Chinese Journal of Chromatography ›› 2025, Vol. 43 ›› Issue (4): 309-316.DOI: 10.3724/SP.J.1123.2024.07010
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TANG Yan1,2, WEN Sheng2, CAO Wencheng2, LIU Xiao2, LEI Chenglin2,3, CHENG Qingyun2, CHEN Haichuan2, LIU Ling2, LIU Xiaofang2,*(), ZHOU Yan2,*(
)
Received:
2024-07-11
Online:
2025-04-08
Published:
2025-03-26
Supported by:
CLC Number:
TANG Yan, WEN Sheng, CAO Wencheng, LIU Xiao, LEI Chenglin, CHENG Qingyun, CHEN Haichuan, LIU Ling, LIU Xiaofang, ZHOU Yan. Determination of eight organophosphate esters in animal-derived foods by ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2025, 43(4): 309-316.
Compound | CAS No. | tR/min | Parent ion (m/z) | Product ions (m/z) | DP/V | CEs/eV |
---|---|---|---|---|---|---|
Triethyl phosphate (TEP) | 78-40-8 | 1.98 | 183.1 | 99.0*, 127.0 | 25 | 19, 12 |
Tripropyl phosphate (TPrP) | 513-08-6 | 3.24 | 225.1 | 99.0*, 141.0 | 20 | 17, 10 |
Tri-n-butyl phosphate (TnBP) | 126-73-8 | 4.30 | 267.1 | 99.0*, 155.0 | 30 | 17, 9 |
Tri(2-chloroethyl) phosphate (TCEP) | 115-96-6 | 2.66 | 286.9 | 98.9*, 125.0 | 30 | 22, 16 |
Tris(2-chloroisopropyl) phosphate (TCIPP) | 13674-84-5 | 3.44 | 327.0 | 99.0*, 175.0 | 30 | 19, 12 |
Triphenyl phosphate (TPHP) | 115-86-6 | 4.20 | 327.1 | 215.0*, 152.0 | 30 | 26, 40 |
Tri(1,3-dichloro-2-propyl)phosphate (TDCIPP) | 13674-87-8 | 4.03 | 430.8 | 99.0*, 320.9 | 30 | 24, 12 |
2,2-Bis(chloromethyl)trimethylenebis | 38051-10-4 | 3.51 | 583.0 | 361.0*, 235.0 | 30 | 17, 30 |
[Bis(2-chloroethyl) phosphate] (V6) | ||||||
D15-Triethyl phosphate (TEP-D15) | 135942-11-9 | 1.94 | 198.2 | 102.0*, 134.0 | 25 | 20, 12 |
D21-Tripropyl phosphate (TPrP-D21) | 1219794-92-9 | 3.20 | 246.0 | 102.0*, 105.0 | 15 | 15, 10 |
D27-Tri-n-butyl phosphate (TnBP-D27) | 61196-26-7 | 4.23 | 294.3 | 102.0*, 166.2 | 30 | 25, 25 |
D12-Tri(2-chloroethyl) phosphate (TCEP-D12) | 1276500-47-0 | 2.65 | 299.1 | 130.0*, 102.0 | 30 | 16, 25 |
D18-Tris(2-chloroisopropyl) phosphate (TCIPP-D18) | 1447569-78-9 | 3.41 | 345.1 | 102.0*, 183.0 | 25 | 22, 14 |
D15-Triphenyl phosphate (TPHP-D15) | 1173020-30-8 | 4.16 | 342.2 | 223.0*, 262.1 | 30 | 25, 27 |
D15-Tri(1,3-dichloro-2-propyl)phosphate (TDCIPP-D15) | 1447569-77-8 | 4.01 | 446.2 | 102.0*, 216.0 | 30 | 28, 16 |
Table 1 Retention times and MS parameters of the eight target compounds and their isotope internal standards
