Table 3.
Analytical methods applied for the determination of the most commonly detected PPCPs in water samples (2010–present).
| Analyte | Matrix | Extraction Method | Analytical Technique | Analytical Conditions | Analysis Time (min) | Analytical Parameters | Ref. |
|---|---|---|---|---|---|---|---|
| Ofloxacin and ciprofloxacin | WWTP influent | SPE Oasis HLB | LC-ESI-MS/MS | C18 column (125 mm× 2.0 mm, particle size 5 μm) MP: acetonitrile (A) and HPLC grade water with 0.1% formic acid (B) Flow rate= 0.2 mL/min |
45 min | Recovery = 93–107% LOD = 1–3 ng/L |
[31] |
| Ibuprofen, carbamazepine, and triclosan | WWTP effluent | SPE Oasis HLB | LC-ESI-MS/MS | C18 Column (100 mm× 2.1 mm, particle size 3 μm). MP: acetonitrile/methanol (A) and HPLC grade water with 0.1% formic acid (B), Flow rate = 0.25 mL/min |
35 min | Recovery = >80% LOQ = 1–2 ng/L |
[79] |
| Amoxicillin | STP | SPE Oasis HLB | HPLC-PDA | λ: 228 nm C18 Column (250 mm × 4.6 mm, 5 μm) MP: isocratic program of 0.45% Na2HPO4 in water (A) and Methanol (B) in the fixed ratio of 2:1 Flow rate = 1.5 mL/min |
4.9 min | Recovery = 64–88% LOD = 1 ng/L LOQ =10 ng/L R2 = 0.998 |
[33] |
| Ampicillin, ciprofloxacin, gatifloxacin, sparfloxacin and cefuroxime | STP | SPE Oasis HLB | HPLC-PDA | λ: 215 and 280 nm C18 Column (250 mm × 4.6 mm, 5 μm) MP: 0.1% aqueous TFA (A) and acetonitrile (B) Flow rate = 1.0 mL/min |
30 min | Recovery = 25–108% LOD = 10 ng/L LOQ =30 ng/L R2 = 0.9806–0.9957 |
[80] |
| Sulfapyridine, sulfadiazine, sulfamethoxazole, sulfamethazine, and three sulfonamide acetylated metabolites | WWTP (effluent and influent) | SPE Oasis HLB | LC-ESI-MS/MS | C18 column (100 mm × 2.1 mm, particle size 2.6 μm) MP: methanol (A) and distilled water (B) Flow rate = 0.3 mL/min |
6 min | Recovery = 77.7–148.1% LOD = 0.01–0.23 ng/L LOQ = 0.03–0.78 ng/L R2 = 0.995–0.999 |
[35] |
| Sulfathiazole, sulfamethazine, sulfamethoxazole, oxytetracycline, and chlortetracycline | WWTP effluent | SPE Oasis HLB and MCX | LC-ESI-IT–TOF/MS | C18 column (75 mm× 3.0 mm, particle size 3.0 μm). MP: 0.3% formic acid and 0.1% ammonium acetate in water (A) and methanol and Acetonitrile (1:1) (B). |
6 min | Recovery = 63–118% LOD = 9.8–25.8 ng/L R2 = 0.9964–0.9996 |
[81] |
| Estrone, 17β-Estradiol, estriol, 2-Hydroxyestrone, 16α-Hydroxyestrone, 4-Hydroxyestrone, 2-Hydroxyestradiol, 4- Hydroxyestradiol, 17-Epiestriol, 16keto-estradiol, and 16-Epiestriol |
WWTP (effluent and influent) and river water |
SPE Oasis HLB Derivatization |
GC-MS | HP-5 MS capillary column (30 m × 0.25 mm × 0.25 μm) Flow rate = 0.85 mL/min Temperature program: start with 100 °C, rising at 10 °C/min to 200 °C, then 8 °C/min to 260 °C, then 3 °C/min to 310 °C, and finally held at 310 °C for 2 min |
