Development and validation of a liquid chromatography-mass spectrometry method for simultaneous analysis of...

In the present study, a novel and reliable analytical method was developed and validated for the simultaneous determination of 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TDBP-TAZTO) and 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) in environmental samples using high-performance liquid chromatography coupled to a tandem mass spectrometer. Firstly, for optimization of the liquid chromatography separation, mobile phases, oven temperatures, modifiers, and buffers were varied. Afterwards, the extraction efficiency of sediment and fish samples was tested with different techniques (pressurized liquid, solid-liquid, ultrasound-assisted, and Soxhlet extraction). Additionally, cleanup using modified multilayer silica gel (sediment) and gel permeation chromatography as well as Florisil® columns (fish) with several solvent mixtures were performed. The best results were obtained with the pressurized liquid extraction (optimal conditions: extraction solvent 100% toluene, extraction time 20 min, cycles two, extraction temperature 100 °C, and flushing volume 60%) compared to other solvent extraction methods. On the basis of this optimized analytical procedure, the method was validated with satisfactory values of correlation coefficient (R²) between 0.998 and 0.999 for both matrices in the calibration range of 2.0-502.0 μg kg^-1 for TDBP-TAZTO and 16.6-770.6 μg kg^-1 for TTBP-TAZ in sediment samples as well as 4.8-303.5 μg kg^-1 and 47.4-742.5 μg kg^-1 in fish samples (bream), respectively. Mean recoveries (n = 5) were calculated for both analytes with spiked matrices at one concentration level (100 μg kg^-1) between 98 and 114% with intra-day relative standard deviations less than 11%. The inter-day precision (n = 15) was also acceptable for both compounds < 11%. It was found that the limit of detection and limit of quantification were in the range of 0.4-1.3 μg kg^-1 for TDBP-TAZTO and 10-28 μg kg^-1 for TTBP-TAZ in surface sediment samples and 7-25 μg kg^-1 and 22-80 μg kg^-1 in fish samples (bream), respectively. The results indicated that these analytical methods could provide reliable and efficient approaches for quantification of TDBP-TAZTO and TTBP-TAZ in sediment and fish samples. Graphical abstract.