Chinese Journal of Chromatography ›› 2025, Vol. 43 ›› Issue (1): 68-77.DOI: 10.3724/SP.J.1123.2023.12028
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ZHU Yizhe1, ZHENG Ruifen1, FAN Zihao1, LIU Ling1, YE Jingyao1, WANG Kai1, TANG Caiming1,2,*()
Received:
2023-12-27
Online:
2025-01-08
Published:
2024-12-26
Supported by:
CLC Number:
ZHU Yizhe, ZHENG Ruifen, FAN Zihao, LIU Ling, YE Jingyao, WANG Kai, TANG Caiming. Determination of 12 halogenated organic pollutants in edible fish by ultra performance liquid chromatography-high resolution mass spectrometry combined with ultrasound-assisted extraction and gel permeation chromatography purification[J]. Chinese Journal of Chromatography, 2025, 43(1): 68-77.
Compound | Formula | Retention time/min | Ion type | Measured accurate mass (m/z) | Theoretical exact mass (m/z) | Mass error/ 10-6 (ppm) | IS |
---|---|---|---|---|---|---|---|
Chloramphenicol (CPL) | C11H12Cl2N2O5 | 4.53 | [M-H]- | 321.00537 | 321.00505 | 0.996 | TBBPA-D10 |
Pentachlorophenol (PCP) | C6HCl5O | 5.78 | [M-H]- | 264.83704 | 264.83678 | 0.995 | TBBPA-D10 |
Forchlorfenuron (CPPU) | C12H10ClN3O | 6.34 | [M-H]- | 246.04419 | 246.04396 | 0.923 | TCS-D3 |
p-Choro-m-cresol (PCMC) | C7H7ClO | 6.65 | [M-H]- | 141.01137 | 141.01126 | 0.738 | TCS-D3 |
2-Iodophenol (IPL) | C6H4IOH | 6.63 | [M-H]- | 218.93132 | 218.93123 | 0.406 | TBBPA-D10 |
4-Chloro-3,5-dimethylphenol (PCMX) | C8H9OCl | 7.35 | [M-H]- | 155.02702 | 155.02691 | 0.671 | TBBPA-D10 |
Bromchlorophen (BCP) | C13H8Br2Cl2O2 | 7.77 | [M-H]- | 424.81787 | 424.81749 | 0.902 | TBBPA-D10 |
Clorofene (CLF) | C13H11ClO | 8.79 | [M-H]- | 217.04269 | 217.04256 | 0.571 | TCC-D4 |
Triclosan (TCS) | C12H7Cl3O2 | 9.72 | [M-H]- | 286.94427 | 286.94388 | 1.339 | TCS-D3 |
Bithionol (BHL) | C12H6Cl4O2S | 8.09 | [M-H]- | 354.87442 | 354.87403 | 1.087 | TCS-D3 |
Tetrachlorobisphenol A (TCBPA) | C15H12Cl4O2 | 8.98 | [M-H]- | 364.94934 | 364.94891 | 1.168 | TBBPA-D10 |
Tetrabromobisphenol A (TBBPA) | C15H12Br4O2 | 9.57 | [M-H]- | 542.74640 | 542.74571 | 1.271 | TBBPA-D10 |
TBBPA-D10 | C15H2D10Br4O2 | 9.53 | [M-H]- | 552.80939 | 552.80848 | 1.650 | |
TCS-D3 | C12H4D3Cl3O2 | 9.69 | [M-H]- | 289.96280 | 289.96271 | 0.289 | |
TCC-D4 | C13H5D4Cl3N2O | 9.64 | [M-H]- | 316.99615 | 316.99587 | 0.863 | |
13C6-PCP | 13C6HCl5O | 5.79 | [M-H]- | 270.85703 | 270.85691 | 0.461 | |
BPA-D16 | C15D16O2 | 6.47 | [M-H]- | 241.19600 | 241.19562 | 1.544 |
Table 1 Compound information, retention times and MS parameters of the 12 halogenated organic pollutants (HOPs) and 5 isotope internal standards (ISs)
Compound | Formula | Retention time/min | Ion type | Measured accurate mass (m/z) | Theoretical exact mass (m/z) | Mass error/ 10-6 (ppm) | IS |
---|---|---|---|---|---|---|---|
Chloramphenicol (CPL) | C11H12Cl2N2O5 | 4.53 | [M-H]- | 321.00537 | 321.00505 | 0.996 | TBBPA-D10 |
