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  • Development of a SPE-UHPLC-MS/MS methodology for the determination of non-steroidal anti-inflammatory and analgesic pharmaceuticals in seawater.

Development of a SPE-UHPLC-MS/MS methodology for the determination of non-steroidal anti-inflammatory and analgesic pharmaceuticals in seawater.

Journal of pharmaceutical and biomedical analysis (2014-07-09)
Paula Paíga, Aleksandar Lolić, Floris Hellebuyck, Lúcia H M L M Santos, Manuela Correia, Cristina Delerue-Matos
ABSTRACT

An analytical methodology for the simultaneous determination of seven pharmaceuticals and two metabolites belonging to the non-steroidal anti-inflammatory drugs (NSAIDs) and analgesics therapeutic groups was developed based on off-line solid-phase extraction and ultra-high performance liquid chromatography coupled to tandem mass spectrometry (SPE-UHPLC-MS/MS). Extraction conditions were optimized taking into account parameters like sorbent material, sample volume and sample pH. Method detection limits (MDLs) ranging from 0.02 to 8.18 ng/L were obtained. This methodology was successfully applied to the determination of the selected pharmaceuticals in seawater samples of Atlantic Ocean in the Northern Portuguese coast. All the pharmaceuticals have been detected in the seawater samples, with pharmaceuticals like ibuprofen, acetaminophen, ketoprofen and the metabolite hydroxyibuprofen being the most frequently detected at concentrations that can reach some hundreds of ng/L.

MATERIALS
Product Number
Brand
Product Description

USP
Acetaminophen, United States Pharmacopeia (USP) Reference Standard
USP
Aspirin, United States Pharmacopeia (USP) Reference Standard
Sigma-Aldrich
4-Aminophenol, ≥98%
Sigma-Aldrich
Methanol-12C, 99.95 atom % 12C
Sigma-Aldrich
(S)-(+)-6-Methoxy-α-methyl-2-naphthaleneacetic acid, 98%
Sigma-Aldrich
Formic acid, ≥95%, FCC, FG
Supelco
Acetaminophen, Pharmaceutical Secondary Standard; Certified Reference Material
Supelco
Naproxen, Pharmaceutical Secondary Standard; Certified Reference Material
Supelco
Aspirin (Acetyl Salicylic Acid), Pharmaceutical Secondary Standard; Certified Reference Material
USP
4-Aminophenol, United States Pharmacopeia (USP) Reference Standard
Supelco
Ketoprofen, Pharmaceutical Secondary Standard; Certified Reference Material
Nimesulide for peak identification, European Pharmacopoeia (EP) Reference Standard
USP
Diclofenac sodium, United States Pharmacopeia (USP) Reference Standard
USP
Ketoprofen, United States Pharmacopeia (USP) Reference Standard
USP
Naproxen, United States Pharmacopeia (USP) Reference Standard
Sigma-Aldrich
Methanol solution, NMR reference standard, 4% in methanol-d4 (99.8 atom % D), NMR tube size 3 mm × 8 in.
Supelco
4-Aminophenol (Acetaminophen Related Compound K) (Paracetamol Impurity K), Pharmaceutical Secondary Standard; Certified Reference Material
Sigma-Aldrich
Nimesulide
Sigma-Aldrich
Ammonium hydroxide solution, BioUltra, ~1 M NH3 in H2O (T)
Supelco
Ketoprofen, VETRANAL®, analytical standard
Supelco
Nimesulide, Pharmaceutical Secondary Standard; Certified Reference Material
Diclofenac sodium, European Pharmacopoeia (EP) Reference Standard
Nimesulide, European Pharmacopoeia (EP) Reference Standard
Sigma-Aldrich
Formic acid, ACS reagent, ≥88%
Naproxen, European Pharmacopoeia (EP) Reference Standard
Sigma-Aldrich
Formic acid, ACS reagent, ≥96%
Sigma-Aldrich
Ammonium hydroxide solution, ACS reagent, 28.0-30.0% NH3 basis
Sigma-Aldrich
Formic acid, reagent grade, ≥95%
USP
Methyl alcohol, United States Pharmacopeia (USP) Reference Standard
Sigma-Aldrich
Acetaminophen, analytical standard