Method validation parameters: linearity, linear range, limits of detection (LODs), limits of quantification (LOQs), mean recoveries (%) and relative standard deviations (RSDs%, n = 5) of three different spiked levels (n = 5) studied for intra-day and inter-day, matrix effect (ME%) and process efficiency (PE%) for pharmaceutical residues in seawater
| Pharmaceuticals | Linearity (r2) | Linear range(ng L–1) | LOD(ng L–1) | LOQ(ng L–1) | 25 ng L–1 | 100 ng L–1 | 250 ng L–1 | 25 ng L–1 | 100 ng L–1 | 250 ng L–1 | ME% | PE% | ||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Rec (%) | RSDr% | Rec (%) | RSDr% | Rec (%) | RSDr% | Rec (%) | RSDR% | Rec(%) | RSDR% | Rec (%) | RSDR% | |||||||
| Antibiotics | ||||||||||||||||||
| Erythromycin-H2O | 0.9977 | 25–250 | 6.0 | 18.5 | 76.2 | 1.1 | 87.6 | 1.3 | 87.0 | 0.9 | 76.0 | 1.7 | 87.4 | 1.1 | 86.8 | 1.1 | 14.9 | 100.7 |
| N-Acetyl sulfamethoxazole | 0.9989 | 25–250 | 1.8 | 5.3 | 76.4 | 0.8 | 79.2 | 1.7 | 75.6 | 1.3 | 74.0 | 1.4 | 76.8 | 2.1 | 78.2 | 1.9 | 0.6 | 79.6 |
| Oxolinic acid | 0.9976 | 25–250 | 9.8 | 26.4 | 85.2 | 0.9 | 85.0 | 1.2 | 88.6 | 1.3 | 78.6 | 1.5 | 2.0 | 86.9 | ||||
| Oxytetracycline | 0.9996 | 12.5–125 | 5.0 | 16.7 | 81.4 | 1.2 | 90.0 | 0.8 | 86.2 | 1.3 | 77.4 | 1.6 | 86.0 | 1.3 | 82.2 | 1.5 | 9.2 | 98.3 |
| Sulfadiazine | 0.9995 | 25–250 | 2.5 | 8.5 | 86.6 | 1.1 | 89.0 | 1.2 | 76.6 | 1.1 | 82.4 | 1.2 | 94.8 | 2.4 | 82.4 | 1.2 | –18.8 | 72.2 |
| Sulfamethazine | 0.9996 | 25–250 | 2.1 | 6.0 | 81.4 | 1.1 | 88.8 | 1.3 | 86.0 | 1.4 | 78.2 | 2.3 | 85.4 | 2.5 | 82.6 | 1.4 | 5.7 | 93.9 |
| Sulfamethizole | 0.9994 | 25–250 | 2.5 | 6.6 | 61.6 | 1.3 | 65.0 | 1.7 | 62.4 | 1.3 | 62.0 | 1.8 | 65.4 | 2.0 | 62.8 | 2.2 | 5.6 | 68.6 |
| Sulfamethoxazole | 1.0000 | 25–250 | 1.1 | 3.0 | 92.0 | 1.7 | 98.6 | 1.9 | 92.6 | 1.8 | 98.2 | 1.9 | 95.0 | 2.9 | 90.8 | 1.8 | –1.8 | 96.8 |
| Sulfamethoxypyridazine | 0.9997 | 25–250 | 3.4 | 10.3 | 79.4 | 1.2 | 87.2 | 0.8 | 84.2 | 1.2 | 77.4 | 1.4 | 85.0 | 2.9 | 82.0 | 2.1 | 3.1 | 89.9 |
| Sulfapyridine | 0.9995 | 25–250 | 3.0 | 10.0 | 90.2 | 1.1 | 96.8 | 1.5 | 96.2 | 0.9 | 74.8 | 1.4 | 76.6 | 1.5 | 76.0 | 0.9 | 0.9 | 97.7 |
| Sulfaquinoxaline | 0.9907 | 25–250 | 3.3 | 10.0 | 71.2 | 1.0 | 75.8 | 1.7 | 76.2 | 1.1 | 70.4 | 1.3 | 70.0 | 2.4 | 70.4 | 2.4 | 6.0 | 80.3 |
