Chinese Journal of Chromatography ›› 2023, Vol. 41 ›› Issue (4): 312-322.DOI: 10.3724/SP.J.1123.2022.05032
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HAN Linxue, ZHANG Xu, HU Xiaojian, ZHANG Haijing, QIU Tian, LIN Xiao*(), ZHU Ying*()
Received:
2022-05-30
Online:
2023-04-08
Published:
2023-04-03
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CLC Number:
HAN Linxue, ZHANG Xu, HU Xiaojian, ZHANG Haijing, QIU Tian, LIN Xiao, ZHU Ying. Determination of 12 typical personal care products in human urine samples by ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2023, 41(4): 312-322.
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URL: https://www.chrom-china.com/EN/10.3724/SP.J.1123.2022.05032
Time/min | φ(Water)/% | φ(Acetonitrile)/% |
---|---|---|
0 | 80.0 | 20.0 |
2.00 | 80.0 | 20.0 |
16.00 | 20.0 | 80.0 |
16.30 | 20.0 | 80.0 |
Table 1 Gradient elution procedure
Time/min | φ(Water)/% | φ(Acetonitrile)/% |
---|---|---|
0 | 80.0 | 20.0 |
2.00 | 80.0 | 20.0 |
16.00 | 20.0 | 80.0 |
16.30 | 20.0 | 80.0 |
Type | Compound | Retention time/min | Parent ion (m/z) | Daughter ion (m/z) | Cone voltage/V | Collision energy/eV |
---|---|---|---|---|---|---|
Parabens | methyl paraben (MeP) | 4.44 | 151.02 | 91.95* | -8 | -20 |
135.97 | -8 | -14 | ||||
ethyl paraben (EtP) | 6.55 | 165.03 | 92.00* | -24 | -20 | |
137.00 | -24 | -20 | ||||
propyl paraben (PrP) | 8.36 | 179.07 | 92.07* | -16 | -20 | |
136.00 | -16 | -14 | ||||
butyl paraben (BuP) | 9.91 | 193.00 | 92.07* | -36 | -22 | |
136.32 | -36 | -16 | ||||
benzyl paraben (BzP) | 9.99 | 226.98 | 92.00* | -28 | -14 | |
136.06 | -28 | -24 | ||||
MeP-13C6 | 4.44 | 157.07 | 97.78 | -2 | -18 | |
EtP-13C6 | 6.54 | 171.10 | 98.03 | -8 | -20 | |
PrP-13C6 | 8.33 | 185.06 | 97.84 | -10 | -22 | |
BuP-13C6 | 9.90 | 199.08 | 97.90 | -16 | -22 | |
BzP-D7 | 9.94 | 234.13 | 91.77 | -8 | -26 | |
Benzophenones | benzophenone-1 (BP-1) | 9.14 | 212.97 | 135.04* | -16 | -24 |
91.03 | -16 | -20 | ||||
benzophenone-2 (BP-2) | 5.66 | 245.02 | 135.03* | -10 | -28 | |
91.03 | -10 | -16 | ||||
benzophenone-3 (BP-3) | 12.17 | 227.14 | 211.16* | -8 | -34 | |
167.02 | -8 | -16 | ||||
benzophenone-8 (BP-8) | 10.21 | 243.87 | 93.10* | -20 | -22 | |
123.51 | -20 | -16 | ||||
4-hydroxy benzophenone (4-OHBP) | 7.87 | 196.91 | 91.95* | -10 | -28 | |
120.07 | -10 | -24 | ||||
BP-1-D5 | 9.13 | 218.09 | 134.87 | -36 | -20 | |
BP-2-D4 | 5.64 | 249.08 | 136.82 | -4 | -16 | |
