Abstract:

Organophosphate ester (OPE)-based flame retardants and plasticizers are widely utilized in various industrial products, and are being increasingly used as substitutes for gradually phased brominated flame retardants (BFRs). According to the different types of substituents used, OPEs are mainly divided into alkyls, halogenated compounds, and aromatics, which have widely varying physicochemical properties. OPEs can induce neurotoxicity, carcinogenicity, and damage in endocrine and reproductive systems in humans. Examples of halogenated OPE are tris(2-chloroisopropyl) phosphate (TCIPP) and tris(1,3-dichloropropyl) phosphate (TDCIPP), which are suspected to be carcinogenic. OPEs have emerged as pollutants in environmental and food matrices as a result of volatilization and abrasion processes. Due to its low content in the food matrix and serious background interference, there is a lack of reliable and sensitive analytical methods. Recently, there has been a focus on the detection of OPE flame retardants in food. In this paper, we have reviewed the current status and development trends of OPE detection methods in various foodstuffs. First, the physicochemical properties of more than 30 common OPEs were summarized. Even when using the same extraction solvent, there are obvious differences in extraction efficiency according to different compound properties. To simultaneously analyze multi-component OPE flame retardants in food, it is very important to choose the appropriate extraction solvent to meet the required extraction efficiency of compounds with a wide range of polarities. In addition, although OPE flame retardants are not easily hydrolyzed under neutral conditions, they will degrade to a certain extent under strong acidic and alkaline conditions. It is worth mentioning that avoiding the removal of lipids and other interferences in food matrices under strong acidic and alkaline conditions. Different pretreatment methods, such as accelerated solvent extraction, matrix solid-phase dispersion extraction, microwave-assisted extraction, ultrasonic-assisted extraction, QuEChERS, solid-phase extraction, gel permeation chromatography, and dispersive solid-phase extraction are also compared. Combining the advantages of ultrasonic assisted extraction (UAE) and QuEChERS pretreatment technology can reduce the waste of extraction solvent and internal standard solution. For lipid-rich matrices like biological samples, it is necessary to remove lipid interference by SPE columns or GPC purification. Furthermore, the characteristics of separation and detection techniques, such as GC, GC-MS/MS, and LC-MS/MS, are discussed. Comparing detection limits and recovery data with those reported in the literature, GC-MS/MS can provide improved selectivity, precision, and limits of detection in complex food matrices, but LC-MS often suffers from ion suppression, matrix interferences, and incomplete separation of some OPEs. Since electron impact (EI) has higher ionization efficiency, it produces many fragment ions, thus creating a more complete spectral library, which is conducive to structural identification. When using GC-MS/MS to determine OPE flame retardants, the EI mode was usually used. However, positive chemical ionization (PCI) and electron capture negative ionization (ECNI) modes were also used sometimes. In the section on quality control, the main sources of standards and internal standards, possible sources of blank contamination, and the research status of measures to reduce matrix effects have been reviewed. To avoid blank contamination, all the laboratory equipment should be carefully cleaned, heated at high temperatures, and rinsed with polar or non-polar organic solvents in order to remove all interfering organic residues. Isotopically labeled internal standard and isotopic dilution mass spectrum quantification methods are used to reduce matrix effects. Owing to the limited availability of commercial standards and the relatively high cost, alternative approaches, such as matrix-matched calibration or standard addition methods, are required. The screening and identification of unknown metabolites of OPEs and related analytical methods based on high resolution mass spectrometry could also be studied for precursor OPEs in foodstuffs in the future.

Key words: sample pretreatment, detection technology, organophosphate esters (OPEs), flame retardants, food, review