Compound | CAS No. | tR/min | Parent ion (m/z) | Product ions (m/z) | DP/V | CEs/eV |
---|---|---|---|---|---|---|
Triethyl phosphate (TEP) | 78-40-8 | 1.98 | 183.1 | 99.0*, 127.0 | 25 | 19, 12 |
Tripropyl phosphate (TPrP) | 513-08-6 | 3.24 | 225.1 | 99.0*, 141.0 | 20 | 17, 10 |
Tri-n-butyl phosphate (TnBP) | 126-73-8 | 4.30 | 267.1 | 99.0*, 155.0 | 30 | 17, 9 |
Tri(2-chloroethyl) phosphate (TCEP) | 115-96-6 | 2.66 | 286.9 | 98.9*, 125.0 | 30 | 22, 16 |
Tris(2-chloroisopropyl) phosphate (TCIPP) | 13674-84-5 | 3.44 | 327.0 | 99.0*, 175.0 | 30 | 19, 12 |
Triphenyl phosphate (TPHP) | 115-86-6 | 4.20 | 327.1 | 215.0*, 152.0 | 30 | 26, 40 |
Tri(1,3-dichloro-2-propyl)phosphate (TDCIPP) | 13674-87-8 | 4.03 | 430.8 | 99.0*, 320.9 | 30 | 24, 12 |
2,2-Bis(chloromethyl)trimethylenebis | 38051-10-4 | 3.51 | 583.0 | 361.0*, 235.0 | 30 | 17, 30 |
[Bis(2-chloroethyl) phosphate] (V6) | ||||||
D15-Triethyl phosphate (TEP-D15) | 135942-11-9 | 1.94 | 198.2 | 102.0*, 134.0 | 25 | 20, 12 |
D21-Tripropyl phosphate (TPrP-D21) | 1219794-92-9 | 3.20 | 246.0 | 102.0*, 105.0 | 15 | 15, 10 |
D27-Tri-n-butyl phosphate (TnBP-D27) | 61196-26-7 | 4.23 | 294.3 | 102.0*, 166.2 | 30 | 25, 25 |
D12-Tri(2-chloroethyl) phosphate (TCEP-D12) | 1276500-47-0 | 2.65 | 299.1 | 130.0*, 102.0 | 30 | 16, 25 |
D18-Tris(2-chloroisopropyl) phosphate (TCIPP-D18) | 1447569-78-9 | 3.41 | 345.1 | 102.0*, 183.0 | 25 | 22, 14 |
D15-Triphenyl phosphate (TPHP-D15) | 1173020-30-8 | 4.16 | 342.2 | 223.0*, 262.1 | 30 | 25, 27 |
D15-Tri(1,3-dichloro-2-propyl)phosphate (TDCIPP-D15) | 1447569-77-8 | 4.01 | 446.2 | 102.0*, 216.0 | 30 | 28, 16 |
Compound | Linear equation | r2 | Pork | Bass | Milk | Egg | |||||||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
LOD/ (μg/kg) | LOQ/ (μg/kg) | LOD/ (μg/kg) | LOQ/ (μg/kg) | LOD/ (μg/kg) | LOQ/ (μg/kg) | LOD/ (μg/kg) | LOQ/ (μg/kg) | ||||||||||||||||||
TEP | Y=0.6593X+0.0272 | 0.9994 | 0.09 | 0.26 | 0.02 | 0.06 | 0.02 | 0.06 | 0.08 | 0.25 | |||||||||||||||
TPrP | Y=0.3096X-0.0038 | 0.9997 | 0.01 | 0.02 | 0.04 | 0.11 | 0.02 | 0.05 | 0.14 | 0.42 | |||||||||||||||
TnBP | Y=0.9581X+0.0663 | 0.9998 | 0.07 | 0.22 | 0.11 | 0.32 | 0.13 | 0.38 | 0.03 | 0.09 | |||||||||||||||
TCEP | Y=0.8667X+0.0590 | 0.9990 | 0.07 | 0.21 | 0.04 | 0.12 | 0.03 | 0.09 | 0.01 | 0.04 | |||||||||||||||
TCIPP | Y=0.9607X+0.9232 | 0.9900 | 0.44 | 1.31 | 0.55 | 1.64 | 0.47 | 1.42 | 0.87 | 2.62 | |||||||||||||||