BP-3-13C12 | 12.15 | 233.10 | 217.20 | -44 | -16 | |
BP-8-D3 | 10.19 | 246.10 | 125.94 | -20 | -18 | |
4-OHBP-D4 | 7.86 | 200.95 | 95.82 | -6 | -30 | |
Antimicrobials | triclocarban (TCC) | 13.77 | 313.01 | 160.00* | -1 | -12 |
126.10 | -12 | -28 | ||||
triclosan (TCS) | 14.01 | 286.80 | 35.00* | -20 | -10 | |
289.00 | 35.00 | -20 | -12 | |||
TCC-D4 | 13.76 | 317.00 | 160.00 | -12 | -12 | |
TCS-13C12 | 13.99 | 299.00 | 34.90 | -20 | -5 |
Table 2 Mass spectrometric parameters of the 12 targeted compounds and their stable isotope internal standards
Type | Compound | Retention time/min | Parent ion (m/z) | Daughter ion (m/z) | Cone voltage/V | Collision energy/eV |
---|---|---|---|---|---|---|
Parabens | methyl paraben (MeP) | 4.44 | 151.02 | 91.95* | -8 | -20 |
135.97 | -8 | -14 | ||||
ethyl paraben (EtP) | 6.55 | 165.03 | 92.00* | -24 | -20 | |
137.00 | -24 | -20 | ||||
propyl paraben (PrP) | 8.36 | 179.07 | 92.07* | -16 | -20 | |
136.00 | -16 | -14 | ||||
butyl paraben (BuP) | 9.91 | 193.00 | 92.07* | -36 | -22 | |
136.32 | -36 | -16 | ||||
benzyl paraben (BzP) | 9.99 | 226.98 | 92.00* | -28 | -14 | |
136.06 | -28 | -24 | ||||
MeP-13C6 | 4.44 | 157.07 | 97.78 | -2 | -18 | |
EtP-13C6 | 6.54 | 171.10 | 98.03 | -8 | -20 | |
PrP-13C6 | 8.33 | 185.06 | 97.84 | -10 | -22 | |
BuP-13C6 | 9.90 | 199.08 | 97.90 | -16 | -22 | |
BzP-D7 | 9.94 | 234.13 | 91.77 | -8 | -26 | |
Benzophenones | benzophenone-1 (BP-1) | 9.14 | 212.97 | 135.04* | -16 | -24 |
91.03 | -16 | -20 | ||||
benzophenone-2 (BP-2) | 5.66 | 245.02 | 135.03* | -10 | -28 | |
91.03 | -10 | -16 | ||||
benzophenone-3 (BP-3) | 12.17 | 227.14 | 211.16* | -8 | -34 | |
167.02 | -8 | -16 | ||||
benzophenone-8 (BP-8) | 10.21 | 243.87 | 93.10* | -20 | -22 | |
123.51 | -20 | -16 | ||||
4-hydroxy benzophenone (4-OHBP) | 7.87 | 196.91 | 91.95* | -10 | -28 | |
120.07 | -10 | -24 | ||||
BP-1-D5 | 9.13 | 218.09 | 134.87 | -36 | -20 | |
BP-2-D4 | 5.64 | 249.08 | 136.82 | -4 | -16 | |
BP-3-13C12 | 12.15 | 233.10 | 217.20 | -44 | -16 | |
BP-8-D3 | 10.19 | 246.10 | 125.94 | -20 | -18 | |
4-OHBP-D4 | 7.86 | 200.95 | 95.82 | -6 | -30 | |
Antimicrobials | triclocarban (TCC) | 13.77 | 313.01 | 160.00* | -1 | -12 |
126.10 | -12 | -28 | ||||
triclosan (TCS) | 14.01 | 286.80 | 35.00* | -20 | -10 | |
289.00 | 35.00 | -20 | -12 | |||
TCC-D4 | 13.76 | 317.00 | 160.00 | -12 | -12 | |
TCS-13C12 | 13.99 | 299.00 | 34.90 | -20 | -5 |
