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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
Naproxen, meets USP testing specifications
Supelco
4-Aminophenol (Acetaminophen Related Compound K) (Paracetamol Impurity K), Pharmaceutical Secondary Standard; Certified Reference Material
Sigma-Aldrich
Methanol solution, NMR reference standard, 4% in methanol-d4 (99.8 atom % D), NMR tube size 3 mm × 8 in.
Supelco
Methanol solution, contains 0.10 % (v/v) formic acid, UHPLC, suitable for mass spectrometry (MS), ≥99.5%
Sigma-Aldrich
(S)-(+)-6-Methoxy-α-methyl-2-naphthaleneacetic acid, 98%
Sigma-Aldrich
Ammonium hydroxide solution, BioUltra, ~1 M NH3 in H2O (T)
Sigma-Aldrich
Hydrogen chloride, ReagentPlus®, ≥99%
Sigma-Aldrich
Methanol-12C, 99.95 atom % 12C
Sigma-Aldrich
Nimesulide
Sigma-Aldrich
Ketoprofen, meets USP testing specifications
Supelco
Naproxen, Pharmaceutical Secondary Standard; Certified Reference Material
Sigma-Aldrich
Ammonium hydroxide solution, puriss. p.a. plus, ≥25% NH3 in H2O
Sigma-Aldrich
Formic acid, ACS reagent, ≥96%
Sigma-Aldrich
Formic acid, puriss., meets analytical specifications of DAC, FCC, 98.0-100%
Sigma-Aldrich
Ammonium hydroxide solution, puriss. p.a., reag. ISO, reag. Ph. Eur., ~25% NH3 basis
Sigma-Aldrich
Ammonium hydroxide solution, ACS reagent, 28.0-30.0% NH3 basis
Sigma-Aldrich
Ammonium hydroxide solution, 28% NH3 in H2O, ≥99.99% trace metals basis
Mesalazine impurity A, European Pharmacopoeia (EP) Reference Standard
Naproxen, European Pharmacopoeia (EP) Reference Standard
Sigma-Aldrich
Ammonium hydroxide solution, puriss., 30-33% NH3 in H2O
Sigma-Aldrich
Ammonium hydroxide solution, puriss., meets analytical specification of Ph. Eur., 25-30% NH3 basis
Nimesulide, European Pharmacopoeia (EP) Reference Standard
Nimesulide for peak identification, European Pharmacopoeia (EP) Reference Standard
Supelco
Nimesulide, Pharmaceutical Secondary Standard; Certified Reference Material
USP
Methyl alcohol, United States Pharmacopeia (USP) Reference Standard
Supelco
Acetaminophen solution, 1.0 mg/mL in methanol, ampule of 1 mL, certified reference material, Cerilliant®
Ketoprofen, European Pharmacopoeia (EP) Reference Standard
Diclofenac sodium, European Pharmacopoeia (EP) Reference Standard
USP
Ketoprofen, United States Pharmacopeia (USP) Reference Standard
USP
Naproxen, United States Pharmacopeia (USP) Reference Standard