Table 1.
Identified TPHP metabolites in earthworms from LC-QTOF spectra after 28 days of TPHP exposure in soil.
| Type | Metabolites | Adducts | Formula | Theoretical m/z | Experimental m/z | Mass error (ppm) | Theoretical isotope ratio (%) | Experimental isotope ratio (%) | Retention time (min) | Characteristic product ions |
|---|---|---|---|---|---|---|---|---|---|---|
| phase I metabolites | DPHP | [M + H]+ | C12H12O4P1 | 251.0468 | 251.0458 | 3.7 | 13.6 | 13.5 | 10.52 | 152.0608, 175.0128, 215.0245, 233.0353 |
| OH-TPHP (3 isomers) | [M + H]+ | C18H16O5P1 | 343.0730 | 343.0726 | 1.2 | 20.4 | 19.5 | 12.27, 13.95, 16.72 | 152.0608, 215.0245, 233.0353, 357.0335 | |
| [M-H]− | C18H14O5P1 | 341.0584 | 341.0596 | 3.3 | 20.4 | 20.6 | 13.49, 16.71, 17.10 | 93.0345, 185.0614, 233.0383, 249.0347 | ||
| di-OH-TPHP (4 isomers) | [M + H]+ | C18H16O6P1 | 359.0679 | 359.0680 | 0.2 | 20.4 | 19.5 | 12.85, 13.07, 13.43, 16.22 | 153.0709, 215.0245, 233.0353, 251.0456 | |
| thiol conjugates | mercaptolactic acid-TPHP (3 isomers) | [M + H]+ | C21H20O7S1P1 | 447.0662 | 447.0656 | 1.3 | 24.6 | 22.6 | 13.14, 13.94, 16.24 | 152.0608, 215.0245, 233.0353, 357.0335 |
| [M + NH4]+ | C21H23O7N1S1P1 | 464.0927 | 464.0925 | 0.5 | 25.0 | 30.0 | 12.08, 13.91, 16.25 | 152.0608, 215.0245, 233.0353, 357.0335 | ||
| [M-H]− | C21H18O7S1P1 | 445.0516 | 445.0518 | 0.4 | 24.6 | 24.6 | 13.38,15.64 | 177.0355, 249.0347, 267.1975, 357.0363 | ||
| cysteine-TPHP (2 isomers) | [M + H]+ | C21H21O6N1S1P1 | 446.0822 | 446.0813 | 2.0 | 25.0 | 23.8 | 12.05, 13.15 | 152.0608, 215.0245, 233.0353, 357.0335 | |
| cysteinylglycine-TPHP (2 isomers) | [M + H]+ | C23H24O7N2S1P1 | 503.1036 | 503.1028 | 1.7 | 27.6 | 30.5 | 11.85, 12.80 | 152.0608, 215.0245, 233.0353, 357.0335 | |
| mercaptoethanol-TPHP (2 isomers) | [M + H]+ | C20H20O5S1P1 | 403.0764 | 403.0762 | 0.1 | 23.4 | 25.1 | 14.69, 17.45 | 152.0608, 215.0245, 233.0353, 357.0335 | |
| glutathione-TPHP | [M+H]+ | C28H31O10N3P1S1 | 632.1462 | 632.1444 | 2.9 | 33.7 | 30.5 | 13.06 | — | |
| glucoside conjugates | glucoside-TPHP | [M+NH4]+ | C24H29O10N1P1 | 522.1524 | 522.1511 | 2.4 | 27.8 | 24.4 | 13.55 | 343.0732 |
| [M+COOH]− | C25H26O12P1 | 549.1167 | 549.1186 | 3.4 | 28.5 | 27.6 | 13.57 | 233.0366, 249.0330, 341.0598, 503.1092 | ||
| phosphate-glucoside-TPHP | [M+H]+ | C24H27O13P2 | 585.0921 | 585.0911 | 1.8 | 27.5 | 23.7 | 13.11 | 343.0732 | |
| [M-H]− | C24H25O13P2 | 583.0776 | 583.0786 | 1.7 | 27.5 | 27.5 | 12.66 | 78.9586, 241.0018, 291.0917, 537.3042 | ||
| C14H19O10P-TPHP (3 isomers) | [M+H]+ | C32H33O14P2 | 703.1340 | 703.1327 | 1.9 | 36.5 | 34.8 | 15.67, 16.31 | 91.0534, 127.0385, 263.0913, 343.0732 | |
| [M-H]− | C32H31O14 P2 | 701.1195 | 701.1221 | 3.8 | 36.5 | 35.0 | 14.66, 15.16 | 78.9586, 223.0013, 359.0560, 583.0755 | ||
| [M+NH4]+ | C32H36O14N1P2 | 720.1606 | 720.1578 | 3.9 | 36.9 | 39.2 | 14.72, 14.95, 16.30 | 127.0385, 263.0913, 343.0732, 703.1316 | ||
| C14H19O10P-TPHP-OH (3 isomers) | [M+H]+ | C32H33O15P2 | 719.1289 | 719.1271 | 2.6 | 36.5 | 38.1 | 14.13, 14.72, 16.24 | 107.0478, 279.0848, 343.0732, 469.1023 | |
| [M-H]− | C32H31O15P2 | 717.1144 | 717.1175 | 4.3 | 36.5 | 37.0 | 13.46, 13.98, 15.13 | 78.9586, 359.0560 |
The structure of C14H19O10P could not be unambiguously identified by MS/MS spectra, and are tentatively proposed in Supplementary Fig. S2.