High-resolution mass spectrometry-based screening and dietary intake assessment of organophosphate esters in foodstuffs from South China

Organophosphate esters (OPEs) are a group of emerging contaminants with widespread environmental occurrence, yet research on their occurrence in foodstuffs is limited. We collected 100 foodstuff samples in South China using a market basket method, and analyzed food extracts for the presence of OPEs and organophosphite antioxidants (OPAs) by suspect and nontarget screening through high-resolution mass spectrometry. Our analysis resulted in the identification of 30 OPEs, comprised of 25 OPEs with a confidence level (CL) of 1 (unequivocal identification using standards) and five OPEs with CL = 2b (probable structure based on diagnostic evidence). Interestingly, 11 of these identified OPEs had not been previously reported in food. No OPA was identified. The occurrence of identified OPEs within the food samples was further investigated. The highest median concentration of OPEs in all food samples was reached by tris(2-chloroisopropyl) phosphate (TCPP) (1.55 ng/g ww, range < 0.74-12.0 ng/g wet weight (ww)). Cereals demonstrated the highest median concentration of the cumulative 30 OPEs. Tris(2-chloroethyl) phosphate (TCEP), TCPP, and triethyl phosphate (TEP) predominantly contributed to OPEs contamination in most food categories. Eight OPEs, namely TEP, tris(2-ethylhexyl) phosphate (TEHP), TCEP, triphenyl phosphate (TPhP), 2-ethylhexyl diphenyl phosphate (EHDPP), bis(2-ethylhexyl) phenyl phosphate (BEHPP), resorcinol bis(diphenyl phosphate) (RDP), and methyl diphenyl phosphate (MDPP) exhibited significantly higher concentrations in the processed group as compared to non-processed group, suggesting that food processing may result in contamination of these OPEs. The median sum of estimated dietary intake (ΣEDI) of all OPEs was determined to be 161 ng/kg body weight/day. Cereals (38.5 %) and vegetables (23.5 %) were the predominant food categories contributing to ΣEDI, and TEP (29.0 %), TCEP (20.2 %), and TCPP (18.3 %) were three major OPEs contributing to ΣEDI. This study for the first time offered a comprehensive overview of OPE species and revealed their occurrence in foodstuffs from South China.