Chinese Journal of Chromatography ›› 2021, Vol. 39 ›› Issue (1): 69-76.DOI: 10.3724/SP.J.1123.2020.07033
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HOU Minmin1,2, SHI Yali1,2,*(), CAI Yaqi1,2
Received:
2020-07-29
Online:
2021-01-08
Published:
2020-12-20
Contact:
SHI Yali
Supported by:
CLC Number:
HOU Minmin, SHI Yali, CAI Yaqi. Determination of 16 organophosphate esters in human blood by high performance liquid chromatography-tandem mass spectrometry combined with liquid-liquid extraction and solid phase extraction[J]. Chinese Journal of Chromatography, 2021, 39(1): 69-76.
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URL: https://www.chrom-china.com/EN/10.3724/SP.J.1123.2020.07033
Compound | Abbreviation | Formula | Mr | CAS No. |
---|---|---|---|---|
Trimethyl phosphate | TMP | C3H9O4P | 140.08 | 512-56-1 |
Triethyl phosphate | TEP | C6H15O4P | 182.16 | 78-40-0 |
Tripropyl phosphate | TPrP | C9H21O4P | 224.23 | 513-08-06 |
Tri-n-butyl phosphate | TnBP | C12H27O4P | 266.31 | 126-73-8 |
Tri-iso-butyl phosphate | TiBP | C12H27O4P | 266.31 | 126-71-6 |
Tris(2-ethylhexyl) phosphate | TEHP | C24H51O4P | 434.63 | 78-42-2 |
Tri(2-butoxyethyl) phosphate | TBOEP | C18H39O7P | 398.47 | 78-51-3 |
Tri(1-chloro-2-propyl) phosphate | TCIPP | C9H18Cl3O4P | 327.57 | 13674-84-5 |
Tri(2-chloroethyl) phosphate | TCEP | C6H12Cl3O4P | 285.49 | 115-96-8 |
Tri(1,3-dichloro-2-propyl) phosphate | TDCPP | C9H15Cl6O4P | 430.90 | 13674-87-8 |
Tri-phenyl phosphate | TPHP | C18H15O4P | 326.28 | 115-86-6 |
Trimethylphenyl phosphate | TMPP | C21H21O4P | 368.36 | 563-04-2 |
Cresyl diphenyl phosphate | CDPP | C19H17O4P | 340.31 | 26444-49-5 |
2-Ethylhexyl di-phenyl phosphate | EHDPP | C20H27O4P | 362.41 | 1241-94-7 |
Resorcinol bis(diphenyl phosphate) | RDP | C30H24O8P2 | 574.45 | 57583-54-7 |
Bisphenol-A bis(diphenyl phosphate) | BABP | C39H34O8P2 | 692.63 | 5945-33-5 |
Table 1 English name, abbreviation, formula, relative molecular mass, and CAS numbers of the 16 OPEs
Compound | Abbreviation | Formula | Mr | CAS No. |
---|---|---|---|---|
Trimethyl phosphate | TMP | C3H9O4P | 140.08 | 512-56-1 |
Triethyl phosphate | TEP | C6H15O4P | 182.16 | 78-40-0 |
Tripropyl phosphate | TPrP | C9H21O4P | 224.23 | 513-08-06 |