37 min | LOD =1.4–6.0 ng/L LOQ =4.8–19.8 ng/L R2 = 0.9838–0.9995 |
[38] |
| Atenolol, bisoprolol, ciprofloxacin, ofloxacin, sulfamethoxazole, clarithromycin, trimethoprim, ketoprofen, diphenhydramine HCl, ranitidine, and carbamazepine | WWTP (effluent and influent) | SPE Oasis HLB | LC-ESI-MS/MS | C18 column (30 mm × 2.1 mm, particle size 1.9 μm) MP: 0.1% formic acid in water (A) and ethanol (B) Flow rate = 0.5 mL/min |
7.2 min | Recovery = 70.4–112.2% LOD = 0.06–16.0 ng/L LOQ = 0.20–52.8 ng/L R2 = 0.9921–0.9992 |
[39] |
| Sulfapyridine, sulfamethazine, sulfamethoxazole and sulfaphenazole | Surface water | Deep eutectic solvent (DES) and liquid–liquid microextraction | UHPLC-PDA | λ: 270 nm. C18 column (30 mm × 2.1 mm, particle size 1.7 μm) MP: 0.1% formic acid in water (A) and 90% acetonitrile in ethanol (B) Flow rate = 1 mL/min |
3.5 min | Recovery = 78.2–105.2% LOD = 0.78–3.42 ng/L LOQ = 2.38–10.37 ng/L R2 = 0.9991–0.9997 |
[77] |
| Lincomycin, ibuprofen, paraxanthin, and naproxen | Lake | SPE Oasis HLB | LC-ESI-MS/MS | C18 column (150 mm × 2.1 mm, particle size 3.5 μm) MP: ammonium formate/formic acid buffer (A) and acetonitrile (B) Flow rate = 0.2 mL/min |
50 min | Recovery = 78–118% LOD = 1.7–25 ng/L LOQ = 2.5–25 ng/L R2 ≥ 0.99 |
[82] |
| Acetaminophen, caffeine, carbamazepine, ibuprofen, ketoprofen, fenoprofen, naproxen, propyphenazone, clofibric acid, gemfibrozil, diclofenac, indomethacin, salicylic acid, crotamiton, and trimethoprim | Raw wastewater, surface water and groundwater samples | SPE Oasis HLB | LC-ESI-MS/MS | C18 column (150 mm × 2.1 mm, particle size 3.5 μm). MP: ammonium acetate in water (A) and ammonium acetate in methanol (B) Flow rate = 0.25 mL/min |
18 min | Recovery = 66.5–102% LOD = 0.1–5 ng/L LOQ = 0.3–10 ng/L R2 ≥ 0.996 |
[83] |
| Estrone, 17 α-estradiol, estriol, progesterone, pquiline, diethylstilbestrol, and ethinylestradiol | Sea water, mineral water, and tap water | Air-agitated liquid–liquid microextraction method based on solidification of a floating organic droplet (AALLME-SFO) | LC-ESI-MS/MS | C18 column (50 mm × 2.1 mm, particle size 1.7 μm) MP: 0.1% formic acid in water (A) and ethanol (B) Flow rate = 0.4 mL/min Flow rate = 0.05 mL/min |
6.7 min | Recovery = 90.14–99.60% LOD = 0.021–0.034 ng/L LOQ = 0.046–0.103 ng/L R2 = 0.9990–0.9998 |
[84] |
| Atrazine, bisphenol-A, caffeine, carbamazepine, gemfibrozil, ibuprofen, naproxen, simazine, sulfamethoxazole, and trimethoprim | Raw and treated water | SPE Oasis HLB | LC-MS/MS | N.R. | N.R. | Recovery = 70–128% LOD = 1–2.5 ng/L |
[85] |