Pentachlorophenol (PCP) | C6HCl5O | 5.78 | [M-H]- | 264.83704 | 264.83678 | 0.995 | TBBPA-D10 |
Forchlorfenuron (CPPU) | C12H10ClN3O | 6.34 | [M-H]- | 246.04419 | 246.04396 | 0.923 | TCS-D3 |
p-Choro-m-cresol (PCMC) | C7H7ClO | 6.65 | [M-H]- | 141.01137 | 141.01126 | 0.738 | TCS-D3 |
2-Iodophenol (IPL) | C6H4IOH | 6.63 | [M-H]- | 218.93132 | 218.93123 | 0.406 | TBBPA-D10 |
4-Chloro-3,5-dimethylphenol (PCMX) | C8H9OCl | 7.35 | [M-H]- | 155.02702 | 155.02691 | 0.671 | TBBPA-D10 |
Bromchlorophen (BCP) | C13H8Br2Cl2O2 | 7.77 | [M-H]- | 424.81787 | 424.81749 | 0.902 | TBBPA-D10 |
Clorofene (CLF) | C13H11ClO | 8.79 | [M-H]- | 217.04269 | 217.04256 | 0.571 | TCC-D4 |
Triclosan (TCS) | C12H7Cl3O2 | 9.72 | [M-H]- | 286.94427 | 286.94388 | 1.339 | TCS-D3 |
Bithionol (BHL) | C12H6Cl4O2S | 8.09 | [M-H]- | 354.87442 | 354.87403 | 1.087 | TCS-D3 |
Tetrachlorobisphenol A (TCBPA) | C15H12Cl4O2 | 8.98 | [M-H]- | 364.94934 | 364.94891 | 1.168 | TBBPA-D10 |
Tetrabromobisphenol A (TBBPA) | C15H12Br4O2 | 9.57 | [M-H]- | 542.74640 | 542.74571 | 1.271 | TBBPA-D10 |
TBBPA-D10 | C15H2D10Br4O2 | 9.53 | [M-H]- | 552.80939 | 552.80848 | 1.650 | |
TCS-D3 | C12H4D3Cl3O2 | 9.69 | [M-H]- | 289.96280 | 289.96271 | 0.289 | |
TCC-D4 | C13H5D4Cl3N2O | 9.64 | [M-H]- | 316.99615 | 316.99587 | 0.863 | |
13C6-PCP | 13C6HCl5O | 5.79 | [M-H]- | 270.85703 | 270.85691 | 0.461 | |
BPA-D16 | C15D16O2 | 6.47 | [M-H]- | 241.19600 | 241.19562 | 1.544 |
Compound | Linear range/(ng/mL) | Regression equation | Spiked level/(ng/g) | Recovery/% | RSD/% |
---|---|---|---|---|---|
CPL | 1.0-1000.0 | Y=0.457+0.079X | 400 | 91.8 | 0.6 |
40 | 128.3 | 2.1 | |||
4 | 82.0 | 3.7 | |||
PCP | 1.0-1000.0 | Y=0.038+0.051X | 400 | 80.5 | 0.9 |
40 | 116.2 | 1.9 | |||
4 | 96.1 | 2.8 | |||
CPPU | 1.0-1000.0 | Y=5.356+0.218X | 400 | 84.9 | 0.9 |
40 | 102.0 | 1.2 | |||
4 | 68.9 | 4.5 | |||
PCMC | 1.0-1000.0 | Y=-4.165+1.251X | 400 | 107.1 | 7.8 |
40 | 102.5 | 0.5 | |||
4 | 133.8 | 0.9 | |||
IPL | 1.0-1000.0 | Y=8.471+0.914X | 400 | 107.3 | 4.3 |
40 | 118.4 | 3.2 | |||
4 | 114.6 | 5.1 | |||
PCMX | 1.0-1000.0 | Y=-4.810+0.374X | 400 | 106.1 | 8.1 |
40 | 108.0 | 7.5 | |||
4 | 101.6 | 5.7 | |||
BCP | 1.0-1000.0 | Y=0.017+0.065X | 400 | 102.0 | 5.6 |
40 | 105.4 | 1.9 | |||
4 | 112.0 | 8.1 | |||
CLF | 1.0-1000.0 | Y=1.484+0.366X | 400 | 105.6 | 6.3 |
40 | 102.3 | 12.9 | |||
4 | 71.1 | 8.1 | |||
TCS | 1.0-1000.0 | Y=0.620+0.079X | 400 | 99.8 | 1.5 |
40 | 106.1 | 12.5 | |||
4 | 108.2 | 0.6 | |||
BHL | 1.0-1000.0 | Y=3.873+0.414X | 400 | 101.8 | 5.0 |
40 | 98.2 | 3.3 | |||
4 | 96.5 | 9.2 | |||
TCBPA | 1.0-1000.0 | Y=-2.501+0.209X | 400 | 99.8 | 5.6 |
40 | 105.5 | 7.2 | |||
4 | 67.6 | 3.7 | |||
TBBPA | 1.0-1000.0 | Y=-0.021+0.002X | 400 | 104.3 | 9.9 |
40 | 87.3 | 15.6 | |||
4 | 107.1 | 2.4 |