Tri-n-butyl phosphate | TnBP | C12H27O4P | 266.31 | 126-73-8 |
Tri-iso-butyl phosphate | TiBP | C12H27O4P | 266.31 | 126-71-6 |
Tris(2-ethylhexyl) phosphate | TEHP | C24H51O4P | 434.63 | 78-42-2 |
Tri(2-butoxyethyl) phosphate | TBOEP | C18H39O7P | 398.47 | 78-51-3 |
Tri(1-chloro-2-propyl) phosphate | TCIPP | C9H18Cl3O4P | 327.57 | 13674-84-5 |
Tri(2-chloroethyl) phosphate | TCEP | C6H12Cl3O4P | 285.49 | 115-96-8 |
Tri(1,3-dichloro-2-propyl) phosphate | TDCPP | C9H15Cl6O4P | 430.90 | 13674-87-8 |
Tri-phenyl phosphate | TPHP | C18H15O4P | 326.28 | 115-86-6 |
Trimethylphenyl phosphate | TMPP | C21H21O4P | 368.36 | 563-04-2 |
Cresyl diphenyl phosphate | CDPP | C19H17O4P | 340.31 | 26444-49-5 |
2-Ethylhexyl di-phenyl phosphate | EHDPP | C20H27O4P | 362.41 | 1241-94-7 |
Resorcinol bis(diphenyl phosphate) | RDP | C30H24O8P2 | 574.45 | 57583-54-7 |
Bisphenol-A bis(diphenyl phosphate) | BABP | C39H34O8P2 | 692.63 | 5945-33-5 |
Analyte | Precursor ion (m/z) | Product ion (m/z) | Declustering potential (DP)/V | Entrance potential (EP)/V | Collision cell exit potential (CXP)/V |
---|---|---|---|---|---|
TMP | 141.1 | 109.1* | 60 | 22 | 10 |
79.0 | 60 | 29 | 6 | ||
TEP | 183.0 | 99.0* | 54 | 24 | 7 |
81.0 | 60 | 50 | 8 | ||
TPrP | 225.4 | 99.0* | 60 | 22 | 7 |
141 | 60 | 24 | 10 | ||
TnBP | 267.4 | 99.0* | 60 | 20 | 10 |
155 | 60 | 12 | 10 | ||
TiBP | 267.4 | 99.0* | 60 | 20 | 10 |
155 | 60 | 12 | 10 | ||
TEHP | 435.3 | 99.0* | 140 | 22 | 9 |
113.1 | 120 | 16 | 8 | ||
TBOEP | 399.3 | 299.3* | 95 | 19 | 10 |
199.0 | 95 | 21 | 10 | ||
TCIPP | 327.0 | 99.0* | 70 | 30 | 10 |
329.1 | 99.0 | 70 | 28 | 10 | |
TCEP | 285.0 | 63.0* | 80 | 42 | 10 |
99.2 | 75 | 30 | 10 | ||
TDCPP | 431.1 | 98.9* | 85 | 35 | 9 |
208.9 | 84 | 20 | 8 | ||
TPHP | 327.1 | 152.0* | 130 | 42 | 11 |
77.1 | 130 | 65 | 7 | ||
TMPP | 369.2 | 166.1* | 147 | 37 | 11 |
90.9 | 147 | 61 | 8 | ||
CDPP | 341.1 | 152.1* | 135 | 40 | 10 |
165.1 | 135 | 40 | 10 | ||
EHDPP | 363.2 | 76.9* | 70 | 71 | 7 |
251.0 | 72 | 12 | 9 | ||
RDP | 575.2 | 419.2* | 190 | 46 | 15 |
481.1 | 183 | 46 | 15 | ||
BABP | 693.2 | 367.0* | 200 | 45 | 15 |
693.3 | 200 | 12 | 15 | ||
TMP-d9 | 150.1 | 83.1 | 90 | 31 | 7 |
TEP-d15 | 198.1 | 101.9 | 65 | 27 | 8 |
TPrP-d21 | 246.4 | 102 | 120 | 25 | 9 |
