Chinese Journal of Chromatography ›› 2025, Vol. 43 ›› Issue (8): 926-939.DOI: 10.3724/SP.J.1123.2024.10023
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CHEN Han1, LU Shuang1,*(
), YU Zixuan1, MA Yixuan1, WANG De2, SONG Zhihua1, LYU Min2,3, CHEN Lingxin2, DING Jing1
Received:2024-10-28
Online:2025-08-08
Published:2025-07-28
Contact:
LU Shuang
Supported by:CLC Number:
CHEN Han, LU Shuang, YU Zixuan, MA Yixuan, WANG De, SONG Zhihua, LYU Min, CHEN Lingxin, DING Jing. Distribution, multi-media partitioning behavior and ecological risks of pharmaceuticals and personal care products in offshore waters of Yantai and Weihai[J]. Chinese Journal of Chromatography, 2025, 43(8): 926-939.
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URL: https://www.chrom-china.com/EN/10.3724/SP.J.1123.2024.10023
| Type | Compound | Abbreviation | CAS No. | Molar mass/(g/mol) | Solubility[ |
|---|---|---|---|---|---|
| Non-steroid anti-inflammatory drug(NSAIDs) | ibuprofen | IBU | 15687-27-1 | 206.3 | 2.10×10 |
| paracetamol | PTL | 103-90-2 | 151.2 | 1.40×104 | |
| propyphenazone | PPZ | 479-92-5 | 230.3 | 2.40×103 | |
| ethenzamide | EZM | 938-73-8 | 165.2 | 1.41×104 | |
| phenazone | PHZ | 61-68-7 | 241.3 | 5.19×104 | |
| naproxene | NPX | 22204-53-1 | 230.3 | 1.59×10 | |
| indomethacine | IND | 53-86-1 | 357.8 | 9.37×10-1 | |
| fenoprofen calcium dihydrate | FPF | 53746-45-5 | 522.6 | 3.01×10 | |
| ketoprofen | KPF | 22071-15-4 | 254.3 | 5.10×10 | |
| Preservative | methyl paraben | MPB | 99-76-3 | 152.2 | 2.50×103 |
| ethyl paraben | EPB | 120-47-8 | 166.2 | 8.85×102 | |
| propyl paraben | PPB | 94-13-3 | 180.2 | 5.00×102 | |
| butyl paraben | BUT | 94-26-8 | 194.2 | 2.07×102 | |
| heptyl paraben | HPB | 1085-12-7 | 236.3 | 2.00×10 | |
| benzyl paraben | BPBen | 94-18-8 | 228.3 | 1.08×102 |
Table 1 List of the 15 target pharmaceuticals and personal care products(PPCPs) for this study
| Type | Compound | Abbreviation | CAS No. | Molar mass/(g/mol) | Solubility[ |
|---|---|---|---|---|---|
| Non-steroid anti-inflammatory drug(NSAIDs) | ibuprofen | IBU | 15687-27-1 | 206.3 | 2.10×10 |
| paracetamol | PTL | 103-90-2 | 151.2 | 1.40×104 | |
| propyphenazone | PPZ | 479-92-5 | 230.3 | 2.40×103 | |
| ethenzamide | EZM | 938-73-8 | 165.2 | 1.41×104 | |
| phenazone | PHZ | 61-68-7 | 241.3 | 5.19×104 | |
| naproxene | NPX | 22204-53-1 | 230.3 | 1.59×10 | |
| indomethacine | IND | 53-86-1 | 357.8 | 9.37×10-1 | |
| fenoprofen calcium dihydrate | FPF | 53746-45-5 | 522.6 | 3.01×10 | |
| ketoprofen | KPF | 22071-15-4 | 254.3 | 5.10×10 | |
| Preservative | methyl paraben | MPB | 99-76-3 | 152.2 | 2.50×103 |
| ethyl paraben | EPB | 120-47-8 | 166.2 | 8.85×102 | |
| propyl paraben | PPB | 94-13-3 | 180.2 | 5.00×102 | |
| butyl paraben | BUT | 94-26-8 | 194.2 | 2.07×102 | |
| heptyl paraben | HPB | 1085-12-7 | 236.3 | 2.00×10 | |
| benzyl paraben | BPBen | 94-18-8 | 228.3 | 1.08×102 |