TPHP | Y=4.0582X+0.0936 | 0.9994 | 0.07 | 0.21 | 0.03 | 0.09 | 0.02 | 0.07 | 0.06 | 0.17 | |||||||||||||||
TDCIPP | Y=1.5617X+0.1166 | 0.9992 | 0.02 | 0.06 | 0.02 | 0.05 | 0.02 | 0.05 | 0.01 | 0.03 | |||||||||||||||
V6 | y=2734.09x+148.50 | 0.9991 | 0.04 | 0.11 | 0.02 | 0.06 | 0.03 | 0.08 | 0.03 | 0.08 |
Table 4 Linear equations, correlation coefficients (r2), limits of detection (LODs) and limits of quantification (LOQs) of the targets
Compound | Linear equation | r2 | Pork | Bass | Milk | Egg | |||||||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
LOD/ (μg/kg) | LOQ/ (μg/kg) | LOD/ (μg/kg) | LOQ/ (μg/kg) | LOD/ (μg/kg) | LOQ/ (μg/kg) | LOD/ (μg/kg) | LOQ/ (μg/kg) | ||||||||||||||||||
TEP | Y=0.6593X+0.0272 | 0.9994 | 0.09 | 0.26 | 0.02 | 0.06 | 0.02 | 0.06 | 0.08 | 0.25 | |||||||||||||||
TPrP | Y=0.3096X-0.0038 | 0.9997 | 0.01 | 0.02 | 0.04 | 0.11 | 0.02 | 0.05 | 0.14 | 0.42 | |||||||||||||||
TnBP | Y=0.9581X+0.0663 | 0.9998 | 0.07 | 0.22 | 0.11 | 0.32 | 0.13 | 0.38 | 0.03 | 0.09 | |||||||||||||||
TCEP | Y=0.8667X+0.0590 | 0.9990 | 0.07 | 0.21 | 0.04 | 0.12 | 0.03 | 0.09 | 0.01 | 0.04 | |||||||||||||||
TCIPP | Y=0.9607X+0.9232 | 0.9900 | 0.44 | 1.31 | 0.55 | 1.64 | 0.47 | 1.42 | 0.87 | 2.62 | |||||||||||||||
TPHP | Y=4.0582X+0.0936 | 0.9994 | 0.07 | 0.21 | 0.03 | 0.09 | 0.02 | 0.07 | 0.06 | 0.17 | |||||||||||||||
TDCIPP | Y=1.5617X+0.1166 | 0.9992 | 0.02 | 0.06 | 0.02 | 0.05 | 0.02 | 0.05 | 0.01 | 0.03 | |||||||||||||||
V6 | y=2734.09x+148.50 | 0.9991 | 0.04 | 0.11 | 0.02 | 0.06 | 0.03 | 0.08 | 0.03 | 0.08 |
Compound | Added/ (μg/kg) | Pig | Bass | Milk | Egg | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Recovery/% | RSD/% | Recovery/% | RSD/% | Recovery/% | RSD/% | Recovery/% | RSD/% | |||||
TEP | 2 | 100.9 | 5.6 | 94.0 | 5.7 | 105.7 | 4.0 | 113.5 | 3.1 | |||
20 | 98.4 | 1.4 | 82.2 | 0.3 | 105.8 | 0.8 | 100.4 | 1.4 | ||||
100 | 96.8 | 1.2 | 95.5 | 0.5 | 99.1 | 4.6 | 97.5 | 1.2 | ||||
TPrP | 2 | 93.4 | 3.8 | 86.8 | 3.0 | 97.4 | 7.4 | 98.1 | 9.3 | |||
20 | 98.3 | 0.7 | 85.6 | 2.2 | 103.4 | 1.2 | 103.5 | 0.7 | ||||
100 | 92.4 | 1.2 | 95.1 | 3.7 | 100.9 | 2.7 | 95.1 | 1.2 | ||||
TnBP | 2 | 92.5 | 2.9 | 95.0 | 1.1 | 96.0 | 3.7 | 85.8 | 3.8 | |||
20 | 109.8 | 1.9 | 93.9 | 3.6 | 115.3 | 1.2 | 113.4 | 1.9 | ||||
100 | 80.5 | 0.8 | 93.1 | 8.7 | 101.8 | 2.8 | 95.8 | 0.8 | ||||
TCEP | 2 | 96.3 | 12.1 | 99.1 | 4.2 | 87.1 | 3.1 | 82.4 | 6.8 | |||