TCEP-d12 | 299.1 | 102 | 75 | 30 | 6 |
TnBP-d27 | 294.4 | 101.9 | 140 | 25 | 10 |
TPHP-d15 | 342.3 | 160 | 135 | 47 | 10 |
TCIPP-d18 | 345.1 | 101.9 | 75 | 30 | 8 |
Table 2 MS parameters for the 16 OPEs
Analyte | Precursor ion (m/z) | Product ion (m/z) | Declustering potential (DP)/V | Entrance potential (EP)/V | Collision cell exit potential (CXP)/V |
---|---|---|---|---|---|
TMP | 141.1 | 109.1* | 60 | 22 | 10 |
79.0 | 60 | 29 | 6 | ||
TEP | 183.0 | 99.0* | 54 | 24 | 7 |
81.0 | 60 | 50 | 8 | ||
TPrP | 225.4 | 99.0* | 60 | 22 | 7 |
141 | 60 | 24 | 10 | ||
TnBP | 267.4 | 99.0* | 60 | 20 | 10 |
155 | 60 | 12 | 10 | ||
TiBP | 267.4 | 99.0* | 60 | 20 | 10 |
155 | 60 | 12 | 10 | ||
TEHP | 435.3 | 99.0* | 140 | 22 | 9 |
113.1 | 120 | 16 | 8 | ||
TBOEP | 399.3 | 299.3* | 95 | 19 | 10 |
199.0 | 95 | 21 | 10 | ||
TCIPP | 327.0 | 99.0* | 70 | 30 | 10 |
329.1 | 99.0 | 70 | 28 | 10 | |
TCEP | 285.0 | 63.0* | 80 | 42 | 10 |
99.2 | 75 | 30 | 10 | ||
TDCPP | 431.1 | 98.9* | 85 | 35 | 9 |
208.9 | 84 | 20 | 8 | ||
TPHP | 327.1 | 152.0* | 130 | 42 | 11 |
77.1 | 130 | 65 | 7 | ||
TMPP | 369.2 | 166.1* | 147 | 37 | 11 |
90.9 | 147 | 61 | 8 | ||
CDPP | 341.1 | 152.1* | 135 | 40 | 10 |
165.1 | 135 | 40 | 10 | ||
EHDPP | 363.2 | 76.9* | 70 | 71 | 7 |
251.0 | 72 | 12 | 9 | ||
RDP | 575.2 | 419.2* | 190 | 46 | 15 |
481.1 | 183 | 46 | 15 | ||
BABP | 693.2 | 367.0* | 200 | 45 | 15 |
693.3 | 200 | 12 | 15 | ||
TMP-d9 | 150.1 | 83.1 | 90 | 31 | 7 |
TEP-d15 | 198.1 | 101.9 | 65 | 27 | 8 |
TPrP-d21 | 246.4 | 102 | 120 | 25 | 9 |
TCEP-d12 | 299.1 | 102 | 75 | 30 | 6 |
TnBP-d27 | 294.4 | 101.9 | 140 | 25 | 10 |
TPHP-d15 | 342.3 | 160 | 135 | 47 | 10 |
TCIPP-d18 | 345.1 | 101.9 | 75 | 30 | 8 |
Analyte | Recoveries/% | RSD/% | |||
---|---|---|---|---|---|
1 | 2 | 3 | Mean | ||
TMP | 52.7 | 59.3 | 51.6 | 54.6 | 4.2 |
TEP | 63.0 | 68.8 | 67.3 | 66.3 | 3.0 |
TPrP | 79.5 | 79.5 | 84.3 | 81.1 | 2.7 |
TnBP | 76.2 | 77.2 | 80.5 | 78.0 | 2.3 |
TiBP | 77.6 | 80.3 | 78.5 | 78.8 | 1.4 |
TEHP | 73.3 | 78.8 | 74.9 | 75.7 | 2.8 |
TBOEP | 81.4 | 89.3 | 94.9 | 88.5 | 6.8 |
TCEP | 80.8 | 88.1 | 73.7 | 80.9 | 7.2 |
TCIPP | 87.9 | 91.5 | 87.9 | 89.1 | 2.1 |
TDCPP | 66.3 | 74.8 | 70.8 | 70.6 | 4.2 |
TPHP | 82.6 | 83.0 | 81.4 | 82.3 | 0.8 |
EHDPP | 69.7 | 90.5 | 81.8 | 80.7 | 10 |