Fig. 2 Ratios of experimental results to reference values for the six personal care products (PCPs) in NIST SRM 3672 at different (a) enzymatic activities and (b) enzymatic times
Compound | Pipette tips | Solvents | Centrifuge tubeb | |||||
---|---|---|---|---|---|---|---|---|
1000 μLa | 200 μLa | Dispenser tipb | MeOHc | NH4AC bufferc | Enzymed | |||
MeP | / | 1.69 | 2.02 | / | / | 2.83 | / | |
EtP | 1.56 | 2.61 | 3.07 | / | / | 1.04 | 0.91 | |
PrP | 0.55 | 1.19 | 1.28 | / | / | 0.57 | / | |
BP-3 | 1.36 | 3.11 | 2.83 | 0.34 | 0.51 | 1.42 | 0.80 |
Table 3 PCPs blank concentration resultsμg/L
Compound | Pipette tips | Solvents | Centrifuge tubeb | |||||
---|---|---|---|---|---|---|---|---|
1000 μLa | 200 μLa | Dispenser tipb | MeOHc | NH4AC bufferc | Enzymed | |||
MeP | / | 1.69 | 2.02 | / | / | 2.83 | / | |
EtP | 1.56 | 2.61 | 3.07 | / | / | 1.04 | 0.91 | |
PrP | 0.55 | 1.19 | 1.28 | / | / | 0.57 | / | |
BP-3 | 1.36 | 3.11 | 2.83 | 0.34 | 0.51 | 1.42 | 0.80 |
Compound | Linear range/ (μg/L) | r | MDL/ (μg/L) | MQL/ (μg/L) |
---|---|---|---|---|
MeP | 4.00-800 | 0.9995 | 0.94 | 1.15 |
EtP | 1.00-200 | 0.9998 | 0.51 | 0.60 |
PrP | 1.00-200 | 0.9996 | 0.43 | 0.76 |
BuP | 1.00-200 | 0.9998 | 0.22 | 0.24 |
BzP | 1.00-200 | 0.9998 | 0.19 | 0.20 |
BP-1 | 1.00-200 | 0.9994 | 0.06 | 0.08 |
BP-2 | 1.00-200 | 0.9994 | 0.12 | 0.12 |
BP-3 | 4.00-800 | 0.9998 | 0.49 | 0.70 |
BP-8 | 1.00-200 | 0.9997 | 0.36 | 0.39 |
4-OHBP | 1.00-200 | 0.9994 | 0.13 | 0.21 |
TCC | 1.00-200 | 0.9992 | 0.32 | 0.75 |
TCS | 5.00-200 | 0.9992 | 1.09 | 3.63 |
Table 4 Linear ranges, correlation coefficients (r), MDLs and MQLs of the 12 targeted compounds
Compound | Linear range/ (μg/L) | r | MDL/ (μg/L) | MQL/ (μg/L) |
---|---|---|---|---|
MeP | 4.00-800 | 0.9995 | 0.94 | 1.15 |
EtP | 1.00-200 | 0.9998 | 0.51 | 0.60 |
PrP | 1.00-200 | 0.9996 | 0.43 | 0.76 |
BuP | 1.00-200 | 0.9998 | 0.22 | 0.24 |
BzP | 1.00-200 | 0.9998 | 0.19 | 0.20 |
BP-1 | 1.00-200 | 0.9994 | 0.06 | 0.08 |
BP-2 | 1.00-200 | 0.9994 | 0.12 | 0.12 |
BP-3 | 4.00-800 | 0.9998 | 0.49 | 0.70 |
BP-8 | 1.00-200 | 0.9997 | 0.36 | 0.39 |
4-OHBP | 1.00-200 | 0.9994 | 0.13 | 0.21 |
TCC | 1.00-200 | 0.9992 | 0.32 | 0.75 |
TCS | 5.00-200 | 0.9992 | 1.09 | 3.63 |
Compound | Low | Medium | High | Inter-day RSD/% | Intra-day RSD/% | |||||
---|---|---|---|---|---|---|---|---|---|---|
Recovery/% | RSD/% | Recovery/% | RSD/% | Recovery/% | RSD/% | |||||
MeP | 93.2 | 2.2 | 100.7 | 2.1 | 107.3 | 3.4 | 4.9 | 2.0 | ||