| Sulfathiazole | 0.9970 | 25–250 | 3.0 | 9.3 | 86.8 | 1.1 | 86.6 | 1.5 | 87.0 | 1.5 | 88.4 | 1.2 | 88.2 | 1.9 | 88.6 | 1.7 | –3.1 | 84.5 |
| Trimethoprim | 0.9975 | 50–250 | 5.0 | 18.0 | 98.8 | 0.6 | 101.2 | 1.6 | 98.2 | 2.2 | 92.0 | 1.3 | 93.0 | 3.1 | 95.0 | 4.2 | –0.9 | 100.2 |
| Stimulant | ||||||||||||||||||
| Caffeine | 0.9998 | 50–250 | 3.3 | 10.6 | 85.2 | 1.0 | 105.6 | 0.5 | 110.8 | 0.7 | 95.0 | 1.1 | 115.4 | 1.3 | 118.8 | 1.0 | –0.2 | 105.4 |
| Analgesics | ||||||||||||||||||
| Paracetamol | 0.9962 | 25–250 | 3.6 | 9.8 | 93.4 | 1.3 | 110.2 | 1.0 | 116.2 | 0.5 | 81.8 | 1.4 | 98.6 | 1.5 | 104.6 | 1.1 | –15.8 | 92.8 |
| Phenazone | 0.9998 | 25–250 | 2.5 | 8.3 | 81.6 | 1.1 | 93.0 | 0.9 | 80.8 | 1.0 | 85.4 | 2.1 | 96.8 | 1.7 | 84.4 | 1.0 | –14.4 | 79.6 |
| Anticonvulsants | ||||||||||||||||||
| Carbamazepine | 1.0000 | 25–250 | 0.5 | 1.2 | 92.6 | 1.5 | 92.0 | 1.3 | 87.8 | 0.8 | 91.8 | 1.6 | 91.2 | 1.3 | 87.0 | 1.5 | –0.9 | 91.2 |
| Carbamazepine-10.11-epoxide (M) | 0.9949 | 12.5–125 | 1.5 | 4.5 | 80.0 | 1.6 | 83.2 | 3.9 | 84.0 | 1.2 | 77.4 | 1.3 | 80.4 | 2.2 | 83.2 | 4.8 | –8.3 | 76.3 |
| Antidepressants | ||||||||||||||||||
| Citalopram | 0.9998 | 25–250 | 0.7 | 2.1 | 62.6 | 1.8 | 81.6 | 1.0 | 96.0 | 1.0 | 62.0 | 1.6 | 88.6 | 1.5 | 82.8 | 1.6 | 18.1 | 96.4 |
| Fluoxetine | 0.9944 | 12.5–250 | 1.4 | 4.1 | 84.6 | 0.6 | 86.8 | 1.1 | 82.0 | 1.2 | 85.6 | 1.1 | 87.8 | 2.2 | 83.0 | 1.5 | 14.8 | 99.6 |
| N-Desmethyl sertraline (M) | 0.9942 | 50–500 | 3.1 | 8.5 | 62.0 | 1.8 | 65.4 | 2.6 | 68.8 | 0.9 | 61.8 | 3.2 | 64.0 | 2.6 | 64.4 | 1.8 | –0.9 | 67.8 |
| Norfluoxetine (M) | 0.9925 | 100–500 | 2.2 | 6.0 | 64.6 | 1.7 | 69.8 | 1.2 | 71.6 | 1.6 | 66.6 | 1.7 | 64.8 | 2.0 | 66.4 | 1.7 | –14.1 | 60.0 |
| O-Desmethyl venlafaxine | 0.9960 | 25–250 | 0.8 | 2.0 | 77.0 | 1.4 | 110.0 | 1.3 | 101.0 | 1.0 | 74.4 | 1.9 | 103.0 | 1.3 | 93.8 | 1.4 | 8.7 | 119.6 |
| Sertraline | 0.9987 | 2.5–500 | 1.3 | 4.2 | 85.6 | 1.4 | 86.4 | 1.8 | 87.8 | 1.7 | 82.1 | 1.1 | 85.0 | 2.3 | 87.8 | 1.7 | 0.7 | 82.7 |
| Venlafaxine | 0.9981 | 25–250 | 0.3 | 1.5 | 68.0 | 1.2 | 98.8 | 1.3 | 91.0 | 1.1 | 69.2 | 1.2 | 100.0 | 1.1 | 92.4 | 1.5 | 4.9 | 103.7 |
RSDr repeatability relative standard deviation; RSDR reproducibility relative standard deviation