Validation results of the developed procedure for PBDEs’ (polybrominated diphenyl ethers) and nBFRs’ (novel brominated flame retardants sums in soil
| LOD (ng/g. d.m.) | 0.014 | 0.049 | 0.022 | 0.022 | 0.057 |
| LOQ (ng/g d.m.) | 0.045 | 0.162 | 0.072 | 0.072 | 0.192 |
| Level 1 | |||||
| Fortification (ng/g. d.m.) | 24 | 34 | 1.3 | 2.3 | 36 |
| Repeatability | |||||
| Trueness (%) | 9 | 7 | 5 | 6 | 7 |
| CV (%) | 6.2 | 5.4 | 1.2 | 5.0 | 5.1 |
| Reproducibility | |||||
| Trueness (%) | –1 | 1 | 3 | 2 | 1 |
| CV (%) | 0.7 | 0.9 | 3.6 | 7.9 | 5.1 |
| Uncertainty (%) | 27 | 23 | 12 | 21 | 23 |
| Level 2 | |||||
| Fortification (ng/g. d.m.) | 48 | 68 | 25 | 45 | 113 |
| Trueness (%) | 5 | 4 | –5 | 12 | 7 |
| CV (%) | 3.6 | 4.2 | 3.6 | 2.9 | 3.0 |
| Uncertainty (%) | 16 | 16 | 15 | 27 | 19 |
| Level 3 | |||||
| Fortification (ng/g. d.m.) | 1200 | 1700 | 625 | 1130 | 2830 |
| Trueness (%) | –13 | –12 | –9 | –15 | –13 |
| CV (%) | 0.9 | 2.0 | 4.5 | 8.8 | 2.6 |
| Uncertainty (%) | 26 | 26 | 23 | 40 | 28 |
| R2 | 0.99995 | 0.99996 | 1.00000 | 0.99986 | 0.99993 |
| β0 | 0.87 | 0.87 | 0.91 | 0.85 | 0.86 |
| β1 | 4.58 | 6.01 | 0.41 | 4.12 | 10.24 |
Validation results of the developed method for polybrominated diphenyl ether quantification in soil
| BDE-28 | BDE-47 | BDE-49 | BDE-99 | BDE-100 | BDE-138 | BDE-153 | BDE-154 | BDE-183 | BDE-209 | |
|---|---|---|---|---|---|---|---|---|---|---|
| LOD (ng/g d.m.) | 0.0005 | 0.005 | 0.003 | 0.002 | 0.001 | 0.0006 | 0.0006 | 0.002 | 0.003 | 0.05 |
| LOQ (ng/g d.m.) | 0.002 | 0.016 | 0.009 | 0.006 | 0.004 | 0.002 | 0.002 | 0.005 | 0.011 | 0.15 |
| Level 1 | ||||||||||
| Fortification (ng/g d.m.) | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 3.0 | 3.0 | 3.0 | 3.0 | 10.0 |
| Repeatability | ||||||||||
| Trueness (%) | 10 | 8 | 1 | 11 | 11 | 8 | 6 | 9 | 12 | 5 |
| CV (%) | 4.3 | 7.0 | 6.4 | 7.7 | 7.4 | 5.7 | 6.1 | 4.9 | 8.2 | 3.8 |
| Reproducibility | ||||||||||
| Trueness (%) | 6.0 | 3.6 | –2.2 | 4.4 | 5.1 | 4.3 | 2.4 | 4.5 | 5.9 | 4.9 |
| CV (%) | 5.1 | 6.5 | 5.7 | 8.7 | 8.1 | 5.7 | 5.9 | 5.6 | 8.6 | 3.1 |
| Uncertainty (%) | 64 | 25 | 21 | 27 | 28 | 26 | 25 | 22 | 59 | 32 |
| Level 2 | ||||||||||
| Fortification (ng/g d.m.) | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 6.0 | 6.0 | 6.0 | 6.0 | 20 |
| Trueness (%) | 5 | 4 | 2 | 6 | 7 | 6 | 3 | 6 | 9 | 2 |
| CV (%) | 4.1 | 5.5 | 8.8 | 4.5 | 4.0 | 2.1 | 2.8 | 1.6 | 6.0 | 6.8 |
| Uncertainty (%) | 64 | 23 | 29 | 22 | 24 | 15 | 21 | 19 | 57 | 34 |
| Level 3 | ||||||||||
| Fortification (ng/g d.m.) | 100 | 100 | 100 | 100 | 100 | 150 | 150 | 150 | 150 | 500 |
| Trueness (%) | –3 | –14 | –18 | –14 | –13 | –12 | –13 | –11 | –14 | –11 |
| CV (%) | 7.4 | 1.7 | 12.3 | 3.3 | 4.1 | 1.4 | 3.4 | 1.5 | 4.3 | 6.2 |
| Uncertainty (%) | 65 | 19 | 52 | 21 | 24 | 27 | 22 | 19 | 56 | 34 |
| Linearity | ||||||||||
| R2 | 1.0000 | 0.9994 | 0.9999 | 0.9999 | 0.9999 | 1.0000 | 1.0000 | 1.0000 | 0.9999 | 1.0000 |
| β1 | 0.965 | 0.868 | 0.814 | 0.852 | 0.861 | 0.875 | 0.865 | 0.883 | 0.852 | 0.884 |
| β0 | 0.196 | –0.352 | 0.402 | 0.443 | 0.443 | 0.565 | 0.515 | 0.548 | 0.730 | 1.429 |