| Compound | Parent ion(m/z) | Daughter ionsa (m/z) | DPs/V | EPs/V | CEs/eV | CXPs/V | Mode |
|---|---|---|---|---|---|---|---|
| IBU | 205.0 | 159.0/161.0 | -50 | -10 | -9/-12 | -2 | ESI- |
| PTL | 152.0 | 110.0 | 61 | 4.5 | 21 | 4 | ESI+ |
| PPZ | 231.0 | 56/189 | 86 | 11 | 49/38 | 4 | ESI+ |
| EZM | 166.0 | 121.0/149.0 | 31 | 9.0 | 25/15 | 4 | ESI+ |
| PHZ | 189.0 | 77.3/146.6 | 61 | 4.5 | 40/30 | 4 | ESI+ |
| NPX | 229.1 | 169.0/185.0 | -40/-30 | -7.5 | -41/-15 | -2 | ESI- |
| IND | 358.0 | 139.0/174.0 | 61 | 4.5 | 27/19 | 4 | ESI+ |
| FPF | 241.0 | 93.0/196.9 | -13/-15 | -3.0 | -47/-12 | -3/-7 | ESI- |
| KPF | 253.1 | 197.0/209.0 | -26 | -5/-8 | -10/-10 | -9 | ESI- |
| MPB | 150.9 | 91.3 | -49 | -10 | -28 | -10 | ESI- |
| EPB | 165.1 | 137.0/92.1 | -92/-94 | -10 | -18/-31 | -7 | ESI- |
| PPB | 178.9 | 136.0/91.8 | -102/-98 | -7.5 | -21/-30 | 0 | ESI- |
| BUT | 192.9 | 92.1/136.0 | -94 | -6.0 | -32/-23 | -6/-4 | ESI- |
| HPB | 235.0 | 137.0/92.1 | -109 | -10 | -25/-41 | -4 | ESI- |
| BPBen | 227.0 | 136.0/92.0 | -100/-97 | -2.0/-3.0 | -21/-31 | -4/-6 | ESI- |
| MBP-13C6 | 157.0 | 98.1 | -49 | -10 | -28 | -10 | ESI- |
Table 2 MS/MS parameters of the target PPCPs and internal standards
| Compound | Parent ion(m/z) | Daughter ionsa (m/z) | DPs/V | EPs/V | CEs/eV | CXPs/V | Mode |
|---|---|---|---|---|---|---|---|
| IBU | 205.0 | 159.0/161.0 | -50 | -10 | -9/-12 | -2 | ESI- |
| PTL | 152.0 | 110.0 | 61 | 4.5 | 21 | 4 | ESI+ |
| PPZ | 231.0 | 56/189 | 86 | 11 | 49/38 | 4 | ESI+ |
| EZM | 166.0 | 121.0/149.0 | 31 | 9.0 | 25/15 | 4 | ESI+ |
| PHZ | 189.0 | 77.3/146.6 | 61 | 4.5 | 40/30 | 4 | ESI+ |
| NPX | 229.1 | 169.0/185.0 | -40/-30 | -7.5 | -41/-15 | -2 | ESI- |
| IND | 358.0 | 139.0/174.0 | 61 | 4.5 | 27/19 | 4 | ESI+ |
| FPF | 241.0 | 93.0/196.9 | -13/-15 | -3.0 | -47/-12 | -3/-7 | ESI- |
| KPF | 253.1 | 197.0/209.0 | -26 | -5/-8 | -10/-10 | -9 | ESI- |
| MPB | 150.9 | 91.3 | -49 | -10 | -28 | -10 | ESI- |
| EPB | 165.1 | 137.0/92.1 | -92/-94 | -10 | -18/-31 | -7 | ESI- |
| PPB | 178.9 | 136.0/91.8 | -102/-98 | -7.5 | -21/-30 | 0 | ESI- |
| BUT | 192.9 | 92.1/136.0 | -94 | -6.0 | -32/-23 | -6/-4 | ESI- |
| HPB | 235.0 | 137.0/92.1 | -109 | -10 | -25/-41 | -4 | ESI- |
| BPBen | 227.0 | 136.0/92.0 | -100/-97 | -2.0/-3.0 | -21/-31 | -4/-6 | ESI- |
| MBP-13C6 | 157.0 | 98.1 | -49 | -10 | -28 | -10 | ESI- |
| Compound | Taxonomic group | Endpoint | Toxic data/(µg/L) | Toxicity | AF | PNEC/(ng/L) |
|---|---|---|---|---|---|---|
| BUT | algae | NOEC | 2.30×103 | chronic | 10 | 2.30×105 |
| BUT | crustaceans | NOEC | 7.06×102 | chronic | 10 | 7.06×104 |
| BUT | fish | LOEC | 8.76×102 | chronic | 10 | 8.76×104 |
| BPBen | algae | LOEC | 1.95×103 | chronic | 10 | 1.95×105 |
| BPBen | crustaceans | NOEC | 5.55×102 | chronic | 10 | 5.55×104 |
| BPBen | fish | NOEC | 6.50×102 | chronic | 10 | 6.50×104 |
| EZM | algae | LOEC | 8.23×104 | chronic | 10 | 8.23×106 |