TMPP | 76.8 | 83.0 | 82.6 | 80.8 | 3.5 |
CDPP | 101 | 106 | 104 | 104 | 2.6 |
RDP | 85.1 | 92.0 | 92.3 | 89.8 | 4.1 |
BABP | 79.1 | 82.3 | 89.2 | 83.5 | 5.1 |
Table 3 Extraction efficiency of ENVI-18 column for OPEs
Analyte | Recoveries/% | RSD/% | |||
---|---|---|---|---|---|
1 | 2 | 3 | Mean | ||
TMP | 52.7 | 59.3 | 51.6 | 54.6 | 4.2 |
TEP | 63.0 | 68.8 | 67.3 | 66.3 | 3.0 |
TPrP | 79.5 | 79.5 | 84.3 | 81.1 | 2.7 |
TnBP | 76.2 | 77.2 | 80.5 | 78.0 | 2.3 |
TiBP | 77.6 | 80.3 | 78.5 | 78.8 | 1.4 |
TEHP | 73.3 | 78.8 | 74.9 | 75.7 | 2.8 |
TBOEP | 81.4 | 89.3 | 94.9 | 88.5 | 6.8 |
TCEP | 80.8 | 88.1 | 73.7 | 80.9 | 7.2 |
TCIPP | 87.9 | 91.5 | 87.9 | 89.1 | 2.1 |
TDCPP | 66.3 | 74.8 | 70.8 | 70.6 | 4.2 |
TPHP | 82.6 | 83.0 | 81.4 | 82.3 | 0.8 |
EHDPP | 69.7 | 90.5 | 81.8 | 80.7 | 10 |
TMPP | 76.8 | 83.0 | 82.6 | 80.8 | 3.5 |
CDPP | 101 | 106 | 104 | 104 | 2.6 |
RDP | 85.1 | 92.0 | 92.3 | 89.8 | 4.1 |
BABP | 79.1 | 82.3 | 89.2 | 83.5 | 5.1 |
Analyte | Spiked 2 ng/mL | Spiked 20 ng/mL | Spiked 40 ng/mL | LOD/(ng/mL) | |||||
---|---|---|---|---|---|---|---|---|---|
Recovery/% | RSD/% | Recovery/% | RSD/% | Recovery/% | RSD/% | ||||
TMP | 30.6 | 2.2 | 33.3 | 1.0 | 37.3 | 6.0 | 0.83 | ||
TEP | 72.6 | 5.7 | 70.6 | 6.6 | 71.1 | 3.8 | 0.17 | ||
TPrP | 82.2 | 1.9 | 78.5 | 1.4 | 70.8 | 1.4 | 0.038 | ||
TnBP | 88.1 | 7.6 | 78.6 | 3.0 | 71.0 | 2.9 | 0.042 | ||
TiBP | 79.9 | 12.3 | 70.6 | 8.4 | 77.3 | 10.4 | 0.020 | ||
TEHP | 63.6 | 7.9 | 53.1 | 12.3 | 72.7 | 12.6 | 0.070 | ||
TBOEP | 85.9 | 4.9 | 84.3 | 5.7 | 77.8 | 3.0 | 0.015 | ||
TCIPP | 72.1 | 4.7 | 79.9 | 4.2 | 74.2 | 2.9 | 0.26 | ||
TCEP | 79.4 | 3.5 | 71.6 | 7.0 | 70.8 | 1.4 | 0.26 | ||
TDCPP | 64.9 | 8.9 | 70.6 | 4.2 | 74.3 | 1.8 | 0.15 | ||
TPHP | 75.4 | 1.0 | 77.1 | 10.4 | 75.7 | 4.5 | 0.15 | ||
TMPP | 60.2 | 1.4 | 65.2 | 0.71 | 65.5 | 0.15 | 0.028 | ||
CDPP | 126 | 12.1 | 114 | 5.2 | 111 | 6.5 | 0.88 | ||
EHDPP | 58.1 | 2.2 | 55.0 | 6.8 | 68.5 | 3.6 | 0.034 | ||
RDP | 69.1 | 4.7 | 62.1 | 4.7 | 64.1 | 2.0 | 0.024 | ||
BABP | 63.5 | 8.6 | 67.6 | 3.7 | 63.5 | 3.9 | 0.0038 |
Table 4 Spiked recoveries of the 16 OPEs in human blood at three levels (n=3)
Analyte | Spiked 2 ng/mL | Spiked 20 ng/mL | Spiked 40 ng/mL | LOD/(ng/mL) | |||||
---|---|---|---|---|---|---|---|---|---|
