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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

Sigma-Aldrich
Formic acid, ACS reagent, ≥96%
Sigma-Aldrich
Ammonium hydroxide solution, 28% NH3 in H2O, ≥99.99% trace metals basis
Sigma-Aldrich
Ammonium hydroxide solution, puriss., meets analytical specification of Ph. Eur., 25-30% NH3 basis
Naproxen, European Pharmacopoeia (EP) Reference Standard
Supelco
Ketoprofen, Pharmaceutical Secondary Standard; Certified Reference Material
Mesalazine impurity A, European Pharmacopoeia (EP) Reference Standard
USP
Methyl alcohol, United States Pharmacopeia (USP) Reference Standard
Nimesulide for peak identification, European Pharmacopoeia (EP) Reference Standard
Sigma-Aldrich
Ammonium hydroxide solution, ACS reagent, 28.0-30.0% NH3 basis
Sigma-Aldrich
Formic acid, reagent grade, ≥95%
Supelco
Aspirin (Acetyl Salicylic Acid), Pharmaceutical Secondary Standard; Certified Reference Material
Supelco
Naproxen, Pharmaceutical Secondary Standard; Certified Reference Material
Supelco
Acetaminophen, Pharmaceutical Secondary Standard; Certified Reference Material
Sigma-Aldrich
Methanol-12C, 99.95 atom % 12C
Sigma-Aldrich
(S)-(+)-6-Methoxy-α-methyl-2-naphthaleneacetic acid, 98%
Sigma-Aldrich
Methanol solution, NMR reference standard, 4% in methanol-d4 (99.8 atom % D), NMR tube size 3 mm × 8 in.
Supelco
Naproxen, VETRANAL®, analytical standard
Sigma-Aldrich
Formic acid, ≥95%, FCC, FG
Sigma-Aldrich
Ketoprofen, meets USP testing specifications
Sigma-Aldrich
Ketoprofen, ≥98% (TLC)
Sigma-Aldrich
Acetaminophen, meets USP testing specifications, 98.0-102.0%, powder
Sigma-Aldrich
Acetaminophen, analytical standard
Sigma-Aldrich
Aspirin, meets USP testing specifications
Supelco
Ketoprofen, VETRANAL®, analytical standard
Sigma-Aldrich
Acetaminophen, BioXtra, ≥99.0%
USP
Naproxen, United States Pharmacopeia (USP) Reference Standard
USP
4-Aminophenol, United States Pharmacopeia (USP) Reference Standard
USP
Acetaminophen, United States Pharmacopeia (USP) Reference Standard
USP
Aspirin, United States Pharmacopeia (USP) Reference Standard
Ketoprofen, European Pharmacopoeia (EP) Reference Standard