| Sulfadiazine, sulfapyridine, sulfathiazole, trimethoprim, sulfamerazine, sulfamethazine, sulfamethoxazole, naproxen, paracetamol, diclofenac acid, ibuprofen, ketoprofen, flumequine, ciprofloxacin, norfloxacin, ofloxacin, macrolides, clarithromycin, roxithromycin, erythromycin, tetracyclines, oxytetracycline, isochlortetracycline, tetracycline, cephalexin monohydrate, cefotaxime sodium, penicillin G, amphenicols, chloramphenicol, thiamphenicol, triclocarban, triclosan, carbamazepine, aminoglycoside, spectinomycin, antihyperlipidemic, gemfibrozil, diltiazem, diphenhydramine, and bisphenol A. | Lake | SPE Oasis HLB | LC-ESI-MS/MS | C18 column (50 mm × 2.1 mm, particle size 1.8 μm). MP: Water (A) and Acetonitril (B) fro −ESI and 0.1% formic acid in water (A) and acetonitrile (B) for +ESI. Flow rate = 0.25 mL/min |
N.R. | Recovery = 70–125% LOD = 0.01–1.1 ng/L LOQ = 0.03–3.3 ng/L R2 = 0.9937–0.9999 |
[86] |
| Ibuprofen, diclofenac, fexofenadine, atorvastatin, irbesartan, triclosan, sulfasalazine, benzophenone 1, 2, and 4, methylparaben, diazepam, and oxazepam | WWTP (effluent and influent) and surface water |
SPE Oasis HLB | LC-ESI-MS/MS | Separation of acidic analytes: C18 column (150 mm × 1.0 mm, particle size 1.7 μm). MP: (80:20) Water:Methanol conatin 1 mM Ammonium fluoride (A) and (5:95) Water:Methanol conatin 1 mM Ammonium fluoride (B) Flow rate = 0.04 mL/min Separation of basicanalytes: CHIRALPAK CBH HPLC column. MP: 1 mM ammonium acetate/methanol 85:15 (v/v) (Isocratic). Flow rate = 0.1 mL/min |
N.R. | Recovery = 44.6–120% LOQ = 0.31–41.43 ng/L |
[87] |
| Azithromycin, clarithromycin, metronidazole, ciprofloxacin, norfloxacin, vancomycin, and sulfamethoxazole | WWTP (effluent and influent) and surface water |
SPE Oasis HLB | LC-coupled to hybrid MS/MS/Ion trap | C18 column (100 mm × 4.6 mm, particle size 2.6 μm). MP: 0.2% formic acid (A) and acetonitrile with 0.2% formic acid (B) Flow rate = 0.5 mL/min |
35 min | LOD = 0.03–15 ng/L LOQ = 0.9–50 ng/L |
[88] |
| Acetylsalicylic acid, naproxen, methyl and ethyl paraben, estrone, 17β-estradiol | Drinking water | SPE-DEX | LC-ESI-MS/MS | In −ESI: C18 column (50 mm × 2.1 mm, particle size 2.7 μm). MP: 10 mM N-methylmorpholine (A) and methanol (B). Flow rate = 0.5 mL/min In +ESI: Kinetex PFP HPLC column column (50 mm × 2.1 mm, particle size 2.6 μm). MP: 5 mM ammonium acetate (A) and methanol (B). Flow rate = 0.8 mL/min |
5.5 min (−ESI) 6.5 min (+ESI) |
Recovery = 32.9–130.1% LOD = 0.2–0.9 ng/L LOQ = 1.0–2.3 ng/L R2 = 0.9976–0.9996 |
[89] |
| Chloroform, tribromomethane, and dichloroacetonitrile | Drinking water | SPE-DEX | GC-ECD | DB1701 column | N.R. | LOD = 0.01–0.03 μg/L LOQ = 0.2 μg/L R2 = 0.9926–0.9992 |
[89] |
MP: mobile phase; LOD: limit of detection; LOQ: limit of quantification; λ: wavelength; ESI: electrospray ionization; IT: ion trap; TOF: time of Flight; PDA: photo diode array; ECD: electron capture detector; N.R.: not reported.