Determination of fluoroquinolones in aquaculture products by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)

Abstract

An ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was developed for the determination of fluoroquinolones–ciprofloxacin (CIPRO), danofloxacin (DANO), enrofloxacin (ENRO) and sarafloxacin (SARA)–in aquaculture products, specifically salmon, shrimp and tilapia. After initial sample extraction with an acidic acetonitrile solution, the extract was diluted with dichloromethane and centrifuged, then an aliquot was concentrated and applied to a C18 solid-phase extraction cartridge and concentrated for a second time. The resultant residue was dissolved in acetonitrile, diluted with water, and then further defatted with hexane. The fluoroquinolone residues were determined by UPLC with an HSS T3 C18 reverse-phase column using an ammonium hydroxide-formic acid buffer in an acetonitrile gradient with MS/MS detection using multiple reaction monitoring. Average recoveries for salmon tissue ranged from 73% for DANO to 95% for SARA, for shrimp from 71% for DANO to 109% for SARA, and from 62% for DANO to 111% for SARA in tilapia, fortified at the 1.0 ng g⁻¹ level. Standard curves were linear between 0.002 and 0.5 ng injected for all compounds. Detection limits of 0.2 ng g⁻¹ for CIPRO, DANO, ENRO, and SARA were easily obtainable. The operational errors, interferences, and recoveries for fortified samples demonstrate that this described method is suitable for routine use in a regulatory programme. The recommended method is simple, rapid, specific and reliable for the routine monitoring of fluoroquinolone residues in aquatic species such as salmon, tilapia and shrimp.

Keywords:

• ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)
• ciprofloxacin
• danofloxacin, enrofloxacin
• sarafloxacin
• aquacultured products
• multiresidue method
• fluoroquinolones