The Development Of Determination For Plasticizer And Mineral Oil Pollutants And The Application Of The New Methods

Plasticizer mainly consists of phthalate esters(PAEs)and bisphenol A(BPA).PAEs and BPA are also a typical representative of the environmental estrogen,as well as the environmental endocrine disruptors;it has male reproductive toxicity that can make the male feminization.The male reproductive toxicity can be easily released because it integrate with base material by non covalent bond in the packaging materials.This kind of material can be absorbed from the mouth,skin and respiratory tract thus cause lesions of the human nervous system as well as reproductive system to varying degrees.In this case,it is necessary to monitor the plasticizer in environment and human body to control the pollution and prevent disease.Mineral oil is a kind of hydrocarbons that formed in the process of physical separation and chemical conversion,including Mineral oil saturated hydrocarbons(MOSH)and Mineral oil aromatic hydrocarbons(MOAH)that consist of linear,branched chain and ring,it may exists in the packaging materials.It is necessary to control its content in food packaging materials in order to avoid its hazards to human health.So far,there is no unified criteria of the detection of mineral oil from domestic to abroad,therefore,the establishment of a method for the detection of mineral oils in food is of great significance.It is a challenge to depose of samples before the detection,due to the low residual trace as well as concentration of PAEs and BPA in biological matrix and food.The traditional classic pretreatment methods mainly include liquid-liquid extraction(LLE),solid phase extraction(SPE),and solid phase microextraction(SPME),however,LLE is cumbersome to operate with a large organic solvent consumption and easily emulsifying;SPME is too expensive for the detection of the large quantities of sample;although the SPE overcome the drawbacks of LLE,it still need various operation steps,that is because the traditional solid phase extraction adsorbents are mostly particle adsorbents over micron size,the desorption efficiency of adsorption was not maximized.By contrast,nanomaterials as adsorbents are currently the focus of research,among which nano-fibers as SPE adsorbents have the characteristics of high selectivity,large adsorption capacity,fast adsorption,easy elution,and lowamount of organic solvent.In this essay,the pretreatment of plasticizer and mineral oil was studied based on nanofiber-based SPE technology,and the methods of testing representative plasticizers in environmental as well as human samples were studied.The target compounds include diethyl-o-phthalate(DEP),dibutyl-o-phthalate(DBP),BPA,benzyl butyl phathalate(BBP),di(2-ethylhexyl)pHathalate(DEHP),di-n-octyl phthalate(DNOP),BPA,etc.In addition,a comparative study on plasticizer exposure in population cohort was designed and carried out.The main contents are as follows.1.The study and the application of the detection of plasticizer in human urinePolystyrene nanofibers were packed in the small column to extract four kinds of PAEs in human urine;It was established that the detection method of four kinds of PAEs in human urine by combining SPE,GC/FID and GC-MS.Under the optimized conditions,the recovery ranges from 80.4% to111.7%,RSD from 1.5% to 10.9%,and LOD is from 0.1 to 0.5 ng/mL.And the established method was used for the detection of PAEs in urine samples from 23 obese children and 30 health children,47 ASD children and 39 health children.The results shows that PAEs in urine from obese children and autistic children are higher than that from the normal group.2.Research on the analysis of plasticizer in foods(milk,beverage)Polystyrene/pyridine composite(PS/PD)nanofibers were prepared and filled into the extraction column for solid phase extraction of PAEs and BPA in milk and juice.The extraction efficiency of PS/PD nanofibers for PAEs was increased by 20-30% comparing to PS nanofibers.The chromatography-mass spectrometry method has been successfully applied to the detection of PAEs and BPA in three kinds of milk and fruit juice.3.The study and the application of the detection of plasticizer in air particulate matterThe PS-PD nanofibers were made as filter for trapping PAEs and BPA in air particulate matter,and combined with GC-MS to establish the detection method for the detremination of five kinds of PAEs and BPA in air particulate matter.Under the optimized conditions,the recovery rate ranges from87.0 to 109.9%,LOD from 0.01 to 0.1?g/L,and the RSD from 0.6 to 10.9%.And this method was applied to the analysis of PAEs and BPA in atmospheric dust in samples from 10 laboratories,10 dormitory,and kindergarten in different zone of Suzhou.Simultaneously,children's urine samples were collected to detect plasticizers.The correlation between exposure level of air plasticizers and urinary plasticizers level in children was analyzed.The results shows that there was a correlationbetween them.4.Preliminary study on risk assessment of plasticizer exposure in Jiangsu Province.Risk assessments of human exposure to phthalate esters and BPA are carried out in children and Jiangsu province population through external exposure method,and the results shows that the maximum cumulative Hazard index(HI)of DBP and DEHP was 0.672 in dietary,0.005 in cosmetics,and 0.029 in atmosphere.Plus other environmental factors,HI may be increased and being harmful to human body,thus relevant control and adjust are needed.5.Exploration on the pretreatment of mineral oilA exploration on the adsorption and separation of MOAH and MOSH in mineral oil using nanofiber materials was carried out,which can provide adsorption material and research data for subsequent analysis of mineral oil in food.