EtP | 95.4 | 4.4 | 97.8 | 2.3 | 104.4 | 1.5 | 3.7 | 2.7 | ||
PrP | 97.1 | 1.3 | 97.1 | 1.3 | 103.5 | 4.6 | 4.4 | 4.0 | ||
BuP | 94.7 | 4.2 | 100.3 | 2.0 | 101.8 | 2.9 | 3.8 | 3.5 | ||
BzP | 103.5 | 2.9 | 104.9 | 2.3 | 108.0 | 3.7 | 4.2 | 3.9 | ||
BP-1 | 89.5 | 4.1 | 99.5 | 1.1 | 101.4 | 1.2 | 4.2 | 3.3 | ||
BP-2 | 99.7 | 2.3 | 105.3 | 3.9 | 97.1 | 1.5 | 3.9 | 5.2 | ||
BP-3 | 89.8 | 2.6 | 91.0 | 2.4 | 99.0 | 1.2 | 7.1 | 2.1 | ||
BP-8 | 105.0 | 8.5 | 101.4 | 2.8 | 103.9 | 4.5 | 7.1 | 4.9 | ||
4-OHBP | 100.2 | 3.0 | 102.8 | 3.0 | 106.3 | 3.2 | 3.7 | 5.1 | ||
TCC | 94.8 | 7.4 | 99.9 | 3.2 | 100.7 | 2.1 | 4.3 | 5.5 | ||
TCS | 111.8 | 7.1 | 95.1 | 12.8 | 98.0 | 7.1 | 8.9 | 10.6 |
Table 5 Spiked recoveries, relative standard deviations (RSDs) of inter-day and intra-day for the 12 targeted compounds (n=6)
Compound | Low | Medium | High | Inter-day RSD/% | Intra-day RSD/% | |||||
---|---|---|---|---|---|---|---|---|---|---|
Recovery/% | RSD/% | Recovery/% | RSD/% | Recovery/% | RSD/% | |||||
MeP | 93.2 | 2.2 | 100.7 | 2.1 | 107.3 | 3.4 | 4.9 | 2.0 | ||
EtP | 95.4 | 4.4 | 97.8 | 2.3 | 104.4 | 1.5 | 3.7 | 2.7 | ||
PrP | 97.1 | 1.3 | 97.1 | 1.3 | 103.5 | 4.6 | 4.4 | 4.0 | ||
BuP | 94.7 | 4.2 | 100.3 | 2.0 | 101.8 | 2.9 | 3.8 | 3.5 | ||
BzP | 103.5 | 2.9 | 104.9 | 2.3 | 108.0 | 3.7 | 4.2 | 3.9 | ||
BP-1 | 89.5 | 4.1 | 99.5 | 1.1 | 101.4 | 1.2 | 4.2 | 3.3 | ||
BP-2 | 99.7 | 2.3 | 105.3 | 3.9 | 97.1 | 1.5 | 3.9 | 5.2 | ||
BP-3 | 89.8 | 2.6 | 91.0 | 2.4 | 99.0 | 1.2 | 7.1 | 2.1 | ||
BP-8 | 105.0 | 8.5 | 101.4 | 2.8 | 103.9 | 4.5 | 7.1 | 4.9 | ||
4-OHBP | 100.2 | 3.0 | 102.8 | 3.0 | 106.3 | 3.2 | 3.7 | 5.1 | ||
TCC | 94.8 | 7.4 | 99.9 | 3.2 | 100.7 | 2.1 | 4.3 | 5.5 | ||
TCS | 111.8 | 7.1 | 95.1 | 12.8 | 98.0 | 7.1 | 8.9 | 10.6 |
Compound | Reference value/(μg/kg) | Experimental result/(μg/kg) | RSD/% | |
---|---|---|---|---|
MeP | 113± | 2 | 102-110 | 3.1 |
EtP | 8.1± | 0.2 | 7.90-8.27 | 1.8 |
PrP | 17.6± | 0.3 | 16.6-17.7 | 2.3 |
BuP | 11.1± | 0.2 | 10.7-11.1 | 1.2 |
BP-3 | 191± | 5 | 191-209 | 3.5 |
TCS | 17.7± | 0.5 | 15.1-16.9 | 4.0 |
Table 6 Comparison of experimental results and reference values of NIST SRM 3672 (n=7)
Compound | Reference value/(μg/kg) | Experimental result/(μg/kg) | RSD/% | |
---|---|---|---|---|
MeP | 113± | 2 | 102-110 | 3.1 |
EtP | 8.1± | 0.2 | 7.90-8.27 | 1.8 |
PrP | 17.6± | 0.3 | 16.6-17.7 | 2.3 |
BuP | 11.1± | 0.2 | 10.7-11.1 | 1.2 |
BP-3 | 191± | 5 | 191-209 | 3.5 |
TCS | 17.7± | 0.5 | 15.1-16.9 | 4.0 |
