Determination of 15 PAEs in Fatty Food by SPE-GC/MS

Abstract:

Phthalic acid esters (PAEs) may be used as plasticizer and softener for the manufacturing of plastic products, especially in polyvinyl chloride (PVC). The residue of PAEs in food may affect human health. The method of qualitative analysis and quantitative analysis of 15 PAEs are established by total ion chromatogram (TIC) and select ion monitor (SIM) of gas chromatography-mass spectrometry (GC/MS). Combined with the solid phase extraction (SPE) method, PAEs residue of some fatty food in plastic packaging was detected, with the assessment of PAEs residual be discussed. The correlation coefficient was higher than 0.99. The limit of quantity was 2.93~105.23μg/kg and the limits of detection (LOD) for PAEs had values from 0.97μg/kg to 34.73μg/kg. This method was used for quantification of traces of PAEs in fatty food. The results showed that 9 PAEs residual in fatty food were at the range of <50~1160μg/kg and detection rates were between 16.67 %( 1:6) ~83.33 %( 5:6). None of them was out of national standard.

• Periodical: Applied Mechanics and Materials (Volume 469)
• Pages: 458-463
• DOI: https://doi.org/10.4028/www.scientific.net/AMM.469.458
• Online since: November 2013
• Authors: Ying Hao Xing, Jun Wu*
• Keywords: Determination, Fatty Food, Phthalate Esters, SPE-GC/MS

References

[7] 861 Dimethyl phthalate(DMP) 998. 7 131-11-3.

[5] 00 163 77, 135, 194 2.

[8] 723 Diethyl phthalate(DEP) 1007 84-66-2.

[8] 30 149 177, 121, 222 3.

[10] 485 Diisobutylphthalate (DIBP) 1003 84-69-5.

[10] 00 149 223, 205, 167 4.

[11] 235 Di-n-butyl phthalate(DBP) 999. 9 84-74-2.

[10] 70 149 223, 205, 121 5.

[11] 585 Bis(2-methoxyethyl) phthalate(DMEP) 1007 117-82-8.

[10] 70 59 149, 193, 251 6.

[12] 335 Bis(4-methyl-2-pentyl) phthalate(BMPP) 1004 146-50-9.

[11] 90 149 251, 167, 121 7.

[12] 66 Bis( 2-ethoxyethyl) phthalate(DEEP) 1008 605-54-9.

[11] 90 45 72, 149, 221 8.

[13] 035 Diamyl phthalate(DPP) 1003 131-18-0.

[12] 85 149 237, 219, 167 9.

[15] 196 Dihexyl phthalate(DHXP) 999. 2 84-75-3.

[14] 60 104(149) 104, 76, 251 NO. Retention time(min) Compound Concentration (mg/kg) CAS No. Acquisition time(min) quantitative ions(m/z) Qualitative ions(m/z) 10.

[15] 346 Butyl benzyl phthalate( BBP) 1014 85-68-7.

[14] 60 149 91, 206, 238 11.

[16] 783 Bis(2-n-butoxyethyl) phthalate(DBEP) 1001 117-83-9.

[16] 20 149(57) 223, 205, 278 12.

[17] 458 Dicyclohexyl phthalate(DCHP) 1000 84-61-7.

[17] 10 149 167, 83, 249 13.

[17] 696 Bis(2-ethylhexyl) phthalate(DEHP) 1002 117-81-7.

[17] 10 149 167, 279, 113 14.

[17] 821 Diphenyl phthalate(DPhP) 1004 84-62-8.

[17] 10 225 77, 153, 197 15.

[20] 07 Di-n-octyl phthalate(DNOP) 1002 117-84-0.

[19] 10 149 279, 167, 261 Fig. 1 Chromatographic picture of 15 kinds of PAEs Standard Curve. The linear equation of 15 PAEs was shown in Tab. 2. The average peak intensity (Ab*s) of triplicate experiments with concentration (µg/kg) was used to draw linear equation. The RSD range was calculated by triplicate peak intensity of corresponding PAEs with the different diluted concentrations. Because the peak intensity of the lowest concentrations of PAEs nearly reached 3times of S/N, the RSD of some PAEs is relatively high. The RSD were between 0. 11%~20. 93%. The correlation coefficients were all higher than 0. 99, the linear range were in 49. 9~2, 028μg/kg. LOQ is 10 times of the signal-to-noise ratio (S/N), with LOD be 3 times of S/N. LOQ of 15 PAEs were between 2. 93~105. 23μg/kg, with LOD 0. 97~34. 73μg/kg. Accuracy and Precision. Based on the established method, the recoveries were calculated with n-hexane acted as the stimulant sample. The recoveries and precision of the 15 PAEs were calculated. The recovery rate was from 84. 49% to 125. 35% and RSD was between 1. 29% and 9. 43%. That data wasn't shown. Tab. 2 The linear equations of 15 PAEs under GC-MS SIM conditions No. Compound k* m* R2 RSD% content ρ(μg/kg) LOQ (μg/kg) LOD (μg/kg) 1 DMP 990. 0139 -42829.

9959.

[1] 35-11. 28.

[49] 9-1997. 4.

[4] 55.

