Fully-Automated SPE Coupled to UPLC-MS/MS Method for Simultaneous Detection of Trace Sulfonamides, Quinolones, and Macrolide antibiotics in Water

Abstract

A fully automated solid-phase extraction (SPE) coupled ultra-high-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) method was developed for analysis of antibiotics (sulfonamides, quinolones, and macrolide) in water matrices. Sample preparation optimization included the selection of the best SPE material and configuration (HLB disks), sample volume (500−1000 mL water sample (pH = 3)) with a flow rate at 1−2 mL min− 1, and an elution procedure with 2 ⋅ 6 mL methanol, 2 ⋅ 6 mL acetone-methanol (V/V = 1/1). Meanwhile, the parameters for UPLC-MS/S detection of each analyte was optimized, including LC retention time, and MS parameters. The instrumental limits of detection (LOD) and quantification (LOQ) of analytes ranged from 0.01−0.72 µg L− 1 and 0.05−2.39 µg L− 1, respectively, with good linear correlation (R2 > 0.995) and precision (< 9.9%). Matrix spike recoveries ranged between 63.3−99.2% in pure water, 60.8−91.3% in surface water (SW), and 59.9−102.8% in wastewater effluent (WWE) with relative standard deviations (RSD) below 11%. The matrix effects (MEs) observed for most of the analytes were ion suppression (0−25.8%) except for four compounds that had enhancement (0−8.0 %) in SW or WWE. This method can basically meet the needs of trace antibiotic residues detection in waters. Trace levels of sulfonamides, quinolones and macrolides using the developed antibiotic method were below LOQ (BQL) −94.47 ng L− 1 in WWEs and BQL−15.47 ng L− 1 in SW in the lower reaches of the Yangtze River Basin.

Toxicity of fluoroquinolones on the cladoceran Daphnia magna

“…Also, norfloxacin (4.3%; 1/23) and ofloxacin (7.4%; 2/27) molecules represent a risk (RQ > 1) for river water samples from Australia (Watkinson et al, 2009) and Spain (Ginebreda et al, 2010; López‐Roldán et al, 2010), respectively. On the contrary, low risks are presented for levofloxacin (RQ: 0.013–0.076) and marbofloxacin (RQ: 0.003–0.010), due to the low concentrations reported in countries such as China (Pan et al, 2020; Zheng et al, 2021), Kenya (Madikizela et al, 2017), and the United States (Conley et al, 2008; Wolfe et al, 2015).…”

“…In this regard, fluoroquinolones (FQs) were detected in river water in various countries, such as Argentina (Teglia et al, 2019; Valdés et al, 2014), Australia (Watkinson et al, 2009), China (Huang et al, 2020; Li et al, 2012; Lyu et al, 2020; Pan et al, 2020; Wei et al, 2012; Zheng et al, 2021; Zou et al, 2011), Finland (Vieno et al, 2006), France (Coetsier et al, 2009; Conley et al, 2008; Cui et al, 2011; Dinh et al, 2011), Hong Kong (Minh et al, 2009), Ghana (Azanu et al, 2018), Iran (Mirzaei et al, 2018), Italy (Sturini et al, 2009), Kenia (Madikizela et al, 2017), South Africa (Agunbiade & Moodley, 2016), Romania (Chitescu et al, 2015), Spain (López‐Serna et al, 2011), Sri Lanka (Guruge et al, 2019), the United States (Wolfe et al, 2015), among others. Also, FQs molecules have been reported in lake surface water in various countries such as Brazil (Sodré et al, 2010), China (Tong et al, 2011), India (Rao et al, 2008), Italy (Sturini et al, 2009), and Vietnam (Duong et al, 2021).…”