20 | 102.8 | 3.0 | 83.7 | 1.9 | 97.7 | 2.2 | 100.0 | 3.0 | ||||
100 | 101.1 | 1.0 | 97.8 | 2.2 | 94.0 | 4.0 | 96.3 | 1.0 | ||||
TCIPP | 2 | 106.8 | 3.5 | 106.5 | 0.7 | 110.2 | 1.3 | 87.9 | 5.2 | |||
20 | 98.4 | 1.9 | 90.4 | 4.3 | 102.5 | 1.9 | 93.4 | 3.6 | ||||
100 | 101.5 | 2.4 | 98.4 | 4.1 | 96.4 | 3.8 | 98.4 | 4.5 | ||||
TPHP | 2 | 93.3 | 3.4 | 88.7 | 3.2 | 93.6 | 4.5 | 97.2 | 7.6 | |||
20 | 90.0 | 2.6 | 94.6 | 4.0 | 102.3 | 3.0 | 109.3 | 2.6 | ||||
100 | 83.7 | 2.5 | 117.8 | 6.4 | 97.1 | 2.4 | 99.7 | 2.5 | ||||
TDCIPP | 2 | 96.1 | 10.7 | 85.3 | 5.3 | 95.5 | 3.0 | 81.9 | 8.0 | |||
20 | 101.8 | 3.1 | 89.6 | 5.8 | 96.2 | 5.0 | 96.2 | 3.1 | ||||
100 | 103.4 | 2.0 | 101.6 | 2.0 | 91.8 | 4.4 | 88.1 | 2.0 | ||||
V6 | 2 | 103.5 | 7.0 | 104.7 | 10.0 | 81.4 | 14.8 | 86.2 | 4.8 | |||
20 | 86.2 | 2.7 | 93.2 | 4.5 | 85.0 | 5.6 | 97.0 | 2.7 | ||||
100 | 104.9 | 1.9 | 85.6 | 8.1 | 87.9 | 6.2 | 86.2 | 1.9 |
Table 3 Recoveries and precisions of the eight targets spiked at three levels in pork, bass, milk and egg (n=6)
Compound | Added/ (μg/kg) | Pig | Bass | Milk | Egg | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Recovery/% | RSD/% | Recovery/% | RSD/% | Recovery/% | RSD/% | Recovery/% | RSD/% | |||||
TEP | 2 | 100.9 | 5.6 | 94.0 | 5.7 | 105.7 | 4.0 | 113.5 | 3.1 | |||
20 | 98.4 | 1.4 | 82.2 | 0.3 | 105.8 | 0.8 | 100.4 | 1.4 | ||||
100 | 96.8 | 1.2 | 95.5 | 0.5 | 99.1 | 4.6 | 97.5 | 1.2 | ||||
TPrP | 2 | 93.4 | 3.8 | 86.8 | 3.0 | 97.4 | 7.4 | 98.1 | 9.3 | |||
20 | 98.3 | 0.7 | 85.6 | 2.2 | 103.4 | 1.2 | 103.5 | 0.7 | ||||
100 | 92.4 | 1.2 | 95.1 | 3.7 | 100.9 | 2.7 | 95.1 | 1.2 | ||||
TnBP | 2 | 92.5 | 2.9 | 95.0 | 1.1 | 96.0 | 3.7 | 85.8 | 3.8 | |||
20 | 109.8 | 1.9 | 93.9 | 3.6 | 115.3 | 1.2 | 113.4 | 1.9 | ||||
100 | 80.5 | 0.8 | 93.1 | 8.7 | 101.8 | 2.8 | 95.8 | 0.8 | ||||
TCEP | 2 | 96.3 | 12.1 | 99.1 | 4.2 | 87.1 | 3.1 | 82.4 | 6.8 | |||
20 | 102.8 | 3.0 | 83.7 | 1.9 | 97.7 | 2.2 | 100.0 | 3.0 | ||||
100 | 101.1 | 1.0 | 97.8 | 2.2 | 94.0 | 4.0 | 96.3 | 1.0 | ||||
TCIPP | 2 | 106.8 | 3.5 | 106.5 | 0.7 | 110.2 | 1.3 | 87.9 | 5.2 | |||
20 | 98.4 | 1.9 | 90.4 | 4.3 | 102.5 | 1.9 | 93.4 | 3.6 | ||||
100 | 101.5 | 2.4 | 98.4 | 4.1 | 96.4 | 3.8 | 98.4 | 4.5 | ||||
TPHP | 2 | 93.3 | 3.4 | 88.7 | 3.2 | 93.6 | 4.5 | 97.2 | 7.6 | |||
20 | 90.0 | 2.6 | 94.6 | 4.0 | 102.3 | 3.0 | 109.3 | 2.6 | ||||
100 | 83.7 | 2.5 | 117.8 | 6.4 | 97.1 | 2.4 | 99.7 | 2.5 | ||||
