ranged from-3.9-13.0%.MDLs and MQLs were 0.002-0.014 and 0.020-0.200 ?g/g dry weight(dw),respectively.The validation of the method shows that this strategy has good performance and meets the basic requirements of sediment analysis.