Recovery/% | RSD/% | Recovery/% | RSD/% | Recovery/% | RSD/% | ||||
TMP | 30.6 | 2.2 | 33.3 | 1.0 | 37.3 | 6.0 | 0.83 | ||
TEP | 72.6 | 5.7 | 70.6 | 6.6 | 71.1 | 3.8 | 0.17 | ||
TPrP | 82.2 | 1.9 | 78.5 | 1.4 | 70.8 | 1.4 | 0.038 | ||
TnBP | 88.1 | 7.6 | 78.6 | 3.0 | 71.0 | 2.9 | 0.042 | ||
TiBP | 79.9 | 12.3 | 70.6 | 8.4 | 77.3 | 10.4 | 0.020 | ||
TEHP | 63.6 | 7.9 | 53.1 | 12.3 | 72.7 | 12.6 | 0.070 | ||
TBOEP | 85.9 | 4.9 | 84.3 | 5.7 | 77.8 | 3.0 | 0.015 | ||
TCIPP | 72.1 | 4.7 | 79.9 | 4.2 | 74.2 | 2.9 | 0.26 | ||
TCEP | 79.4 | 3.5 | 71.6 | 7.0 | 70.8 | 1.4 | 0.26 | ||
TDCPP | 64.9 | 8.9 | 70.6 | 4.2 | 74.3 | 1.8 | 0.15 | ||
TPHP | 75.4 | 1.0 | 77.1 | 10.4 | 75.7 | 4.5 | 0.15 | ||
TMPP | 60.2 | 1.4 | 65.2 | 0.71 | 65.5 | 0.15 | 0.028 | ||
CDPP | 126 | 12.1 | 114 | 5.2 | 111 | 6.5 | 0.88 | ||
EHDPP | 58.1 | 2.2 | 55.0 | 6.8 | 68.5 | 3.6 | 0.034 | ||
RDP | 69.1 | 4.7 | 62.1 | 4.7 | 64.1 | 2.0 | 0.024 | ||
BABP | 63.5 | 8.6 | 67.6 | 3.7 | 63.5 | 3.9 | 0.0038 |
No. | TMP | TEP | TPrP | TnBP | TiBP | TEHP | TBOEP | TPHP | EHDPP | CDPP | TMPP | BABP | RDP | TCEP | TCIPP | TDCPP | ∑16OPE |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1 | - | 0.160 | - | - | 0.235 | - | 0.793 | 0.462 | 0.485 | - | - | 0.029 | - | 2.490 | 0.290 | - | 4.94 |
2 | - | - | - | - | 0.960 | - | - | 0.332 | - | - | - | - | - | 1.378 | 0.590 | - | 3.26 |
3 | - | - | - | - | 0.378 | 0.115 | - | 0.335 | 0.165 | - | - | - | - | 2.415 | 0.415 | - | 3.82 |
4 | - | - | - | - | - | 0.178 | - | 0.392 | 0.153 | - | - | - | - | - | 1.615 | - | 2.34 |
5 | - | - | - | - | 0.953 | 0.290 | 0.245 | 0.390 | 0.230 | - | - | 0.023 | - | 0.298 | 0.765 | 0.460 | 3.65 |
6 | - | - | - | 0.225 | - | 0.398 | 0.185 | 0.270 | 0.155 | - | - | - | - | 0.523 | - | - | 1.76 |
7 | - | - | - | 0.218 | 0.920 | 0.138 | - | - | 0.048 | - | - | - | 0.132 | - | 0.240 | - | 1.69 |
8 | - | 0.118 | - | - | 0.365 | 0.163 | 0.238 | 0.252 | 0.070 | - | - | - | - | - | 0.640 | - | 1.85 |
9 | - | - | - | 0.673 | 1.413 | - | - | 0.485 | 0.123 | - | - | - | - | - | 1.440 | - | 4.13 |
10 | - | 0.263 | - | 1.173 | 1.488 | 0.375 | 0.713 | 0.330 | 0.128 | 0.795 | - | - | - | 0.708 | 2.015 | - | 7.99 |
11 | - | - | - | 0.538 | 0.803 | - | 1.010 | 0.910 | 0.280 | - | - | - | - | 0.820 | 2.140 | - | 6.50 |