Table 2 Linear ranges, regression equations, spiked recoveries and precisions of the 12 HOPs (n=3)
Compound | Linear range/(ng/mL) | Regression equation | Spiked level/(ng/g) | Recovery/% | RSD/% |
---|---|---|---|---|---|
CPL | 1.0-1000.0 | Y=0.457+0.079X | 400 | 91.8 | 0.6 |
40 | 128.3 | 2.1 | |||
4 | 82.0 | 3.7 | |||
PCP | 1.0-1000.0 | Y=0.038+0.051X | 400 | 80.5 | 0.9 |
40 | 116.2 | 1.9 | |||
4 | 96.1 | 2.8 | |||
CPPU | 1.0-1000.0 | Y=5.356+0.218X | 400 | 84.9 | 0.9 |
40 | 102.0 | 1.2 | |||
4 | 68.9 | 4.5 | |||
PCMC | 1.0-1000.0 | Y=-4.165+1.251X | 400 | 107.1 | 7.8 |
40 | 102.5 | 0.5 | |||
4 | 133.8 | 0.9 | |||
IPL | 1.0-1000.0 | Y=8.471+0.914X | 400 | 107.3 | 4.3 |
40 | 118.4 | 3.2 | |||
4 | 114.6 | 5.1 | |||
PCMX | 1.0-1000.0 | Y=-4.810+0.374X | 400 | 106.1 | 8.1 |
40 | 108.0 | 7.5 | |||
4 | 101.6 | 5.7 | |||
BCP | 1.0-1000.0 | Y=0.017+0.065X | 400 | 102.0 | 5.6 |
40 | 105.4 | 1.9 | |||
4 | 112.0 | 8.1 | |||
CLF | 1.0-1000.0 | Y=1.484+0.366X | 400 | 105.6 | 6.3 |
40 | 102.3 | 12.9 | |||
4 | 71.1 | 8.1 | |||
TCS | 1.0-1000.0 | Y=0.620+0.079X | 400 | 99.8 | 1.5 |
40 | 106.1 | 12.5 | |||
4 | 108.2 | 0.6 | |||
BHL | 1.0-1000.0 | Y=3.873+0.414X | 400 | 101.8 | 5.0 |
40 | 98.2 | 3.3 | |||
4 | 96.5 | 9.2 | |||
TCBPA | 1.0-1000.0 | Y=-2.501+0.209X | 400 | 99.8 | 5.6 |
40 | 105.5 | 7.2 | |||
4 | 67.6 | 3.7 | |||
TBBPA | 1.0-1000.0 | Y=-0.021+0.002X | 400 | 104.3 | 9.9 |
40 | 87.3 | 15.6 | |||
4 | 107.1 | 2.4 |
Sample No. | CPL | PCP | CPPU | PCMC | IPL | PCMX | BCP | CLF | TCS | BHL | TCBPA | TBBPA |
---|---|---|---|---|---|---|---|---|---|---|---|---|
1 | <LOQ | ND | ND | ND | 0.50 | ND | ND | ND | ND | ND | ND | ND |
2 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
3 | ND | ND | ND | ND | 0.51 | ND | ND | ND | ND | ND | ND | ND |
4 | <LOQ | 3.58 | <LOQ | ND | 1.10 | <LOQ | ND | <LOQ | ND | ND | ND | ND |
5 | 1.22 | 4.52 | <LOQ | ND | 0.65 | <LOQ | ND | <LOQ | ND | ND | ND | ND |
6 | <LOQ | 3.15 | <LOQ | ND | 1.05 | <LOQ | ND | <LOQ | <LOQ | ND | ND | 1.54 |
7 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
8 | ND | ND | ND | ND | 0.51 | 0.87 | ND | ND | ND | ND | ND | 3.67 |
9 | ND | ND | ND | ND | <LOQ | <LOQ | ND | ND | ND | ND | ND | ND |
10 | ND | ND | <LOQ | ND | <LOQ | ND | ND | ND | <LOQ | ND | ND | ND |
11 | <LOQ | ND | <LOQ | ND | ND | ND | ND | <LOQ | <LOQ | ND | ND | 0.84 |
12 | ND | 1.76 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
13 | ND | ND | ND | ND | <LOQ | <LOQ | ND | ND | ND | ND | ND | ND |
14 | 0.59 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
15 | ND | 1.59 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
16 | <LOQ | 1.67 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
17 | <LOQ | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
18 | ND | 1.49 | ND | ND | <LOQ | ND | ND | ND | ND | ND | ND | <LOQ |