| EZM | crustaceans | LOEC | 6.17×104 | chronic | 10 | 6.17×106 |
| EZM | fish | NOEC | 1.46×105 | chronic | 10 | 1.46×107 |
| EPB | algae | NOEC | 7.68×103 | chronic | 10 | 7.68×105 |
| EPB | crustaceans | LOEC | 3.27×103 | chronic | 10 | 3.27×105 |
| EPB | fish | LOEC | 5.13×103 | chronic | 10 | 5.13×105 |
| FPF | algae | NOEC | 1.57×104 | chronic | 10 | 1.57×106 |
| FPF | crustaceans | NOEC | 4.19×103 | chronic | 10 | 4.19×105 |
| FPF | fish | LOEC | 4.68×103 | chronic | 10 | 4.68×105 |
| HPB | algae | LOEC | 3.61×102 | chronic | 10 | 3.61×104 |
| HPB | crustaceans | LOEC | 6.80×101 | chronic | 10 | 6.80×103 |
| HPB | fish | LOEC | 5.90×101 | chronic | 10 | 5.90×103 |
| IBU | algae | LOEC | 1.56×104 | chronic | 10 | 1.56×106 |
| IBU | crustaceans | NOEC | 4.31×103 | chronic | 10 | 4.31×105 |
| IBU | fish | NOEC | 4.94×103 | chronic | 10 | 4.94×105 |
| IND | algae | NOEC | 1.48×104 | chronic | 10 | 1.48×106 |
| IND | crustaceans | NOEC | 3.54×103 | chronic | 10 | 3.54×105 |
| IND | fish | NOEC | 3.66×103 | chronic | 10 | 3.66×105 |
| KPF | algae | NOEC | 5.77×104 | chronic | 10 | 5.77×106 |
| KPF | crustaceans | LOEC | 2.07×104 | chronic | 10 | 2.07×106 |
| KPF | fish | LOEC | 2.88×104 | chronic | 10 | 2.88×106 |
| MPB | algae | LOEC | 1.39×104 | chronic | 10 | 1.39×106 |
| MPB | crustaceans | LOEC | 6.96×103 | chronic | 10 | 6.96×105 |
| MPB | fish | LOEC | 1.23×104 | chronic | 10 | 1.23×106 |
| NPX | algae | LOEC | 4.53×104 | chronic | 10 | 4.53×106 |
| NPX | crustaceans | NOEC | 8.20×104 | chronic | 10 | 8.20×106 |
| NPX | fish | NOEC | 2.13×104 | chronic | 10 | 2.13×106 |
| PPZ | algae | NOEC | 1.96×104 | chronic | 10 | 1.96×106 |
| PPZ | crustaceans | NOEC | 9.64×103 | chronic | 10 | 9.64×105 |
| PPZ | fish | LOEC | 1.68×104 | chronic | 10 | 1.68×106 |
| PHZ | algae | LOEC | 1.21×105 | chronic | 10 | 1.21×107 |
| PHZ | crustaceans | LOEC | 9.62×104 | chronic | 10 | 9.62×106 |
| PHZ | fish | NOEC | 2.38×105 | chronic | 10 | 2.38×107 |
| PPB | algae | NOEC | 4.21×103 | chronic | 10 | 4.21×105 |
| PPB | crustaceans | LOEC | 1.52×103 | chronic | 10 | 1.52×105 |
| PPB | fish | LOEC | 2.13×103 | chronic | 10 | 2.13×105 |
| PTL | algae | LOEC | 1.52×105 | chronic | 10 | 1.52×107 |
| PTL | crustaceans | NOEC | 1.35×105 | chronic | 10 | 1.35×107 |
| PTL | fish | NOEC | 3.61×105 | chronic | 10 | 3.61×107 |
Table 3 Chronic toxic data and predicted no-effect concentrations of the targeted PPCPs for aquatic organisms
| Compound | Taxonomic group | Endpoint | Toxic data/(µg/L) | Toxicity | AF | PNEC/(ng/L) |
|---|---|---|---|---|---|---|
| BUT | algae | NOEC | 2.30×103 | chronic | 10 | 2.30×105 |
| BUT | crustaceans | NOEC | 7.06×102 | chronic | 10 | 7.06×104 |
| BUT | fish | LOEC | 8.76×102 | chronic | 10 | 8.76×104 |
| BPBen | algae | LOEC | 1.95×103 | chronic | 10 | 1.95×105 |
| BPBen | crustaceans | NOEC | 5.55×102 | chronic | 10 | 5.55×104 |
| BPBen | fish | NOEC | 6.50×102 | chronic | 10 | 6.50×104 |