12 | - | 0.115 | - | 0.200 | 0.313 | 0.878 | 0.750 | 0.151 | 0.210 | - | - | 0.006 | - | - | 0.165 | - | 2.79 |
13 | - | - | - | 1.505 | 1.693 | 0.363 | 0.410 | - | 0.325 | - | - | 0.007 | - | 0.628 | 2.365 | 0.538 | 7.83 |
14 | - | - | - | - | 0.270 | - | 0.153 | 0.335 | - | - | - | 0.005 | - | - | 0.740 | - | 1.50 |
15 | - | - | - | 0.230 | 0.813 | 0.365 | 0.598 | - | 0.383 | - | - | - | - | - | 0.415 | - | 2.80 |
Table 5 Analytical results of human blood samplesng/mL
No. | TMP | TEP | TPrP | TnBP | TiBP | TEHP | TBOEP | TPHP | EHDPP | CDPP | TMPP | BABP | RDP | TCEP | TCIPP | TDCPP | ∑16OPE |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1 | - | 0.160 | - | - | 0.235 | - | 0.793 | 0.462 | 0.485 | - | - | 0.029 | - | 2.490 | 0.290 | - | 4.94 |
2 | - | - | - | - | 0.960 | - | - | 0.332 | - | - | - | - | - | 1.378 | 0.590 | - | 3.26 |
3 | - | - | - | - | 0.378 | 0.115 | - | 0.335 | 0.165 | - | - | - | - | 2.415 | 0.415 | - | 3.82 |
4 | - | - | - | - | - | 0.178 | - | 0.392 | 0.153 | - | - | - | - | - | 1.615 | - | 2.34 |
5 | - | - | - | - | 0.953 | 0.290 | 0.245 | 0.390 | 0.230 | - | - | 0.023 | - | 0.298 | 0.765 | 0.460 | 3.65 |
6 | - | - | - | 0.225 | - | 0.398 | 0.185 | 0.270 | 0.155 | - | - | - | - | 0.523 | - | - | 1.76 |
7 | - | - | - | 0.218 | 0.920 | 0.138 | - | - | 0.048 | - | - | - | 0.132 | - | 0.240 | - | 1.69 |
8 | - | 0.118 | - | - | 0.365 | 0.163 | 0.238 | 0.252 | 0.070 | - | - | - | - | - | 0.640 | - | 1.85 |
9 | - | - | - | 0.673 | 1.413 | - | - | 0.485 | 0.123 | - | - | - | - | - | 1.440 | - | 4.13 |
10 | - | 0.263 | - | 1.173 | 1.488 | 0.375 | 0.713 | 0.330 | 0.128 | 0.795 | - | - | - | 0.708 | 2.015 | - | 7.99 |
11 | - | - | - | 0.538 | 0.803 | - | 1.010 | 0.910 | 0.280 | - | - | - | - | 0.820 | 2.140 | - | 6.50 |
12 | - | 0.115 | - | 0.200 | 0.313 | 0.878 | 0.750 | 0.151 | 0.210 | - | - | 0.006 | - | - | 0.165 | - | 2.79 |
13 | - | - | - | 1.505 | 1.693 | 0.363 | 0.410 | - | 0.325 | - | - | 0.007 | - | 0.628 | 2.365 | 0.538 | 7.83 |
14 | - | - | - | - | 0.270 | - | 0.153 | 0.335 | - | - | - | 0.005 | - | - | 0.740 | - | 1.50 |
15 | - | - | - | 0.230 | 0.813 | 0.365 | 0.598 | - | 0.383 | - | - | - | - | - | 0.415 | - | 2.80 |
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