Analysis And Hazard Assessment Of Organophosphate Esters

Organophosphate esters（OPEs）are widely used in food packaging materials,furniture,textiles,electronic appliances and building fire protection materials as plasticizers or flame retardants.To date,OPEs have been detected in a variety of foods such as grains,vegetables,fruits and meat products.OPEs enter food mainly through environmental migration,bioaccumulation,and production and processing.However,few studies have reported the environmental levels,pollution characteristics,and endocrine disrupting effects of OPEs.This project collected air samples in the offices and laboratory from one campus,and established OPEs analytical method using liquid chromatography-mass spectrometry/mass spectrometry（LC-MS/MS）.The aim of this project is to study the pollution level,characteristics and seasonal variation of OPEs in indoor air.In addition,human respiratory exposure levels of OPEs were estimated and compared with their reference dose values.The results have been shown as follows:（1）Six traditional OPEs were detected in indoor air from offices and laboratories.The concentrations of∑_traditionalOPEs in office air were 8470-232000 pg/m³;and the concentrations of∑_traditionalOPEs in laboratory air were 332-190000 pg/m³.Tris（1-chloro-2-propyl）phosphate（TCIPP）accounted for 97.3%and 90.7%of traditional OPEs in indoor air from offices and laboratories,respectively.（2）8 emerging OPEs were analyzed in office and laboratory air,and 5 emerging OPEs were detected.Emerging OPEs have lower levels and detection rates than traditional OPEs in indoor air.The concentrations of∑_emergingOPEs in office and laboratory air were<m LOQ-199 pg/m³ and<m LOQ-170 pg/m³,respectively.Tetrakis（2-chloroethyl）dichloroisopentyl diphosphate（V6）,isodecyl diphenyl phosphate（IDDPP）and trixylyl phosphate（TXP）were not detected in office air.The detection rates of bisphenol A BIS(Diphenyl phosphate（BPA-BDPP）were relatively high in indoor air,with the detection rates ranging from 35%to-79%.（3）Tris（2-isopropylphenyl）phosphate（TIPPP）was detected in indoor air for the first time,and the detection rates ranged from 27%to 57%.（4）The abundance rank order for traditional OPEs in office air was:winter<spring<autumn<summer.However,the levels of∑_emergingOPEs did not change significantly with seasons.Temperature had a great influence on concentrations of∑_traditionalOPEs,and high temperature was favorable to the release of traditional OPEs.（5）Spearman correlation analysis showed that the number of indoor electrical appliances was significantly positively correlated with the level of tris（2-chloroethyl）phosphate（TCEP）（p<0.05）,while there was no significant correlation with other OPEs monomer compounds（p>0.05）.（6）Estrogen effect of resorcinol-bis（diphenyl）phosphate（RDP）was evaluated with breast cancer cells in vitro.It was found that RDP significantly promoted the proliferation of breast cancer cells and activated estrogen receptor ER in reporter gene experiment.Molecular docking simulation showed that RDP had a strong binding ability with ER.The results showed that RDP had estrogenic interference and was stronger than its substitute triphenyl phosphate（TPHP）.（7）The respiratory exposure of OPEs were much lower than their reference dose.By studying the pollution levels of emerging OPEs in the air of offices and laboratories and evaluating estrogen effect of resorcinol-bis（diphenyl）phosphate（RDP）,this project is helpful for people to preliminarily understand the health risks of emerging OPEs and their human respiratory exposure levels.