| EZM | algae | LOEC | 8.23×104 | chronic | 10 | 8.23×106 |
| EZM | crustaceans | LOEC | 6.17×104 | chronic | 10 | 6.17×106 |
| EZM | fish | NOEC | 1.46×105 | chronic | 10 | 1.46×107 |
| EPB | algae | NOEC | 7.68×103 | chronic | 10 | 7.68×105 |
| EPB | crustaceans | LOEC | 3.27×103 | chronic | 10 | 3.27×105 |
| EPB | fish | LOEC | 5.13×103 | chronic | 10 | 5.13×105 |
| FPF | algae | NOEC | 1.57×104 | chronic | 10 | 1.57×106 |
| FPF | crustaceans | NOEC | 4.19×103 | chronic | 10 | 4.19×105 |
| FPF | fish | LOEC | 4.68×103 | chronic | 10 | 4.68×105 |
| HPB | algae | LOEC | 3.61×102 | chronic | 10 | 3.61×104 |
| HPB | crustaceans | LOEC | 6.80×101 | chronic | 10 | 6.80×103 |
| HPB | fish | LOEC | 5.90×101 | chronic | 10 | 5.90×103 |
| IBU | algae | LOEC | 1.56×104 | chronic | 10 | 1.56×106 |
| IBU | crustaceans | NOEC | 4.31×103 | chronic | 10 | 4.31×105 |
| IBU | fish | NOEC | 4.94×103 | chronic | 10 | 4.94×105 |
| IND | algae | NOEC | 1.48×104 | chronic | 10 | 1.48×106 |
| IND | crustaceans | NOEC | 3.54×103 | chronic | 10 | 3.54×105 |
| IND | fish | NOEC | 3.66×103 | chronic | 10 | 3.66×105 |
| KPF | algae | NOEC | 5.77×104 | chronic | 10 | 5.77×106 |
| KPF | crustaceans | LOEC | 2.07×104 | chronic | 10 | 2.07×106 |
| KPF | fish | LOEC | 2.88×104 | chronic | 10 | 2.88×106 |
| MPB | algae | LOEC | 1.39×104 | chronic | 10 | 1.39×106 |
| MPB | crustaceans | LOEC | 6.96×103 | chronic | 10 | 6.96×105 |
| MPB | fish | LOEC | 1.23×104 | chronic | 10 | 1.23×106 |
| NPX | algae | LOEC | 4.53×104 | chronic | 10 | 4.53×106 |
| NPX | crustaceans | NOEC | 8.20×104 | chronic | 10 | 8.20×106 |
| NPX | fish | NOEC | 2.13×104 | chronic | 10 | 2.13×106 |
| PPZ | algae | NOEC | 1.96×104 | chronic | 10 | 1.96×106 |
| PPZ | crustaceans | NOEC | 9.64×103 | chronic | 10 | 9.64×105 |
| PPZ | fish | LOEC | 1.68×104 | chronic | 10 | 1.68×106 |
| PHZ | algae | LOEC | 1.21×105 | chronic | 10 | 1.21×107 |
| PHZ | crustaceans | LOEC | 9.62×104 | chronic | 10 | 9.62×106 |
| PHZ | fish | NOEC | 2.38×105 | chronic | 10 | 2.38×107 |
| PPB | algae | NOEC | 4.21×103 | chronic | 10 | 4.21×105 |
| PPB | crustaceans | LOEC | 1.52×103 | chronic | 10 | 1.52×105 |
| PPB | fish | LOEC | 2.13×103 | chronic | 10 | 2.13×105 |
| PTL | algae | LOEC | 1.52×105 | chronic | 10 | 1.52×107 |
| PTL | crustaceans | NOEC | 1.35×105 | chronic | 10 | 1.35×107 |
| PTL | fish | NOEC | 3.61×105 | chronic | 10 | 3.61×107 |
Fig. 2 (a) Detection frequencies of the target PPCPs in seawater and sediment,(b) mass concentrations of the target PPCPs in seawater,(c) relative abundances of the target PPCPs in seawater and sediment, and(d) contents of the target PPCPs in sediment
Fig. 7 (a) Total risk quotients of PPCP mixtures to different aquatic organisms(numbers above the boxes represent significant levels);(b) risk quotients and prioritization index of each PPCP(detection frequency>50%)
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