A gas chromatography/mass spectrometric method was developed for the simultaneous determination of eight phthalic acid esters (PAEs) in toys and child care articles that are made of plasticized plastic. The novel method was used to determine the total concentration of the PAEs in addition to the migrated PAEs values into artificial saliva, under conditions that simulate real life situations. The extraction method, which was developed for the first time to determine the total concentration of PAEs, utilized a novel optimization of four parameters involving the solvent, time, temperature and weight of sample. The PAEs were extracted with tetrahydrofuran, as extraction the solvent, and using the ultrasonic water bath shaker for 30min, at room temperature. Another extraction method was developed to determine the migrated PAEs into artificial saliva at pH 6.2 and 37°C, implementing a liquid-liquid extraction with chloroform. Both methods were subjected to validation steps in terms of linearity, precision, accuracy and recovery, which ensured that all obtained results were well within the norms of acceptable limits and specifications. The analytes were separated at the following retention times: 4.99, 5.21, 5.31, 6.63, 7.41, 9.05min for di-"isobutyl" phthalate (DIBP), dibutyl phthalate (DBP), bis(2-methoxyethyl)phthalate (DMEP), benzyl butyl phthalate (BBP), dibutyl phthalate (DEHP) and di-n-octyl phthalate (DnOP), respectively. The chromatographic peaks corresponding to di-"isononyl" phthalate (DINP) and di-"isononyl" phthalate (DIDP), were separated, using the extracted ion chromatogram (EIC) mode within the time ranges of 8.05-12.10min for DINP and 8.50-14.50min for DIDP. The instrument detection limits for DIBP, DBP, DMEP, BBP, DEHP, DnOP, DINP and DIDP were determined at 0.100, 0.100, 0.045, 0.035, 0.015, 0.370, 0.320, 0.260μg/ml, respectively. The calibration curve working ranges were determined at 0.5-25μg/ml for DIBP, DBP, DMEP, BBP and DEHP, 2-100μg/ml for DnOP and 5-100μg/ml for DINP and DIDP. The coefficients of variation (precision) for the total PAEs method were in the range 0.55-12.10% and for the migration method were in the range 0.72-7.70%. Recovery values for total PAEs and for the migrated PAEs were ranged within 90.6-111.7% and 86.3-117.2%; respectively. Both developed methods were used to survey the Jordanian market, where twenty seven samples were collected and tested for plastic type, total PAEs and migrated PAEs. Seventeen of those samples were found to be polyvinyl chloride (PVC), and all of them containing total PAEs having concentrations in excess of the allowed limit of 0.1% (w/w). The rest of the samples were non-PVC and only one of them containing PAEs, but below the allowed limit. In contrast, all the migration results were found to be well within the allowed limits. It was also found that as the PAEs total concentration increase, the corresponding migrated value increase, while the opposite trend holds for in the PAEs molecular weight.
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