19 | <LOQ | 1.52 | <LOQ | ND | 0.51 | <LOQ | ND | <LOQ | <LOQ | ND | ND | ND |
20 | ND | ND | <LOQ | ND | <LOQ | <LOQ | ND | ND | ND | ND | ND | ND |
21 | 1.16 | 1.73 | ND | ND | ND | <LOQ | ND | ND | ND | ND | ND | ND |
22 | ND | ND | ND | ND | ND | <LOQ | ND | ND | ND | ND | ND | <LOQ |
23 | ND | 1.77 | ND | ND | ND | ND | ND | ND | ND | ND | ND | 0.74 |
24 | ND | ND | <LOQ | ND | <LOQ | ND | ND | ND | ND | ND | ND | ND |
25 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
26 | ND | ND | ND | ND | <LOQ | <LOQ | ND | ND | ND | ND | ND | ND |
27 | ND | ND | <LOQ | ND | ND | ND | ND | ND | ND | ND | ND | ND |
Table 3 Contents of the 12 HOPs in actual samples ng/g
Sample No. | CPL | PCP | CPPU | PCMC | IPL | PCMX | BCP | CLF | TCS | BHL | TCBPA | TBBPA |
---|---|---|---|---|---|---|---|---|---|---|---|---|
1 | <LOQ | ND | ND | ND | 0.50 | ND | ND | ND | ND | ND | ND | ND |
2 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
3 | ND | ND | ND | ND | 0.51 | ND | ND | ND | ND | ND | ND | ND |
4 | <LOQ | 3.58 | <LOQ | ND | 1.10 | <LOQ | ND | <LOQ | ND | ND | ND | ND |
5 | 1.22 | 4.52 | <LOQ | ND | 0.65 | <LOQ | ND | <LOQ | ND | ND | ND | ND |
6 | <LOQ | 3.15 | <LOQ | ND | 1.05 | <LOQ | ND | <LOQ | <LOQ | ND | ND | 1.54 |
7 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
8 | ND | ND | ND | ND | 0.51 | 0.87 | ND | ND | ND | ND | ND | 3.67 |
9 | ND | ND | ND | ND | <LOQ | <LOQ | ND | ND | ND | ND | ND | ND |
10 | ND | ND | <LOQ | ND | <LOQ | ND | ND | ND | <LOQ | ND | ND | ND |
11 | <LOQ | ND | <LOQ | ND | ND | ND | ND | <LOQ | <LOQ | ND | ND | 0.84 |
12 | ND | 1.76 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
13 | ND | ND | ND | ND | <LOQ | <LOQ | ND | ND | ND | ND | ND | ND |
14 | 0.59 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
15 | ND | 1.59 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
16 | <LOQ | 1.67 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
17 | <LOQ | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
18 | ND | 1.49 | ND | ND | <LOQ | ND | ND | ND | ND | ND | ND | <LOQ |
19 | <LOQ | 1.52 | <LOQ | ND | 0.51 | <LOQ | ND | <LOQ | <LOQ | ND | ND | ND |
20 | ND | ND | <LOQ | ND | <LOQ | <LOQ | ND | ND | ND | ND | ND | ND |
21 | 1.16 | 1.73 | ND | ND | ND | <LOQ | ND | ND | ND | ND | ND | ND |
22 | ND | ND | ND | ND | ND | <LOQ | ND | ND | ND | ND | ND | <LOQ |
23 | ND | 1.77 | ND | ND | ND | ND | ND | ND | ND | ND | ND | 0.74 |
24 | ND | ND | <LOQ | ND | <LOQ | ND | ND | ND | ND | ND | ND | ND |
25 | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND | ND |
26 | ND | ND | ND | ND | <LOQ | <LOQ | ND | ND | ND | ND | ND | ND |
27 | ND | ND | <LOQ | ND | ND | ND | ND | ND | ND | ND | ND | ND |
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Abstract 195
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