[1] 50 2 DEP 1171. 745 -82795. 9.

9958.

68-11. 36.

[50] 4-(2014).

[3] 84.

[1] 27 3 DIBP 1502. 638 -127762.

9919.

[1] 01-7. 75.

[50] 2-(2006).

[3] 00.

99 4 DBP 1535. 285 -130649.

9914.

66-8. 71.

[49] 9-1999. 8.

[2] 93.

97 5 DMEP 265. 8576 -24143. 4.

9970.

[1] 0-11. 7.

[50] 4-(2014).

[16] 95.

[5] 59 6 BMPP 366. 3406 -33826. 7.

9912.

[4] 72-16. 54.

[50] 2-(2008).

[12] 30.

[4] 06 7 DEEP 153. 9259 -17839. 3.

9932.

[1] 32-13. 42.

[50] 4-(2016).

[29] 27.

[9] 66 8 DPP 1241. 333 -150147.

9952.

[2] 77-15. 38.

[50] 15-(2006).

[3] 63.

[1] 20 9 DHXP 633. 7229 -56926. 3.

9921.

[4] 66-15. 89.

[49] 9-1998. 4.

[7] 11.

[2] 35 10 BBP 199. 6752 -20153. 8.

9987.

[4] 84-14. 33.

[50] 7-(2028).

[22] 56.

[7] 45 11 DBEP.

[42] 81019 -1692. 27.

9911.

[3] 12-12. 18 105. 2-2002 105. 23.

[34] 73 12 DCHP 379. 902 -29497. 9.

9929.

92-19. 70 50-(2000).

[11] 86.

[3] 91 13 DEHP 380. 783 -30141.

9905.

89-12. 84.

[50] 1-(2004).

[11] 83.

[3] 90 14 DPhP 102. 9869 -6056. 79.

9907.

11-20. 20.

[50] 2-(2008).

[43] 74.

[14] 44 15 DNOP 151. 8839 -7672. 01.

9909.

[1] 82-20. 93.

[50] 1-(2004).

[29] 66.

[9] 79 * k, m are factors of y=kx+m Detection of Residue Assessment. The residue concentrations were shown in tab. 3. most of the solvents didn't contain PAEs residual. But ethyl acetate: n-hexane (50: 50, v/v) contained 111μg/kg of DEHP , with acetone 87μg/kg of DIBP and 88μg/kg of DBP. acetonitrile: methyl tertiary butyl ether (9: 1, v/v) 87μg/kg of DBP. As the results also show, short time and rapid operation of the pipettors and Multipette plus dispenser couldn't cause notable migration of the PAEs. But the pipette head, which was used for a long time (n=50), would cause the migration, as shown 157μg/kg of DBEP. So using one pipette head for a long time should be avoided. Tab. 3 The residual of 15 PAEs in Solvents and pipette head (n=3, unit: μg/kg) Solvent DMP DEP DIBP DBP DMEP BMPP DEEP DPP DHXP BBP DBEP DCHP DEHP DPhP DNOP aA 87 bB cC dD 111 eE 87 88 fF gG hH 157 a~g A~G were respectively represent of Acetonitrile: methyl tertiary butyl ether (9: 1, V/V), acetonitrile, n-hexane, ethyl acetate: n-hexane (50: 50, V/V), acetone, n-hexane with the pipette head, n-hexane with Combitips advanced pipe. hH was represent n-hexane which was drew with pipette head for repeating fifty times. Detection of Samples. The detected results were fit into the arithmetic linear regression. The final results were shown in tab. 4. As shown, DMP, DIBP, DBP, DPP, DHXP, BBP, DBEP, DEHP and DPhP were detected at the range of <50~1160μg/kg and the range of detection rates were 16. 67 %( 1: 6) ~83. 33 %( 5: 6). Some of the results may be less than 50μg/kg, because the final results are from the detected results minus the blank. Tab. 4 The results of 15 PAEs in high-fat sample (O) and low-fat sample (P) (n=3, unit: μg/kg) Sample DMP DEP DIBP DBP DMEP BMPP DEEP DPP DHXP BBP DBEP DCHP DEHP DPhP DNOP O1 1160 O2 50 16 125 93 50 P1 154 P2 143 95 P3 56 151 90 104 196 85 P4 147 182 93 Conclusion The method for determination of 15 phthalates in puffed food and edible vegetable oil samples was established by SPE-GC/MS. The 15 PAEs were well separated within less than 26 min without marked interference from the sample matrix. The SIM with qualifier ions and quantifier ions were applied to identify the PAEs. Assessment of PAEs residual, which could be used for eliminating effects of residual PAEs in solvents and pipettes, was necessary during the process of experiment. The method is sensitive and reliable in determination of traces of PAEs in fatty food. The survey of 6 samples showed the method of linear equation was effective to get the concentration accurately. The final results showed that 9 PAEs were detected at the range of <50~1160μg/kg and the range of detection rates were 16. 67%(1: 6)~83. 33%(5: 6), but none of them was higher than national standard. Acknowledgments This work is supported by Beijing Municipal Education Commission key disciplines of agricultural products processing and storage engineering construction(PXM2009_014207_078172).