List of novel brominated flame retardants (nBFRs) and polybrominated diphenyl ethers (PBDEs) determined in soil using the developed method
| Name | CAS No. | Structural formula | Acronym | m/z | |
|---|---|---|---|---|---|
| nBFR | 2,3,5,6-Tetrabromo-p-xylene | 23488-38-2 | TBX | 419.7182 | |
| 2,3,4,5,6-Pentabromotoluene | 87-83-2 | PBT | 491.6307 | ||
| 2,3,4,5,6-Pentabromoethylbenzene | 85-22-3 | PBEB | 485.6105 | ||
| Hexabromobenzene | 87-82-1 | HBB | 547.5074 | ||
| 2-Ethylhexyl 2,3,4,5-tetrabromobenzoate | 183658-27-7 | EH-TBB | 418.6735 | ||
| 1,2-Bis(2,4,6-tribromophenoxy)ethane | 37853-59-1 | BTBPE | 356.7948 | ||
| Bis(2-ethylhexyl) tetrabromophthalate | 26040-51-7 | BEH-TBPH | 462.6633 | ||
| 1,2-Bis(2,3,4,5,6-pentabromophenyl)ethane | 84852-53-9 | DBDPE | 484.6032 | ||
| 2,4,4′-2,4,4′-Tribromodiphenylether | 41318-75-6 | BDE-28 | 405.8027 | ||
| PBDE | 2,2′,4,4′-Tetrabromodiphenyl ether | 5436-43-1 | BDE-47 | 483.7132 | |
| 2,2′,4,5′-Tetrabromodiphenyl ether | 243982-82-3 | BDE-49 | 483.7132 | ||
| 2,2′,4,4′,5-Pentabromodiphenyl ether | 60348-60-9 | BDE-99 | 492.9691 | ||
| 2,2′,4,4′,6-Pentabromodiphenyl ether | 189084-64-8 | BDE-100 | 492.9691 | ||
| 2,2,3,4,4,5-Hexabromodiphenyl ether | 67888-98-6 | BDE-138 | 481.6980 | ||
| 2,2′,4,4′,5,5′-Hexabromodiphenyl ether | 68631-49-2 | BDE-153 | 481.6980 | ||
| 2,2′,4,4′,5,6′-Hexabromodiphenyl ether | 207122-15-4 | BDE-154 | 481.6980 | ||
| 2,2′,3,4,4′,5′,6-Heptabromodiphenyl ether | 207122-16-5 | BDE-183 | 561.6060 | ||
| Decabromodiphenyl ether | 1163-19-5 | BDE-209 | 799.3330 |
Validation results of the developed method for novel brominated flame retardant quantification in soil
| TBX | PBT | PBEB | HBB | EH-TBB | BTBPE | BEH-TBPH | DBDPE | |
|---|---|---|---|---|---|---|---|---|
| LOD (ng/g d.m.) | 0.0007 | 0.001 | 0.001 | 0.002 | 0.018 | 0.0014 | 0.005 | 0.005 |
| LOQ (ng/g d.m.) | 0.002 | 0.004 | 0.003 | 0.005 | 0.061 | 0.005 | 0.018 | 0.015 |
| Level 1 | ||||||||
| Fortification (ng/g d.m.) | 0.050 | 0.050 | 0.20 | 0.050 | 0.20 | 0.20 | 0.50 | 1.0 |
| Repeatability | ||||||||
| Trueness (%) | 14 | 0 | 1 | 12 | 2 | 1 | 7 | 7 |
| CV (%) | 7.5 | 9.5 | 7.1 | 8.8 | 6.4 | 3.5 | 6.2 | 11.7 |
| Reproducibility | ||||||||
| Trueness (%) | 6.4 | 7.3 | 8.2 | 10.1 | 4.9 | 4.3 | 8.5 | 16.0 |
| CV (%) | 17 | 2 | –5 | 18 | 1 | 3 | 3 | 0 |
| Uncertainty (%) | 18 | 30 | 23 | 39 | 22 | 13 | 27 | 40 |
| Level 2 | ||||||||
| Fortification (ng/g d.m.) | 1.00 | 1.00 | 4.0 | 1.0 | 4.0 | 4.0 | 10.0 | 20 |
| Trueness (%) | –4 | –11 | –7 | 3 | –10 | –5 | –2 | 33 |
| CV (%) | 2.9 | 4.6 | 4.6 | 6.4 | 3.7 | 2.8 | 5.2 | 2.8 |
| Uncertainty (%) | 14 | 28 | 22 | 22 | 25 | 15 | 18 | 68 |
| Level 3 | ||||||||
| Fortification (ng/g. d.m.) | 25 | 25 | 100 | 25 | 100 | 100 | 250 | 505 |
| Trueness (%) | –7 | –9 | –18 | –2 | 5 | –9 | –11 | –22 |
| CV (%) | 5.2 | 6.6 | 3.3 | 4.9 | 6.4 | 5.2 | 8.6 | 19.6 |
| Uncertainty (%) | 23 | 28 | 40 | 17 | 24 | 25 | 36 | 71 |
| Linearity | ||||||||
| R2 | 1.00000 | 1.00000 | 0.99997 | 1.00000 | 0.99997 | 1.00000 | 0.99998 | 0.99928 |
| β1 | 0.927 | 0.911 | 0.817 | 0.974 | 1.047 | 0.912 | 0.885 | 0.776 |
| β0 | 0.014 | –0.005 | 0.158 | 0.022 | –0.187 | 0.062 | 0.343 | 3.710 |