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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
Sigma-Aldrich
4-Aminophenol, ≥98%
Sigma-Aldrich
Methanol-12C, 99.95 atom % 12C
Sigma-Aldrich
Formic acid, ≥95%, FCC, FG
Supelco
Acetaminophen, 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
4-Aminophenol (Acetaminophen Related Compound K) (Paracetamol Impurity K), Pharmaceutical Secondary Standard; Certified Reference Material
Sigma-Aldrich
Ammonium hydroxide solution, BioUltra, ~1 M NH3 in H2O (T)
Diclofenac sodium, 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%
Sigma-Aldrich
Ammonium hydroxide solution, ACS reagent, 28.0-30.0% NH3 basis
Sigma-Aldrich
Acetaminophen, BioXtra, ≥99.0%
Ketoprofen, European Pharmacopoeia (EP) Reference Standard
Sigma-Aldrich
Hydrochloric acid, 36.5-38.0%, BioReagent, for molecular biology
Supelco
Hydrochloric acid solution, volumetric, 0.1 M HCl (0.1N), endotoxin free
Sigma-Aldrich
Acetylsalicylic acid, ≥99.0%
Sigma-Aldrich
Methanol, Absolute - Acetone free
Sigma-Aldrich
Methanol, ACS spectrophotometric grade, ≥99.9%
Sigma-Aldrich
Methanol, BioReagent, ≥99.93%
Sigma-Aldrich
Hydrochloric acid, ACS reagent, 37%
Sigma-Aldrich
Methanol, ACS reagent, ≥99.8%
Sigma-Aldrich
Hydrochloric acid solution, 32 wt. % in H2O, FCC
Supelco
Methanol, Pharmaceutical Secondary Standard; Certified Reference Material
Supelco
Diclofenac sodium salt, Pharmaceutical Secondary Standard; Certified Reference Material
Sigma-Aldrich
Methanol, NMR reference standard
Supelco
Ibuprofen, Pharmaceutical Secondary Standard; Certified Reference Material
Ibuprofen for peak identification, European Pharmacopoeia (EP) Reference Standard
Sigma-Aldrich
Ibuprofen, meets USP testing specifications