TDCIPP | 2 | 96.1 | 10.7 | 85.3 | 5.3 | 95.5 | 3.0 | 81.9 | 8.0 | |||
20 | 101.8 | 3.1 | 89.6 | 5.8 | 96.2 | 5.0 | 96.2 | 3.1 | ||||
100 | 103.4 | 2.0 | 101.6 | 2.0 | 91.8 | 4.4 | 88.1 | 2.0 | ||||
V6 | 2 | 103.5 | 7.0 | 104.7 | 10.0 | 81.4 | 14.8 | 86.2 | 4.8 | |||
20 | 86.2 | 2.7 | 93.2 | 4.5 | 85.0 | 5.6 | 97.0 | 2.7 | ||||
100 | 104.9 | 1.9 | 85.6 | 8.1 | 87.9 | 6.2 | 86.2 | 1.9 |
Sample | TEP | TPrP | TnBP | TCEP | TCIPP | TPHP | TDCIPP | V6 |
---|---|---|---|---|---|---|---|---|
Grass carp | 0.721 | <LOD | 0.119 | 0.421 | 12.899 | 0.074 | 0.199 | <LOD |
Bass | 2.564 | <LOD | 0.391 | 0.459 | 13.68 | 0.105 | 0.144 | <LOD |
Procambarus clarkii | 0.797 | <LOD | 0.406 | 1.234 | 69.314 | 0.183 | 0.187 | <LOD |
Milk | 0.238 | <LOD | 0.569 | <LOD | 37.243 | 0.04 | 0.185 | <LOD |
Milk powder | 101.638 | <LOD | 0.932 | 2.633 | 7.252 | 0.518 | 0.139 | <LOD |
Yogurt | 0.251 | <LOD | 0.288 | 0.064 | 47.359 | 0.064 | 0.149 | <LOD |
Pork | 1.084 | <LOD | 0.252 | 0.171 | 11.15 | 0.121 | <LOD | <LOD |
Beef | 0.661 | <LOD | 0.192 | 0.47 | 42.153 | <LOD | <LOD | <LOD |
Chicken | 0.953 | <LOD | 0.128 | 0.462 | 5.58 | 0.133 | <LOD | <LOD |
Duck meet | 1.162 | <LOD | 0.272 | 0.613 | 7.038 | 0.17 | <LOD | <LOD |
Egg | 1.602 | <LOD | 0.269 | 0.472 | 23.829 | <LOD | <LOD | <LOD |
Duck egg | <LOD | <LOD | 0.154 | 0.042 | 5.977 | <LOD | <LOD | <LOD |
Table 4 Contents of the eight targets in real samples (n=3) μg/kg
Sample | TEP | TPrP | TnBP | TCEP | TCIPP | TPHP | TDCIPP | V6 |
---|---|---|---|---|---|---|---|---|
Grass carp | 0.721 | <LOD | 0.119 | 0.421 | 12.899 | 0.074 | 0.199 | <LOD |
Bass | 2.564 | <LOD | 0.391 | 0.459 | 13.68 | 0.105 | 0.144 | <LOD |
Procambarus clarkii | 0.797 | <LOD | 0.406 | 1.234 | 69.314 | 0.183 | 0.187 | <LOD |
Milk | 0.238 | <LOD | 0.569 | <LOD | 37.243 | 0.04 | 0.185 | <LOD |
Milk powder | 101.638 | <LOD | 0.932 | 2.633 | 7.252 | 0.518 | 0.139 | <LOD |
Yogurt | 0.251 | <LOD | 0.288 | 0.064 | 47.359 | 0.064 | 0.149 | <LOD |
Pork | 1.084 | <LOD | 0.252 | 0.171 | 11.15 | 0.121 | <LOD | <LOD |
Beef | 0.661 | <LOD | 0.192 | 0.47 | 42.153 | <LOD | <LOD | <LOD |
Chicken | 0.953 | <LOD | 0.128 | 0.462 | 5.58 | 0.133 | <LOD | <LOD |
Duck meet | 1.162 | <LOD | 0.272 | 0.613 | 7.038 | 0.17 | <LOD | <LOD |
Egg | 1.602 | <LOD | 0.269 | 0.472 | 23.829 | <LOD | <LOD | <LOD |
Duck egg | <LOD | <LOD | 0.154 | 0.042 | 5.977 | <LOD | <LOD | <LOD |
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