Compound | DF/% | Contents/(μg/L) | ||||
---|---|---|---|---|---|---|
P5 | P25 | P50 | P75 | P95 | ||
MeP | 99.7 | 2.10 | 5.72 | 13.3 | 51.5 | 347 |
EtP | 66.1 | ND | ND | 1.04 | 5.37 | 80.3 |
PrP | 58.2 | ND | ND | 0.83 | 18.0 | 125 |
BuP | 7.9 | ND | ND | ND | ND | 0.61 |
BzP | 0.0 | ND | ND | ND | ND | ND |
BP-1 | 39.7 | ND | ND | ND | 0.18 | 4.60 |
BP-2 | 1.7 | ND | ND | ND | ND | ND |
BP-3 | 35.3 | ND | ND | ND | 0.71 | 18.1 |
BP-8 | 0.0 | ND | ND | ND | ND | ND |
4-OHBP | 4.4 | ND | ND | ND | ND | ND |
TCC | 5.1 | ND | ND | ND | ND | 0.54 |
TCS | 13.7 | ND | ND | ND | ND | 15.6 |
Table 7 Determination concentrations of the 12 typical PCPs in human urine
Compound | DF/% | Contents/(μg/L) | ||||
---|---|---|---|---|---|---|
P5 | P25 | P50 | P75 | P95 | ||
MeP | 99.7 | 2.10 | 5.72 | 13.3 | 51.5 | 347 |
EtP | 66.1 | ND | ND | 1.04 | 5.37 | 80.3 |
PrP | 58.2 | ND | ND | 0.83 | 18.0 | 125 |
BuP | 7.9 | ND | ND | ND | ND | 0.61 |
BzP | 0.0 | ND | ND | ND | ND | ND |
BP-1 | 39.7 | ND | ND | ND | 0.18 | 4.60 |
BP-2 | 1.7 | ND | ND | ND | ND | ND |
BP-3 | 35.3 | ND | ND | ND | 0.71 | 18.1 |
BP-8 | 0.0 | ND | ND | ND | ND | ND |
4-OHBP | 4.4 | ND | ND | ND | ND | ND |
TCC | 5.1 | ND | ND | ND | ND | 0.54 |
TCS | 13.7 | ND | ND | ND | ND | 15.6 |
No. | Target compounds | Urine sample/mL | Extraction method | Instrumental analysis method | MDL/ (μg/L) | Ref. | |||
---|---|---|---|---|---|---|---|---|---|
Paraben | Benzophenone | Antiseptic | n | ||||||
1 | √ | √ | / | 12 | 3.0 | SPE | UPLC-MS/MS | ≤1.23 | [ |
2 | √ | / | √ | 8 | 4.0 | SPE | LC-MS/MS | ≤0.05 | [ |
3 | √ | / | √ | 13 | 1.0 | SPE | HPLC-MS/MS | ≤1.0 | [ |
4 | √ | √ | √ | 8 | 0.1 | On-line SPE | HPLC-MS/MS | ≤2.0 | [ |
5 | √ | √ | √ | 12 | 1.0 | SPE | UPLC-MS/MS | ≤1.0 | this study |
Table 8 Comparison of the developed method with other reported methods for the determination of PCPs in human urine
No. | Target compounds | Urine sample/mL | Extraction method | Instrumental analysis method | MDL/ (μg/L) | Ref. | |||
---|---|---|---|---|---|---|---|---|---|
Paraben | Benzophenone | Antiseptic | n | ||||||
1 | √ | √ | / | 12 | 3.0 | SPE | UPLC-MS/MS | ≤1.23 | [ |
2 | √ | / | √ | 8 | 4.0 | SPE | LC-MS/MS | ≤0.05 | [ |
3 | √ | / | √ | 13 | 1.0 | SPE | HPLC-MS/MS | ≤1.0 | [ |
4 | √ | √ | √ | 8 | 0.1 | On-line SPE | HPLC-MS/MS | ≤2.0 | [ |
5 | √ | √ | √ | 12 | 1.0 | SPE | UPLC-MS/MS | ≤1.0 | this study |
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