Detection Of Phthalate Esters And Butylated Hydroxytoluene In Antarctic Krill

Background Antarctic krill is a type of planktonic crustacean distributed in the Southern Ocean,which is a key specie for maintaining the stability of the Southern Ocean ecosystem.Antarctic krill is rich in protein,vitamin A,vitamin E and unsaturated fatty acids,and is one of the food resources for human development and application.At present,the research on Antarctic krill pollutants mainly focuses on heavy metals,fluorine,organic chlorines and polychlorinated biphenyls.Phthalate Esters(PAEs)have estrogen-like effects and anti-androgenic effects,and are physiologically harmful to development,metabolism,and reproduction.PAEs are commonly used as plasticizers.The bonding between PAEs and plastics is weak and PAEs can be easily released into the environment and transported to the Southern Ocean through a variety of routes such as hydrosphere and atmospheric transport,human activities,and species migration.Butylated Hydroxytoluene(BHT)is a common phenolic antioxidant and environmental estrogen,which can be concentrated through the food chain and has acute,chronic toxicity and cancer-promoting properties.Therefore,it is of scientific significance to detect the presence of PAEs and BHT in Antarctic krill.Purpose The purpose of this study is to establish methods for the efficient extraction and detection of 16 PAEs and BHT in Antarctic krill,to explore the existence of 16 PAEs and BHT in Antarctic krill,to divide the Antarctic krill with different ages and genders,to detect PAEs and BHT in Antarctic krill individuals with different ages and genders,and to obtain the change trend of the content.Methods Extraction and detection methods of PAEs in Antarctic krill: the extraction efficiency of three extraction solvents(cyclohexane and absolute ethanol(8:2,v/v),ethyl acetate and acetonitrile)and effects of two common purification conditions(the PAS/silica glass solid phase extraction column and Gel Permeation Chromatography)on the impurity peak in the chromatogram and recoveries were compared to explore the best extraction and purification methods for 16 PAEs.Extraction and detection methods of BHT in Antarctic krill: the extraction efficiency of three extraction solvents(ethyl acetate,methanol and dichloromethane)and effects of two common purification conditions(Florisil solid phase extraction column and HLB solid phase extraction column)on the impurity peak in the chromatogram and recoveries were compared to explore the best extraction and purification methods for BHT.After determining the best detection method,the existence of 16 PAEs and BHT in Antarctic krill was explored,the Antarctic krill was divided into male and female,and the changes of PAEs and BHT in Antarctic krill with different ages and genders were further tested,and the possible causes were analyzed.Results The method for extraction and detection of PAEs about blank treatments(activated carbon adsorption and high temperature distillation),acetonitrile ultrasonic extraction,the PAS/silica glass solid phase extraction column purification and Gas Chromatography-Mass Spectrography(GC-MS)detection was established.The recoveries of the samples were80.32?104.36%,and the Relative Standard Deviation(RSD)was 1.16?9.40%.It was an accurate,convenient and suitable PAEs detection method for Antarctic krill.According to the established experimental method,the presence of 16 PAEs in Antarctic krill was tested.The results showed that DIBP,DBP and DEHP were detected in 20 g fresh Antarctic krill samples,respectively,with a content of 14.55 ?g/kg,364.50 ?g/kg,21.56 ?g/kg,and the remaining PAEs were not detected.The content of DBP in Antarctic krill was significantly higher than that of DIBP and DEHP,and was increased in females.The content of DBP in males exhibited a significant upward trend from age one to four,and a significant downward trend from age four to five.The content of DEHP in males clearly decreased from age two to five.The trend of DIBP in males and females was similar.The method for extraction and detection of BHT about dichloromethane ultrasonic extraction,the Florisil solid phase extraction column purification and GC-MS detection was established.The recoveries of the samples were 88.65?94.12%,and the RSD was 2.52?5.74%.The method had the characteristics of simple operation,accuracy and convenience,and was suitable for detecting BHT in Antarctic krill.According to the established experimental method,the presence of BHT in Antarctic krill was tested.The results showed that the BHT content in the20 g fresh Antarctic krill samples was 7.69 ?g/kg.In males and females,the overall changes of BHT from age one to five were similar,showing an upward trend.