Ecological And Population Health Risk Assessment Of Phthalate Acid Esters(PAEs)

ObjectivesAn accurate,rapid,and efficient method was developed for the determination of16 phthalic acid esters（PAEs）in bottled water,liquor and surface water samples.By analyzing the exposure level of PAEs in the collected samples,the pollution degree of PAEs,assessment of dietary health risks and ecological environmental risks of the population were discussed.This work provides analysis method and research means for the rapid detection of plasticizer residue,and also provides scientific basis for ensuring food safety,protecting human health and preventing and controlling surface water pollution.MethodsBottled water and liquor samples of different brands,including Chinese rice wine,wine and integrated alcoholic beverages,were purchased from supermarkets in urban areas of Hainan province.Eight sampling sites were set up in Haikou City to collect surface water samples,including seawater,reservoir water and pond water.The PAEs in the samples were determined by salting-out assisted liquid-liquid extraction（SALLE）combined with gas chromatography tandem mass spectrometry（GC-MS/MS）.The main factors affecting the SALLE efficiency,such as sample p H,salting-out solution volume and p H were investigated with the aid of orthogonal design,and the detection conditions of GC-MS/MS were optimized.Method validation was performed compared with the National Standard Method of the People’s Republic of China（GB5009.271）and published PAEs testing methods.Dietary and environmental risk of PAEs in all the samples were assessed by health risk index（HI）and risk quotient（RQ）method.Research results1.According to the results of orthogonal experiment,the optimal extraction conditions of SALLE were selected,that is,sample p H was 5,salting-out solution p H was 7,and salting-out solution volume was 6 m L.The most critical parameter affecting the extraction efficiency of the 16 PAEs was the sample p H.Under the optimum conditions,good linearities for PAEs were obtained in a range of 1–200 ng/m L,with the coefficient（R²）above 0.995.The limits of detection（LODs）were between 0.01–2.00 ng/m L.The recoveries under three concentrations were 70-118%with the RSD in the range of 0.15-10.03%.2.Five PAEs（DMP,DEP,DIBP,DBP and DEHP）were detected in bottled water,and the average concentrations were 2.7×10^-4,3.4×10^-4,7.00×10^-5 and 2.14×10^-3 mg/kg,respectively.DBP and DEEP were detected in surface water with average concentrations of 9.92×10^-3and 5.1×10^-4 mg/kg,respectively.Six PAEs including DMP,DEP,DIBP,DBP,DCHP and DEHP were detected in liquor samples mentioned.The mean concentrations were 1.01×10^-2,4.06×10^-3,1.47×10^-2,4.23×10^-2,4.08×10^-3and 1.53×10^-3 mg/kg,respectively.The mean exposure concentrations of the total PAEs（∑16 PAEs）in bottled water,surface water and liquor samples were 8.35,10.4,and 156ng/m L.The detection frequencies of DMP,DEP,DIBP,DBP,DEEP,DCHP and DEHP were 93,49,34,74,1.7,23 and 40%,respectively.3.The test result of the sample is consistent with that of GB5009.271 method,which verifies the accuracy of the method.4.For liquor samples and bottled water samples,the HI value is less than 1 when the intake is less than 1 kg/d.5.DBP RQ values of surface water in S1,S2,S3,S4,S6 and S7 sampling areas and DEEP RQ values of S2 and S7 sampling areas are greater than 10.Conclusion1.SALLE has the advantages of simple operation,sensitive,and environmentally safe,and is an alternative to the method conventionally used bulk organic solvent and those which need large instrument and equipment.2.The content of PAEs in liquor samples is higher than that in bottled water and surface water,because PAEs is more soluble in organic solvents,and liquor is more likely to be polluted by plasticizers during production,transportation and storage.PAEs pollution in surface water is closely related to human activities,such as human uncivilized behavior,ship operation,sewage discharge,etc.3.When the intake of bottled water and liquor samples is less than 1 kg/d,the HI value is far lower than the health guideline value and will not cause damage to human body.The risk of PAEs was higher in surface water,and PAEs at most sampling sites were more harmful to algae,crustaceans and fish.