Phthalate Ester Environmental Hormone Detection Technology And Health Risk Assessment In Coastal Marine Sediments And Organisms In Zhejiang Province

In this paper,efficient,rapid,and sensitive detection methods for Phthalic Acid Esters(PAEs)in marine sediments and marine organisms collected along the Zhejiang coast(Wenzhou,Taizhou and Zhoushan)were established.The level of interal PAEs of typical marine organisms,pollution characteristics and health risks were studied.The main contents are as follows:1.A solid phase extraction-gas chromatography-mass spectrometry method was developed for the determination of PAEs in marine sediments of Ningbo hangzhou bay(coastal area of beilun district,coastal area of zhenhai)and Waters of Dongji,Zhoushan.The extraction solvent,the type of solid phase extraction column and the eluent were optimized.Linear relationships between values of peak area and mass concentration of the15 phthalic acid esters were kept in the same range of 1~1000 ?g/L with detection limits(3S/N)in the range of 0.1~0.25 ?g/kg.Giving values of recovery and RSD?s(n=5)in the ranges of 79%~118% and 1.5%~6.3%,respectively.The method can meet the detection of PAEs content in different marine sediments.The main detections were: dimethyl phthalate(DMP),diethyl phthalate(DEP),diisobutyl phthalate(DIBP),dibutyl phthalate(DBP),Di(2-ethylhexyl)phthalate(DEHP),with a content of 5.08~298?g/kg,and the total content of 15 PAEs was 138~354 ?g/kg.2.A solid-phase extraction-gas chromatography-mass spectrometry method was developed for the determination of 16 PAEs in marine organisms(Changbai Island,Zhoushan,and Dongtou,Wenzhou).The extraction solvent,the type of solid phase extraction column and eluent were optimized.Linear relationships between values of peak area and mass concentration of the 16 phthalic acid esters were kept in the same range of1~1000 ?g/L with detection limits(3S/N)in the range of 0.15~0.30 ?g/kg.The relative recoveries of spiked PAEs in marine organisms were 76.4%~117%,and with relative standard deviations of 2.1%~6.7%(n=5).This method can meet the analysis of PAEs content in different marine organisms.The main detections were: DMP,DEP,DIBP.,DBP,DEHP,the content was 0.39~211 ?g/kg,and the total content of 16 PAEs was 296~426?g/kg.3.A method for the determination of 16 PAEs by ultrasonic extraction-dispersive solid phase extraction purification-gas chromatography-mass spectrometry was established.The extraction solvent,the type and content of the solid phase adsorbent,the dispersant andother conditions were optimized.Linear relationships between values of peak area and mass concentration of the 16 phthalic acid esters were kept in the same range of 1~1000?g/L with detection limits(3S/N)in the range of 0.15~0.30 ?g/kg.Giving values of recovery and RSD?s in the ranges of 74%~116% and 2.5%~6.9%(n=5),respectively.Compared with solid-phase extraction-gas chromatography mass spectrometry,this method is saves time,simple,sensitive,small matrix interference,wide linear range,precise and accurate.It can better meet the analysis of PAEs content in different marine organisms,and the established method was applied to the detection of 29 species and 387 marine biological samples(fish,crustaceans,molluscs,cephalopods,etc.)collected along the Zhejiang coast(Wenzhou,Taizhou,Zhoushan,etc.).The main detections were: DMP,DEP,DIBP,DBP,DEHP,content was 0.22 ~ 2657 ?g/kg,the total content of 16 PAEs was 63.5~ 2840 ?g/kg,and the average total content was 238 ± 243 ?g/kg.The di(2-methoxyethyl)phthalate(DMEP),di(2-butoxy)ethyl phthalate(DBEP),dicyclohexyl phthalate(DCHP),dinonyl phthalate(DNP),and diisodecyl phthalate(DINP)were detected in partial samples.4.Total of 29 species and 387 marine biological samples(fish,crustaceans,molluscs,cephalopods,etc.)collected along the Zhejiang coast(Wenzhou,Taizhou,Zhoushan,etc.)were subjected to human health assessment of PAEs intake through marine organisms.The results showed that the PAEs pollution in marine organisms in Zhejiang Province was at a lower level than that in other water bodies at home and abroad,and the main PAEs components detected were basically the same.Health risk is within an acceptable range.PAEs pose a slightly higher risk to children than adults.The carcinogenic risk of DEHP in Ribbon fish is slightly higher than other marine organisms.